Charaterising water-rock interaction in a mixed carbonate-evaporite karstified aquifer system, Qatar

NASA Astrophysics Data System (ADS)

Thirathititham, R.; Whitaker, F.

2017-12-01

Qatar is an arid country, most of the rainfall (80 mm/yr) occurring during intense storms. Surface runoff is endorheic and recharge is facilitated by karst features developed over an extended (c.30 Ma) period of exposure of the carbonate bedrock. In December 2016, we sampled a rare intense rainfall event (41 mm over 3 days), after which waters ponded within low-relief terminal depressions prior to infiltration. We compare the chemistry of these recharge waters with that of ground waters from 76 wells distributed across Qatar to understand the nature and spatial distribution of water-rock interaction. Using Cl- as a conservative tracer for seawater mixing, we calculate concentrations of rock-derived Ca2+, Mg2+ and SO42-. During surface detention, rain chemistry is modified by evaporation and interaction with clays and the surface bedrock over days to weeks. However, groundwater chemistry is dominated by subsurface interaction between recharge waters and the karstified Tertiary aquifers. These include the largely dolomitic Paleocene to Lower Eocene Umm er Radhuma (UER) and overlying Lower Eocene Rus, with the Middle Eocene Abarug limestone forming a locally important aquifer in the south west. Away from coastal areas which show clear evidence of salinisation, TDS of groundwaters in the interior of the peninsula increases from north to south. All groundwaters are significantly enriched in SO42-, but this enrichment is marked greater in the south. This likely reflects the presence of a unit of middle Rus gypsum that in the south of the country confines the Lower Rus and UER aquifers, whilst in the north either gypsum was not deposited or has been dissolved. Waters in the Abarug limestone show limited sulfate enrichment and a 1:1 molar ratio of rock-derived SO42-: Ca2+, but across much of the country both SO42- enrichment and SO42-: Ca2+ molar ratio are significantly higher, the latter reaching 2:1 and suggesting an additional sink for Ca2+. The dolomite aquifer waters are also enriched in Mg2+, indicating replacement of dolomite by calcite (dedolomitization), driven by the release of Ca2+ from gypsum dissolution. Whilst current rates of gypsum dissolution and dedolomitization may be limited by the arid climate, this process is likely to have been more active during pluvial periods and to have played a role in karst development.

The stratigraphic record of Khawr Al Maqta, Abu Dhabi, United Arab Emirates

NASA Astrophysics Data System (ADS)

Lokier, S. W.; Herrmann, S.

2012-04-01

Well-constrained modern depositional analogues are vital to the development of accurate geological reservoir models. The development of realistic hydrocarbon reservoir models requires the application of high-precision, well-constrained outcrop and sub-surface data sets with accurately-documented facies geometries and depositional sequence architectures. The Abu Dhabi coastline provides the best modern analogue for the study of ramp-style carbonate depositional facies akin to those observed in the sub-surface reservoirs of the United Arab Emirates (UAE). However, all previous studies have relied on temporally limited surface datasets. This study employed thirty five shallow subsurface cores spanning the width of the Khawr Al Maqta - the narrow shallow tidal channel that separates Abu Dhabi Island from the mainland. The cores were taken over a transect measuring 1.2 km in length by 50 m wide thus providing a high-resolution record of sub-surface facies geometries in a stratigraphically complex setting. Geometries in these Pleistocene to Holocene facies are complex with interdigitating, laterally heterogeneous carbonate, siliciclastic and evaporite units represented throughout the area of the study. Carbonate facies range from molluscan rudstones to marls and are all indicative of deposition in a shallow, relatively low energy marine setting akin to that seen in the environs of Abu Dhabi Island today. Texturally mature quartz sands occur as thin lenses and as thin cross bedded or laminated horizons up to twenty five centimetres thick. Glauconitic mudstones are common and locally exhibit evidence of rootlets and desiccation cracks. Evaporites are present in the form of gypsum occurring as isolated crystals and nodules or as massive chicken-wire units in excess of three metres thick. All of these textures are consistent with evaporite development in the shallow subsurface. Early, shallow-burial diagenesis has been important. Bioclasts are pervasively leached throughout the stratigraphic sequence thereby resulting in a significant enhancement in porosity in the carbonate lithologies. This pervasive mouldic porosity is locally occluded by the precipitation of gypsum cements. The displacive precipitation of significant quantities of gypsum has resulted in the deformation of primary sedimentary structures. This complex sequence of mixed carbonate-siliciclastic-evaporite lithofacies is interpreted to record repeated episodes of flooding and sub-aerial exposure associated with the waxing and waning of the Pleistocene ice-sheets. During periods of relative sea-level fall carbonate sequences entered the meteoric realm with the consequent dissolution of unstable bioclasts. Transgression and reflooding once again isolated Abu Dhabi Island from the mainland, thus permitting the precipitation of shallow-water carbonate lithofacies. During sea-level highstands the north-westerly Shamal wind transported carbonate sediments into the lee-of the island resulting in the south-easterly shore-wards development of a tombolo. However, the strong tidal currents of the Khawr Al Maqta prevented final connection to the mainland, thus ensuring the isolation of Abu Dhabi until the subsequent regression.

Cation and anion leaching and growth of Acacia saligna in bauxite residue sand amended with residue mud, poultry manure and phosphogypsum.

PubMed

Jones, B E H; Haynes, R J; Phillips, I R

2012-03-01

To examine (1) the effect of organic (poultry manure) and inorganic (residue mud and phosphogypsum) amendments on nutrient leaching losses from residue sand and (2) whether amendments improve the growth of plants in residue sand. Leaching columns were established using residue sand. The phosphogypsum-treated surface layer (0-15 cm) was amended with poultry manure and/or bauxite residue mud and the subsurface layer (15-45 cm) was either left untreated or amended with phosphogypsum. Much of the Na⁺, K⁺, Cl⁻ and SO₄²⁻ was lost during the first four leachings. Additions of phosphogypsum to both surface and subsurface layers resulted in partial neutralization of soluble alkalinity. Mean pH of leachates ranged from 8.0 to 8.4, the major cation leached was Na⁺ and the major balancing anion was SO₄²⁻ . Where gypsum was not applied to the subsurface, mean pH of leachates was 10.0-10.9, the main cation leached was still Na⁺ and the main balancing anions were a combination of SO₄²⁻ and HCO₃⁻/CO₃²⁻. At the end of the experiment, concentrations of exchangeable Na⁺ in the subsurface layers were similar regardless of whether gypsum had been applied to that layer or not. Yields of Acacia saligna were promoted by additions of poultry manure to the surface layer but unaffected by gypsum incorporation into the subsurface layer. Lack of reaction of phosphogypsum with the subsurface layer is unlikely to be a major factor limiting revegetation of residue sand since in the absence of phosphogypsum the excess Na⁺ leaches with the residual alkalinity (HCO₃⁻/CO₃²⁻) rather than SO₄²⁻.

Implications of Earth analogs to Martian sulfate-filled Fractures

NASA Astrophysics Data System (ADS)

Holt, R. M.; Powers, D. W.

2017-12-01

Sulfate-filled fractures in fine-grained sediments on Mars are interpreted to be the result of fluid movement during deep burial. Fractures in the Dewey Lake (aka Quartermaster) Formation of southeastern New Mexico and west Texas are filled with gypsum that is at least partially synsedimentary. Sulfate in the Dewey Lake takes two principal forms: gypsum cement and gypsum (mainly fibrous) that fills fractures ranging from horizontal to vertical. Apertures are mainly mm-scale, though some are > 1 cm. The gypsum is antitaxial, fibrous, commonly approximately perpendicular to the wall rock, and displays suture lines and relics of the wall rock. Direct evidence of synsedimentary, near-surface origin includes gypsum intraclasts, intraclasts that include smaller intraclasts that contain gypsum clasts, intraclasts of gypsum with suture lines, gypsum concentrated in small desiccation cracks, and intraclasts that include fibrous gypsum-filled fractures that terminate at the eroded clast boundary. Dewey Lake fracture fillings suggest that their Martian analogs may also have originated in the shallow subsurface, shortly following the deposition of Martian sediments, in the presence of shallow aquifers.

Origin of increased sulfate in groundwater at the ETF disposal site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thornton, E.C.

1997-09-01

Treated effluent being discharged to the vadose zone from the C-018H Effluent Treatment Facility (ETF) at the Hanford Site has infiltrated vertically to the unconfined aquifer, as indicated by increasing tritium activity levels in the groundwater. Well 699-48-77A, in particular, exhibits increased levels of tritium and also sulfate in the groundwater. The origin of increased sulfate levels in the groundwater is attributed to the dissolution of gypsum as the effluent flows through the vadose zone. This is supported by the observation that sulfate was found to be present in soils collected from the vadose zone at an average value ofmore » about 10.6 ppm. The maximum observed sulfate concentration of 190 mg/L from well 699-48-77A was observed on August 6, 1996, and is less than the maximum value of 879 mg/L that potentially could be achieved if water in the vadose zone was to attain saturation with respect to gypsum and calcite. It is suggested that infiltration rates were high enough that the effluent did not completely equilibrate with gypsum in the vadose zone, and thus, sulfate levels remained below gypsum saturation levels. Sulfate levels appear to be dropping, which may be attributed to the completion of the dissolution of the bulk of gypsum present along the vadose zone flow path traversed by the effluent. Geochemical modeling was undertaken to evaluate the influence of effluent chemistry on sulfate concentration levels in the presence of excess calcite and gypsum. In general, the effect is fairly minor for dilute solutions, but becomes more significant for concentrated solutions.« less

Hydrobiogeochemical interactions in 'anoxic' limestone drains for neutralization of acidic mine drainage

USGS Publications Warehouse

Robbins, E.I.; Cravotta, C.A.; Savela, C.E.; Nord, G.L.

1999-01-01

Processes affecting neutralization of acidic coal mine drainage were evaluated within 'anoxic' limestone drains (ALDs). Influents had pH???3.5 and dissolved oxygen <2 mg/l. Even though effluents were near neutral (pH 6 and alkalinity acidity), two of the four ALDs were failing due to clogging. Mineral-saturation indices indicated the potential for dissolution of calcite and gypsum, and precipitation of Al3+ and Fe3+ compounds. Cleavage mounts of calcite and gypsum that were suspended within the ALDs and later examined microscopically showed dissolution features despite coatings by numerous bacteria, biofilms, and Fe-Al-Si precipitates. In the drain exhibiting the greatest flow reduction, Al-hydroxysulfates had accumulated on limestone surfaces and calcite etch points, thus causing the decline in transmissivity and dissolution. Therefore, where Al loadings are high and flow rates are low, a pre-treatment step is indicated to promote Al removal before diverting acidic mine water into alkalinity-producing materials. ?? 1998 Elsevier Science Ltd.

Mineral dissolution and secondary precipitation on quartz sand in simulated Hanford tank solutions affecting subsurface porosity

NASA Astrophysics Data System (ADS)

Wang, Guohui; Um, Wooyong

2012-11-01

Highly alkaline nuclear waste solutions have been released from underground nuclear waste storage tanks and pipelines into the vadose zone at the US Department of Energy's Hanford Site in Washington, causing mineral dissolution and re-precipitation upon contact with subsurface sediments. High pH caustic NaNO3 solutions with and without dissolved Al were reacted with quartz sand through flow-through columns stepwise at 45, 51, and 89 °C to simulate possible reactions between leaked nuclear waste solution and primary subsurface mineral. Upon reaction, Si was released from the dissolution of quartz sand, and nitrate-cancrinite [Na8Si6Al6O24(NO3)2] precipitated on the quartz surface as a secondary mineral phase. Both steady-state dissolution and precipitation kinetics were quantified, and quartz dissolution apparent activation energy was determined. Mineral alteration through dissolution and precipitation processes results in pore volume and structure changes in the subsurface porous media. In this study, the column porosity increased up to 40.3% in the pure dissolution column when no dissolved Al was present in the leachate, whereas up to a 26.5% porosity decrease was found in columns where both dissolution and precipitation were observed because of the presence of Al in the input solution. The porosity change was also confirmed by calculation using the dissolution and precipitation rates and mineral volume changes.

Processes of mineralization in the Hauran Basin (Syria and Jordan) and in adjoining areas

NASA Astrophysics Data System (ADS)

Raggad, Marwan Al; Elias, Salameh; Inbar, Nimrod; Rosenthal, Eliahu; Möller, Peter; Siebert, Christian; Magri, Fabien

2017-04-01

Volcanic rocks covering vast areas in central north Jordan and in central and southern Syria erupted during 6 different phases starting in Miocene and continuing - with major interruptions - into the Holocene. The petrological composition of the different flows of the Harrat ash Shaam Basalt complex is quite homogeneous with the major minerals: Plagioclase, K-feldspar, clinopyroxene, amphibole, biotite, olivine, magnetite, limonite, goethite, pyrite and chalcopyrite. The oldest basalts cover Cretaceous and Paleogene sediments, which at that time formed the land surface of drainage basins. The basaltic aquifer contains groundwater with a wide range of salinities. They represent a continuous sequence of increasingly mineralized groundwater originating from precipitation over Jebel Druz flowing radially into all directions, in coincidence with the topographic slopes. Along the flow-paths halite and gypsum are dissolved. Ca2+ not only depends on gypsum dissolution but also increases proportionally to Mg. This may suggest that the combination of Ca2+, Mg2+ and sulfate is a saline endmember fluid originating from the underlying carbonate formations of the basalt. Mixing with recharge water could explain the chemical composition of the various types of water. The signature of dissolved gypsum and halite indicates dissolution of evaporites that might have formed by evaporation either before the basalt covered the area or due to the hot basalts heating up the underlying carbonates and their enclosed fluids. Evaporation of water precipitated evaporites. Ca and Mg halides are hygroscopic, thus they are only present in solution. Such saline water, however, has not affected the low saline groundwater because their increase in Ca depends neither on the increase of Mg2+ nor of SO42-. This leaves the formation of clay minerals as the probably sink for Na. Inverse modelling applying PHREEQC with phreeq.dat database reveals that the mineralization of groundwater increases due to dissolution of increasing amounts of halite and gypsum which are mass-wise, the most important reactants. Concurrently, albite increasingly precipitates. Montmorillonite, gibbsite and calcite form, whereas kaolinite is consumed. Sulfides are oxidized. δD and δ18O of well and springs fit an evaporation line rooted on the Ajloun MWL. Hydrochemically, there are two sources of salts: Mixing with a saline endmember brine and/or dissolution of evaporites. Near Jebel Druz, dissolution of evaporites dominates, whereas mixing with a saline endmember and formation of clay minerals occur at greater distances.

Use of laboratory geophysical and geotechnical investigation methods to characterize gypsum rich soils

NASA Astrophysics Data System (ADS)

Bhamidipati, Raghava A.

Gypsum rich soils are found in many parts of the world, particularly in arid and semi-arid regions. Most gypsum occurs in the form of evaporites, which are minerals that precipitate out of water due to a high rate of evaporation and a high mineral concentration. Gypsum rich soils make good foundation material under dry conditions but pose major engineering hazards when exposed to water. Gypsum acts as a weak cementing material and has a moderate solubility of about 2.5 g/liter. The dissolution of gypsum causes the soils to undergo unpredictable collapse settlement leading to severe structural damages. The damages incur heavy financial losses every year. The objective of this research was to use geophysical methods such as free-free resonant column testing and electrical resistivity testing to characterize gypsum rich soils based on the shear wave velocity and electrical resistivity values. The geophysical testing methods could provide quick, non-intrusive and cost-effective methodologies to screen sites known to contain gypsum deposits. Reconstituted specimens of ground gypsum and quartz sand were prepared in the laboratory with varying amounts of gypsum and tested. Additionally geotechnical tests such as direct shear strength tests and consolidation tests were conducted to estimate the shear strength parameters (drained friction angle and cohesion) and the collapse potential of the soils. The effect of gypsum content on the geophysical and geotechnical parameters of soil was of particular interest. It was found that gypsum content had an influence on the shear wave velocity but had minimal effect on electrical resistivity. The collapsibility and friction angle of the soil increased with increase in gypsum. The information derived from the geophysical and geotechnical tests was used to develop statistical design equations and correlations to estimate gypsum content and soil collapse potential.

Mineral Dissolution and Secondary Precipitation on Quartz Sand in Simulated Hanford Tank Solutions Affecting Subsurface Porosity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Guohui; Um, Wooyong

2012-11-23

Highly alkaline nuclear waste solutions have been released from underground nuclear waste storage tanks and pipelines into the vadose zone at the U.S. Department of Energy’s Hanford Site in Washington, causing mineral dissolution and re-precipitation upon contact with subsurface sediments. High pH caustic NaNO3 solutions with and without dissolved Al were reacted with quartz sand through flow-through columns stepwise at 45, 51, and 89°C to simulate possible reactions between leaked nuclear waste solution and primary subsurface mineral. Upon reaction, Si was released from the dissolution of quartz sand, and nitrate-cancrinite [Na8Si6Al6O24(NO3)2] precipitated on the quartz surface as a secondary mineralmore » phase. Both steady-state dissolution and precipitation kinetics were quantified, and quartz dissolution apparent activation energy was determined. Mineral alteration through dissolution and precipitation processes results in pore volume and structure changes in the subsurface porous media. In this study, the column porosity increased up to 40.3% in the pure dissolution column when no dissolved Al was present in the leachate, whereas up to a 26.5% porosity decrease was found in columns where both dissolution and precipitation were observed because of the presence of Al in the input solution. The porosity change was also confirmed by calculation using the dissolution and precipitation rates and mineral volume changes.« less

The Jettencave, Southern Harz Mountains, Germany: Geophysical observations and a structural model of a shallow cave in gypsum/anhydrite-bearing rocks

NASA Astrophysics Data System (ADS)

Kaufmann, Georg; Romanov, Douchko

2017-12-01

Gypsum and anhydrite are soluble rocks, where fissures and bedding partings can be enlarged with time by the dissolution of the mineral species through water. The selective enlargement results in sub-surface voids acting as preferential flow path for the drainage of the rock. With time, larger cavities develop, and a network of cave passages can evolve. If the enlarged cave voids are not too deep under the surface, geophysical measurements can be used to detect, identify and trace these structures. We have used gravity measurements (GRAV), electrical resistivity imaging (ERI), self-potential measurements (SP), electrical conductivity measurements (EC), and ground-penetrating radar (GPR) above the cave Jettenhöhle, a cave located in the southern Harz Mountains in Germany. The Jettencave is developed in the Hauptanhydrit formation of the Permian Zechstein sequence, characterised by large breakdown rooms and an exposed water table. The overburden of the cave is only around 10-15 m, and dolomitic rocks are located in close vicinity. We present results from our geophysical surveys in vicinity of the cave. We are able to identify the cave geometry from GRAV, ERI, and GPR measurements, which distinguish the local lithology of the Permian Zechstein rocks in the area. From the ERI and EC measurements, we derive information on the void volume in the soluble rocks. We finally present a three-dimensional structural model of the Jettencave and its surroundings, based on our geophysical results and the hydrological interpretation.

Dynamic controls on accretion and lithification of modern gypsum-dominated thrombolites, Los Roques, Venezuela

NASA Astrophysics Data System (ADS)

Petrash, Daniel A.; Gingras, Murray K.; Lalonde, Stefan V.; Orange, François; Pecoits, Ernesto; Konhauser, Kurt O.

2012-03-01

Meter-sized thrombolites coated by well developed zonally differentiated microbial mats have been found growing in the shallow waters (depth < 1 m) of a restricted hypersaline lagoon on the Archipelago Los Roques in Venezuela. By contrast, within the deeper parts of the studied lagoon, sedimentation is characterized by several decimeters of organic-rich material containing gypsum granules lacking carbonate cementation. The lithification of the thrombolites is thought to have proceeded as follows. First, extracellular polymeric substances (EPS) comprising the microbial mat concentrate Ca2 + and other metal cations by adsorption from the hypersaline waters. Second, some of these bound metals then serve as nucleation sites for primary calcium carbonate (CaCO3) precipitation. Third, while carbonate phases are forming in some zones of the mat, in others zones they are being re-dissolved due to the acidity generated through the metabolism of sulfide-oxidizing bacteria, Fourth, as the dissolved sulfide is oxidized into sulfate, the pore-water become saturated with respect to gypsum (CaSO4·2H2O). Fifth, as primary gypsum precipitates within the structures, endolithic sulfate-reducing bacteria metabolize the sulfate moiety in the mineral phase, while simultaneously oxidizing the EPS trapped during accretion. Sixth, as microbial EPS degradation proceeds, the anaerobic oxidation of specific protein fractions of the EPS matrix leads to increased alkalinity, the partial dissolution of gypsum, supersaturation with respect to calcium carbonate, and ultimately pseudomorphic aragonite replacement; this differs from secondary calcite cements in being enriched in 12C, and depleted in minor and trace metals initially associated with the EPS. The biogeochemical processes occurring in this thrombolite-constructing lagoon represent a novel field site for studying the chemical and isotopic processes characterizing early diagenetic gypsum and the role microbes play in its precipitation, dissolution and calcification. In this regard, insights gained from this modern field site will help to better understand mechanisms by which some Precambrian microbialites were lithified.

Detailed 3D Geophysical Model of the Shallow Subsurface (Zancara River Basin, Iberian Peninsula)

NASA Astrophysics Data System (ADS)

Carbonell, R.; Marzán, I.; Martí, D.; Lobo, A.; Jean, K.; Alvarez-Marrón, J.

2016-12-01

Detailed knowledge of the structure and lithologies of the shallow subsurface is required when designing and building singular geological storage facilities this is the case of the study area in Villar de Cañas (Cuenca, Central Spain). In which an extensive multidisciplinary data acquisition program has been carried out. This include studies on: geology, hydrology, geochemistry, geophysics, borehole logging, etc. Because of this data infrastructure, it can be considered a subsurface imaging laboratory to test and validate indirect underground characterization approaches. The field area is located in a Miocene syncline within the Záncara River Basin (Cuenca, Spain). The sedimentary sequence consists in a transition from shales to massive gypsums, and underlying gravels. The stratigraphic succession features a complex internal structure, diffused lithological boundaries and relatively large variability of properties within the same lithology, these makes direct geological interpretation very difficult and requires of the integration of all the measured physical properties. The ERT survey, the seismic tomography data and the logs have been used jointly to build a 3-D multi-parameter model of the subsurface in a surface of 500x500 m. The Vp model (a 10x20x5 m grid) is able to map the high velocities of the massive gypsum, however it was neither able to map the details of the shale-gypsm transition (low velocity contrast) nor to differentiate the outcropping altered gypsum from the weathered shales. The integration of the electrical resistivity and the log data by means of a supervised statistical tools (Linear Discriminant Analysis, LDA) resulted in a new 3D multiparametric subsurface model. This new model integrates the different data sets resolving the uncertainties characteristic of the models obtained independently by the different techniques separately. Furthermore, this test seismic dataset has been used to test FWI approaches in order to study their capacities. (Research supports: CGL2014-56548-P, 2009-SGR-1595, CGL2013-47412-C2-1-P).

Gypsum ground: a new occurrence of gypsum sediment in playas of central Australia

NASA Astrophysics Data System (ADS)

Xiang Yang Chen; Bowler, James M.; Magee, John W.

1991-06-01

There are many playas (dry salt lakes) in arid central Australia (regional rainfall about 250 mm/y and pan evaporation around 3000 mm/y). Highly soluble salts, such as halite, only appear as a thin (several centimetres thick), white, ephemeral efflorescent crust on the dry surface. Gypsum is the major evaporite precipitating both at present and preserved in sediment sequences. One type of gypsum deposit forms a distinctive surface feature, which is here termed "gypsum ground". It consists of a thick (up to 80 cm) gypsum zone which rises from the surrounding smooth white playa surface and is overlain by a heaved brown crust. The gypsum zone, with an average gypsum content above 60%, consists of pure gypsum sublayers and interlayered clastic bands of sandy clay. The gypsum crystals are highly corroded, especially in the direction parallel to the c-axis and on the upper sides where illuviated clay has accumulated in corrosion hollows. Overgrowth parallel to the a- and b-axes is very common, forming highly discoidal habits. These secondary changes (corrosion and overgrowth) are well-developed in the vadose zone and absent from crystals below the long-term watertable (depth around 40 cm). These crystal characteristics indicate a rainwater leaching process. At Lake Amadeus, one of the largest playas (800 km 2) of central Australia, such gypsum ground occupies 16% of the total area. The gypsum ground is interpreted as an alteration of a pre-existing gypsum deposit which probably extended across the whole playa before breaking down, leaving a playa marginal terrace and several terrace islands within the gypsum ground. This pre-existing gypsum deposit, preserved in the residual islands, consists of pure, pale, sand-sized lenticular crystals. It is believed to have been deposited during an episode of high regional watertable, causing active groundwater seepage and more frequent surface brine in the playa. A later fall in watertable, probably resulting from climatic change, caused the degradation of the gypsum deposit by dissolution and leaching processes. The common distribution of the gypsum ground and marginal terraces in the playas of central Australia demonstrates the extent of this hydrologic and climatic history.

Sinkhole Geohazard In Deformed Sulphates at Marina di Lesina (Gargano Promontory, Italy): a Combination of Anthropogenic, Lithologic, and Structural Causes

NASA Astrophysics Data System (ADS)

Gabbianelli, G.; Antonellini, M.; Mancini, F.; Stecchi, F.; Castellarin, A.

2009-04-01

Sinkhole development and collapse of underground caves within a gypsum substrate is focused in proximity to the beach resort of Marina di Lesina on the Adriatic coast of Southern Italy. This situation constitutes a serious geohazard for the local community and a threat to the development of the tourist activity. Fast sinkhole development has been reported in the last two decades both in terms of newly formed cavities and of widening of already existing ones. Morphologically, the apparent sinkholes are small (from a few meters to a few tens of meters) and restricted to the area of the harbour canal. The substratum of the area consists of evaporite and carbonate platfom sediments of the Apulian margin, Triassic to Cretaceous in age, above which there is a thin layer (2 to 4 m) of Quaternary fine to medium sand deposits. Sheared marls, sub-volcanic igneous rocks, and bituminous limestone connected to a fault scarp, as well as small salt diapirs have been observed in proximity to the city. Below the urban area of Marina di Lesina, the platform sediments consist of fractured, sheared, and karstified sulfates (Burano Formation). Given solubility larger than that of carbonate rock, sulfates is a focus for the dissolution process. From a structural point of view, the Marina di Lesina area is probably in a push-up step between two secondary segments of East-West trending left lateral strike-slip faults with the same trend of the Mattinata fault system. The presence of a push-up structure is confirmed by the existing geological maps, the morphological, and the altimetry data available for the area that point out the presence of arcuate relief structures next to the Pietre Nere (Black Rocks) Head. These high relief areas are probable NW-SE oriented high angle reverse faults in the compressional quadrant of the southernmost strike-slip fault segment. The area within a push-up step is undergoing an intense compressive stress that results in strong pressure solution phenomena, uplift, fracturing, and shearing. This specific structural setting is likely to cause the intense deformation localization of the sulphates ( mainly gypsum) observed in the boreholes drilled around the city. It is well known that the presence of structures, such as fault and fractures, focuses fluid flow and intensifies the dissolution and the karst evolution processes. An alignment of the sinkholes as well as their shape anisotropy, west of the harbour canal, suggests also a strong structural control. Considering the combined effects of a gypsum lithology very sensitive to dissolution and the probable structural localization of faults and fractures in a fault step, it becomes apparent that Marina di Lesina is an area prone to strong karst development. Sinkhole formation and growth can be further enhanced by any anthropogenic activity especially those aimed to control the surface drainage, the infiltration of the water in the subsurface, the height of the watertable or the intrusion of seawater inland. The excavation of the harbour canal, in particular, seems to have enhanced the dissolution process as witnessed by the alignment of the sinkholes with the trend of the canal. The ongoing research of IGRG (Integrated Geosciences Research Group) at the University of Bologna is aimed to characterize the lithologic, structural, hydrologic, and anthropogenic drivers causing karst development, also for minimizing the risk on the urbanizated area and connected to sinkhole-related subsidence and collapse.

Geophysical and Geochemical Characterization of Subsurface Drip Irrigation Sites, Powder River Basin, Wyoming

NASA Astrophysics Data System (ADS)

Burton, B. L.; Bern, C. R.; Sams, J. I., III; Veloski, G.; Minsley, B. J.; Smith, B. D.

2010-12-01

Coalbed natural gas (CBNG) production in the Powder River Basin (PRB) in northeastern Wyoming has increased rapidly since 1997. CBNG production involves the extraction of large amounts of water containing >2000 mg/L total dissolved solids, dominantly sodium bicarbonate. Subsurface drip irrigation (SDI) is a beneficial disposal method of produced waters, provided that waters and associated salts are managed properly. We are studying how water and solute distributions change in soils with progressive irrigation at two PRB sites using a combination of geophysical, geochemical, and mineralogical analyses. Perennial crops are grown at both sites, drip tapes are located at 92 cm depth, and water is applied year-round. The first SDI site is located at the confluence of Crazy Woman Creek and the Powder River. Baseline ground-based and helicopter-borne frequency domain electromagnetic induction (EMI) surveys were completed in 2007 and 2008, respectively, prior to the installation of the SDI system. Since installation, additional ground-based EMI, resistivity, and downhole geophysical log surveys have been completed along with soil geochemical and mineralogical analyses. Determining baseline physical, chemical, and electrical soil characteristics at this study site is an important step in linking the EMI measurements to the soil characteristics they are intended to assess. EMI surveys indicate that soil conductivity has generally increased with irrigation, but lateral migration of water away from the irrigated blocks is minimal. Median downhole electrical conductivity was positively correlated with soil mass wetness but not correlated with soil mineralogy. Soil-water extract results indicate existing salts are chemically heterogeneous throughout the site and in depth. The observed EMI conductivity variations are therefore primarily attributed to water content changes and secondarily to soil texture. The second SDI site, located northeast of Sheridan, WY, has been operating for six years and includes irrigated alfalfa and grass and adjacent non-irrigated grass fields. A single ground-based EMI survey was performed in Feb. 2010, which helped direct subsequent soil sampling. Gypsum distribution can be differentiated into two soil zones: an upper, gypsum-poor zone and a lower gypsum-rich zone. The break between zones is 30 cm deeper in the irrigated soil and is probably due to dissolution and displacement of gypsum by SDI waters infiltrating from the drip tape. Resistivity profiles were acquired in June 2010 over the soil sampling sites and are consistent with the EMI data, which show higher conductivity values in the irrigated fields. In the SDI alfalfa field, there is a strong negative correlation between mass wetness and resistivity with a 75% increase in mass wetness (0.2-0.35 g/g) at 3 m depth corresponding to a 30% resistivity decrease (15-10 ohm-m). When compared to the non-irrigated field profile, the SDI alfalfa field data show a 50% resistivity decrease (20-10 ohm-m) below 3 m depth, indicating a possible accumulation of irrigated waters below the SDI system.

In Situ Observation of Gypsum-Anhydrite Transition at High Pressure and High Temperature

NASA Astrophysics Data System (ADS)

Liu, Chuan-Jiang; Zheng, Hai-Fei

2012-04-01

An in-situ Raman spectroscopic study of gypsum-anhydrite transition under a saturated water condition at high pressure and high temperature is performed using a hydrothermal diamond anvil cell (HDAC). The experimental results show that gypsum dissolvs in water at ambient temperature and above 496 MPa. With increasing temperature, the anhydrite (CaSO4) phase precipitates at 250-320°C in the pressure range of 1.0-1.5GPa, indicating that under a saturated water condition, both stable conditions of pressure and temperature and high levels of Ca and SO4 ion concentrations in aqueous solution are essential for the formation of anhydrite. A linear relationship between the pressure and temperature for the precipitation of anhydrite is established as P(GPa) = 0.0068T-0.7126 (250°C<=T<=320°C). Anhydrite remained stable during rapid cooling of the sample chamber, showing that the gypsum-anhydrite transition involving both dissolution and precipitation processes is irreversible at high pressure and high temperature.

Properties of mortars made by uncalcined FGD gypsum-fly ash-ground granulated blast furnace slag composite binder

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhong Shiyun, E-mail: tjzhongshiyun@163.com; Ni Kun; Li Jinmei

2012-07-15

Highlights: Black-Right-Pointing-Pointer The mortar with uncalcined FGD gypsum has suitable workability. Black-Right-Pointing-Pointer The strength of mortar with uncalcined FGD gypsum is higher than that of mortar without uncalcined FGD gypsum. Black-Right-Pointing-Pointer The dry shrinkage of mortar with uncalcined FGD gypsum is lower than that of mortar without uncalcined FGD gypsum. Black-Right-Pointing-Pointer The leaching of sulfate ion of mortar is studied. - Abstract: A series of novel mortars were developed from composite binder of uncalcined FGD gypsum, fly ash (FA) and ground granulated blast furnace slag (GGBFS) for the good utilization of flue gas desulphurization (FGD) gypsum. At a fixed ratiomore » (20%) of GGBFS to the composite binder, keeping consistency of the mortar between 9.5 and 10.0 cm, the properties of the composite mortar were studied. The results show that higher water/binder (W/B) is required to keep the consistency when increasing the percentage of FGD gypsum. No obvious influences of the W/B and content of FGD gypsum on the bleeding of paste were observed which keeps lower than 2% under all experimental conditions tried. The highest compressive and flexural strengths (ratio is 20% FGD gypsum, 20% GGBFS and 60% FA) are 22.6 and 4.3 MPa at 28 days, respectively. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) results indicate that massive ettringite crystals and C-S-H gels exist in the hydration products. At 90 days the mortars with FGD gypsum is dramatically smaller drying shrinkage (563-938 micro strain) than that without FGD gypsum (about 2250 micro strain). The release of the SO{sub 4}{sup 2-} from the mortar was analyzed, indicating that the dissolution of sulfate increases with FGD gypsum. The concentration of SO{sub 4}{sup 2-} releasing from the mortar with 10% FGD gypsum is almost equal to that obtained from the mortar without FGD gypsum. The release of SO{sub 4}{sup 2-} from the mortar with 20% FGD gypsum is 9200 mg{center_dot}m{sup -2}, which is lower than that from the mortar with 95% cement clinker and 5% FGD gypsum.« less

Formation of natural gypsum megacrystals in Naica, Mexico

NASA Astrophysics Data System (ADS)

García-Ruiz, Juan Manuel; Villasuso, Roberto; Ayora, Carlos; Canals, Angels; Otálora, Fermín

2007-04-01

Exploration in the Naica mine (Chihuahua, Mexico) recently unveiled several caves containing giant, faceted, and transparent single crystals of gypsum (CaSO4•2H2O) as long as 11 m. These large crystals form at very low supersaturation. The problem is to explain how proper geochemical conditions can be sustained for a long time without large fluctuations that would trigger substantial nucleation. Fluid inclusion analyses show that the crystals grew from low-salinity solutions at a temperature of ˜54 °C, slightly below the one at which the solubility of anhydrite equals that of gypsum. Sulfur and oxygen isotopic compositions of gypsum crystals are compatible with growth from solutions resulting from dissolution of anhydrite previously precipitated during late hydrothermal mineralization, suggesting that these megacrystals formed by a self-feeding mechanism driven by a solution-mediated, anhydrite-gypsum phase transition. Nucleation kinetics calculations based on laboratory data show that this mechanism can account for the formation of these giant crystals, yet only when operating within the very narrow range of temperature identified by our fluid inclusion study. These singular conditions create a mineral wonderland, a site of scientific interest, and an extraordinary phenomenon worthy of preservation.

Questa baseline and pre-mining ground-water quality investigation. 3. Historical ground-water quality for the Red River Valley, New Mexico

USGS Publications Warehouse

LoVetere, Sara H.; Nordstrom, D. Kirk; Maest, Ann S.; Naus, Cheryl A.

2003-01-01

Historical ground-water quality data for 100 wells in the Red River Valley between the U.S. Geological Survey streamflow-gaging station (08265000), near Questa, and Placer Creek east of the town of Red River, New Mexico, were compiled and reviewed. The tabulation included 608 water-quality records from 23 sources entered into an electronic database. Groundwater quality data were first collected at the Red River wastewater-treatment facility in 1982. Most analyses, however, were obtained between 1994 and 2002, even though the first wells were developed in 1962. The data were evaluated by considering (a) temporal consistency, (b) quality of sampling methods, (c) charge imbalance, and (d) replicate analyses. Analyses that qualified on the basis of these criteria were modeled to obtain saturation indices for gypsum, calcite, fluorite, gibbsite, manganite, and rhodocrosite. Plots created from the data illustrate that water chemistry in the Red River Valley is predominantly controlled by calcite dissolution, congruent gypsum dissolution, and pyrite oxidation.

Biological influences on modern sulfates: Textures and composition of gypsum deposits from Guerrero Negro, Baja California Sur, Mexico

NASA Astrophysics Data System (ADS)

Vogel, Marilyn B.; Des Marais, David J.; Parenteau, Mary N.; Jahnke, Linda L.; Turk, Kendra A.; Kubo, Michael D. Y.

2010-01-01

Gypsum (CaSO 4·2H 2O) deposits from a range of sedimentary environments at Guerrero Negro, Baja California Sur, Mexico were investigated for microscale texture and composition in order to differentiate features formed under substantial microbial influence from those for which microbial effects were relatively minor or absent. Gypsum deposits were classified according to their sedimentary environment, textures, crystal habit, brine composition and other geochemical factors. The environments studied included subaqueous sediments in anchialine pools and in solar salterns, as well as subsurface sediments of mudflats and saltpans. Gypsum that developed in the apparent absence of biofilms included crystals precipitated in the water column and subsedimentary discs that precipitated from phreatic brines. Subsedimentary gypsum developed in sabkha environments exhibited a sinuous microtexture and poikilitically enclosed detrital particles. Water column precipitates had euhedral prismatic habits and extensive penetrative twinning. Gypsum deposits influenced by biofilms included bottom nucleated crusts and gypsolites developing in anchialine pools and saltern ponds. Gypsum precipitating within benthic biofilms, and in biofilms within subaerial sediment surfaces provided compelling evidence of biological influences on crystal textures and habits. This evidence included irregular, high relief surface textures, accessory minerals (S°, Ca-carbonate, Sr/Ca-sulfate and Mg-hydroxide) and distinctive crystal habits such as equant forms and crystals having distorted prism faces.

Geochemical evolution of groundwater in the Culebra dolomite near the Waste Isolation Pilot Plant, southeastern New Mexico, USA

USGS Publications Warehouse

Siegel, M.D.; Anderholm, S.

1994-01-01

The Culebra Dolomite Member of the Rustler Formation, a thin (10 m) fractured dolomite aquifer, lies approximately 450 m above the repository horizon of the Waste Isolation Pilot Plant (WIPP) in southeastern New Mexico, USA. Salinities of water in the Culebra range roughly from 10,000 to 200,000 mg/L within the WIPP site. A proposed model for the post-Pleistocene hydrochemical evolution of the Culebra tentatively identifies the major sources and sinks for many of the groundwater solutes. Reaction-path simulations with the PHRQPITZ code suggest that the Culebra dolomite is a partial chemical equilibrium system whose composition is controlled by an irreversible process (dissolution of evaporites) and equilibrium with gypsum and calcite. Net geochemical reactions along postulated modern flow paths, calculated with the NETPATH code, include dissolution of halite, carbonate and evaporite salts, and ion exchange. R-mode principal component analysis revealed correlations among the concentrations of Si, Mg, pH, Li, and B that are consistent with several clay-water reactions. The results of the geochemical calculations and mineralogical data are consistent with the following hydrochemical model: 1. (1) solutes are added to the Culebra by dissolution of evaporite minerals 2. (2) the solubilities of gypsum and calcite increase as the salinity increases; these minerals dissolve as chemical equilibrium is maintained between them and the groundwater 3. (3) equilibrium is not maintained between the waters and dolomite; sufficient Mg is added to the waters by dissolution of accessory carnallite or polyhalite such that the degree of dolomite supersaturation increases with ionic strength 4. (4) clays within the fractures and rock matrix exert some control on the distribution of Li, B, Mg, and Si via sorption, ion exchange, and dissolution. ?? 1994.

Fabrication of B-type carbonate apatite blocks by the phosphorization of free-molding gypsum-calcite composite.

PubMed

Zaman, Chowdury Tanira; Takeuchi, Akari; Matsuya, Shigeki; Zaman, Q H M Shawket; Ishikawa, Kunio

2008-09-01

B-type carbonate apatite (CO3Ap) block may be an ideal artificial bone substitute because it is closer in chemical composition to bone mineral. In the present study, the feasibility to fabricate CO3Ap blocks was investigated using compositional transformation, which was based on the dissolution-precipitation reaction of a gypsum-calcite composite with free-molding behavior. For the compositional change, or phosphorization, gypsum-calcite composites of varying CaCO3 contents were immersed in 1 mol/L (NH4)3PO4 aqueous solution at 100 degrees C for 24 hours. No macroscopic changes were found after the treatment, whereas microscopic change was observed at SEM level. X-ray diffraction, Fourier transform infrared spectroscopy and CHN analysis indicated that the composites were B-type CO3Ap containing approximately 6-7 wt% of CO3, a value similar to that of biological bone apatite. Diametral tensile strength of the CO3Ap block was approximately 1-3 MPa. Based on the results obtained, it was therefore concluded that gypsum-calcite was a good candidate for the fabrication of CO3Ap blocks, coupled with the advantage that the composite can be molded to any shape by virtue of the setting property of gypsum.

Fibrous gypsum veins as diffuse features and within fault zones: the case study of the Pisco Basin (Ica desert, southern Peru)

NASA Astrophysics Data System (ADS)

Rustichelli, Andrea; Di Celma, Claudio; Tondi, Emanuele; Baud, Patrick; Vinciguerra, Sergio

2016-04-01

New knowledge on patterns of fibrous gypsum veins, their genetic mechanisms, deformation style and weathering are provided by a field- and laboratory-based study carried out on the Neogene to Quaternary Pisco Basin sedimentary strata (porous sandstones, siltstones and diatomites) exposed in the Ica desert, southern Peru. Gypsum veins vary considerably in dimensions, attitudes and timing and can develop in layered and moderately fractured rocks also in the absence of evaporitic layers. Veins occur both as diffuse features, confined to certain stratigraphic levels, and localised within fault zones. Arrays formed by layer-bounded, mutually orthogonal sets of steeply-dipping gypsum veins are reported for the first time. Vein length, height and spacing depend on the thickness of the bed packages in which they are confined. Within fault zones, veins are partly a product of faulting but also inherited layer-bounded features along which faults are superimposed. Due to the different petrophysical properties with respect to the parent rocks and their susceptibility to textural and mineralogical modifications, water dissolution and rupture, gypsum veins may have a significant role in geofluid management. Depending on their patterns and grade of physical and chemical alteration, veins may influence geofluid circulation and storage, acting as barriers to flow and possibly also as conduits.

Gypsum and hydrohalite dynamics in sea ice brines

NASA Astrophysics Data System (ADS)

Butler, Benjamin M.; Papadimitriou, Stathys; Day, Sarah J.; Kennedy, Hilary

2017-09-01

Mineral authigenesis from their dissolved sea salt matrix is an emergent feature of sea ice brines, fuelled by dramatic equilibrium solubility changes in the large sub-zero temperature range of this cryospheric system on the surface of high latitude oceans. The multi-electrolyte composition of seawater results in the potential for several minerals to precipitate in sea ice, each affecting the in-situ geochemical properties of the sea ice brine system, the habitat of sympagic biota. The solubility of two of these minerals, gypsum (CaSO4 ·2H2O) and hydrohalite (NaCl · 2H2O), was investigated in high ionic strength multi-electrolyte solutions at below-zero temperatures to examine their dissolution-precipitation dynamics in the sea ice brine system. The gypsum dynamics in sea ice were found to be highly dependent on the solubilities of mirabilite and hydrohalite between 0.2 and - 25.0 ° C. The hydrohalite solubility between - 14.3 and - 25.0 ° C exhibits a sharp change between undersaturated and supersaturated conditions, and, thus, distinct temperature fields of precipitation and dissolution in sea ice, with saturation occurring at - 22.9 ° C. The sharp changes in hydrohalite solubility at temperatures ⩽-22.9 °C result from the formation of an ice-hydrohalite aggregate, which alters the structural properties of brine inclusions in cold sea ice. Favourable conditions for gypsum precipitation in sea ice were determined to occur in the region of hydrohalite precipitation below - 22.9 ° C and in conditions of metastable mirabilite supersaturation above - 22.9 ° C (investigated at - 7.1 and - 8.2 ° C here) but gypsum is unlikely to persist once mirabilite forms at these warmer (>-22.9 °C) temperatures. The dynamics of hydrohalite in sea ice brines based on its experimental solubility were consistent with that derived from thermodynamic modelling (FREZCHEM code) but the gypsum dynamics derived from the code were inconsistent with that indicated by its experimental solubility in this system. Incorporation of hydrohalite solubility into a 1D thermodynamic model of the growth of first-year Arctic sea ice showed its precipitation to initiate once the incoming shortwave radiation dropped to 0 W m-2, and that it can reach concentrations of 9.9 g kg-1 within the upper and coldest layers of the ice pack. This suggests a limited effect of hydrohalite on the albedo of sea ice. The insights provided by the solubility measurements into the behaviour of gypsum and hydrohalite in the ice-brine system cannot be gleaned from field investigations at present.

Geochemical and isotopic composition of ground water with emphasis on sources of sulfate in the upper Floridan Aquifer and intermediate aquifer system in southwest Florida

USGS Publications Warehouse

Sacks, Laura A.; Tihansky, Ann B.

1996-01-01

In southwest Florida, sulfate concentrations in water from the Upper Floridan aquifer and overlying intermediate aquifer system are commonly above 250 milligrams per liter (the drinking water standard), particularly in coastal areas. Possible sources of sulfate include dissolution of gypsum from the deeper part of the Upper Floridan aquifer or the middle confining unit, saltwater in the aquifer, and saline waters from the middle confining unit and Lower Floridan aquifer. The sources of sulfate and geochemical processes controlling ground-water composition were evaluated for the Peace and Myakka River Basins and adjacent coastal areas of southwest Florida. Samples were collected from 63 wells and a saline spring, including wells finished at different depth intervals of the Upper Floridan aquifer and intermediate aquifer system at about 25 locations. Sampling focused along three ground-water flow paths (selected based on a predevelopment potentiometric-surface map). Ground water was analyzed for major ions, selected trace constituents, dissolved organic carbon, and stable isotopes (delta deuterium, oxygen-18, carbon-13 of inorganic carbon, and sulfur-34 of sulfate and sulfide); the ratio of strontium-87 to strontium-86 was analyzed for waters along one of the flow paths. Chemical and isotopic data indicate that dedolomitization reactions (gypsum and dolomite dissolution and calcite precipitation) control the chemical composition of water in the Upper Floridan aquifer in inland areas. This is confirmed by mass-balance modeling between wells in the shallowest interval in the aquifer along the flow paths. However, gypsum occurs deeper in the aquifer than these wells. Upwelling of sulfate-rich water that previously dissolved gypsum in deeper parts of the aquifer is a more likely source of sulfate than gypsum dissolution in shallow parts of the aquifer. This deep ground water moves to shallower zones in the aquifer discharge area. Saltwater from the Upper Floridan aquifer has not dissolved significant amounts of gypsum compared to fresher water in the aquifer. This is consistent with a shallow seawater source for the saltwater, rather than a deeper source from the underlying middle confining unit or Lower Floridan aquifer, which would have elevated sulfate concentrations. Ion exchange and dolomitization may be important reactions for saltwater in the aquifer. According to geochemical modeling, the freshwater end member for water in the saltwater mixing zone in the southwestern part of the study area is not upgradient water from the Upper Floridan aquifer that dissolved gypsum. Instead, this water appears to be isolated from the regional freshwater flow system and may be part of a more localized flow system. The chemical and isotopic composition of water in the intermediate aquifer system is controlled by differences in extent of reactions with aquifer minerals, upward leakage from the Upper Floridan aquifer, and saltwater mixing. In inland areas, water generally is characterized by relatively low sulfate concentrations (less than 250 milligrams per liter) and differences in extent of carbonate mineral dissolution. Some inland waters have elevated chloride concentrations, which may be related to evaporation prior to recharge. In coastal Sarasota County and in isolated inland areas, water from the intermediate aquifer system has high sulfate concentrations characteristic of dedolomitization waters from the Upper Floridan aquifer. The chemical and isotopic composition of these waters is controlled by upward leakage from the Upper Floridan aquifer, which naturally occurs in the discharge area but may be locally enhanced by pumping or interconnection of wells open to both aquifer systems. In western Charlotte County, the waters are dominated by sodium and chloride, and their compositions are consistent with mixing between saltwater and inland intermediate aquifer system water that has not been influenced by discharge from the

Karst-on-a-chip: microfluidic studies of dissolution of a gypsum fracture

NASA Astrophysics Data System (ADS)

Szymczak, Piotr; Dutka, Filip; Osselin, Florian

2017-04-01

Dissolution of fractured and porous media introduces a positive feedback between fluid transport and chemical reactions at mineral surfaces leading to self-focusing of the flow in pronounced wormhole-like channels [1,2]. We study the flow-induced dissolution in a simple microfluidic setup, with a gypsum block inserted in between two polycarbonate plates, which is the simplest model of a fracture [3]. This gives us a unique opportunity to observe the evolution of the dissolution patterns in-situ and in real-time. By changing the flow rate and the aperture of the fracture we can scan a relatively wide range of Peclet and Damkohler numbers, characterizing the relative magnitude of advection, diffusion and reaction in the system. Additionally, as the aperture is increased, a transition is observed between the fractal and regular dissolution patterns. For small gaps, the patterns are ramified fractals. For larger gaps, the dissolution fingers are found to have regular forms of two different kinds: either linear (for high flow rates) or parabolic (for lower flow rates). The experiments are supplemented with numerical simulations and analytical modeling which allow for a better understanding of evolving flow patterns. In particular, we find the shapes and propagation velocities of dominant fingers for different widths of the system, flow rates and reaction rates. Finally, we comment on the link between the experimentally observed patterns and the natural karst systems - both cave conduits and epikarst solution pipes. [1] Hoefner, M. L. and Fogler, H. S. Pore evolution and channel formation during flow and reaction in porous media. AIChE J. 34, 45-54, 1988 [2] P. Szymczak, A. J. C. Ladd, Wormhole formation in dissolving fractures, J. Geophys. Res., 114, B06203, 2009 [3] F. Osselin, P. Kondratiuk, A Budek, O. Cybulski, P. Garstecki, P. Szymczak Microfluidic observation of the onset of reactive infiltration instability in an analog fracture, Geophys. Res. Lett., 43, 6907-6915, 2016

Reactive transport modelling to infer changes in soil hydraulic properties induced by non-conventional water irrigation

NASA Astrophysics Data System (ADS)

Valdes-Abellan, Javier; Jiménez-Martínez, Joaquín; Candela, Lucila; Jacques, Diederik; Kohfahl, Claus; Tamoh, Karim

2017-06-01

The use of non-conventional water (e.g., treated wastewater, desalinated water) for different purposes is increasing in many water scarce regions of the world. Its use for irrigation may have potential drawbacks, because of mineral dissolution/precipitation processes, such as changes in soil physical and hydraulic properties (e.g., porosity, permeability), modifying infiltration and aquifer recharge processes or blocking root growth. Prediction of soil and groundwater impacts is essential for achieving sustainable agricultural practices. A numerical model to solve unsaturated water flow and non-isothermal multicomponent reactive transport has been modified implementing the spatio-temporal evolution of soil physical and hydraulic properties. A long-term process simulation (30 years) of agricultural irrigation with desalinated water, based on a calibrated/validated 1D numerical model in a semi-arid region, is presented. Different scenarios conditioning reactive transport (i.e., rainwater irrigation, lack of gypsum in the soil profile, and lower partial pressure of CO2 (pCO2)) have also been considered. Results show that although boundary conditions and mineral soil composition highly influence the reactive processes, dissolution/precipitation of carbonate species is triggered mainly by pCO2, closely related to plant roots. Calcite dissolution occurs in the root zone, precipitation takes place under it and at the soil surface, which will lead a root growth blockage and a direct soil evaporation decrease, respectively. For the studied soil, a gypsum dissolution up to 40 cm depth is expected at long-term, with a general increase of porosity and hydraulic conductivity.

Influence of FGD gypsum on the properties of a highly erodible soil under conservation tillage

USDA-ARS?s Scientific Manuscript database

The performance of conservation tillage practices imposed on highly erodible soils may be improved by the use of amendments with a high solubility rate, and whose dissolution products are translocated at depth in the soil profile faster than normally used agricultural lime and fertilizer products. T...

Calcium sulfate crystallization along citrus root channels in a Florida soil exhibiting acid sulfate properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Syslo, S.K.; Myhre, D.L.; Harris, W.G.

1988-02-01

The authors observed euhedral crystals in Manatee soil in a citrus grove in St. Lucie County, Florida. The material was identified as gypsum (CaSO/sub 4/ /times/ 2H/sub 2/O) using x-ray diffraction and infrared spectra. Photomicrography and scanning electron microscopy revealed that gypsum accumulated both in old root channels and within citrus root tissue of the Btg horizon. The subsurface horizons had elevated sulfate levels, a low initial pH, a drop (0.5 unit) in pH upon air-drying. Electrical conductivity paralleled the concentration of water-soluble sulfate. High levels of calcium and sulfate occurred for horizons above the water table. This accumulation ismore » attributed to groundwater bearing these ions and subsequently discharging them to the overlying soil. Dead citrus roots appear to act as wicks to aid water transfer from lower to higher horizons. The roots and their empty channels provide spaces in which the gypsum can precipitate if the concentrations of calcium and sulfate in the evaporating groundwater exceed the solubility product of gypsum.« less

Basic processes and factors determining the evolution of collapse sinkholes: a sensitivity study

NASA Astrophysics Data System (ADS)

Romanov, Douchko; Kaufmann, Georg

2017-04-01

Collapse sinkholes appear as closed depressions at the surface. The origin of these karst features is related to the continuous dissolution of the soluble rock caused by a focussed sub-surface flow. Water flowing along a preferential pathway through fissures and fractures within the phreatic part of a karst aquifer is able to dissolve the rock (limestone, gypsum, anhydrite). With time, the dissolved void volume increases and part of the ceiling above the stream can become unstable, collapses, and accumulates as debris in the flow path. The debris partially blocks the flow and thus activates new pathways. Because of the low compaction of the debris (high hydraulic conductivity), the flow and the dissolution rates within this crushed zone remain high. This allows a relatively fast dissolutional and erosional removal of the crushed material and the development of new empty voids. The void volume expands upwards towards the surface until a collapse sinkhole is formed. The collapse sinkholes exhibit a large variety of shapes (cylindrical, cone-, bowl-shaped), depths (from few to few hundred meters) and diameters (meters up to hundreds of meters). Two major processes are responsible for this diversity: a) the karst evolution of the aquifer - responsible for the dissolutional and erosional removal of material; b) the mechanical evolution of the host rock and the existence of structural features, faults for example, which determine the stability and the magnitude of the subsequent collapses. In this work we demonstrate the influence of the host rock type, the hydrological and geological boundary conditions, the chemical composition of the flowing water, and the geometry and the scale of the crushed zone, on the location and the evolution of the growing sinkhole. We demonstrate the ability of the karst evolution models to explain, at least qualitatively, the growth and the morphology of the collapse sinkholes and to roughly predict their shape and location. Implementing simple rules that describe the mechanical collapse, we come to the conclusion that a complete quantitative and qualitative description of a collapse sinkhole is possible, but for this it is necessary to take into account also the mechanical properties of the rock and the processes determining the mechanics of the collapses.

Speleothems in a wave-cut notch, Cayman Brac, British West Indies: The integrated product of subaerial precipitation, dissolution, and microbes

NASA Astrophysics Data System (ADS)

Jones, Brian

2010-12-01

A wave-cut notch that is deeply incised into the vertical cliff faces of Cayman Brac is adorned with stalactites, stalagmites, and columns. The prefix "notch" is applied to each type of speleothem in order to distinguish them from cave speleothems. These speleothemic deposits must have formed since the highstand, ~ 125,000 years ago, which was responsible for the development of the notch. The laminated notch speleothems are formed largely of aragonite (small and large crystals) and calcite (columnar, fiber, and grain-coating mats) along with minor amounts of dolomite, a Mg-Si precipitate (kerolite?), gypsum, and halite. Laminae, typically < 2 mm thick, are commonly bounded by dissolution discontinuities that truncate the older laminae and their formative aragonite and calcite crystals. The patchy tan, grey, to green surface coloration of the notch speleothems reflects the random distribution of the subaerial biofilms, which are formed of a diverse array of filamentous and non-filamentous microbes. The notch speleothems are the integrated product of precipitation and dissolution that was, in some places, microbially mediated. Interpretations based on their mineralogy and internal structures indicate that the composition of the formative waters must have temporally fluctuated with periods of precipitation being interrupted by periods of dissolution. The microbes that formed the subaerial biofilms may have influenced some of these processes. The aragonite, calcite, and kerolite (?) probably formed as evaporation and loss of Ca through precipitation progressively increased the Mg:Ca and the Si/(Ca + Mg) ratios. The dolomite, gypsum, and halite probably formed during early diagenesis during the evaporation of seawater that percolated into the interiors of the notch speleothems.

Audio-magnetotelluric surveys to constrain the origin of a network of narrow synclines in Eocene limestone, Western Desert, Egypt

NASA Astrophysics Data System (ADS)

Tarabees, Elhamy A.; Tewksbury, Barbara J.; Mehrtens, Charlotte J.; Younis, Abdellatif

2017-12-01

Recent work with high resolution satellite imagery has revealed a network of narrow synclines developed during the Oligocene or Miocene over tens of thousands of square kilometers in Eocene limestone of the Thebes Group in the Western Desert of Egypt. The synclines are non-tectonic, and their scale and geometry strongly resemble sag synclines in Qatar that were produced by dissolution of subsurface evaporites and resulting sag of overlying layers. Evaporite dissolution cannot explain the Egypt synclines, because subsurface evaporites of any significance have never been reported in this part of Egypt. In this study, we use audio-magnetotelluric surveys to illuminate the subsurface under the synclines in order to constrain possible models for their formation. We suspected karst dissolution at depth, and, given a modern water table depth of over 400 m, we expected that dry fracture networks and void spaces under the synclines might result in higher electrical resistivities than surrounding coherent limestone. We also anticipated a significant change from high to low resistivity at the contact between the Thebes Group and the underlying Esna Shale at depths of 400 m or more. Instead, we found localized low resistivity zones extending from about 50-100 m below the surface to depths of more than 400 m that are strongly correlated with synclines. We suggest that these localized low resistivity zones are filled with artesian groundwater that has insufficient hydraulic head to rise to the modern topographic surface and that is localized in subsurface voids and collapse breccias produced by dissolution. Sag of overlying limestone layers is a reasonable model for syncline formation but, given the Oligocene/Miocene age of the synclines, dissolution and sag would be unrelated to young groundwater processes.

Mineral resources of the Scorpion Wilderness study area, Garfield and Kane counties, Utah

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bartsch-Winkler, S.; Jones, J.L.; Kilburn, J.E.

1989-01-01

This paper reports on the Scorpion Wilderness Study Area which covers 14,978 acres in south- central Utah in Garfield and Kane counties. No mining claims or oil and gas leases or lease applications extend inside this study-area boundary. Demonstrated subeconomic resources of less than 30,000 tons of gypsum are in this study area. The mineral resource potential is low for undiscovered gypsum in the Carmel Formation, for undiscovered uranium in the Chinle Formation in the subsurface, and for undiscovered metals other than uranium. The energy resource potential is low for geothermal resources and is moderate for oil, gas, and carbonmore » dioxide.« less

In-situ early-age hydration study of sulfobelite cements by synchrotron powder diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Álvarez-Pinazo, G.; Cuesta, A.; García-Maté, M.

Eco-friendly belite calcium sulfoaluminate (BCSA) cement hydration behavior is not yet well understood. Here, we report an in-situ synchrotron X-ray powder diffraction study for the first hours of hydration of BCSA cements. Rietveld quantitative phase analysis has been used to establish the degree of reaction (α). The hydration of a mixture of ye'elimite and gypsum revealed that ettringite formation (α ∼ 70% at 50 h) is limited by ye'elimite dissolution. Two laboratory-prepared BCSA cements were also studied: non-active-BCSA and active-BCSA cements, with β- and α′{sub H}-belite as main phases, respectively. Ye'elimite, in the non-active-BCSA system, dissolves at higher pace (αmore » ∼ 25% at 1 h) than in the active-BCSA one (α ∼ 10% at 1 h), with differences in the crystallization of ettringite (α ∼ 30% and α ∼ 5%, respectively). This behavior has strongly affected subsequent belite and ferrite reactivities, yielding stratlingite and other layered phases in non-active-BCSA. The dissolution and crystallization processes are reported and discussed in detail. -- Highlights: •Belite calcium sulfoaluminate cements early hydration mechanism has been determined. •Belite hydration strongly depends on availability of aluminum hydroxide. •Orthorhombic ye’elimite dissolved at a higher pace than cubic one. •Ye’elimite larger reaction degree yields stratlingite formation by belite reaction. •Rietveld method quantified gypsum, anhydrite and bassanite dissolution rates.« less

Interpreting Biosignatures in the Context of Marine Evaporitic Environments

NASA Astrophysics Data System (ADS)

Des Marais, D. J.; Vogel, M. B.

2008-12-01

A biosignature is an object, substance and/or pattern whose origin specifically requires a biological agent. The usefulness of a biosignature is determined, not only by the probability of life creating it, but also by the improbability of nonbiological processes producing it. So what sets life apart from the rest? Life as we know it is the harnessing of free energy to sustain and perpetuate, by molecular replication and evolution, a high density of information in the form of functional complex molecules and functionally-related larger structures. Accordingly, biosignatures can arise from key attributes such as converting solar to chemical energy, exploiting the versatility of organic chemistry to sustain metabolic processes and preserve information, and maintaining microenvironments that enhance these functions. The external environment affects such functions and so it must be defined in order to interpret effectively the biosignatures that emerge from them. Hypersaline benthic cyanobacterial communities at Guerrero Negro, Baja California Sur, Mexico provide illustrative examples of biosignatures research that is relevant to our early biosphere and to Mars. Where brines are undersaturated with respect to gypsum, filamentous cyanobacteria dominate over unicellular cyanobacteria and can trap and bind sedimentary grains more effectively, thus altering their response to sedimentary processes and creating laminated fabrics. Biofilms in gypsiferrous sediments also can alter the response of the clastic or crystal matrix to chemical and physical sedimentary processes such as erosion or precipitate accumulation. Gypsum precipitating within biofilms offers compelling evidence of biological influences on crystal textures and habits. Such gypsum exhibits dissolution textures, accessory mineral precipitation and unique crystal form aspect ratios. Irregular textures include conchoidal and globular features associated with both dissolution and nucleation that are likely affected by biofilm pore water compositions. The accessory phases forming in association with gypsum-hosted biofilms (Sº, Ca-carbonate, and Sr/Ca-sulfate) are known byproducts of bacterially mediated sulfate reduction. Light penetrates the relatively transparent gypsum to sustain discretely layered successions of orange-, green-, purple-, pink-, and black-pigmented endoevaporitic biofilms. Lipid biosignatures include carotenoids, tricyclic terpenoids, benzothiophenes, thiacycloalkanes and methylhopanoids. These represent the aggregate effects of light regimes and hypersaline conditions. Features that could be preserved over geological timescales therefore include sedimentary textures, minerals, crystal forms, and lipids. Collectively these features can serve both as biosignatures and paleoenvironmental indicators on early Earth and on Mars.

Hydrogeochemical signatures of catchment evolution - the role of calcium and sulphate release in the constructed Hühnerwasser ("Chicken Creek") catchment

NASA Astrophysics Data System (ADS)

Pohle, Ina; Hu, Yuzhu; Schaaf, Wolfgang; Gerwin, Werner; Hinz, Christoph

2016-04-01

The constructed Hühnerwasser ("Chicken Creek") catchment is an ecohydrological system in an initial state of development. The catchment with an area of 6 ha was built up from quaternary sediments in the post-mining landscape of Lusatia in Eastern Germany and serves as a critical zone observatory for detecting ecosystem transition. The soil substrate is characterized as sands to loamy sands with low carbonate contents but significant amounts of gypsum in the sediments of the catchment. The catchment undergoes a strong transition from an abiotic system in the initial years to a system with growing influence of biota. Concerning the hydrology, a regime shift from surface runoff to groundwater flow dominated processes is significant. It is of interest, whether the catchment transition is also reflected by hydrogeochemical indicators. We assume gypsum dissolution as dominant process at the catchment scale. In order to investigate the hydrogeochemical evolution of the catchment we analysed electric conductivity, calcium and sulphate concentrations and pH-values of biweekly composite samples from 2007-2013 of the atmospheric deposition, of runoff and soil water. The two observation points in the flowing water represent surface runoff and groundwater discharge respectively. Soil water has been analysed at four soil pits in three depths. The monitoring data were provided by the Research Platform Chicken Creek (https://www.tu-cottbus.de/projekte/en/oekosysteme/startseite.html). From the macroscopic data analysis we found an exponential decay of the electric conductivity, calcium and sulphate concentrations in the flowing waters and some of the soil pits. In the flowing water, the decrease slope of the electric conductivity and the calcium and sulphate concentrations is almost identical. The calcium / sulphate molar ratio as an indicator of gypsum dissolution is almost equal to one up to 2010, afterwards more calcium than sulphate is released. The pH-values in the flowing and soil water are generally higher than in the atmospheric deposition, they do show variabilites but no trend behaviour. The time series analyses showed that the interannual variability of the hydrogeochemical properties is less pronounced in the first years of ecosystem development than in the later years. This leads to the conclusion, that in the first years, gypsum dissolution is the major source for calcium and sulphate in the soil and the flowing waters. The increasing interannual variability and changes in the calcium / sulphate ratio in the later years might be interpreted as hydrogeochemical response to the development of vegetation and acidification due to the development of the rhizosphere.

Dissolution of alkaline earth sulfates in the presence of montmorillonite

USGS Publications Warehouse

Eberl, D.D.; Landa, E.R.

1985-01-01

In a study of the effect of montmorillonite on the dissolution of BaSO4 (barite), SrSO4 (celestite), and 226Ra from U mill tailings, it was found that: (1) More of these substances dissolve in an aqueous system that contains montmorillonite than dissolve in a similar system without clay, due to the ion exchange properties of the clay; (2) Na-montmorillonite is more effective in aiding dissolution than is Ca-montmorillonite; (3) the amount of Ra that moves from mill tailings to an exchanger increases as solution sulfate activity decreases. Leaching experiments suggest that 226Ra from H2SO4-circuit U mill tailings from Edgemont, South Dakota, is not present as pure Ra sulfate or as an impurity in anhydrite or gypsum; it is less soluble, and probably occurs as a trace constituent in barite.

Testing CO2 Sequestration in an Alkaline Soil Treated with Flue Gas Desulfurization Gypsum (FGDG)

NASA Astrophysics Data System (ADS)

Han, Y.; Tokunaga, T. K.

2012-12-01

Identifying effective and economical methods for increasing carbon storage in soils is of interest for reducing soil CO2 fluxes to the atmosphere in order to partially offset anthropogenic CO2 contributions to climate change This study investigates an alternative strategy for increasing carbon retention in soils by accelerating calcite (CaCO3) precipitation and promoting soil organic carbon (SOC) complexation on mineral surfaces. The addition of calcium ion to soils with pH > 8, often found in arid and semi-arid regions, may accelerate the slow process of calcite precipitation. Increased ionic strength from addition of a soluble Ca source also suppresses microbial activity which oxidizes SOC to gaseous CO2. Through obtaining C mass balances in soil profiles, this study is quantifying the efficiency of gypsum amendments for mitigating C losses to the atmosphere. The objective of this study is to identify conditions in which inorganic and organic C sequestration is practical in semi-arid and arid soils by gypsum treatment. As an inexpensive calcium source, we proposed to use flue gas desulfurization gypsum (FGDG), a byproduct of fossil fuel burning electric power plants. To test the hypothesis, laboratory column experiments have been conducted in calcite-buffered soil with addition of gypsum and FGDG. The results of several months of column monitoring are demonstrating that gypsum-treated soil have lowered amounts of soil organic carbon loss and increased inorganic carbon (calcite) production. The excess generation of FGDG relative to industrial and agricultural needs, FGDG, is currently regarded as waste. Thus application of FGDG application in some soils may be an effective and economical means for fixing CO2 in soil organic and inorganic carbon forms.Soil carbon cycle, with proposed increased C retention by calcite precipitation and by SOC binding onto soil mineral surfaces, with both processes driven by calcium released from gypsum dissolution.

Geochemical and isotopic composition of ground water with emphasis on sources of sulfate in the upper Floridan Aquifer in parts of Marion, Sumter, and Citrus counties, Florida

USGS Publications Warehouse

Sacks, Laura A.

1996-01-01

In inland areas of northwest central Florida, sulfate concentrations in the Upper Floridan aquifer are extremely variable and sometimes exceed drinking water standards (250 milligrams per liter). This is unusual because the aquifer is unconfined and near the surface, allowing for active recharge. The sources of sulfate and geochemical processes controlling ground-water composition were evaluated in this area. Water was sampled from thirty-three wells in parts of Marion, Sumter, and Citrus Counties, within the Southwest Florida Water Management District; these included at least a shallow and a deep well at fifteen separate locations. Ground water was analyzed for major ions, selected trace constituents, dissolved organic carbon, and stable isotopes (sulfur-34 of sulfate and sulfide, carbon-13 of inorganic carbon, deuterium, and oxygen-18). Sulfate concentrations ranged from less than 0.2 to 1,400 milligrams per liter, with higher sulfate concentrations usually in water from deeper wells. The samples can be categorized into a low sulfate group (less than 30 milligrams per liter) and a high sulfate group (greater than 30 milligrams per liter). For the high sulfate water, concentrations of calcium and magnesium increased concurrently with sulfate. Chemical and isotopic data and mass-balance modeling indicate that the composition of high sulfate waters is controlled by dedolomitization reactions (dolomite dissolution and calcite precipitation, driven by dissolution of gypsum). Gypsum occurs deeper in the aquifer than open intervals of sampled wells. Upward flow has been documented in deeper parts of the aquifer in the study area, which may be driven by localized discharge areas or rapid flow in shallow parts of the aquifer. Mixing between shallow ground water and sulfate-rich water that dissolved gypsum at the base of the aquifer is probably responsible for the range of concentrations observed in the study area. Other solutes that increased with sulfate apparently originate from the gypsum itself, from other mineral assemblages found deeper in the aquifer in association with gypsum, and from residual seawater from less- flushed, deeper parts of the aquifer. These ions are subsequently transported with sulfate to shallower parts of the aquifer where gypsum is not present. The composition of low sulfate ground water is controlled by differences in the extent of microbially mediated reactions, which produce carbon dioxide. This, in turn, influences the extent of calcite dissolution. Ground waters which underwent limited microbial reactions contained dissolved oxygen and were usually in ridge areas where recharge typically is rapid. Anaerobic waters were in lower lying areas of Sumter County, where soils are poorly drained and aquifer recharge is slow. Anaerobic waters had higher concentrations of calcium, bicarbonate, sulfide, dissolved organic carbon, iron, manganese, and silica, and had lower concentrations of nitrate than aerobic ground waters. For low sulfate waters, sulfate generally originates from meteoric sources (atmospheric precipitation), with variable amounts of oxidation of reduced sulfur and sulfate reduction. Sulfide is sometimes removed from solution, probably by precipitation of a sulfide minerals such as pyrite. In areas where deep ground water has low sulfate concentrations, the shallow flow system is apparently deeper than where high sulfate concentrations occur, and upwelling sulfate-rich water is negligible. The range of sulfate concentrations observed in the study areas and differences in sulfate concentrations with depth indicate a complex interaction between shallow and deep ground-water flow systems.

Pyrite formation driven by MSW landfill leachate in the Madrid Basin, Spain

NASA Astrophysics Data System (ADS)

Castelló, Ricardo; Recio, Clemente; Morillas, Pilar; Vizcayno, Carmen

2008-04-01

The role of municipal solid waste (MSW) landfill leachate on the genesis of minor amounts of pyrite associated with gypsum in an otherwise predominantly evaporitic sequence was studied in geological and geochemical terms. The potential association between landfill leachate and the conditions required for bacterial reduction of sulfate and fixation of H2S as pyrite were examined. The lithological column was generally found to contain little or no Fe. The δ34S values for sulfates were consistent with previously reported data; however, the measured δ18O values were slightly higher. Sulfides disseminated in the marl/lutite exhibited higher δ34S values (≈-8‰) than gypsum-coating pyrite crystals (δ34S < -30‰). Dissolution of gypsum to sulfate and the supply of metabolizable organic matter and Fe required for H2S fixation as sulfides may have originated from landfill leachate. Intermittent availability of leachate, a result of the precipitation regime, can facilitate sulfur disproportionation and lead to fractionations as high as δ_{text{SO}4^{2-}-{text{S}^{2-}}}≈ - {text{50}}permille.

Petrophysical Effects during karstification

NASA Astrophysics Data System (ADS)

Mai, Franziska; Kirsch, Reinhard; Rücker, Carsten; Börner, Frank

2017-04-01

Sinkholes are depression or collapse structures caused by dissolution in the subsurface or subrosion processes and occur in a vast variety of geological settings. They pose a considerable threat to people's safety and can cause severe economic loss, especially in highly populated areas. Commonly, sinkholes are linked to anomalies in groundwater flow and to the heterogeneities in the soluble sediment. To develop an early recognition system of sinkhole instability, unrest and collapse it is necessary to obtain a better understanding of sinkhole generation. With this intent the joint project "SIMULTAN" studies sinkholes applying a combination of structural, geophysical, petrophysical, and hydrological mapping methods, accompanied by sensor development, and multi-scale monitoring. Studying the solution process of gypsum and limestone as well as the accompanying processes and their relation to hydrologic mechanisms from a petrophysical point of view is essential to understand geophysically detected anomalies related to sinkholes. The focus lies on measurements of the complex, frequency dependent electrical conductivity, the self potential and the travel time of elastic waves. First, systematic laboratory measurements of the complex electrical conductivity were conducted on samples consisting of unconsolidated sand. The fully saturated samples differed in the ionic composition of their pore water (e.g. calcium sulfate and/or sodium chloride). The results indicate that it is possible to detect effects of higher gypsum concentration in the ground- or pore-water using electrical conductivity. This includes both the karstificable sediments as well as the adjacent, non-soluble sediments like e.g. clean sand or shaly sand. To monitor karstification and subrosion processes on a field scale, a stationary measuring system was installed in Münsterdorf, Schleswig-Holstein in northern Germany, an area highly at risk of sinkhole development. The complex electrical conductivity is measured in two boreholes, located 5 meters apart. The results of these measurements are used to investigate possible solution of the subterranean chalk.

Sources of dissolved salts in the central Murray Basin, Australia

USGS Publications Warehouse

Jones, B.F.; Hanor, J.S.; Evans, W.R.

1994-01-01

Large areas of the Australian continent contain scattered saline lakes underlain by shallow saline groundwaters of regional extent and debated origin. The normative salt composition of subsurface pore fluids extracted by squeezing cores collected during deep drilling at Piangil West 2 in the central Murray Basin in southeastern Australia, and of surface and shallow subsurface brines produced by subaerial evaporation in the nearby Lake Tyrrell systems, helps constrain interpretation of the origin of dissolved solutes in the groundwaters of this part of the continent. Although regional sedimentation in the Murray Basin has been dominantly continental except for a marine transgression in Oligocene-Pliocene time, most of the solutes in saline surface and subsurface waters in the central Murray Basin have a distinctly marine character. Some of the Tyrrell waters, to the southwest of Piangil West 2, show the increase in NaCl and decrease in sulfate salts expected with evaporative concentration and gypsum precipitation in an ephemeral saline lake or playa environment. The salt norms for most of the subsurface saline waters at Piangil West 2 are compatible with the dilution of variably fractionated marine bitterns slightly depleted in sodium salts, similar to the more evolved brines at Lake Tyrrell, which have recharged downward after evaporation at the surface and then dissolved a variable amount of gypsum at depth. Apparently over the last 0.5 Ma significant quantities of marine salt have been blown into the Murray Basin as aerosols which have subsequently been leached into shallow regional groundwater systems basin-wide, and have been transported laterally into areas of large evaporative loss in the central part of the basin. This origin for the solutes helps explain why the isotopic compositions of most of the subsurface saline waters at Piangil West 2 have a strong meteoric signature, whereas the dissolved salts in these waters appear similar to a marine assemblage. ?? 1994.

CONTAMINANT TRANSPORT RESULTING FROM MULTICOMPONENT NONAQUEOUS PHASE LIQUID POOL DISSOLUTION IN THREE-DIMENSIONAL SUBSURFACE FORMATIONS (R823579)

EPA Science Inventory

A semi-analytical method for simulating transient contaminant transport originating from the dissolution of multicomponent nonaqueous phase liquid (NAPL) pools in three-dimensional, saturated, homogeneous porous media is presented. Each dissolved component may undergo first-order...

Synthesis of high-purity precipitated calcium carbonate during the process of recovery of elemental sulphur from gypsum waste.

PubMed

de Beer, M; Doucet, F J; Maree, J P; Liebenberg, L

2015-12-01

We recently showed that the production of elemental sulphur and calcium carbonate (CaCO3) from gypsum waste by thermally reducing the waste into calcium sulphide (CaS) followed by its direct aqueous carbonation yielded low-grade carbonate products (i.e. <90 mass% as CaCO3). In this study, we used the insight gained from our previous work and developed an indirect aqueous CaS carbonation process for the production of high-grade CaCO3 (i.e. >99 mass% as CaCO3) or precipitated calcium carbonate (PCC). The process used an acid gas (H2S) to improve the aqueous dissolution of CaS, which is otherwise poorly soluble. The carbonate product was primarily calcite (99.5%) with traces of quartz (0.5%). Calcite was the only CaCO3 polymorph obtained; no vaterite or aragonite was detected. The product was made up of micron-size particles, which were further characterised by XRD, TGA, SEM, BET and true density. Results showed that about 0.37 ton of high-grade PCC can be produced from 1.0 ton of gypsum waste, and generates about 0.19 ton of residue, a reduction of 80% from original waste gypsum mass to mass of residue that needs to be discarded off. The use of gypsum waste as primary material in replacement of mined limestone for the production of PPC could alleviate waste disposal problems, along with converting significant volumes of waste materials into marketable commodities. Copyright © 2015 Elsevier Ltd. All rights reserved.

Modeling NAPL dissolution from pendular rings in idealized porous media

EPA Science Inventory

The rate of NAPL dissolution often governs the clean-up time for subsurface hazardous waste sites. Most formulations for estimating this rate are empirical and assume that the NAPL is the non-wetting fluid. However, field evidence suggests that some waste sites might be organic...

Histological Comparison in Rats between Carbonate Apatite Fabricated from Gypsum and Sintered Hydroxyapatite on Bone Remodeling

PubMed Central

Ayukawa, Yasunori; Suzuki, Yumiko; Tsuru, Kanji; Koyano, Kiyoshi; Ishikawa, Kunio

2015-01-01

Carbonate apatite (CO3Ap), the form of apatite found in bone, has recently attracted attention. The purpose of the present study was to histologically evaluate the tissue/cellular response toward the low-crystalline CO3Ap fabricated using a dissolution-precipitation reaction with set gypsum as a precursor. When set gypsum was immersed in a 100°C 1 mol/L Na3PO4 aqueous solution for 24 h, the set gypsum transformed into CO3Ap. Both CO3Ap and sintered hydroxyapatite (s-HAp), which was used as a control, were implanted into surgically created tibial bone defects of rats for histological evaluation. Two and 4 weeks after the implantation, histological sections were created and observed using light microscopy. The CO3Ap granules revealed both direct apposition of the bone matrix by osteoblasts and osteoclastic resorption. In contrast, the s-HAp granules maintained their contour even after 4 weeks following implantation which implied that there was a lack of replacement into the bone. The s-HAp granules were sometimes encapsulated with fibrous tissue, and macrophage polykaryon was occasionally observed directly apposed to the implanted granules. From the viewpoint of bone remodeling, the CO3Ap granules mimicked the bone matrix, suggesting that CO3Ap may be an appropriate bone substitute. PMID:26504813

Subsurface drainage erodes forested granitic terrane

Treesearch

Philip Durgin

1984-01-01

Abstract - Solution and landsliding, the dominant erosion processes in undisturbed forested mountainous watersheds, are both influenced by subsurface drainage. Biological processes that generate organic acids accelerate loss of dissolved solids by promoting the dissolution of primary minerals in granitic rock. These organic acids can also disperse the secondary...

Size-dependent reactivity of magnetite nanoparticles: a field-laboratory comparison

USGS Publications Warehouse

Swindle, Andrew L.; Elwood Madden, Andrew S.; Cozzarelli, Isabelle M.; Benamara, Mourad

2014-01-01

Logistic challenges make direct comparisons between laboratory- and field-based investigations into the size-dependent reactivity of nanomaterials difficult. This investigation sought to compare the size-dependent reactivity of nanoparticles in a field setting to a laboratory analog using the specific example of magnetite dissolution. Synthetic magnetite nanoparticles of three size intervals, ∼6 nm, ∼44 nm, and ∼90 nm were emplaced in the subsurface of the USGS research site at the Norman Landfill for up to 30 days using custom-made subsurface nanoparticle holders. Laboratory analog dissolution experiments were conducted using synthetic groundwater. Reaction products were analyzed via TEM and SEM and compared to initial particle characterizations. Field results indicated that an organic coating developed on the particle surfaces largely inhibiting reactivity. Limited dissolution occurred, with the amount of dissolution decreasing as particle size decreased. Conversely, the laboratory analogs without organics revealed greater dissolution of the smaller particles. These results showed that the presence of dissolved organics led to a nearly complete reversal in the size-dependent reactivity trends displayed between the field and laboratory experiments indicating that size-dependent trends observed in laboratory investigations may not be relevant in organic-rich natural systems.

Transport-Induced Spatial Patterns of Sulfur Isotopes (δ34S) as Biosignatures

NASA Astrophysics Data System (ADS)

Mansor, Muammar; Harouaka, Khadouja; Gonzales, Matthew S.; Macalady, Jennifer L.; Fantle, Matthew S.

2018-01-01

Cave minerals deposited in the presence of microbes may host geochemical biosignatures that can be utilized to detect subsurface life on Earth, Mars, or other habitable worlds. The sulfur isotopic composition of gypsum (CaSO4·2H2O) formed in the presence of sulfur-oxidizing microbes in the Frasassi cave system, Italy, was evaluated as a biosignature. Sulfur isotopic compositions (δ34SV-CDT) of gypsum sampled from cave rooms with sulfidic air varied from -11 to -24‰, with minor deposits of elemental sulfur having δ34S values between -17 and -19‰. Over centimeter-length scales, the δ34S values of gypsum varied by up to 8.5‰. Complementary laboratory experiments showed negligible fractionation during the oxidation of elemental sulfur to sulfate by Acidithiobacillus thiooxidans isolated from the caves. Additionally, gypsum precipitated in the presence and absence of microbes at acidic pH characteristic of the sulfidic cave walls has δ34S values that are on average 1‰ higher than sulfate. We therefore interpret the 8.5‰ variation in cave gypsum δ34S (toward more negative values) to reflect the isotopic effect of microbial sulfide oxidation directly to sulfate or via elemental sulfur intermediate. This range is similar to that expected by abiotic sulfide oxidation with oxygen, thus complicating the use of sulfur isotopes as a biosignature at centimeter-length scales. However, at the cave room (meter-length) scale, reactive transport modeling suggests that the overall ˜13‰ variability in gypsum δ34S reflects isotopic distillation of circulating H2S gas due to microbial sulfide oxidation occurring along the cave wall-atmosphere interface. Systematic variations of gypsum δ34S along gas flow paths can thus be interpreted as biogenic given that slow, abiotic oxidation cannot produce the same spatial patterns over similar length scales. The expression and preservation potential of this biosignature is dependent on gas flow parameters and diagenetic processes that modify gypsum δ34S values over geological timescales.

Dissolution Kinetics of Meta-Torbernite under Circum-neutral to Alkaline Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wellman, Dawn M.; McNamara, Bruce K.; Bacon, Diana H.

2009-12-21

Autunite group minerals have been identified in contaminated sediments as the long-term controlling phase of uranium. Meta-torbernite, has been identified in subsurface environments which were subjected to co-contaminant disposal practices from past nuclear weapons and fuel operations. Under these conditions the mobility of uranium in subsurface pore waters is limited by the rate of meta-torbernite dissolution; however, there are no known investigations which report the dissolution behavior of meta-torbernite. The purpose of this investigation was to conduct a series of single-pass flow-through (SPFT) tests to 1) quantify the effect of temperature (23 - 90oC) and pH (6 -10) on meta-torbernitemore » dissolution, 2) compare the dissolution of meta-torbernite to other autunite-group minerals, and 3) evaluate the effect of aqueous phosphate on the dissolution kinetics of meta-torbernite. Results presented here illustrate meta-torbernite dissolution rates increase by ~100X over the pH interval of 6 to 10 (eta = 0.59 ± 0.07), irrespective of temperature. The power law coefficient for meta-torbernite, eta = 0.59 ± 0.07, is greater than that quantified for Ca-meta-autunite, eta = 0.42 ± 0.12. This suggests the stability of meta-torbernite is greater than that of meta-autunite, which is reflected in the predicted stability constants. The rate equation for the dissolution of meta-torbernite as a function of aqueous phosphate concentration is log rdissol (mol m-2 sec-1) = -4.7 x 10-13 + 4.1 x 10-10 [PO43-].« less

Paleoclimatic interpretations for clay-rich paleosols--Potential and limitations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blodgett, R.H.

1992-01-01

A worldwide survey of Quaternary Vertisols and pre-Quaternary vertic paleosols indicates that these soils have morphologic features which may allow for a refined assessment of seasonal wet-dry paleoclimates. Optimal development of vertisols occurs under wet/dry tropical and subtropical climates with annual rainfall of 500-1,000 mm/yr. These typic Vertisols'' have well-developed gilgai, subsurface bowl and dome macrostructure, cross-cutting slickensided surfaces, and disseminated pedogenic carbonate nodules. Typic Vertisols occur in central Texas, East Africa, India and Australia. Corresponding typic vertic paleosols have been found in 14 Paleozoic formations of Pangea. Humid Vertisols can be difficult to distinguish from typic forms. In themore » humid group, carbonate nodules are absent or few in number and smaller in size. Nodules commonly show surficial pitting from dissolution. Humid Vertisols occur in East Texas, the central Gulf Coast, Central America, Caribbean, and Papau-New Guinea. Paleosol equivalents have been described in Mesozoic and Carboniferous rocks of North America. Dry Vertisols have subdued gilgai, well-developed surficial mulch, large sediment-filled desiccation cracks, common carbonate nodules, and in some areas, disseminated crystals or veins of gypsum. These soils occur in the southwestern U.S., Sahel, and in Australia. Dry vertic paleosols have been identified in Cenozoic deposits of Texas and North Africa. The above assessments may not be possible in composite paleosols or in soils influenced by a shallow water table.« less

Long-term in situ oxidation of biogenic uraninite in an alluvial aquifer: impact of dissolved oxygen and calcium.

PubMed

Lezama-Pacheco, Juan S; Cerrato, José M; Veeramani, Harish; Alessi, Daniel S; Suvorova, Elena; Bernier-Latmani, Rizlan; Giammar, Daniel E; Long, Philip E; Williams, Kenneth H; Bargar, John R

2015-06-16

Oxidative dissolution controls uranium release to (sub)oxic pore waters from biogenic uraninite produced by natural or engineered processes, such as bioremediation. Laboratory studies show that uraninite dissolution is profoundly influenced by dissolved oxygen (DO), carbonate, and solutes such as Ca(2+). In complex and heterogeneous subsurface environments, the concentrations of these solutes vary in time and space. Knowledge of dissolution processes and kinetics occurring over the long-term under such conditions is needed to predict subsurface uranium behavior and optimize the selection and performance of uraninite-based remediation technologies over multiyear periods. We have assessed dissolution of biogenic uraninite deployed in wells at the Rifle, CO, DOE research site over a 22 month period. Uraninite loss rates were highly sensitive to DO, with near-complete loss at >0.6 mg/L over this period but no measurable loss at lower DO. We conclude that uraninite can be stable over decadal time scales in aquifers under low DO conditions. U(VI) solid products were absent over a wide range of DO values, suggesting that dissolution proceeded through complexation and removal of oxidized surface uranium atoms by carbonate. Moreover, under the groundwater conditions present, Ca(2+) binds strongly to uraninite surfaces at structural uranium sites, impacting uranium fate.

Prediction of halite, gypsum, and anhydrite solubility in natural brines under subsurface conditions

NASA Astrophysics Data System (ADS)

He, Shiliang; Morse, John W.

1993-01-01

Prediction of the solubility of the evaporite minerals halite, gypsum, and anhydrite in brines has numerous scientific and practical applications. This paper presents a Pitzer equation-based model for predicting the solubility of these minerals in Na +-K +-H +-Ca 2+-Mg 2+-Cl --OH --SO 42--H 2O solutions of varying composition as a function of temperature and pressure. Model predictions compare well with experimental observations. As an example of the utility of this program, the volume of CaSO 4 precipitated as a brine flows up a pipe from 6000 m depth is predicted. This is done as a function of flow distance for different cooling rates of the brine. Results indicate that if the brine can be cooled to near the geothermal gradient no precipitation will take place.

Halite-clay interplay in the Israeli Messinian

NASA Astrophysics Data System (ADS)

Cohen, Avigdor

1993-08-01

The Mavqi'im Formation in Israel is the equivalent of the evaporite part of the Messinian stage (Upper Miocene). It is found in the subsurface in the offshore with eastward extensions into ancient buried channels in the coastal plain and in the Jordan Rift valley and in a few outcrops southwest of Lake Tiberias. Most of the anhydrite horizons can be used as correlation markers. Lateral facies changes between halite, anhydrite and shales can be traced. This is interpreted as contemporaneous sedimentation in giant marine salt ponds (halite and anhydrite) and in drowned desert valleys and/or salt-marsh coasts (shales with sabkha-like anhydrites). Another type of shale is that directly underflooring halite horizons. It is regarded as deep-water halite facies, in contrast with shallow-water facies where halite overlies gypsum and/or anhydrite. A "twofold bull's-eye model" is proposed, which assumes that either: (a) sedimentation of gypsum and halite was 'separated in space'—i.e., gypsum was deposited in the part of the basin proximal to oceanic inlets or on shallow shelves, whereas halite was deposited in the central deep part of the basin or on its distal edge; or (b) sedimentation of gypsum and halite was not contemporaneous, or 'separated in time'—i.e., in the deep parts of the basin gypsum precipitates were disintegrated by anaerobic bacteria which removed the sulfate. The lower limit of gypsum deposition is considered to be 200 m, which is the lower limit of the photic and wave zones. In the Israeli Messinian there is no difference between the clay minerals of marine and fluvial shales. Differentiation of marine shales from fluvial and mud flat shales is based on their geometry, i.e., thin persistent horizons spreading across the whole area versus thick shale lenses wedging out in 500-1000 m distances. Another consideration is the palynologic and microfauna remains: in the first case the cyst/pollen ratio may be as high as 100, whereas in the second pollen is dominant.

Experimental investigation of the dissolution of fractures. From early stage instability to phase diagram

NASA Astrophysics Data System (ADS)

Osselin, Florian; Budek, Agnieszka; Cybulski, Olgierd; Kondratiuk, Pawel; Garstecki, Piotr; Szymczak, Piotr

2016-04-01

Dissolution of natural rocks is a fundamental geological process and a key part of landscape formation and weathering processes. Moreover, in current hot topics like Carbon Capture and Storage or Enhanced Oil Recovery, mastering dissolution of the host rock is fundamental for the efficiency and the security of the operation. The basic principles of dissolution are well-known and the theory of the reactive infiltration instability has been extensively studied. However, the experimental aspect has proved very challenging because of the strong dependence of the outcome with pore network, chemical composition, flow rate... In this study we are trying to tackle this issue by using a very simple and efficient device consisting of a chip of pure gypsum inserted between two polycarbonate plates and subjected to a constant flow rate of pure water. Thanks to this device, we are able to control all parameters such as flow rate, fracture aperture, roughness of the walls... but also to observe in situ the progression of the dissolution thanks to the transparency of the polycarbonate which is impossible with 3D rocks. We have been using this experimental set-up to explore and investigate all aspects of the dissolution in a fracture, such as initial instability and phase diagram of different dissolution patterns, and to compare it with theory and simulations, yielding very good agreement and interesting feedbacks on the coupling between flow and chemistry in geological media

Gypsum, jarosite, and hydrous iron-phosphate in Martian meteorite Roberts Massif 04262: Implications for sulfate geochemistry on Mars.

NASA Astrophysics Data System (ADS)

Greenwood, J. P.

2008-12-01

Gypsum has been identified on Mars by MEX OMEGA [1] and jarosite identified via MER-B lander [2] and both minerals are examples of the importance of calcium and iron sulfates in Martian weathering processes. The weathering of Martian basalt to form Ca and iron sulfates should be an important process on Mars. Martian jarosite has been identified in MIL 03346 [3] and Ca-sulfate has been identified in EETA 79001 [4], but both phases have yet to be identified in the same Martian sample. In Roberts Massif 04262, an olivine-phyric shergottite, iron-sulfide and calcium-phosphate minerals are undergoing reaction (dissolution and reprecipitation?) to form gypsum, jarosite, and an iron-phosphate phase, presumably during the meteorite's residence in Antarctica. If true, then an acidic and oxidizing fluid was present in this meteorite, due to the formation of jarosite which requires fluid of this type to form [5]. The weathering of iron-sulfides on Earth to form acidic and oxidizing fluids is common, thus this can be reconciled with the formation of an acidic fluid in a basic rock. Presumably, under more extensive weathering of silicate minerals in Martian basalt, the pH would be raised to values where jarosite would not be stable. While the weathering of RBT 04262 is likely occurring in Antarctica, a similar susceptibility of the apatite and pyrrhotite to incipient weathering on Mars may be expected. Oxidizing crustal fluids on Mars may attack iron- sulfides first in Martian basalts. The weathering of iron-sulfides leads to increasing acidity of fluids, which would enhance the dissolution of the calcium-phosphate minerals [6]. The formation of jarosite, gypsum, and iron-phosphate minerals during the early stages of weathering of Martian basalts may be an important process on Mars globally. [1] Gendrin, A. et al. (2005) Science, 307, 1587-1591. [2] Klingelhöfer et al. (2004) Science, 306, 1740- 1745. [3] Vicenzi E. P. et al. (2007) LPSC XXXVIII, Abstract 2335. [4] Gooding J. L. et al. (1988) GCA, 52, 909-915. [5] Greenwood J. P. et al. (2005) LPSC XXXVI, Abstract 2348. [6] Greenwood J. P. and Blake R. E. (2006) Geology, 34, 953-956.

Assessment of groundwater contamination by gypsum dissolution in San Luis Potosí (México) using geoelectrical characterization

NASA Astrophysics Data System (ADS)

Arango-Galvan, C.; Ramos-Leal, J. A.; Yáñez-Rodríguez, M. A.; Corbo-Camargo, F.

2017-12-01

The Cerritos and Río Verde aquifers in San Luis Potosí (central México) make up a very complex aquifer system that is seriously affected by the overexploitation and the high concentration of sulphates. Currently, it is partially closed for extraction causing a substantial decrease in per capita drinking water availability affecting to more than 50,000 inhabitants in the region. Therefore, a very comprehensive study has been proposed in order to evaluate not only the groundwater contamination distribution but also to better know the aquifer configuration and its main hydrogeological characteristics as well. These studies include a detailed geological reconnaissance, hydrogeochemical analyses and a geoelectrical characterization. The main goal is to assess the aquifer geometry and to identify the gypsum horizons causing the presence of higher concentrations of sulphates in drinking water. A total of 26 audiomagnetotelluric soundings were measured and modelled along profiles following a perpendicular direction to the NW regional trending. Two-dimensional resistivity models suggest the presence of a shallow conductive layer (C1) with resistivity values ranging from 10 to 20 Ohm.m. It is related to the upper aquifer with a very low exploitation potential. A less conductive horizon (C2; 50 Ohm.m) underlying the shallow aquifer could be related to a very fractured limestone horizon forming a confined aquifer in the middle of the valley. A very resistive layer (R1) is observed underlying C1 and C2 units. This strata shows higher resistivity values (>100 Ohm.m) and could be associated with a reefal limestone identified as El Abra Formation. Finally, a conductive layer (<100 Ohm.m) observed beneath this horizon could be related to the oldest stratigraphic unit outcropping on the region, the Guaxcamá Formation, a gypsum-enriched unit, that contributes to the presence of sulphates in the upper aquifers by dissolution processes.

Experimental determination of methane dissolution from simulated subsurface oil leakages

NASA Astrophysics Data System (ADS)

Sauthoff, W.; Peltzer, E. T.; Walz, P. M.; Brewer, P. G.

2013-12-01

Subsurface oil leakages and increased offshore drilling efforts have raised concern over the fate of hydrocarbon mixtures of oil and gas in ocean environments. Recent wellhead and pipeline failures in the Gulf of Mexico are extreme examples of this problem. Understanding the mechanism and rate of vertical transport of hydrocarbon chemical species is necessary to predict the environmental impact of subsurface leakages. In a series of controlled experiments, we carried out a deep-sea field experiment in Monterey Canyon to investigate the behavior of a gas-saturated liquid hydrocarbon mass rising from the seafloor. Aboard the R/V Rachel Carson, we used the ROV Ventana to transport a laboratory prepared volume of decane (C10H22) saturated with methane gas (CH4) to mimic a subsurface seafloor discharge. We released the oil and gas mixture into a vertically oriented open bottom glass tube followed by methane loss rate measurements both at discrete depths, and during rapid, continuous vehicle ascent from 800 to 100 m water depth to monitor changes in dissolution and bubble nucleation. Using laser Raman techniques and HD video we quantified the chemical state of the hydrocarbon fluid, including rate of methane gas dissolution. The primary methane Raman peak was readily observable within the decane C-H stretching complex. Variation in the amount of gas dissolved in the oil greatly influences oil plume density and in turn oil plume vertical rise rate. Our results show that the rise rate of the hydrocarbon mass significantly exceeds the rate at which the excess methane was lost by dissolution. This result implies that vertical transport of methane in the saturated hydrocarbon liquid phase can greatly exceed a gas bubble plume ascending the water column from a seafloor source. These results and observations may be applicable to improved understanding of the composition, distribution, and environmental fate of leaked hydrocarbon mixtures and inform remediation efforts.

Hydrochemical Characteristics and Formation of the Saline or Salty Springs in Eastern Sichuan Basin of China

NASA Astrophysics Data System (ADS)

Zhou, X.

2017-12-01

Saline or salty springs provide important information on the hydrogeochemical processes and hydrology within subsurface aquifers. More than 20 saline and salty springs occur in the core of anticlines in the eastern Sichuan Basin in southwestern China where the Lower and Middle Triassic carbonates outcrop. Water samples of 8 saline and salty springs (including one saline hot spring) were collected for analyses of the major and minor constituents, trace elements and stable oxygen and hydrogen isotopes. The TDS of the springs range from 4 to 83 g/L, and they are mainly of Cl-Na type. Sr, Ba and Li are the predominant trace elements. The δ2H and δ18O of the water samples indicate that they are of meteoric origin. The source of salinity of the springs originates from dissolution of minerals in the carbonates, including halite, gypsum, calcite and dolomite. The formation mechanism of the springs is that groundwater receives recharge from infiltration of precipitation, undergoes shallow or deep circulation in the core of the anticline and incongruent dissolution of the salt-bearing carbonates occurs, and emerges in the river valley in the form of springs with relatively high TDS. The 8 springs can be classified into 4 springs of shallow groundwater circulation and 4 springs of deep groundwater circulation according to the depth of groundwater circulation, 7 springs of normal temperature and 1 hot spring according to temperature. There are also 2 up-flow springs: the carbonate aquifers are overlain by relatively impervious sandstone and shale, groundwater may flows up to the ground surface through the local portion of the overlying aquiclude where fractures were relatively well developed, and emerges as an up-flow spring. Knowledge of the hydrochemical characteristics and the geneses of the saline and salty springs are of important significance for the utilization and preservation of the springs.

Depleted uranium investigation at missile impact sites in White Sands Missile Range

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Etten, D.M.; Purtymun, W.D.

1994-01-01

An investigation for residual depleted uranium was conducted at Pershing missile impact sites on the White Sands Missile Range. Subsurface core soil samples were taken at Chess, Salt Target, and Mine Impact Sites. A sampling pump was installed in a monitoring well at Site 65 where a Pershing earth penetrator was not recovered. Pumping tests and water samples were taken at this site. Chess Site, located in a gypsum flat, was the only location showing elevated levels of depleted uranium in the subsurface soil or perched groundwater. Small fragments can still be found on the surface of the impact sites.more » The seasonal flooding and near surface water has aided in the movement of surface fragments.« less

Self-accelerated development of salt karst during flash floods along the Dead Sea Coast, Israel

NASA Astrophysics Data System (ADS)

Avni, Yoav; Lensky, Nadav; Dente, Elad; Shviro, Maayan; Arav, Reuma; Gavrieli, Ittai; Yechieli, Yoseph; Abelson, Meir; Lutzky, Hallel; Filin, Sagi; Haviv, Itai; Baer, Gidon

2016-01-01

We document and analyze the rapid development of a real-time karst system within the subsurface salt layers of the Ze'elim Fan, Dead Sea, Israel by a multidisciplinary study that combines interferometric synthetic aperture radar and light detection and ranging measurements, sinkhole mapping, time-lapse camera monitoring, groundwater level measurements and chemical and isotopic analyses of surface runoff and groundwater. The >1 m/yr drop of Dead Sea water level and the subsequent change in the adjacent groundwater system since the 1960s resulted in flushing of the coastal aquifer by fresh groundwater, subsurface salt dissolution, gradual land subsidence and formation of sinkholes. Since 2010 this process accelerated dramatically as flash floods at the Ze'elim Fan were drained by newly formed sinkholes. During and immediately after these flood events the dissolution rates of the subsurface salt layer increased dramatically, the overlying ground surface subsided, a large number of sinkholes developed over short time periods (hours to days), and salt-saturated water resurged downstream. Groundwater flow velocities increased by more than 2 orders of magnitudes compared to previously measured velocities along the Dead Sea. The process is self-accelerating as salt dissolution enhances subsidence and sinkhole formation, which in turn increase the ponding areas of flood water and generate additional draining conduits to the subsurface. The rapid terrain response is predominantly due to the highly soluble salt. It is enhanced by the shallow depth of the salt layer, the low competence of the newly exposed unconsolidated overburden and the moderate topographic gradients of the Ze'elim Fan.

Assessing hydrodynamic effects on jarosite dissolution rates, reaction products, and preservation on Mars

NASA Astrophysics Data System (ADS)

Dixon, Emily M.; Elwood Madden, Andrew S.; Hausrath, Elisabeth M.; Elwood Madden, Megan E.

2015-04-01

Jarosite flow-through dissolution experiments were conducted in ultrapure water (UPW), pH 2 sulfuric acid, and saturated NaCl and CaCl2 brines at 295-298 K to investigate how hydrologic variables may affect jarosite preservation and reaction products on Mars. K+-based dissolution rates in flowing UPW did not vary significantly with flow rate, indicating that mineral surface reactions control dissolution rates over the range of flow rates investigated. In all of the solutions tested, hydrologic variables do not significantly affect extent of jarosite alteration; therefore, jarosite is equally likely to be preserved in flowing or stagnant waters on Mars. However, increasing flow rate did affect the mineralogy and accumulation of secondary reaction products. Iron release rates in dilute solutions increased as the flow rate increased, likely due to nanoscale iron (hydr)oxide transport in flowing water. Anhydrite formed in CaCl2 brine flow-through experiments despite low temperatures, while metastable gypsum and bassanite were observed in batch experiments. Therefore, observations of the hydration state of calcium sulfate minerals on Mars may provide clues to unravel past salinity and hydrologic conditions as well as temperatures and vapor pressures.

The effect of a confining unit on the geochemical evolution of ground water in the Upper Floridan aquifer system

USGS Publications Warehouse

Wicks, C.M.; Herman, J.S.

1994-01-01

In west-central Florida, sections of the Upper Floridan aquifer system range in character from confined to leaky to unconfined. The confining unit is the Hawthorn Formation, a clay-rich sequence. The presence or absence of the Hawthorn Formation affects the geochemical evolution of the ground water in the Upper Floridan aquifer system. Mass-balance and mass-transfer models suggest that, in unconfined areas, the geochemical reactions are dolomite dissolution, ion exchange (Mg for Na, K), sulfate reduction, calcite dissolution, and CO2 exchange. In the areas in which the Hawthorn Formation is leaky, the evolution of the ground water is accounted for by ion exchange, sulfate reduction, calcite dissolution, and CO2 exchange. In the confined areas, no ion exchange and only limited sulfate reduction occur, and the chemical character of the ground water is consistent with dolomite and gypsum dissolution, calcite precipitation, and CO2 ingassing. The Hawthorn Formation acts both as a physical barrier to the transport of CO2 and organic matter and as a source of ion-exchange sites, but the carbonate-mineral reactions are largely unaffected by the extent of confinement of the Upper Floridan aquifer. ?? 1994.

Sulfide weathering in the Werenskioldbreen, Spitsbergen - A polar terrestrial analogue for gypsum deposition in the North Polar Region of Mars

NASA Astrophysics Data System (ADS)

Szynkiewicz, A.; Modelska, M.; Buczynski, S.; Borrok, D.; Pratt, L.

2010-12-01

Hydrated sulfates such as gypsum are important constituents of the low-elevation areas around the North Polar residual ice cap on Mars, but the origin of hydrological process which led to the formation and accumulation of gypsum is poorly understood. To address this uncertainty, we investigated the origin of proglacial gypsum in the Werenskioldbreen, a polythermal glacier of Spitsbergen in the Svalbard archipelago east of Greenland. We measured S isotopes, major chemistry and surface water flow rates to calculate SO4 fluxes from sulfide weathering in this polar climate. Sulfides comprised 0.02 to 0.42 weight % of the fine-grained fraction of proglacial sediments and their δ34S varied over the range of +9 to +16 ‰. The δ34S of dissolved SO4 in glacier melt waters (+9 to +17 ‰) was consistent with SO4 generation being dominated by sulfide oxidation. In summer 2008, the calculated SO4 flux was ~6,200 kg/day in the main glacier stream of the Werenskioldbreen discharging to the Greenland Sea and it translated to 4.3 x 105 mol/yr-km2 based on the scale of the entire Werenskioldbreen catchment (~27.4 km2). Our measured polar SO4 flux was 6 times larger than reported estimates for pyrite-derived SO4 loading in a considerably larger (1.78 x 106 km2) watershed of Northern Canada. This implies that small glacier catchments can generate an important global-scale flux of sulfide-derived SO4. Both evaporation and freezing of glacial waters lead to precipitation, accumulation, and temporary storage of gypsum in the proglacial zone. Poor preservation of gypsum on the surface of proglacial sediments mainly results from its quick dissolution during warmer condition when the hydrological cycle is most active. The observed distribution of gypsum and hydrated sulfates around the north polar ice residual deposits of Planum Boreum on Mars matches the spatial and geochemical patterns of gypsum formation controlled by sulfide weathering in terrestrial polar environments like Werenskioldbreen. The highest occurrences of gypsum are in the eastern part of Olympia Undae Dune Field, nearby plausible fluvio-glacial features and the impact crater which might have activated confined water circulation in the past. Given that ancient aeolian strata underlying Planum Boreum are of basaltic composition and sulfides are common minor minerals in basalt, it is likely that slow weathering of this material in the presence of water ice may have contributed elevated SO4 fluxes during short-lived melting events in the past. The westward gypsum decrease in the Olympia Undae suggests re-distribution of weathering products like gypsum from the confined source area during subsequent aeolian transport. In contrast to Earth, limited water activity and prevailing dry conditions on the surface of Mars are the likely factors that account for the larger accumulation and preservation of polar gypsum on the surface and its broad aeolian distribution in the north polar depression.

Evaluation of geochemical and hydrogeological processes by geochemical modeling in an area affected by evaporite karstification

NASA Astrophysics Data System (ADS)

Acero, P.; Auqué, L. F.; Galve, J. P.; Gutiérrez, F.; Carbonel, D.; Gimeno, M. J.; Yechieli, Y.; Asta, M. P.; Gómez, J. B.

2015-10-01

The Ebro Valley in the outskirts of Zaragoza (NE Spain) is severely affected by evaporite karstification, leading to multiple problems related to subsidence and sinkhole formation. In this work, a combination of inverse (mixing + mass-balance) and forward (reaction-path) geochemical calculations is applied for the quantification of the main karstification processes and seasonal variations in this area. The obtained results prove the suitability of the applied methodology for the characterization of similar problems in other areas with scarce geological and hydrogeological information. The hydrogeology and hydrochemistry of the system can be mainly attributed to the mixing of variable proportions of concentrated groundwater from the evaporitic aquifer and more dilute water from the overlying alluvial aquifer. The existence of a good connection between these aquifers is supported by: (1) the fast changes in the hydrochemistry of the karst aquifer related to recharge by irrigation, and (2) the deduced input of evaporitic groundwater in the alluvial materials. The evolution in some parts of the alluvial/evaporitic aquifer system is clearly dominated by the seasonal variations in the recharge by dilute irrigation waters (up to 95% of water volume in some sinkhole ponds), whereas other points seem to be clearly determined by the hydrochemistry of the concentrated evaporitic aquifer groundwater (up to 50% of the water volume in some springs). The following reactions, previous or superimposed to mixing processes, explain the observed hydrochemistry in the studied area: dissolution of halite (NaCl), gypsum (CaSO4ṡ2H2O)/anhydrite (CaSO4) and dolomite (CaMg(CO3)2), CO2(g) input and degassing and calcite (CaCO3) dissolution/precipitation. The modeling results suggest the existence of a large spatial variability in the composition of the evaporitic groundwater, mainly caused by large differences in the availability of halite in contact with the groundwater. Active subsidence associated with halite dissolution is expected to continue in the study area, together with the episodic increase of gypsum dissolution associated with the input of dilute irrigation waters.

A coupled THMC model of a heating and hydration laboratory experiment in unsaturated compacted FEBEX bentonite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, L.; Samper, J.; Montenegro, L.

2010-05-01

Unsaturated compacted bentonite is foreseen by several countries as a backfill and sealing material in high-level radioactive waste repositories. The strong interplays between thermal (T), hydrodynamic (H), mechanical (M) and chemical (C) processes during the hydration stage of a repository call for fully coupled THMC models. Validation of such THMC models is prevented by the lack of comprehensive THMC experiments and the difficulties of experimental methods to measure accurately the chemical composition of bentonite porewater. We present here a non-isothermal multiphase flow and multicomponent reactive solute transport model for a deformable medium of a heating and hydration experiment performed onmore » a sample of compacted FEBEX bentonite. Besides standard solute transport and geochemical processes, the model accounts for solute cross diffusion and thermal and chemical osmosis. Bentonite swelling is solved with a state-surface approach. The THM model is calibrated with transient temperature, water content and porosity data measured at the end of the experiment. The reactive transport model is calibrated with porewater chemical data derived from aqueous extract data. Model results confirm that thermal osmosis is relevant for the hydration of FEBEX bentonite while chemical osmosis can be safely neglected. Dilution and evaporation are the main processes controlling the concentration of conservative species. Dissolved cations are mostly affected by calcite dissolution-precipitation and cation exchange reactions. Dissolved sulphate is controlled by gypsum/anhydrite dissolution-precipitation. pH is mostly buffered by protonation/deprotonation via surface complexation. Computed concentrations agree well with inferred aqueous extract data at all sections except near the hydration boundary where cation data are affected by a sampling artifact. The fit of Cl{sup -} data is excellent except for the data near the heater. The largest deviations of the model from inferred aqueous extract data occur for dissolved SO{sub 4}{sup 2-} which is underpredicted by the model. There are uncertainties on the amount of gypsum available for dissolution and its dissolution mechanism (kinetics or local equilibrium).« less

High-resolution InSAR constraints on flood-related subsidence and evaporite dissolution along the Dead Sea shores: Interplay between hydrology and rheology

NASA Astrophysics Data System (ADS)

Shviro, Maayan; Haviv, Itai; Baer, Gidon

2017-09-01

Sinkhole generation and land subsidence are commonly attributed to dissolution of subsurface layers by under-saturated groundwater and formation of cavities. Along the Dead Sea (DS) shorelines, this process also involves seasonal flash floods that are drained into the subsurface by existing and newly formed sinkholes. We quantify the contribution of flash-floods to salt dissolution and land subsidence using high-resolution interferometric synthetic aperture radar (InSAR). Subsidence rates during a 3-year period (2012-2015) were calculated from 57 COSMO SkyMed X-band interferograms bracketing major flood events and intra-flood periods in 21 sinkhole sites. The sites are located within channels and alluvial fans along the western shores of the Dead Sea, Israel. The observed subsidence reaches maximum rates of 2.5 mm/day, accumulating in specific sites to 500 mm/year. In most of the sinkhole sites a gradual increase in the annual subsidence rate is observed during the 3-year study period. Three different modes of response to floods were observed: (1) sites where floodwater is not directly channeled into sinkholes do not respond to floods; (2) sites adjacent to active channels with sinkholes are unaffected by specific floods but their subsidence rates increase gradually from early winter to mid-summer, and decay gradually until the following winter; and (3) sites in active channels with sinkholes are characterized by an abrupt increase in subsidence rates immediately after each flood (by a factor of up to 20) and by a subsequent quasi-exponential subsidence decay over periods of several months. In these latter sites, subsidence rates after each flood are temporally correlated with alternating groundwater levels in adjacent boreholes. The rapid rise in groundwater head following floods increases the hydraulic gradient of the under-saturated groundwater and hence also the groundwater discharge and the dissolution rate of the subsurface salt layer. A subsequent quasi-exponential water level drop results in similar deceleration in dissolution and subsidence rates, with a similar characteristic decay time of about 150 days. The observed subsidence decay pattern may also be explained by viscoelastic relaxation of the overburden in response to instantaneously-formed dissolution cavities. Utilizing a Kelvin viscoelastic model, we show that the contribution of this process is most probably < 30% of the total observed subsidence and is sensitive to the sediment mechanical properties. On a broader scale, this study demonstrates how high-resolution InSAR measurements can improve our understanding of subsurface dissolution and subsidence processes and provide independent constraints on the mechanical properties of heterogeneous alluvial sediments.

Insights into the diagenetic environment of fossil marine vertebrates of the Pisco Formation (late Miocene, Peru) from mineralogical and Sr-isotope data

NASA Astrophysics Data System (ADS)

Gioncada, A.; Petrini, R.; Bosio, G.; Gariboldi, K.; Collareta, A.; Malinverno, E.; Bonaccorsi, E.; Di Celma, C.; Pasero, M.; Urbina, M.; Bianucci, G.

2018-01-01

The late Miocene Pisco Formation of Peru is an outstanding example of richness and high-quality preservation of fossil marine vertebrates. In order to reconstruct the fossilization path, we present new textural, mineralogical and Sr-isotope data of diagenetic minerals formed in correspondence of fossil specimens such as marine vertebrates and mollusks. These fossil specimens were found at Cerro los Quesos, in the Ica Desert, within the diatomaceous strata of the Pisco Formation. Dolomite, gypsum, anhydrite and Mn minerals are the main phases found, while the calcium carbonate originally forming the mollusk valves is replaced by gypsum. An early formation of dolomite and of Mn minerals, triggered by the modifications of the geochemical environment due to organic matter degradation, is suggested by the textural relationships and is confirmed by the Sr isotopic ratio of dolomite, which agrees with that of seawater at the time of sedimentation. Instead, gypsum Sr isotopic ratios indicate a pre-Miocene seawater-derived brine circulating within the sedimentary sequence as a source for Sr. Oxidation of diagenetic sulfide causing a lowering of the pH of porewater is proposed as an explanation for Ca-carbonate dissolution. The diagenetic chemical environment was, nevertheless, favorable to bone preservation.

Urbanization impact on sulfur content of groundwater revealed by the study of urban speleothem-like deposits: Case study in Paris, France.

PubMed

Pons-Branchu, E; Roy-Barman, M; Jean-Soro, L; Guillerme, A; Branchu, P; Fernandez, M; Dumont, E; Douville, E; Michelot, J L; Phillips, A M

2017-02-01

Speleothem-like deposits that develop underground in urban areas are an archive of the environmental impact of anthropic activities that has been little studied so far. In this paper, the sulfate content in shallow groundwater from northern Paris (France) is compared with the sulfur content in two 300-year-old urban carbonate deposits that grew in a historical underground aqueduct. The present-day waters of the aqueduct have very high sulfur and calcium contents, suggesting pollution from gypsum dissolution. However, geological gypsum levels are located below the water table. Sulfur content was measured by micro-X-ray fluorescence in these very S-rich carbonate deposits (0.5 to 1% of S). A twofold S increase during the second half of the 1800s was found in both samples. These dates correspond to two major periods of urbanization above the site. We discus three possible S sources: anthropic sources (industries, fertilizers…), volcanic eruptions and input within the water through gypsum brought for urbanization above the studied site (backfill with quarry waste) since the middle of the 19th century. For the younger second half of the studied section, S input from gypsum brought during urbanization was confirmed by the study of isotopic sulfur composition (δ 34 S=+15.2‰ at the top). For the oldest part, several sulfur peaks could be related to early industrial activity in Paris, that caused high local air pollution, as reported in historical archives but also to historical gypsum extraction. This study provides information on the origin and timing of the very high SO 4 2- levels measured nowadays within the shallow groundwater, thus demonstrating the interest in using carbonate deposits in urban areas as a proxy for the history of urbanization or human activities and their impact on water bodies. Copyright © 2016 Elsevier B.V. All rights reserved.

Sulfur speciation and stable isotope trends of water-soluble sulfates in mine tailings profiles.

PubMed

Dold, Bernhard; Spangenberg, Jorge E

2005-08-01

Sulfur speciation and the sources of water-soluble sulfate in three oxidizing sulfidic mine tailings impoundments were investigated by selective dissolution and stable isotopes. The studied tailings impoundments--Piuquenes, Cauquenes, and Salvador No. 1--formed from the exploitation of the Rio Blanco/La Andina, El Teniente, and El Salvador Chilean porphyry copper deposits, which are located in Alpine, Mediterranean, and hyperarid climates, respectively. The water-soluble sulfate may originate from dissolution of primary ore sulfates (e.g., gypsum, anhydrite, jarosite) or from oxidation of sulfide minerals exposed to aerobic conditions during mining activity. With increasing aridity and decreasing pyrite content of the tailings, the sulfur speciation in the unsaturated oxidation zones showed a trend from dominantly Fe(III) oxyhydroxide fixed sulfate (e.g., jarosite and schwertmannite) in Piuquenes toward increasing presence of water-soluble sulfate at Cauquenes and Salvador No. 1. In the saturated primary zones, sulfate is predominantly present in water-soluble form (mainly as anhydrite and/or gypsum). In the unsaturated zone at Piuquenes and Cauquenes, the delta34S(SO4)values ranged from +0.5 per thousand to +2.0 per thousand and from -0.4 per thousand to +1.4 per thousand Vienna Canyon Diablo Troilite (V-CDT), respectively, indicating a major sulfate source from pyrite oxidation (delta34S(pyrite) = -1.1 per thousand and -0.9 per thousand). In the saturated zone at Piuquenes and Cauquenes, the values ranged from -0.8 per thousand to +0.3 per thousand and from +2.2 per thousand to +3.9 per thousand, respectively. At Cauquenes the 34S enrichment in the saturated zone toward depth indicates the increasing contribution of isotopically heavy dissolved sulfate from primary anhydrite (approximately +10.9 per thousand). At El Salvador No. 1, the delta34S(SO4) average value is -0.9 per thousand, suggesting dissolution of supergene sulfate minerals (jarosite, alunite, gypsum) with a delta34S approximately -0.7 per thousand as the most probable sulfate source. The gradual decrease of delta18O(SO4) values from the surface to the oxidation front in the tailings impoundments at Piuquenes (from -4.5 per thousand to -8.6 per thousand Vienna Standard Mean Ocean Water, V-SMOW) and at Cauquenes (from -1.3 per thousand to -3.5 per thousand) indicates the increasing importance of ferric iron as the main electron acceptor in the oxidation of pyrite. The different delta18O(SO4) values between the tailings impoundments studied here reflect the local climates.

Impact of Phosphogypsum waste on the Geochemistry of the coastal water of Ghannouche -Gabes (SE of Tunisia).

NASA Astrophysics Data System (ADS)

Ben Amor, R.; Fathallah, S.; Gueddari, M.

2009-04-01

Impact of Phosphogypsum waste on the Geochemistry of the coastal water of Ghannouche -Gabes (SE of Tunisia). R. Ben Amor, S. Fathallah, M. Gueddari (R.U. of Geochemistry and of Environmental Geology, Faculty of Sciences of Tunis, Department of Geology, 2092 Manar I) Corresponding author: R. Ben Amor; E-mail:magba_rim@yahoo.fr The littoral Ghannouche - Gabes (SE of Tunisia), has been known since the 1970's, an important industrialization especially after the installation of the chemical complex for the treatment of phosphates. These industries are at the origin of various waste materials, the most significant one is phosphogypsum (PG) which is released into the sea. The aim of this paper is to identify and to analyze the different entropic and natural factors, which govern the chemical composition in major elements, dissolved oxygen, pH and temperature of Ghannouche -Gabes coastal water, while studying, in particular, the impact of PG waste on the spatial distribution of these parameters. The result of the chemical analyses of the samples taken in June 2003, show that Na, K and Cl are conserved in solution and they evolve with constant Na/Cl and K/Cl ratio. The values of these ratios are similar to sea water average. The concentration of the other elements are controlled, first, by processes of precipitation or dissolution of the carbonated (Ca, Mg and HCO3) or sulphated (Ca and SO4) minerals, and second, by dilution or evaporation phenomena and by the phosphogypsum waste. The spatial distribution of these elements, of the pH, the dissolved oxygen and the temperature and the result of the saturation index with respect to calcite, gypsum and fluorite, by using of the PhreeqC program, show that the zone, located at north of the study area, between the commercial and the fishing port, is highly influenced by the PG waste. In this area, where the PG is released and which is relatively sheltered by the dams of the commercial and fishing port, waters are characterised by the highest temperatures values, and the lowest pH and the dissolved oxygen values. This water is supersaturated with respect to the fluorite, under saturated with respect to CaCO3 and gypsum. In this zone, the poured gypsum undergoes a quasi-total dissolution. This dissolution would be supported by the acidity of water and the highest temperature values. Keywords: Major ions - Sea water - Phosphogypsum - Saturation indices - Gulf of Gabes - Tunisia.

On Subsurface Fracture Opening and Closure

NASA Astrophysics Data System (ADS)

Wang, Y.

2016-12-01

Mechanistic understanding of fracture opening and closure in geologic media is of significant importance to nature resource extraction and waste management, such as geothermal energy extraction, oil/gas production, radioactive waste disposal, and carbon sequestration and storage). A dynamic model for subsurface fracture opening and closure has been formulated. The model explicitly accounts for the stress concentration around individual aperture channels and the stress-activated mineral dissolution and precipitation. A preliminary model analysis has demonstrated the importance of the stress-activated dissolution mechanism in the evolution of fracture aperture in a stressed geologic medium. The model provides a reasonable explanation for some key features of fracture opening and closure observed in laboratory experiments, including a spontaneous switch from a net permeability reduction to a net permeability increase with no changes in a limestone fracture experiment.

Copahue Volcano: A Modern Terrestrial Analog for the Opportunity Landing Site?

NASA Astrophysics Data System (ADS)

Varekamp, Johan C.

2004-10-01

The Opportunity Rover on Mars encountered an environment that contained grey hematite (specularite) and jarosite, with structures indicative of flowing water. Less firm evidence suggests the presence of gypsum as well, and the environment is overall rich in S, Cl, and Br (NASA news releases, 2004). Such a suite of minerals may form from an iron- and sulfate-rich brine, either through evaporation, cooling or changes in redox conditions (see Hynek et al. [2002] and Christensen et al. [2001], for a discussion of the extent and possible origins of the Mars hematite deposits). On Earth, such an association of minerals is not very common, but is found in alteration zones with fumarolic activity in some volcanic craters. The condensation or dissolution in meteoric waters of S-rich volcanic gases creates acid fluids in the surficial environment that leach rock-forming elements (RFEs) from the surrounding rocks, forming large, bleached areas of mineralizations of hematite, cristobalite, and gypsum, occasionally with zones rich in alunite or jarosite.

Flue gas desulfurization gypsum and fly ash

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1992-05-01

The Cumberland Fossil Plant (CUF) is located in Stewart County, Tennessee, and began commercial operation in 1972. This is the Tennessee Valley Authority`s newest fossil (coal-burning) steam electric generating plant. Under current operating conditions, the plant burns approximately seven million tons of coal annually. By-products from the combustion of coal are fly ash, approximately 428,000 tons annually, and bottom ash, approximately 115,000 tons annually. Based on historical load and projected ash production rates, a study was initially undertaken to identify feasible alternatives for marketing, utilization and disposal of ash by-products. The preferred alternative to ensure that facilities are planned formore » all by-products which will potentially be generated at CUF is to plan facilities to handle wet FGD gypsum and dry fly ash. A number of different sites were evaluated for their suitability for development as FGD gypsum and ash storage facilities. LAW Engineering was contracted to conduct onsite explorations of sites to develop information on the general mature of subsurface soil, rock and groundwater conditions in the site areas. Surveys were also conducted on each site to assess the presence of endangered and threatened species, wetlands and floodplains, archaeological and cultural resources, prime farmland and other site characteristics which must be considered from an environmental perspective.« less

Illite Dissolution Rates and Equation (100 to 280 dec C)

DOE Data Explorer

Carroll, Susan

2014-10-17

The objective of this suite of experiments was to develop a useful kinetic dissolution expression for illite applicable over an expanded range of solution pH and temperature conditions representative of subsurface conditions in natural and/or engineered geothermal reservoirs. Using our new data, the resulting rate equation is dependent on both pH and temperature and utilizes two specific dissolution mechanisms (a “neutral” and a “basic” mechanism). The form of this rate equation should be easily incorporated into most existing reactive transport codes for to predict rock-water interactions in EGS shear zones.

Simultaneous and continuous stabilization of As and Pb in contaminated solution and soil by a ferrihydrite-gypsum sorbent.

PubMed

Kameda, Kentaro; Hashimoto, Yohey; Wang, Shan-Li; Hirai, Yasumasa; Miyahara, Hidetaka

2017-04-05

For the increasing need of stabilization both cationic and anionic metal(loid)s simultaneously, we newly developed a metal sorbent (FIXALL), consisting mainly of ferrihydrite and gypsum. The objectives of this study were to determine the molecular mechanisms of Pb and As stabilization in an aqueous system and to examine a simultaneous and long-term (up to 754days) effect on Pb and As stabilization in an anthropogenically contaminated soil using the FIXALL sorbent. When the solution contained a low concentration of Pb (5mgL -1 ), the mechanisms of Pb removal by FIXALL were based chiefly on the formation of inner-sphere surface complex with ferrihydrite. In the highly concentrated Pb solution (1200mgL -1 ), contrarily, the removal of Pb by FIXALL was the direct consequence of the dissolution of gypsum and subsequent precipitation of PbSO 4 , which strengthens the drawback of low capability of ferrihydrite for Pb removal. Regardless of initial concentrations, the primary mechanism of FIXALL for As stabilization is attributed to the formation of inner-sphere surface complex with ferrihydrite. A contaminated soil study demonstrated that FIXALL could decrease the concentration of water soluble As and Pb simultaneously and continuously for 754days without notable changes in their chemical species and soil pH. Copyright © 2016 Elsevier B.V. All rights reserved.

Experimental study of the replacement of calcite by calcium sulphates

NASA Astrophysics Data System (ADS)

Ruiz-Agudo, E.; Putnis, C. V.; Hövelmann, J.; Álvarez-Lloret, P.; Ibáñez-Velasco, A.; Putnis, A.

2015-05-01

Among the most relevant mineral replacement reactions are those involving sulphates and carbonates, which have important geological and technological implications. Here it is shown experimentally that during the interaction of calcite (CaCO3) cleavage surfaces with sulphate-bearing acidic solutions, calcite is ultimately replaced by gypsum (CaSO4 2H2O) and anhydrite (CaSO4), depending on the reaction temperature. Observations suggest that this occurs most likely via an interface-coupled dissolution-precipitation reaction, in which the substrate is replaced pseudomorphically by the product. At 120 and 200 °C gypsum and/or bassanite (CaSO4·0.5H2O) form as precursor phases for the thermodynamically stable anhydrite. Salinity promotes the formation of less hydrated precursor phases during the replacement of calcite by anhydrite. The reaction stops before equilibrium with respect to calcite is reached and during the course of the reaction most of the bulk solutions are undersaturated with respect to the precipitating phase(s). A mechanism consisting of the dissolution of small amounts of solid in a thin layer of fluid at the mineral-fluid interface and the subsequent precipitation of the product phase from this layer is in agreement with these observations. PHREEQC simulations performed in the framework of this mechanism highlight the relevance of transport and surface reaction kinetics on the volume change associated with the CaCO3-CaSO4 replacement. Under our experimental conditions, this reaction occurs with a positive volume change, which ultimately results in passivation of the unreacted substrate before calcite attains equilibrium with respect to the bulk solution.

Geochemistry of and radioactivity in ground water of the Highland Rim and Central Basin aquifer systems, Hickman and Maury counties, Tennessee

USGS Publications Warehouse

Hileman, G.E.; Lee, R.W.

1993-01-01

A reconnaissance of the geochemistry of and radioactivity in ground water from the Highland Rim and Central Basin aquifer systems in Hickman and Maury Counties, Tennessee, was conducted in 1989. Water in both aquifer systems typically is of the calcium or calcium magnesium bicarbonate type, but concentrations of calcium, magnesium, sodium, potassium, chloride, and sulfate are greater in water of the Central Basin system; differences in the concentrations are statistically significant. Dissolution of calcite, magnesium-calcite, dolomite, and gypsum are the primary geochemical processes controlling ground-water chemistry in both aquifer systems. Saturation-state calculations using the computer code WATEQF indicated that ground water from the Central Basin system is more saturated with respect to calcite, dolomite, and gypsum than water from the Highland Rim system. Geochemical environments within each aquifer system are somewhat different with respect to dissolution of magnesium-bearing minerals. Water samples from the Highland Rim system had a fairly constant calcium to magnesium molar ratio, implying congruent dissolution of magnesium-bearing minerals, whereas water samples from the Central Basin system had highly variable ratios, implying either incongruent dissolution or heterogeneity in soluble constituents of the aquifer matrix. Concentrations of radionuclides in water were low and not greatly different between aquifer systems. Median gross alpha activities were 0.54 picocuries per liter in water from each system; median gross beta activities were 1.1 and 2.3 picocuries per liter in water from the Highland Rim and Central Basin systems, respectively. Radon-222 concentrations were 559 and 422 picocuries per liter, respectively. Concentrations of gross alpha and radium in all samples were substantially less than Tennessee?s maximum permissible levels for community water-supply systems. The data indicated no relations between concentrations of dissolved radionuclides (uranium, radium-226, radium-228, radon-222, gross alpha, and gross beta) and any key indicators of water chemistry, except in water from the Highland Rim system, in which radon-222 was moderately related to pH and weakly related to dissolved magnesium. The only relation among radiochemical constituents indicated by the data was between radium-226 and gross alpha activity; this relation was indicated for water from both aquifer systems.

Influence of acidic and alkaline waste solution properties on uranium migration in subsurface sediments.

PubMed

Szecsody, Jim E; Truex, Mike J; Qafoku, Nikolla P; Wellman, Dawn M; Resch, Tom; Zhong, Lirong

2013-08-01

This study shows that acidic and alkaline wastes co-disposed with uranium into subsurface sediments have significant impact on changes in uranium retardation, concentration, and mass during downward migration. For uranium co-disposal with acidic wastes, significant rapid (i.e., hours) carbonate and slow (i.e., 100 s of hours) clay dissolution resulted, releasing significant sediment-associated uranium, but the extent of uranium release and mobility change was controlled by the acid mass added relative to the sediment proton adsorption capacity. Mineral dissolution in acidic solutions (pH2) resulted in a rapid (<10 h) increase in aqueous carbonate (with Ca(2+), Mg(2+)) and phosphate and a slow (100 s of hours) increase in silica, Al(3+), and K(+), likely from 2:1 clay dissolution. Infiltration of uranium with a strong acid resulted in significant shallow uranium mineral dissolution and deeper uranium precipitation (likely as phosphates and carbonates) with downward uranium migration of three times greater mass at a faster velocity relative to uranium infiltration in pH neutral groundwater. In contrast, mineral dissolution in an alkaline environment (pH13) resulted in a rapid (<10h) increase in carbonate, followed by a slow (10 s to 100 s of hours) increase in silica concentration, likely from montmorillonite, muscovite, and kaolinite dissolution. Infiltration of uranium with a strong base resulted in not only uranium-silicate precipitation (presumed Na-boltwoodite) but also desorption of natural uranium on the sediment due to the high ionic strength solution, or 60% greater mass with greater retardation compared with groundwater. Overall, these results show that acidic or alkaline co-contaminant disposal with uranium can result in complex depth- and time-dependent changes in uranium dissolution/precipitation reactions and uranium sorption, which alter the uranium migration mass, concentration, and velocity. Copyright © 2013 Elsevier B.V. All rights reserved.

Sulfur Isotope Analysis of Minerals and Fluids in a Natural CO2 Reservoir, Green River, Utah

NASA Astrophysics Data System (ADS)

Chen, F.; Kampman, N.; Bickle, M. J.; Busch, A.; Turchyn, A. V.

2013-12-01

Predicting the security of geological CO2 storage sites requires an understanding of the geochemical behavior of the stored CO2, especially of fluid-rock reactions in reservoirs, caprocks and fault zones. Factors that may influence geochemical behavior include co-injection of sulfur gases along with the CO2, either in acid-gas disposal or as contaminants in CO2 storage sites, and microbial activity, such as bacterial sulfate reduction. The latter may play an important role in buffering the redox chemistry of subsurface fluids, which could affect toxic trace metal mobilization and transport in acidic CO2-rich fluids. These processes involving sulfur are poorly understood. Natural CO2-reservoirs provide natural laboratories, where the flow and reactions of the CO2-charged fluids and the activity of microbial communities are integrated over sufficient time-scales to aid prediction of long-term CO2 storage. This study reports on sulfur isotope analyses of sulfate and sulfide minerals in rock core and in CO2-charged fluids collected from a stacked sequence of natural CO2 reservoirs at Green River, Utah. Scientific drilling adjacent to a CO2-degassing normal fault to a depth of 325m retrieved core and fluid samples from two CO2 reservoirs in the Entrada and Navajo Sandstones and from the intervening Carmel Formation caprock. Fluid samples were collected from CO2-charged springs that discharge through the faults. Sulfur exists as sulfate in the fluids, as sedimentary gypsum beds in the Carmel Formation, as remobilized gypsum veins within a fault damage zone in the Carmel Fm. and in the Entrada Sandstone, and as disseminated pyrite and pyrite-mineralized open fractures throughout the cored interval. We use the stable sulfur (δ34S) and oxygen (δ18OSO4) isotopes of the sulfate, gypsum, and pyrite to understand the source of sulfur in the reservoir as well as the timing of gypsum vein and pyrite formation. The hydration water of the gypsum is also reported to explore the different timing of gypsum vein formation. Macroscopic and microscopic gradients in the sulfur isotope composition of pyrite throughout the core and at discernible redox-reaction fronts were examined in detail to assess the role of bacteria in mediating sulfate reduction, sulfide mineralization and buffering of groundwater redox chemistry. The CO2 charged fluids and gypsum veins within the Entrada Sandstone have a narrow and very similar range in both δ34SSO4 and δ18OSO4, suggesting that the fluids (9.1-10.7‰) are the most likely source of the sulfate in the veins (11.4-12.8‰) and that the veins formed during recent fluid flow through the Entrada, with sulfate coming from remobilized gypsum beds in the Carmel. The Carmel also contains two isotopically distinct types of gypsum veins: one with δ34SSO4 values similar to the Entrada veins and one with much higher δ34SSO4 values (15.1-16.1‰). The latter are likely primary gypsum, while the former are likely secondary gypsum. Sulfur isotope fractionation between pyrite (-16.5‰ to -35.7‰) at the Carmel-Navajo interface and reservoir fluids (9.1-10.7‰) suggest that sulfur reducing bacteria play a role in producing the deposited sulfide. This data demonstrates active sulfur cycling in CO2 reservoirs with many different sulfur species cycled among various pools creating the wide isotope dispersion we observe.

New method for mass transfer across the surface of non-spherical particles in turbulence

NASA Astrophysics Data System (ADS)

Oehmke, T.; Variano, E. A.

2016-12-01

We present a method for making model particles that allow for the interfacial mass transfer rate to be measured. This is similar to traditional use of gypsum plaster used to measure erosion rates on the timescale of weeks to years. Our new method is useful for measuring erosion rates on the timescale of minutes. We use this to measure the manner in which particle shape affects its rate of dissolution in turbulent flow. The related questions are relevant to mass transfer in turbulence, e.g. in cases of marine biology and pollution by microplastics.

Complex carbonate and clastic stratigraphy of the inner shelf off west-central Florida

DOE Office of Scientific and Technical Information (OSTI.GOV)

Locker, S.D.; Doyle, L.J.; Hine, A.C.

1990-05-01

The near surface stratigraphy (< 30 m) of the inner shelf off the west coast of Florida was investigated using high-resolution seismic, side-scan sonar, and continuous underwater video camera coverage. The simultaneous operation of all three systems provided a unique opportunity to calibrate acoustic data with actual video images of the sea floor in a geologically complex area characterized by limestone dissolution structures, hard-bottom exposures, and overlain by a limited supply of terrigenous clastics. Three principle bottom types, grass, sand, and hard-bottom mapped using video and side-scan sonographs, show a correlation with two subsurface stratigraphic zones. The nearshore subsurface zonemore » extending to 6-7 m water depth is characterized by flat or rolling strata and sinkholes that increase in size (200-1,200 m in diameter) and become more numerous further offshore. This zone is truncated by a major erosional unconformity overlain by a thin (<3 m) sequence of Holocene sediment, which together form a terrace upon which the Anclote Key barrier island formed. The offshore subsurface zone (7-11 m water depth) exhibits irregular and discontinuous high-amplitude flat or inclined reflections and few sinkholes. Offshore, extensive hard-bottom exposures are common with discontinuous sediment that occur as lenses or sand waves. The complex stratigraphy of the west Florida shelf includes outcropping Neogene limestones that have undergone dissolution during sea level lowstands. Carbonates and clastics dispersed during multiple sea level changes overlie the Neogene limestones. Dissolution styles and erosional unconformities produced bedrock topography and now control modern geological and biological processes.« less

Groundwater Dynamics in Fossil Fractured Carbonate Aquifers in Eastern Arabian Peninsula

NASA Astrophysics Data System (ADS)

Farag, A. Z. A.; Heggy, E.; Helal, M.; Thirunavukkarasu, D.; Scabbia, G.; Palmer, E. M.

2017-12-01

The Eastern Arabian Peninsula, notably the Qatar Peninsula, represents one of the highest natural groundwater discharge areas for the Arabian platform fossil aquifer system. Groundwater flow dynamics in these aquifers trace the paleoclimatic conditions that have prevailed the Arabian Peninsula during the Quaternary. In such settings, connections between aquifers strongly affect the flow dynamics, water quality and availability as well as karst formation and landscape evolution. Geological structures such as folds, faults and fractures are central to aquifer connectivity, yet their role on groundwater flow is poorly understood. Herein, we performed a detailed mapping of exposed and buried structural features in Qatar using Landsat, Sentinel and ALOS-PalSAR scenes, correlated with field and laboratory measurements to understand their role in aquifer connectivity and groundwater dynamics. Our results suggest that E-W oriented fold-related faults act as vertical conduits along which artesian upward leakages from the deep aquifers (e.g. Aruma and Umm er Radhuma) take place into the shallower aquifers (e.g. Rus and Dammam). Evidence includes: (1) the high potentiometric surfaces of deep aquifers (6 to 25 m amsl) compare to the shallower aquifers (2-3 m amsl for the same region); (2) anomalous elevation of groundwater levels and steeper hydraulic gradients in densely faulted regions; (3) mixed isotopic composition in shallow aquifers (δ18O: -5 to -2 ‰, δ2H: -40 to -10 ‰) between reported deep fossil waters (δ18O: -6.3 ‰, δ2H: -55 ‰) and modern meteoric waters (weighted average: δ18O: -0.6 ‰, δ2H: 4 ‰); (4) abundant meso-crystalline fibrous gypsum veins along fault zones in the Dammam Formation (up to 28 m amsl) in southern Qatar where the anhydritic member of the Rus Formation predominates the subsurface leading to gypsum oversaturation of groundwater. The similarity of crystal morphology (platy crystals under SEM), mineralogical compositions from XRD analysis and geologic setting suggest a common genesis from elevated groundwater along faults during wet climatic periods. The present study suggests that ascending gaseous-rich deep waters along faults in Qatar is degrading the water quality and causing dissolution of carbonates and evaporites leading to strong karstification with abundant collapse features.

Natural versus human control on subsurface salt dissolution and development of thousands of sinkholes along the Dead Sea coast

NASA Astrophysics Data System (ADS)

Abelson, Meir; Yechieli, Yoseph; Baer, Gidon; Lapid, Gil; Behar, Nicole; Calvo, Ran; Rosensaft, Marcelo

2017-06-01

One of the most hazardous results of the human-induced Dead Sea (DS) shrinkage is the formation of more than 6000 sinkholes over the last 25 years. The DS shrinkage caused eastward retreat of underground brine replaced by fresh groundwater, which in turn dissolved a subsurface salt layer, to generate cavities and collapse sinkholes. The areal growth rate of sinkhole clusters is considered the most pertinent proxy for sinkholes development. Analysis of light detection and ranging, digital elevation models, and interferometric synthetic aperture radar allows translation of the areal growth rate to a salt dissolution rate of the salt layer, revealing two peaks in the history of the salt dissolution rate. These peaks cannot be attributed to the decline of the DS level. Instead, we show that they are related to long-term variations of precipitation in the groundwater source region, the Judea Mountains, and the delayed response of the aquifer system between the mountains and the DS rift. This response is documented by groundwater levels and salinity variations. We thus conclude that while the DS level decline is the major trigger for sinkholes formation, the rainfall variations more than 30 km to the west dominate their evolution rate. The influence of increasing rainfall in the Judea Mountains reaches the DS at a typical time lag of 4 years, and the resulting increase in the salt dissolution rate lags by a total time of 5-6 years.

The dissolution kinetics of industrial brine sludge wastes from a chlor-alkali industry as a sorbent for wet flue gas desulfurization (FGD).

PubMed

Masilela, E; Lerotholi, L; Seodigeng, T; Rutto, H

2018-02-01

The disposal of industrial brine sludge waste (IBSW) in chlor-alkali plants can be avoided by utilization of IBSW as a sorbent in wet flue gas desulfurization (FGD). The shrinking core model was used to determine the dissolution kinetics of IBSW, which is a vital step in wet FGD. The effects of solid-to-liquid ratio (m/v), temperature, pH, particle size, and stirring speed on the conversion and dissolution rate constant are determined. The conversion and dissolution rate constant decreases as the pH, particle size, and solid-to-liquid ratio are increased and increases as the temperature, concentration of acid, and stirring speed are increased. The sorbents before and after dissolution were characterized using x-ray fluorescence (XRF), x-ray diffraction (XRD), and scanning electron microscopy (SEM). An activation energy of 7.195 kJ/mol was obtained and the product layer diffusion model was found to be the rate-controlling step. The use of industrial brine sludge waste as an alternative sorbent in wet flue gas desulfurization can reduce the amounts of industrial wastes disposed of in landfills. This study has proved that the sorbent can contain up to 91% calcium carbonate and trace amounts of sulfate, magnesium, and so on. This can be used as new sorbent to reduce the amount of sulfur dioxide in the atmosphere and the by-product gypsum can be used in construction, as a plaster ingredient, as a fertilizer, and for soil conditioning. Therefore, the sorbent has both economic and environmental benefits.

What was the groundwater quality before mining in a mineralized region? Lessons from the Questa Project

USGS Publications Warehouse

Nordstrom, D. Kirk

2008-01-01

The U.S. Geological Survey, in cooperation with the New Mexico Environment Department and supported by Molycorp, Inc (currently Chevron Minerals), has completed a 5-year investigation (2001-2006) to determine the pre-mining ground-water quality at Molycorp's Questa molybdenum mine in northern New Mexico. Current mine-site ground waters are often contaminated with mine-waste leachates and no data exists on premining ground-water quality so that pre-mining conditions must be inferred. Ground-water quality undisturbed by mining is often worse than New Mexico standards and data are needed to help establish closure requirements. The key to determining pre-mining conditions was to study the hydrogeochemistry of a proximal natural analog site, the Straight Creek catchment. Main rock types exposed to weathering include a Tertiary andesite and the Tertiary Amalia tuff (rhyolitic composition), both hydrothermally altered to various degrees. Two types of ground water are common in mineralized areas, acidic ground waters in alluvial debris fans with pH 3-4 and bedrock ground waters with pH 6-8. Siderite, ferrihydrite, rhodochrosite, amorphous to microcrystalline Al(OH)3, calcite, gypsum, barite, and amorphous silica mineral solubilities control concentrations of Fe(II), Fe(III), Mn(II), Al, Ca, Ba, and SiO2, depending on pH and solution composition. Concentrations at low pH are governed by element abundance and mineral weathering rates. Concentrations of Zn and Cd range from detection up to about 10 and 0.05 mg/L, respectively, and are derived primarily from sphalerite dissolution. Concentrations of Ni and Co range from detection up to 1 and 0.4 mg/L, respectively, and are derived primarily from pyrite dissolution. Concentrations of Ca and SO4 are derived from secondary gypsum dissolution and weathering of calcite and pyrite. Metal:sulfate concentration ratios are relatively constant for acidic waters, suggesting consistent weathering rates, independent of catchment. These trends, combined with lithology, mineralogy, and mineral solubility controls, provide useful constraints on pre-mining ground-water quality for the mine site where the lithology is known.

Mobilization of selenium from the Mancos Shale and associated soils in the lower Uncompahgre River Basin, Colorado

USGS Publications Warehouse

Mast, M. Alisa; Mills, Taylor J.; Paschke, Suzanne S.; Keith, Gabrielle; Linard, Joshua I.

2014-01-01

This study investigates processes controlling mobilization of selenium in the lower part of the Uncompahgre River Basin in western Colorado. Selenium occurs naturally in the underlying Mancos Shale and is leached to groundwater and surface water by limited natural runoff, agricultural and domestic irrigation, and leakage from irrigation canals. Soil and sediment samples from the study area were tested using sequential extractions to identify the forms of selenium present in solid phases. Selenium speciation was characterized for nonirrigated and irrigated soils from an agricultural site and sediments from a wetland formed by a leaking canal. In nonirrigated areas, selenium was present in highly soluble sodium salts and gypsum. In irrigated soils, soluble forms of selenium were depleted and most selenium was associated with organic matter that was stable under near-surface weathering conditions. Laboratory leaching experiments and geochemical modeling confirm that selenium primarily is released to groundwater and surface water by dissolution of highly soluble selenium-bearing salts and gypsum present in soils and bedrock. Rates of selenium dissolution determined from column leachate experiments indicate that selenium is released most rapidly when water is applied to previously nonirrigated soils and sediment. High concentrations of extractable nitrate also were found in nonirrigated soils and bedrock that appear to be partially derived from weathered organic matter from the shale rather than from agricultural sources. Once selenium is mobilized, dissolved nitrate derived from natural sources appears to inhibit the reduction of dissolved selenium leading to elevated concentrations of selenium in groundwater. A conceptual model of selenium weathering is presented and used to explain seasonal variations in the surface-water chemistry of Loutzenhizer Arroyo, a major tributary contributor of selenium to the lower Uncompahgre River.

Sedimentologic and diagenetic controls on aquifer properties, Lower Cretaceous Edwards Carbonate Aquifer, Texas: Implications for aquifer management

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hovorka, S.D.; Dutton, A.R.; Ruppel, S.C.

1994-09-01

The three-dimensional distribution of water in the Edwards aquifer was assessed using a core and log-based study. Porosity distribution reflects both depositional fabric and subsequent diagenesis. Vertical facies stacking patterns influence the depositional porosity as well as dolomitization and diagentic porosity modification. Subtidal facies deposited during sea level highstands are generally undolomitized and exhibit low porosity (5-10%); platform grainstones typically have high depositional porosity and significant solution enhancement (20-42% porosity). Dolomitized subtidal facies in tidal-flat-capped cycles have very high porosity (20-40%) because of selective dolomite dissolution in the freshwater aquifer. Porosity in gypsum beds is high in some areas becausemore » of dissolution and collapse, but low where gypsum was replaced by calcite cement. Low-energy subtidal and evaporitic units in the Maverick basin have porosity generally less than 15%. The overlying basinal packstones and grainstones have solution-enhanced porosities of 25 to 35%. Diagenesis associated with fluctuations in water chemistry near the saline-freshwater interface may explain one high-porosity trend. Other complex patterns of high and low porosity are attributed to structurally and hydrologically controlled porosity enhancement and cementation. Three-dimensional mapping of porosity trends provides data for improved aquifer management. Only about 3% of the maximum stored water lies above the water table at which natural spring flow is diminished. An average specific yield of 42% in the unconfined aquifer is determined from total porosity, changes in the water-table elevation, and changes in estimated recharge and discharge. Average storativity of 2.6 x 10{sup -4} in the confined Edwards is estimated using average porosity and barometric efficiency calculated from comparing water-level hydrographs and atmospheric pressure changes.« less

Major hydrogeochemical processes in an acid mine drainage affected estuary.

PubMed

Asta, Maria P; Calleja, Maria Ll; Pérez-López, Rafael; Auqué, Luis F

2015-02-15

This study provides geochemical data with the aim of identifying and quantifying the main processes occurring in an Acid Mine Drainage (AMD) affected estuary. With that purpose, water samples of the Huelva estuary were collected during a tidal half-cycle and ion-ion plots and geochemical modeling were performed to obtain a general conceptual model. Modeling results indicated that the main processes responsible for the hydrochemical evolution of the waters are: (i) the mixing of acid fluvial water with alkaline ocean water; (ii) precipitation of Fe oxyhydroxysulfates (schwertmannite) and hydroxides (ferrihydrite); (iii) precipitation of Al hydroxysulfates (jurbanite) and hydroxides (amorphous Al(OH)3); (iv) dissolution of calcite; and (v) dissolution of gypsum. All these processes, thermodynamically feasible in the light of their calculated saturation states, were quantified by mass-balance calculations and validated by reaction-path calculations. In addition, sorption processes were deduced by the non-conservative behavior of some elements (e.g., Cu and Zn). Copyright © 2014 Elsevier Ltd. All rights reserved.

A review of stormwater management in karst

USDA-ARS?s Scientific Manuscript database

Stormwater management can be a challenge in any environment, but it is especially difficult in karst terrain. The characteristic dissolution of bedrock creates depressions in topography as well as voids in the subsurface, resulting in problems such as collapse sinkhole development, groundwater cont...

Microbially Induced Carbonate Precipitation: a Novel Grout for Permeability Control in Subsurface Engineering Works

NASA Astrophysics Data System (ADS)

Minto, J. M.; Hingerl, F.; Lunn, R. J.; Benson, S. M.

2016-12-01

ContextWe utilise the urea hydrolysing capability of soil bacteria Sporosarcina pasteurii to precipitate CaCO3 in a process termed Microbially Induced Carbonate Precipitation (MICP). MICP injection fluid properties are low particle size and low viscosity giving excellent grout penetrability. The CaCO3 grout has been shown to be effective at reducing permeability in porous and fractured media. MICP has consequently been proposed as an alternative to more traditional cement and chemical grouts, particularly in the fields of radioactive waste disposal and geological sequestration of CO2. This study investigates the role of fluid flow/CaCO3 feedback during precipitation and accelerated dissolution to better understand the longevity of an MICP grout under low pH environmental conditions such as found in a carbon sequestration reservoir. MethodsExperiments were conducted on a single Berea sandstone core in a high pressure core holder to characterise permeability, porosity and multiphase flow behaviour at sequestration reservoir temperature and pressure. Characterisation was carried out before MICP, after MICP, and after accelerated dissolution with hydrochloric acid. At each step the entire core was scanned in a medical x-ray CT scanner to spatially resolve (with a resolution of 0.5x0.5x1mm) the changes in porosity and saturation with CaCO3 precipitation and dissolution. Finally, the dried core was scanned with μ-CT at 30μm (full core) and 10μm (sub-volume) resolutions to investigate structural changes to the Berea at near pore scale. ResultsSix MICP treatment cycles over two days reduced core permeability from 886 mDarcy to 40 mDarcy with a greater reduction in porosity at the inlet. Dissolution with acid restored much of the porosity, but did not restore permeability to the same extent. Preferential flow paths formed during the dissolution step were visible in the first 4mm of the 100mm core, but did not extend further into the core. DiscussionThis study provides evidence that MICP can potentially produce a long lasting seal, even in challenging subsurface environments, provided that a thick enough layer of CaCO3 can be precipitated with a low initial permeability. Challenges remain for ensuring that such a barrier can be created in the subsurface and are the subject of further investigation.

Mineralogy and Organic Geochemistry of Acid Sulfate Environments from Valles Caldera, New Mexico: Habitability, Weathering and Biosignatures

NASA Astrophysics Data System (ADS)

Vogel, M. B.; Des Marais, D. J.; Jahnke, L. L.; Kubo, M.

2009-12-01

We report on the mineralogy, organic preservation potential and habitability of sulfate deposits in acid sulfate volcanic settings at Valles Caldera, New Mexico. Fumaroles and acidic springs are potential analogs for aqueous environments on Mars and may offer insights into habitability of sulfate deposits such as those at Meridiani Planum. Sulfates recently detected on Mars are posited to have formed from fluids derived from basaltic weathering and igneous volatile input, ultimately precipitating from acidic brines subjected to desiccation and freeze-thaw cycles (McClennan and Grotzinger, 2008). Key issues concerning martian sulfate deposits are their relationship to aqueous clay deposits, and whether or not specific sulfates deposits represent former habitable environments (see Soderblum and Bell, 2008; Tosca et al., 2008). Modern terrestrial volcanic fumaroles and hot springs precipitate various Ca-, Mg- and Fe- sulfates along with clays, and can help clarify whether certain acid sulfate mineral assemblages reflect habitable environments. Valles caldera is a resurgent caldera last active in the Pleistocene (1.4 - 1.0 Ma) that hosts several active fumaroles and over 40 geothermal exploration wells (see Goff, 2009). Fumaroles and associated mudpots and springs at Valles range from pH < 1 to 3, and affect argillic alteration upon rhylolitic tuffs and sedimentary deposits (Charles et al., 1986). We identified assemblages containing gypsum, quartz, Al-sulfates, elemental sulfur, clays and other minerals using XRD and SEM-EDS. Our previous research has shown that sulfates from different marine depositional environments display textural and morphological traits that are indicative of biological influence, or specific conditions in the depositional environments (Vogel et al., 2009). Gypsum crystals that develop in the presence of microbial biofilms in marine environments may have distorted crystal morphologies, biofilm - associated dissolution features, and accessory carbonate minerals. Gypsum from Valles Caldera fumaroles develops in the absence of microbial biofilms and differs from biologically influenced marine gypsum in terms of is highly prismatic morphology, lack of texture, and association with clays, and other sulfates. Studies of Valles gypsum crystals therefore support the uniqueness of the putative morphological biosignatures in marine gypsum. We also assayed organic matter from fumarole encrustations to understand how low pH and sulfate content may discriminate against or enhance preservation of specific classes of organic compounds in acid sulfate environments. Similar to gypsiferous marine environments, organics are characterized by abundant organosulfur complexes. Long chain alkanes (> nC22) are abundant from acid sulfate environments. As with hypersaline marine depositional environments, sulfidation appears to be a major diagenetic pathway for organic matter in acid sulfate environments.

Geochemistry of surface and subsurface waters in quartz-sandstones: significance for the geomorphic evolution of tepui table mountains (Gran Sabana, Venezuela)

NASA Astrophysics Data System (ADS)

Mecchia, Marco; Sauro, Francesco; Piccini, Leonardo; De Waele, Jo; Sanna, Laura; Tisato, Nicola; Lira, Jesus; Vergara, Freddy

2014-04-01

In situ measurements of discharge, pH, electric conductivity (EC), temperature, and SiO2 content have been carried out during five expeditions in the last 20 years on the summit plateaus, inside caves and along the rivers of the surrounding lowlands of three tepui massifs in Venezuela (Auyan, Roraima, and Chimanta). Additionally, detailed chemical analyses were performed on waters sampled in a newly discovered extensive quartz-sandstone cave system on the Auyan Tepui. Rock samples of the quartz-sandstone bedrock from different locations have been analysed to obtain their chemical composition with a wavelength dispersive X-ray fluorescence spectrometer. These data show that the majority of silica present in surface and subsurface water comes from dissolution of quartz and only in minor amount from hydrolysis of other silicate minerals. Probably the presence of a hardened crust of iron hydroxides limits the dissolution of silica on the top surface of tepuis. Dissolution in the subsurface, instead, is more significant and causes, in the long term, the “arenisation” of the quartz-sandstone and its subsequent removal by mechanical erosion. On the other hand, waters flowing on the arkosic rock outcropping on the lowland below the tepuis obtain their high dissolved silica content mainly from hydrolysis of silicates. The morphological evolution of these table mountains appears thus to be controlled mainly by the underground weathering of the quartz-sandstone, with the opening of deep fractures (grietas) and the collapse of large underground horizontal cave systems. Scarp retreat, instead, seems to be related to the higher weathering rate of the more arkosic formations underlying the quartz-sandstones.

Non-steady state partitioning of dry cleaning surfactants between tetrachloroethylene (PCE) and water in porous media.

PubMed

Hoggan, James L; Bae, Keonbeom; Kibbey, Tohren C G

2007-08-15

Trapped organic solvents, in both the vadose zone and below the water table, are frequent sources of environmental contamination. A common source of organic solvent contamination is spills, leaks, and improper solvent disposal associated with dry cleaning processes. Dry cleaning solvents, such as tetrachloroethylene (PCE), are typically enhanced with the addition of surfactants to improve cleaning performance. The objective of this work was to examine the partitioning behavior of surfactants from PCE in contact with water. The relative rates of surfactants partitioning and PCE dissolution are important for modeling the behavior of waste PCE in the subsurface, in that they influence the interfacial tension of the PCE, and how (or if) interfacial tension changes over time in the subsurface. The work described here uses a flow-through system to examine simultaneous partitioning and PCE dissolution in a porous medium. Results indicate that both nonylphenol ethoxylate nonionic surfactants and a sulfosuccinate anionic surfactant partition out of residual PCE much more rapidly than the PCE dissolves, suggesting that in many cases interfacial tension changes caused by partitioning may influence infiltration and distribution of PCE in the subsurface. Non-steady-state partitioning is found to be well-described by a linear driving force model incorporating measured surfactant partition coefficients.

Evaporite-karst problems and studies in the USA

USGS Publications Warehouse

Johnson, K.S.

2008-01-01

Evaporites, including rock salt (halite) and gypsum (or anhydrite), are the most soluble among common rocks; they dissolve readily to form the same types of karst features that commonly are found in limestones and dolomites. Evaporites are present in 32 of the 48 contiguous states in USA, and they underlie about 40% of the land area. Typical evaporite-karst features observed in outcrops include sinkholes, caves, disappearing streams, and springs, whereas other evidence of active evaporite karst includes surface-collapse structures and saline springs or saline plumes that result from salt dissolution. Many evaporites also contain evidence of paleokarst, such as dissolution breccias, breccia pipes, slumped beds, and collapse structures. All these natural karst phenomena can be sources of engineering or environmental problems. Dangerous sinkholes and caves can form rapidly in evaporite rocks, or pre-existing karst features can be reactivated and open up (collapse) under certain hydrologic conditions or when the land is put to new uses. Many karst features also propagate upward through overlying surficial deposits. Human activities also have caused development of evaporite karst, primarily in salt deposits. Boreholes (petroleum tests or solution-mining operations) or underground mines may enable unsaturated water to flow through or against salt deposits, either intentionally or accidentally, thus allowing development of small to large dissolution cavities. If the dissolution cavity is large enough and shallow enough, successive roof failures can cause land subsidence and/or catastrophic collapse. Evaporite karst, natural and human-induced, is far more prevalent than is commonly believed. ?? 2007 Springer-Verlag.

Hydrogeochemical processes in the Plio-Quaternary Remila aquifer (Khenchela, Algeria)

NASA Astrophysics Data System (ADS)

Aouidane, Laiche; Belhamra, Mohamed

2017-06-01

The Remila Plain is a synclinal structure in northeast Algeria, situated within a semi-arid climate zone and composed of Mio-Pliocene-Quaternary deposits. Within the syncline, the Plio-Quaternary aquifer is the main source of drinking water for cattle and for agricultural irrigation water. This work aims to investigate the origin of groundwater mineralization and to identify the primary hydrogeochemical processes controlling groundwater evolution in the Remila aquifer. A total of 86 water samples from boreholes were analyzed for major, minor and stable isotopes (18O, 2H) over three seasons: first during low water levels in 2013, second during high water levels in 2014 and third for stable isotopes during low water levels in 2015. The analysis showed that the aquifer is controlled by five principal geochemical processes: (I) the dissolution of evaporite rocks, (II) cation exchange and reverse exchange reactions, (III) congruent dissolution of carbonates (calcite, dolomite) coupled with the dissolution of gypsum and calcite precipitation, (IV) sulfate reduction under anaerobic conditions, and (V) saltwater intrusion in the northeastern Sabkha plains. The 18O and deuterium concentrations in groundwater are very low, indicating that the aquifer is recharged by evaporated rainfall originating from the north slope of the Aurès Mountains which confirms that the aquifer is recharged in the southern part of the plain.

Deposition and evolution of the Sivas basin evaporites (Turkey)

NASA Astrophysics Data System (ADS)

Pichat, Alexandre; Hoareau, Guilhem; Rouchy, Jean-Marie; Ribes, Charlotte; Kergaravat, Charlie; Callot, Jean-Paul; Ringenbach, Jean-Claude

2015-04-01

The Oligo-Miocene Sivas basin (Turkey) is strongly affected by salt tectonics, best expressed in its central part. Halokinesis initiated from the Upper Eocene Hafik formation, composed of thick evaporite layers. Salt tectonics induced the formation of numerous mini basins filled with continental to marine deposits, and nowadays separated by diapiric gypsum walls or welds. Continental deposits filling minibasins developed in arid conditions. Minibasin sandstones are frequently interlayered with evaporitic deposits (gypsum and anhydrite). Two types of depositional evaporites can be distinguished: (i) evaporites precipitated in lacustrine to sebkhaic environment, (ii) gypsarenites resulting from clastic gypsum remobilization. Field observations suggest that both types of depositional evaporites were likely sourced from the recycling of adjacent salt structures. Precipitation of lacustro-sebkhaic evaporites may have been triggered by meteoric waters enriched in dissolved sulfate after the chemical dissolution of outcropping evaporites. Gypsarenite deposits can be explained by mechanical dismantling of nearby evaporite structures. Evaporitic deposits were subsequently involved in active salt tectonics. During periods of quiescent diapirism, thick sebkhaic deposits were also deposited in secondary minibasins located on former salt domes. During periods of diapiric growth, linked to regional compressive tectonics, these deposits were then locally deformed and can show strong flowage textures. When rising diapiric evaporites reached the surface, it was also able to mechanically spread out within the minibasins, forming salt glaciers. In this case, if depositional evaporites were overlying the extruded diapir, both diapiric and depositional evaporites were incorporated in salt tectonic structures. Ongoing chemical analysis should help us to precise more accurately the different sources and the dynamics of these multigeneration evaporites.

Pyritized mudstone and associated facies in the Permian-Triassic boundary of the Çürük Daǧ section, Southern Turkey

NASA Astrophysics Data System (ADS)

Varol, Baki; Koşun, Erdal; Ünal Pinar, Neslihan; Ayranci, Korhan

2011-03-01

This paper is the first study of pyritized mudstones (PM) in the Permian-Triassic (P-T) boundary section of the Çürük Dağ (Taurus, Antalya Nappes, Turkey). The mudstones were generally formed as lensoidal-shaped layers or infill materials within nodular platform limestones (hardground). Normal marine fauna is diminished in the pyritized limestones, whereas tube-like microorganisms are apparently increased with the association of pyrite crystals consisting of both framboidal and cubic crystals. The total rock volumes are up to 50-60% clay minerals and are mainly made up of in situ kaolinite and subordinate mixed layer clays (illite-vermiculite). Kaolinite preferentially developed on feldspar crystals, sometimes covering ostracoda bivalves together with gypsum micronodules composed of fan-shaped gypsum crystals. The origin of the kaolinite is, in situ, directly related to feldspar dissolution via heterotrophic bacteria. Thus, kaolinite is found along with bacterial structures. Other mineralogical compositions include established quartz (mostly β-quartz), gypsum crystals (100-200 μm) glauconite and magnetite. Magnetite grains comprise a minor amount (1-2%) and show some bacterial-induced crystal orientations. Glauconite is formed as an accessory mineral that occurs as infill material in biogenic grains. On the other hand, some microspheres represented by a silica-dominated composition are only observed in scanning electron microscopes (SEM) studies under high magnification. Isotope values (d34S) obtained from the pyritized mudstones show an isotopic heterogeneity that suggests that the pyritized mudstone consists of at least two components, with different sulphur-concentrations and d34S values.

Nonaqueous Phase Liquid Dissolution in Porous Media: Multi-Scale Effects of Multi-Component Dissolution Kinetics on Cleanup Time

DOE Office of Scientific and Technical Information (OSTI.GOV)

McNab, W; Ezzedine, S; Detwiler, R

2007-02-26

Industrial organic solvents such as trichloroethylene (TCE) and tetrachloroethylene (PCE) constitute a principal class of groundwater contaminants. Cleanup of groundwater plume source areas associated with these compounds is problematic, in part, because the compounds often exist in the subsurface as dense nonaqueous phase liquids (DNAPLs). Ganglia (or 'blobs') of DNAPL serve as persistent sources of contaminants that are difficult to locate and remediate (e.g. Fenwick and Blunt, 1998). Current understanding of the physical and chemical processes associated with dissolution of DNAPLs in the subsurface is incomplete and yet is critical for evaluating long-term behavior of contaminant migration, groundwater cleanup, andmore » the efficacy of source area cleanup technologies. As such, a goal of this project has been to contribute to this critical understanding by investigating the multi-phase, multi-component physics of DNAPL dissolution using state-of-the-art experimental and computational techniques. Through this research, we have explored efficient and accurate conceptual and numerical models for source area contaminant transport that can be used to better inform the modeling of source area contaminants, including those at the LLNL Superfund sites, to re-evaluate existing remediation technologies, and to inspire or develop new remediation strategies. The problem of DNAPL dissolution in natural porous media must be viewed in the context of several scales (Khachikian and Harmon, 2000), including the microscopic level at which capillary forces, viscous forces, and gravity/buoyancy forces are manifested at the scale of individual pores (Wilson and Conrad, 1984; Chatzis et al., 1988), the mesoscale where dissolution rates are strongly influenced by the local hydrodynamics, and the field-scale. Historically, the physico-chemical processes associated with DNAPL dissolution have been addressed through the use of lumped mass transfer coefficients which attempt to quantify the dissolution rate in response to local dissolved-phase concentrations distributed across the source area using a volume-averaging approach (Figure 1). The fundamental problem with the lumped mass transfer parameter is that its value is typically derived empirically through column-scale experiments that combine the effects of pore-scale flow, diffusion, and pore-scale geometry in a manner that does not provide a robust theoretical basis for upscaling. In our view, upscaling processes from the pore-scale to the field-scale requires new computational approaches (Held and Celia, 2001) that are directly linked to experimental studies of dissolution at the pore scale. As such, our investigation has been multi-pronged, combining theory, experiments, numerical modeling, new data analysis approaches, and a synthesis of previous studies (e.g. Glass et al, 2001; Keller et al., 2002) aimed at quantifying how the mechanisms controlling dissolution at the pore-scale control the long-term dissolution of source areas at larger scales.« less

Depositional setting of the Upper Jurassic Hith Anhydrite of the Arabian Gulf: An analog to holocene evaporites of the United Arab Emirates and Lake MacLeod of Western Australia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alsharhan, A.S.; Kendall, C.G.St.C.

1994-07-01

The Upper Jurassic Hith Anhydrite is a major hydrocarbon seal in the Arabian Gulf region. Outcrops, core samples from the subsurface, and the literature indicate that the Hith Formation is composed mainly of anhydrite. In most locations where a section of the Hith Formation has been measured, this unit contains less than 20% carbonate much of which is in the form of thin laminations. This lack of carbonate, locally thick layers of salt, and the predominance of anhydrite favor a playa for the setting in which this sediment was accumulated. In fact, much of the Hith has the sedimentary characteristicsmore » of the Holocene Lake MacLeod playa of Western Australia, which is dominated by layers of gypsum and halite (what little carbonate that occurs is found in layers at the base of the section). Locally the Hith appears to have accumulated in a sabkha setting, particularly toward central Abu Dhabi where it pinches out into shallow-water, and peritidal carbonate. This sabkha setting is indicated by the interbedded relationship of the Hith anhydrites with these carbonates and the local predominance of horizontally flattened nodules and enterolithic layers of anhydrite. These latter features match some of the characteristic fabrics found in the Holocene coastal sabkhas of the United Arab Emirates. As with the local occurrences in the Hith, the Holocene sabkhas are dominated by carbonates and are divisible into a series of lateral facies belts. These are also expressed as equivalent vertical layers. Traced from seaward to landward, or from the base of the vertical sequence upward, these facies are characterized by (1) algal mat, (2) a layer of a gypsum crystal mush (3) active anhydrite replacement of gypsum (4) anhydrite with no gypsum mush, and (5) recycled eolianite and storm-washover sediments.« less

Natural and human-induced sinkholes in gypsum terrain and associated environmental problems in NE Spain

NASA Astrophysics Data System (ADS)

Benito, G.; Del Campo, P. Pérez; Gutiérrez-Elorza, M.; Sancho, C.

1995-04-01

The central Ebro Basin comprises thick evaporite materials whose high solubility produces typically karstic landforms. The sinkhole morphology developed in the overlying alluvium has been studied using gravimetry and ground-penetrating radar (GPR) on stream terraces, as well as analyzing the evolution of sinkhole morphologies observed in aerial photographs taken in 1928, 1957, and 1985. The sinkhole morphologies give some idea of possible subsurface processes as well as an indication of the final mechanisms involve in sinkhole development. On stream terraces and cover pediments the most commonly encountered dolines are bowl-shaped in their morphology with both diffuse and scarped edges. In contrast, dolines developed in the gypsiferous silt infilled valleys have a funnel and well-shaped morphology. The diffuse-edged bowl-shaped dolines are developed through the progressive subsidence of the alluvial cover, due to washing down of alluvial particles through small voids and cracks into deeper subsurface caves, resulting in a decrease alluvial density. Future compaction of the alluvial cover will produce surface subsidences. This type of dolines are associated with negative gravity anomalies. In contrast, the scarped-edge dolines are formed by the sudden collapse of a cavity roof. The cavities and cracks formed in the gypsum karst may migrate to the surface through the alluvial deposits by piping, and they may subsequently collapse. In this instance, the cavities can be detected by both gravity and GPR anomalies where the voids are not deeper than 4 5 m from the surface. These processes forming sinkholes can be enhanced by man-induced changes in the groundwater hydrologic regime by both inflows, due to irrigation, ditch losses, or pipe leakages, and by outflows from pumping activities.

Supergene destruction of a hydrothermal replacement alunite deposit at Big Rock Candy Mountain, Utah: Mineralogy, spectroscopic remote sensing, stable-isotope, and argon-age evidences

USGS Publications Warehouse

Cunningham, Charles G.; Rye, Robert O.; Rockwell, Barnaby W.; Kunk, Michael J.; Councell, Terry B.

2005-01-01

Big Rock Candy Mountain is a prominent center of variegated altered volcanic rocks in west-central Utah. It consists of the eroded remnants of a hypogene alunite deposit that, at ∼21 Ma, replaced intermediate-composition lava flows. The alunite formed in steam-heated conditions above the upwelling limb of a convection cell that was one of at least six spaced at 3- to 4-km intervals around the margin of a monzonite stock. Big Rock Candy Mountain is horizontally zoned outward from an alunite core to respective kaolinite, dickite, and propylite envelopes. The altered rocks are also vertically zoned from a lower pyrite–propylite assemblage upward through assemblages successively dominated by hypogene alunite, jarosite, and hematite, to a flooded silica cap. This hydrothermal assemblage is undergoing natural destruction in a steep canyon downcut by the Sevier River in Marysvale Canyon. Integrated geological, mineralogical, spectroscopic remote sensing using AVIRIS data, Ar radiometric, and stable isotopic studies trace the hypogene origin and supergene destruction of the deposit and permit distinction of primary (hydrothermal) and secondary (weathering) processes. This destruction has led to the formation of widespread supergene gypsum in cross-cutting fractures and as surficial crusts, and to natrojarosite, that gives the mountain its buff coloration along ridges facing the canyon. A small spring, Lemonade Spring, with a pH of 2.6 and containing Ca, Mg, Si, Al, Fe, Mn, Cl, and SO4, also occurs near the bottom of the canyon. The 40Ar/39Ar age (21.32±0.07 Ma) of the alunite is similar to that for other replacement alunites at Marysvale. However, the age spectrum contains evidence of a 6.6-Ma thermal event that can be related to the tectonic activity responsible for the uplift that led to the downcutting of Big Rock Candy Mountain by the Sevier River. This ∼6.6 Ma event also is present in the age spectrum of supergene natrojarosite forming today, and probably dates the beginning of supergene alteration at Big Rock Candy Mountain. The δ34S value (11.9‰) of alunite is similar to those for replacement alunite from other deposits in the Marysvale volcanic field. The δ34S values of natrojarosite (0.7‰ to −1.2‰) are similar to those for aqueous sulfate in Lemonade Spring, but are larger than those in pyrite (0.4‰ to −4.7‰). The δ34S and δ18OSO4 values of gypsum show an excellent correlation, with values ranging from 15.2‰ to −5.2‰ and 7‰ to −8.2‰, respectively. The stable-isotope data indicate that the aqueous sulfate for gypsum is a mixture derived from the dissolution of hypogene gypsum and alunite, and from the supergene oxidation of pyrite. The aqueous sulfate for the natrojarosite, however, is derived largely from the supergene oxidation of pyrite, with a minor contribution from the dissolution of alunite and gypsum. The exceptional detailed spectral mapping capabilities of AVIRIS led to the recognition of a small amount of jarosite that is probably the top of the steam-heated system that produced the primary hypogene alteration at Big Rock Candy Mountain.

High Resolution ground penetrating radar (GPR) measurements at the laboratory scale to model porosity and permeability in the Miami Limestone in South Florida.

NASA Astrophysics Data System (ADS)

Mount, G. J.; Comas, X.

2015-12-01

Subsurface water flow within the Biscayne aquifer is controlled by the heterogeneous distribution of porosity and permeability in the karst Miami Limestone and the presence of numerous dissolution and mega-porous features. The dissolution features and other high porosity areas can create preferential flow paths and direct recharge to the aquifer, which may not be accurately conceptualized in groundwater flow models. As hydrologic conditions are undergoing restoration in the Everglades, understanding the distribution of these high porosity areas within the subsurface would create a better understanding of subsurface flow. This research utilizes ground penetrating radar to estimate the spatial variability of porosity and dielectric permittivity of the Miami Limestone at centimeter scale resolution at the laboratory scale. High frequency GPR antennas were used to measure changes in electromagnetic wave velocity through limestone samples under varying volumetric water contents. The Complex Refractive Index Model (CRIM) was then applied in order to estimate porosity and dielectric permittivity of the solid phase of the limestone. Porosity estimates ranged from 45.2-66.0% from the CRIM model and correspond well with estimates of porosity from analytical and digital image techniques. Dielectric permittivity values of the limestone solid phase ranged from 7.0 and 13.0, which are similar to values in the literature. This research demonstrates the ability of GPR to identify the cm scale spatial variability of aquifer properties that influence subsurface water flow which could have implications for groundwater flow models in the Biscayne and potentially other shallow karst aquifers.

Dissolution of explosive compounds TNT, RDX, and HMX under continuous flow conditions.

PubMed

Wang, Chao; Fuller, Mark E; Schaefer, Charles; Caplan, Jeffrey L; Jin, Yan

2012-05-30

2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) are common contaminants around active military firing ranges. Dissolution of these compounds is usually the first step prior to their spreading in subsurface environments. Nevertheless, dissolution of individual TNT, RDX, and HMX under continuous flow conditions has not been well investigated. This study applied spectral confocal microscopy to observe and quantify the dissolution of TNT, RDX, and HMX (<100 μm crystals) in micromodel channels. Dissolution models were developed to describe the changes of their radii, surface areas, volumes, and specific surface areas as a function of time. Results indicated that a model incorporating a resistance term that accounts for the surface area in direct contact with the channel surfaces (and hence, was not exposed to the flowing water) described the dissolution processes well. The model without the resistance term, however, could not capture the observed data at the late stage of TNT dissolution. The model-fitted mass transfer coefficients were in agreement with the previous reports. The study highlights the importance of including the resistance term in the dissolution model and illustrates the utility of the newly developed spectral imaging method for quantification of mass transfer of TNT, RDX, and HMX. Copyright © 2012 Elsevier B.V. All rights reserved.

Chemical osmosis, reverse chemical osmosis, and the origin of subsurface brines

NASA Astrophysics Data System (ADS)

Graf, Donald L.

1982-08-01

Calculations using recently-tabulated values of density and osmotic coefficient for NaCl-H 2O indicate that overpressuring is more than adequate to overcome chemical osmosis and drive reverse chemical osmosis in sedimentary sequences. The best-demonstrated overpressuring mechanism is the rapid deposition of fine-grained sediments. The dehydration of gypsum contributes to overpressuring for brief time intervals at shallow depths, whereas water evolved during the protracted conversion of smectite to illite is probably a subordinate, but continuing contributor to overpressuring at greater depth. Occurrences of overpressuring in sedimentary sections older than Cretaceous indicate that post-depositional mechanisms such as tectonic compression and aquathermal pressuring must also operate. The latter may be of major importance in geothermal areas with adequate low-permeability seals, and a nontrivial contributor in areas of normal geothermal gradient because of shales that sharply decrease normal fluid flow. The strongest arguments for the importance to present-day brine compositions of membrane concentration of sea-water solutes are (1) the correlation of δD values of water molecules of pore fluid with those of local meteoric water, (2) the need for major sources of Mg 2+ and Cl - in apparently evaporite-free basins. Even where dissolution of halite is a major contributor of solute, reverse chemical osmosis still operates to leak relatively dilute water. Of the associated diagenetic chemical reactions, that of Mg 2+ with limestone to form dolomite is particularly effective in generating concentrated Cl - brines rich in Ca 2+. It decreases the concentration of Mg 2+, increases that of Ca 2+, and decreases those of both SO 42- and CO 32- by precipitating CaCO 3 and CaSO 4 because of the Ca 2+ common-ion effect.

Shale-brine-CO2 interactions and the long-term stability of carbonate-rich shale caprock

NASA Astrophysics Data System (ADS)

Ilgen, A.; Aman, M.; Espinoza, D. N.; Rodriguez, M. A.; Griego, J.; Dewers, T. A.; Feldman, J.; Stewart, T.; Choens, R. C., II

2017-12-01

Geological carbon storage (GCS) requires an impermeable caprock (e.g., shale) that prevents the upward migration and escape of carbon dioxide (CO2) from the subsurface. Geochemical alteration can occur at the caprock-reservoir rock interface, which could lead to the altering of the rock's mechanical properties, compromising the seal. We performed laboratory experiments on Mancos shale to quantify the coupled chemical-mechanical response of carbonate-rich shale in CO2-brine mixtures at conditions typical to GCS. We constructed geochemical models, calibrated them using laboratory results, and extended to time scales required for GCS. We observed the dissolution of calcite and kaolinite and the precipitation of gypsum and amorphous aluminum (hydr)oxide following the introduction of CO2. To address whether this mineral alteration causes changes in micro-mechanical properties, we examined altered Mancos shale using micro-mechanical (scratch) testing, measuring the scratch toughness of mm-scale shale lithofacies. The quartz-rich regions of the Mancos shale did not show significant changes in scratch toughness following 1-week alteration in a CO2-brine mixture. However, the scratch toughness of the calcite-rich, originally softer regions decreased by about 50%. These observations illustrate a coupled and localized chemical-mechanical response of carbonate-rich shale to the injection of CO2. This suggests a localized weakening of the caprock may occur, potentially leading to the development of preferential flow paths. The identification of vulnerable lithofacies within caprock and a characterization of mineralogical heterogeneity is imperative at prospective GCS sites. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA-0003525.

Hydrology of the Sevier-Sigurd ground-water basin and other ground-water basins, central Sevier Valley, Utah.

USGS Publications Warehouse

Lambert, P.M.; Mason, J.L.; Puchta, R.W

1995-01-01

The hydrologic system in the central Sevier Valley, and more specifically the Sevier-Sigurd basin, is a complex system in which surface- and ground-water systems are interrelated. Seepage from an extensive irrigation system is the primary source of recharge to the basin-fill aquifer in the Sevier-Sigurd basin.Water-quality data indicate that inflow from streams and subsurface inflow that intersect evaporite deposits in the Arapien Shale does not adversely affect ground-water quality in the Sevier-Sigurd basin. Stable-isotope data indicate that large sulfate concentrations in water from wells are from the dissolution of gypsum within the basin fill rather than inflow from the Arapien Shale.A ground-water-flow model of the basin-fill aquifer in the Sevier-Sigurd basin was calibrated to steady-state conditions and transient conditions using yearly water-level changes from 1957-88 and monthly water-level changes from 1958-59. Predictive simulations were made to test the effects of reduced recharge from irrigation and increased well discharge. To simulate the effects of conversion from flood to sprinkler irrigation, recharge from irrigated fields was reduced by 50 percent. After twenty years, this reduction resulted in water-level declines of 1 to 8 feet in most of the basin, and a reduction in ground-water discharge to the Sevier River of 4,800 acre-ft/yr. Water-level declines of as much as 12 feet and a reduction in recharge to the Sevier River of 4,800 acre-ft/yr were the result of increasing well discharge near Richfield and Monroe by 25,000 acre-ft/yr. 

Mineral resource potential map of the Chama River Canyon Wilderness and contiguous roadless area, Rio Arriba County, New Mexico

USGS Publications Warehouse

Ridgley, Jennie L.; Light, Thomas D.

1983-01-01

The Chama River Canyon Wilderness and Roadless Area have a moderate to high potential for the presence of small deposits of copper with associated uranium and silver. These deposits, as yet undetected, would occur in the Permian Cutler Formation and in the lower part of the Triassic Chinle Formation, rock units that are, for the most part, present only in the subsurface. The presence of these deposits is inferred because such deposits occur in rocks of equivalent age in adjacent areas. Gypsum, of probable minable quality and quantity, occurs throughout the area. Oil and gas are possibly present in Pennsylvanian strata in the subsurface, although no drilling in the study area has tested this hypothesis. Other commodities, including noncopper-related uranium, kaolinite, chromium, vanadium, manganese, and bitumen, although present locally in anomalous concentrations, do not appear to constitute potential resources for these commodities.

Detachment of particulate iron sulfide during shale-water interaction

NASA Astrophysics Data System (ADS)

Emmanuel, S.; Kreisserman, Y.

2017-12-01

Hydraulic fracturing, a commonly used technique to extract oil and gas from shales, is controversial in part because of the threat it poses to water resources. The technique involves the injection into the subsurface of large amounts of fluid, which can become contaminated by fluid-rock interaction. The dissolution of pyrite is thought to be a primary pathway for the contamination of fracturing fluids with toxic elements, such as arsenic and lead. In this study, we use direct observations with atomic force microscopy to show that the dissolution of carbonate minerals in Eagle Ford shale leads to the physical detachment of embedded pyrite grains. To simulate the way fluid interacts with a fractured shale surface, we also reacted rock samples in a flow-through cell, and used environmental scanning electron microscopy to compare the surfaces before and after interaction with water. Crucially, our results show that the flux of particulate iron sulfide into the fluid may be orders of magnitude higher than the flux of pyrite from chemical dissolution. This result suggests that mechanical detachment of pyrite grains could be the dominant mode by which arsenic and other inorganic elements are mobilized in the subsurface. Thus, during hydraulic fracturing operations and in groundwater systems containing pyrite, the transport of many toxic species may be controlled by the transport of colloidal iron sulfide particles.

Porosity change after gypsum crust formation on macro-porous limestones

NASA Astrophysics Data System (ADS)

Dewanckele, Jan; Cnudde, Veerle; de Kock, Tim; Boone, Marijn; Boone, Matthieu; van Hoorebeke, Luc; Jacobs, Patric

2010-05-01

The deterioration of stone is a complex process in which physical, biological and chemical mechanisms are involved. In this research, pore structure changes inside two types of porous limestone were analyzed before, during and after strong acid tests with SO2. Sulphatation and crust formation phenomena on natural building stones exposed to a polluted environment, are largely described in literature. As far as rocks rich in calcium carbonate are concerned, the main processes involved are the dissolution of the calcium carbonate and the formation of gypsum (CaSO4.2H2O) in presence of an acid atmosphere. The low mobility of this newly formed salt favours its accumulation in porous materials and at the surface of less porous media. The main actor in the process of gypsum crystallization on limestone is the aggressive sulphur dioxide gas (SO2). In this study, the Savonnières and Euville limestone were subjected to tests with a strong acid. According to the standard EN 13919:2002E, samples were put in acid environment for 21 days. At the bottom of the container a mixture of 500 ± 10 ml H2SO3 and 150 ± 10 ml de-mineralized H2O was added. No airborne particles or oxides of nitrogen (NOx) were added. Before exposure, after 6 days in the polluted environment and at the end of the test, the two samples were scanned with X-ray computed tomography (X-ray CT) at the Centre for X-ray Tomography at Ghent University, Belgium (UGCT; www.ugct.ugent.be). This visualization technique allows 2D and 3D reconstructions on a micrometer scale of the internal structure of an object without damaging the material. It thus enables to scan the same sample in a sequential way. In order to obtain information about the sample's interior of which the characteristics can be compared before, during and after the test, the same scanning parameters (exposure time, amount of frames, energy, etc.) were used. In addition, the same adjustments like beam hardening correction, normalizing, ring and spot filter, etc. were applied for the reconstruction. Total porosity, open and closed porosity and radial porosity were calculated for each sample by using the in-house developed software program Morpho+. The analysis of the various scans revealed that the Euville limestone developed a distinct gypsum crust, behind which a secondary porous layer of 100 μm thickness had developed. Inside the sample the porosity decreased by infilling of the large pore spaces with gypsum. However, after 6 days exposure the total porosity of the sample increased from 5.70% to 8.45%. In this case, the formation of secondary porosity behind the newly formed exterior gypsum layer prevailed upon the crystallizing of gypsum inside the pores located in the sample's interior. Also, the firstly formed gypsum crystals prevented the further interaction of the sulphuric acid with the stone material. After 21 days, the total porosity of the sample still reached 8.45%. The results of the radial porosity measurements were also the same after 6 and 21 days, indicating that the secondary porosity and the filling of pores inside the samples were stabilized. On the other hand, the gypsum crust on the Savonnières limestone was less visible. No secondary formed porous layer was measured and the total porosity decreased from 12.10% to 10.94% after 6 days and further to 10.31% at the end of the test. The decrease of porosity was still measurable at a depth of 500 μm inside the sample. The combination of micro-CT, image analysis and induced weathering tests are a promising combination of tools and techniques that allow for a better understanding of gypsum crust formation and pore structure change just behind the crust and deeper inside the rock sample.

Constraining the origin of the Messinian gypsum deposits using coupled measurement of δ^{18}O$/δD in gypsum hydration water and salinity of fluid inclusions

NASA Astrophysics Data System (ADS)

Evans, Nicholas P.; Gázquez, Fernando; McKenzie, Judith A.; Chapman, Hazel J.; Hodell, David A.

2016-04-01

We used oxygen and hydrogen isotopes of gypsum hydration water (GHW) coupled with salinity deduced from ice melting temperatures of primary fluid inclusions in the same samples (in tandem with 87Sr/86Sr, δ34S and other isotopic measurements) to determine the composition of the mother fluids that formed the gypsum deposits of the Messinian Salinity Crisis from shallow and intermediate-depth basins. Using this method, we constrain the origin of the Messinian Primary Lower Gypsum (PLG) of the Sorbas basin (Betic foreland) and both the Upper Gypsum (UG) and the Lower Gypsum of the Sicilian basin. We then compare these results to measurements made on UG recovered from the deep Ionian and Balearic basins drilled during DSDP Leg 42A. The evolution of GHW δ18O/δD vs. salinity is controlled by mixing processes between fresh and seawater, coupled with the degree of evaporation. Evaporation and subsequent precipitation of gypsum from fluids dominated by freshwater will result in a depressed 87Sr/86Sr values and different trajectory in δ18O/δD vs. salinity space compared to fluids dominated by seawater. The slopes of these regression equations help to define the end-members from which the fluid originated. For example, salinity estimates from PLG cycle 6 in the Sorbas basin range from 18 to 51ppt, and after correction for fractionation factors, estimated δ18O and δD values of the mother water are low (-2.6 < δ18O < 2.7‰ ; -16.2 < δD < 15.8‰). The intercepts of the regression equations (i.e. at zero salinity) are within error of the average isotope composition of the modern precipitation and groundwater in this region of SE Spain. This indicates there was a significant contribution of meteoric water during gypsum deposition, while 87Sr/86Sr (0.708942 < 87Sr/86Sr < 0.708971) indicate the ions originated from the dissolution of previously marine evaporites. Gypsum from cycle 2 displays similar mother water values (-2.4 < δ18O < 2.4‰ ; -13.2 < δD < 17.0‰) to cycle 6, but salinities of fluid inclusions are higher averaging ˜100ppt. In contrast to cycle 6, the intercepts of the regression equations of cycle 2 display more positive δ18O/δD values. While the estimated range in δ18O and δD of the mother water and salinities fall below those expected from the evaporation of seawater alone, the slope of the regression equation is similar to that of seawater evaporation. This implies that there is a change up-section from a dominantly marine environment in cycle 2 to a greater influence of meteoric water in cycle 6. The UG from the Sicilian basin display greater δ18O/δD values (2.9 < δ18O < 6.0‰ ; 16.6 < δD < 38.3‰) compared to the PLG of Sorbas, with average salinities of ˜90ppt. The intercept of the regression equations are similar to those of Sorbas cycle 6, indicating the mother fluid was composed of a large percentage of meteoric water that subsequently underwent intense evaporation. This observation concurs with the low values of 87Sr/86Sr from the same UG samples (0.708745 < 87Sr/86Sr < 0.708810) that have been interpreted previously to reflect a substantial dilution of Mediterranean surface water during this period, and with brackish to fresh-water fauna described from the associated marl of the UG in other studies. Ongoing analyses will test if this pattern of intense evaporation of a predominately meteoric mother fluid is reflected in the isotopic composition of the UG deposited in the deep Ionian and Balearic basins.

Effect of bacteria and dissolved organics on mineral dissolution kinetics:

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg; Shirokova, Liudmila; Benezeth, Pascale; Zabelina, Svetlana

2010-05-01

Quantification of the effect of microorganisms and associated organic ligands on mineral dissolution rate is one among the last remaining challenges in modeling of water-rock interactions under earth surface and subsurface environments. This is especially true for deep underground settings within the context of CO2 capture, sequestration and storage. First, elevated CO2 pressures create numerous experimental difficulties for performing robust flow-through experiments at a given saturation state. Second, reactivity of main rock-forming minerals in abiotic systems at pCO2 >> 1 atm and circumneutral pH is still poorly constrained. And third, most of microbial habitats of the subsurface biosphere are not suitable for routine culturing in the laboratory, many of them are anaerobic and even strictly anaerobic, and many bacteria and archae cultures can live only in the consortium of microorganisms which is very hard to maintain at a controlled and stable biomass concentration. For experimental modeling of bio-mineral interactions in the laboratory, two other main conceptual challenges exist. Typical concentration of dissolved organic carbon that serves as a main nutrient for heterotrophic bacteria in underground waters rarely exceeds 3-5 mg/L. Typical concentration of DOC in nutrient media used for bacteria culturing is between 100 and 10,000 mg/L. Therefore, performing mineral-bacteria interactions in the laboratory under environmentally-sound conditions requires significant dilution of the nutrient media or the use of flow-through reactors. Concerning the effect of organic ligands and bacterial excudates on rock-forming mineral dissolution, at the present time, mostly empirical (phenomenological) approach can be used. Indeed, the pioneering studies of Stumm and co-workers have established a firm basis for modeling the catalyzing and inhibiting effects of ligands on metal oxide dissolution rate. This approach, very efficient for studying the interaction of organic and inorganic ligands with trivalent metal oxides, is based on applying multiple spectroscopic techniques allowing to reveal the chemical structure of adsorbed complexes. However, due to i) low surface area of most rock-forming minerals (carbonates, non-clay silicates), ii) difficulties of applying surface spectroscopic techniques at elevated pressures, and iii) very complex nature of bacterial exometabolites, it is not possible at the present time, to use rigorous surface complexation approach for rationalizing ligand- and bacteria-affected mineral dissolution under sub-surface CO2 storage environment. In this work, we present examples of overcoming these difficulties via concerted study of olivine, wollastonite and calcite interaction with heterotrophic bacteria and methanogenic archaes.

Hydrogeochemistry of high-fluoride groundwater at Yuncheng Basin, northern China.

PubMed

Li, Chengcheng; Gao, Xubo; Wang, Yanxin

2015-03-01

Hydrogeochemical and environmental isotope methods were integrated to delineate the spatial distribution and enrichment of fluoride in groundwater at Yuncheng Basin in northern China. One hundred groundwater samples and 10 Quaternary sediment samples were collected from the Basin. Over 69% of the shallow groundwater (with a F(-) concentration of up to 14.1mg/L), 44% of groundwater samples from the intermediate and 31% from the deep aquifers had F(-) concentrations above the WHO provisional drinking water guideline of 1.5mg/L. Groundwater with high F(-) concentrations displayed a distinctive major ion chemistry: Na-rich and Ca-poor with a high pH value and high HCO3(-) content. Hydrochemical diagrams and profiles and hydrogen and oxygen isotope compositions indicate that variations in the major ion chemistry and pH are controlled by mineral dissolution, cation exchange and evaporation in the aquifer systems, which are important for F(-) mobilization as well. Leakage of shallow groundwater and/or evaporite (gypsum and mirabilite) dissolution may be the major sources for F(-) in groundwater of the intermediate and deep aquifers. Copyright © 2014 Elsevier B.V. All rights reserved.

Water-rock interaction and geochemistry of groundwater from the Ain Azel aquifer, Algeria.

PubMed

Belkhiri, Lazhar; Mouni, Lotfi; Tiri, Ammar

2012-02-01

Hydrochemical, multivariate statistical, and inverse geochemical modeling techniques were used to investigate the hydrochemical evolution within the Ain Azel aquifer, Algeria. Cluster analysis based on major ion contents defined 3 main chemical water types, reflecting different hydrochemical processes. The first group water, group 1, has low salinity (mean EC = 735 μS/cm). The second group waters are classified as Cl-HCO(3)-alkaline earth type. The third group is made up of water samples, the cation composition of which is dominated by Ca and Mg with anion composition varying from dominantly Cl to dominantly HCO(3) plus SO(4). The varifactors obtained from R-mode FA indicate that the parameters responsible for groundwater quality variations are mainly related to the presence and dissolution of some carbonate, silicate, and evaporite minerals in the aquifer. Inverse geochemical modeling along groundwater flow paths indicates the dominant processes are the consumption of CO(2), the dissolution of dolomite, gypsum, and halite, along with the precipitation of calcite, Ca-montmorillonite, illite, kaolinite, and quartz. © Springer Science+Business Media B.V. 2011

4D imaging and quantification of pore structure modifications inside natural building stones by means of high resolution X-ray CT.

PubMed

Dewanckele, J; De Kock, T; Boone, M A; Cnudde, V; Brabant, L; Boone, M N; Fronteau, G; Van Hoorebeke, L; Jacobs, P

2012-02-01

Weathering processes have been studied in detail for many natural building stones. The most commonly used analytical techniques in these studies are thin-section petrography, SEM, XRD and XRF. Most of these techniques are valuable for chemical and mineralogical analysis of the weathering patterns. However, to obtain crucial quantitative information on structural evolutions like porosity changes and growth of weathering crusts in function of time, non-destructive techniques become necessary. In this study, a Belgian historical calcareous sandstone, the Lede stone, was exposed to gaseous SO(2) under wet surface conditions according to the European Standard NBN EN 13919 (2003). Before, during and after the strong acid test, high resolution X-ray tomography has been performed to visualize gypsum crust formation to yield a better insight into the effects of gaseous SO(2) on the pore modification in 3D. The tomographic scans were taken at the Centre for X-ray Tomography at Ghent University (UGCT). With the aid of image analysis, partial porosity changes were calculated in different stadia of the process. Increasing porosity has been observed visually and quantitatively below the new superficial formed layer of gypsum crystals. In some cases micro-cracks and dissolution zones were detected on the grain boundaries of quartz. By using Morpho+, an in-house developed image analysis program, radial porosity, partial porosity, ratio of open and closed porosity and equivalent diameter of individual pore structures have been calculated. The results obtained in this study are promising for a better understanding of gypsum weathering mechanisms, porosity changes and patterns on natural building stones in four dimensions. Copyright © 2011 Elsevier B.V. All rights reserved.

PROTON GENERATION BY DISSOLUTION OF INTRINSIC OR AUGMENTED ALUMINOSILICATE MINERALS FOR IN SITU CONTAMINANT REMEDIATION BY ZERO-VALENCE-STATE IRON

EPA Science Inventory

Metallic, or zero-valence-state, iron is being incorporated into permeable reactive subsurface barriers for remediating a variety of contaminant plume types. The remediation occurs via reductive processes that are associated with surface corrosion of the iron metal. Reaction rate...

Seismic reflection characteristics of naturally-induced subsidence affecting transportation

USGS Publications Warehouse

Miller, R.D.; Xia, J.; Steeples, D.W.

2009-01-01

High-resolution seismic reflections have been used effectively to investigate sinkholes formed from the dissolution of a bedded salt unit found throughout most of Central Kansas. Surface subsidence can have devastating effects on transportation structures. Roads, rails, bridges, and pipelines can even be dramatically affected by minor ground instability. Areas susceptible to surface subsidence can put public safety at risk. Subsurface expressions significantly larger than surface depressions are consistently observed on seismic images recorded over sinkholes in Kansas. Until subsidence reaches the ground surface, failure appears to be controlled by compressional forces evidenced by faults with reverse orientation. Once a surface depression forms or dissolution of the salt slows or stops, subsidence structures are consistent with a tensional stress environment with prevalent normal faults. Detecting areas of rapid subsidence potential, prior to surface failure, is the ultimate goal of any geotechnical survey where the ground surface is susceptible to settling. Seismic reflection images have helped correlate active subsidence to dormant paleofeatures, project horizontal growth of active sinkholes based on subsurface structures, and appraise the risk of catastrophic failure. ?? China University of Geosciences (Wuhan) and Springer-Verlag GmbH 2009.

Authigenic carbonates from active methane seeps offshore southwest Africa

NASA Astrophysics Data System (ADS)

Pierre, Catherine; Blanc-Valleron, Marie-Madeleine; Demange, Jérôme; Boudouma, Omar; Foucher, Jean-Paul; Pape, Thomas; Himmler, Tobias; Fekete, Noemi; Spiess, Volkhard

2012-12-01

The southwest African continental margin is well known for occurrences of active methane-rich fluid seeps associated with seafloor pockmarks at water depths ranging broadly from the shelf to the deep basins, as well as with high gas flares in the water column, gas hydrate accumulations, diagenetic carbonate crusts and highly diverse benthic faunal communities. During the M76/3a expedition of R/V METEOR in 2008, gravity cores recovered abundant authigenic carbonate concretions from three known pockmark sites—Hydrate Hole, Worm Hole, the Regab pockmark—and two sites newly discovered during that cruise, the so-called Deep Hole and Baboon Cluster. The carbonate concretions were commonly associated with seep-benthic macrofauna and occurred within sediments bearing shallow gas hydrates. This study presents selected results from a comprehensive analysis of the mineralogy and isotope geochemistry of diagenetic carbonates sampled at these five pockmark sites. The oxygen isotope stratigraphy obtained from three cores of 2-5 m length indicates a maximum age of about 60,000-80,000 years for these sediments. The authigenic carbonates comprise mostly magnesian calcite and aragonite, associated occasionally with dolomite. Their very low carbon isotopic compositions (-61.0 < δ13C ‰ V-PDB < -40.1) suggest anaerobic oxidation of methane (AOM) as the main process controlling carbonate precipitation. The oxygen isotopic signatures (+2.4 < δ18O ‰ V-PDB < +6.2) lie within the range in equilibrium under present-day/interglacial to glacial conditions of bottom seawater; alternatively, the most positive δ18O values might reflect the contribution of 18O-rich water from gas hydrate decomposition. The frequent occurrence of diagenetic gypsum crystals suggests that reduced sulphur (hydrogen sulphide, pyrite) from sub-seafloor sediments has been oxidized by oxygenated bottom water. The acidity released during this process can potentially induce the dissolution of carbonate, thereby providing enough Ca2+ ions for pore solutions to reach gypsum saturation; this is thought to be promoted by the bio-irrigation and burrowing activity of benthic fauna. The δ18O-δ13C patterns identified in the authigenic carbonates are interpreted to reflect variations in the rate of AOM during the last glacial-interglacial cycle, in turn controlled by variably strong methane fluxes through the pockmarks. These results complement the conclusions of Kasten et al. in this special issue, based on authigenic barite trends at the Hydrate Hole and Worm Hole pockmarks which were interpreted to reflect spatiotemporal variations in AOM related to subsurface gas hydrate formation-decomposition.

The effect of sea-water intrusion due to the large scale construction in a coastal region

NASA Astrophysics Data System (ADS)

Hyun, S.; Jin, S.; Woo, N. C.; Lee, J.; Lee, H.; Kim, Y.

2010-12-01

This study was carried out for estimating the seawater intrusion at the disturbed aquifer by a large scale construction when building a power plant in a coastal region, located in southeastern part of the Korean peninsula. Groundwater sampling and vertical profiling of electrical conductivity(EC) for 8 monitoring wells were carried. EC profiling results shows that maximum EC for PW-5, 6 and 7 is over 40 mS/cm, for PZ-1, 3, 4 and 8 is 18.76, 4.46, 26.16, 21.42 mS/cm and for PZ-2 is 0.79 mS/cm,respectively. Chemical composition of water samples shows that water types of Na-Cl for PZ-5, 6, and 7 (excavated and backfilled area), Na-Cl-SO4 for PZ-4 and PZ-8, Na-Ca-Mg-Cl for PZ-1, Ca-Na-SO4-Cl for PZ-2, and Mg-Ca-Na-SO4 for PZ-3. In addition, the bivariate plot of SO4/Cl(meq ratios) and SO4(mmol/L) indicates that PZ-4, 5, 6, 7 and 8 appear to be seawater, PZ-1 is located at mixing zone between freshwater and seawater, and PZ-2 is freshwater. However, based on the high SO42- level and (HCO3-/Sum anions} ratio less than 0.8, groundwater at PZ-3 seems to show the gypsum dissolution. The gypsum dissolution was attributed to the effect of sea-water intrusion on ageing of lean concrete that was used for backfill around the PZ-3. Key words : large scale construction, EC profiling, hydrochemistry, sea-water intrusion, concrete ageing Acknowledgement This study has been carried out under the Nuclear R&D Program [No. 2010-0001070] supported by the Ministry of Education, Science and Technology, Republic of Korea.

Pervious concrete reactive barrier for removal of heavy metals from acid mine drainage - column study.

PubMed

Shabalala, Ayanda N; Ekolu, Stephen O; Diop, Souleymane; Solomon, Fitsum

2017-02-05

This paper presents a column study conducted to investigate the potential use of pervious concrete as a reactive barrier for treatment of water impacted by mine waste. The study was done using acid mine drainage (AMD) collected from a gold mine (WZ) and a coalfield (TDB). Pervious concrete mixtures consisting of Portland cement CEM I 52.5R with or without 30% fly ash (FA) were prepared at a water-cementitious ratio of 0.27 then used to make cubes which were employed in the reactor columns. It was found that the removal efficiency levels of Al, Fe, Mn, Co and Ni were 75%, 98%, 99%, 94% and 95% for WZ; 87%, 96%, 99%, 98% and 90% for TDB, respectively. The high rate of acid reduction and metal removal by pervious concrete is attributed to dissolution of portlandite which is a typical constituent of concrete. The dominant reaction product in all four columns was gypsum, which also contributed to some removal of sulphate from AMD. Formation of gypsum, goethite, and Glauber's salt were identified. Precipitation of metal hydroxides seems to be the dominant metal removal mechanism. Use of pervious concrete offers a promising alternative treatment method for polluted or acidic mine water. Copyright © 2016 Elsevier B.V. All rights reserved.

Hydrochemistry of surface water and groundwater in the shale bedrock, Cross River Basin and Niger Delta Region, Nigeria

NASA Astrophysics Data System (ADS)

Nganje, T. N.; Hursthouse, A. S.; Edet, Aniekan; Stirling, D.; Adamu, C. I.

2017-05-01

Water chemistry in the shale bedrock of the Cretaceous-Tertiary of the Cross River and Niger Delta hydrological basins has been investigated using major ions. To carry out a characterization of the water bearing units, 30 and 16 representatives surface and groundwater samples were collected. The evolution of the water is characterized by enhanced content of sodium, calcium and sulphate as a result of leaching of shale rock. The spatial changes in groundwater quality of the area shows an anomalous concentrations of ions in the central parts, while lower values characterize the eastern part of the basin covering Ogoja, Ikom and Odukpani areas. The values of total dissolved solids (TDS) and ions increases down gradient in the direction of groundwater flow. The dissolution of halite and gypsum explains part of the contained Na+, Ca2+, Cl- and SO4 2-, but other processes such as ion exchange, silicate weathering and pyrite oxidation also contribute to water composition. The assessment with contamination indicators such as TDS, hardness, chloride, nitrate and sulphate indicates that the water in area is suitable for human consumption in some locations. Modelling using MINTEQA2 program shows that the water from all the shale water bearing units are under saturated with respect to gypsum.

Reactive transport modelling of a high-pH infiltration test in concrete

NASA Astrophysics Data System (ADS)

Chaparro, M. Carme; Soler, Josep M.; Saaltink, Maarten W.; Mäder, Urs K.

2017-06-01

A laboratory-scale tracer test was carried out to characterize the transport properties of concrete from the Radioactive Waste Disposal Facility at El Cabril (Spain). A hyperalkaline solution (K-Ca-OH, pH = 13.2) was injected into a concrete sample under a high entry pressure in order to perform the experiment within a reasonable time span, obtaining a decrease of permeability by a factor of 1000. The concentrations of the tracers, major elements (Ca2+, SO4 2 - , K+ and Na+) and pH were measured at the outlet of the concrete sample. A reactive transport model was built based on a double porosity conceptual model, which considers diffusion between a mobile zone, where water can flow, and an immobile zone without any advective transport. The numerical model assumed that all reactions took place in the immobile zone. The cement paste consists of C-S-H gel, portlandite, ettringite, calcite and gypsum, together with residual alite and belite. Two different models were compared, one with portlandite in equilibrium (high initial surface area) and another one with portlandite reaction controlled by kinetics (low initial surface area). Overall the results show dissolution of alite, belite, gypsum, quartz, C-S-H gel and ettringite and precipitation of portlandite and calcite. Permeability could have decreased due to mineral precipitation.

Suitability of Palestine salt dome, Anderson Co. , Texas for disposal of high-level radioactive waste

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patchick, P.F.

1980-01-01

The suitability of Palestine salt dome, in Anderson County, Texas, is in serious doubt for a repository to isolate high-level nuclear waste because of abandoned salt brining operations. The random geographic and spatial occurrence of 15 collapse sinks over the dome may prevent safe construction of the necessary surface installations for a repository. The dissolution of salt between the caprock and dome, from at least 15 brine wells up to 500 feet deep, may permit increased rates of salt dissolution long into future geologic time. The subsurface dissolution is occurring at a rate difficult, if not impossible, to assess ormore » to calculate. It cannot be shown that this dissolution rate is insignificant to the integrity of a future repository or to ancillary features. The most recent significant collapse was 36 feet in diameter and took place in 1972. The other collapses ranged from 27 to 105 feet in diameter and from 1.5 to more than 15 feet in depth. ONWI recommends that this dome be removed from consideration as a candidate site.« less

Effects of mining activities on evolution of water chemistry in coal-bearing aquifers in karst region of Midwestern Guizhou, China: evidences from δ13C of dissolved inorganic carbon and δ34S of sulfate.

PubMed

Li, Qingguang; Wu, Pan; Zha, Xuefang; Li, Xuexian; Wu, Linna; Gu, Shangyi

2018-04-24

The generation of acid mine drainage (AMD) may accelerate watershed erosion and promote the migration of heavy metals, then threaten local ecosystems such as aquatic life and even human health. Previous studies have focused primarily on influence of AMD in surface environment. In order to reveal the acidizing processes in karst high-sulfur coalfield in Southwest China, this study, by contrast, focused on the hydrogeochemical evolution process and acidification mechanism of mine water in Zhijin coalfield, western Guizhou Province. The oxidation of pyrite and other sulfides induced strong acidification of mine water according to the water chemical analysis. As a result, a series of geochemical processes such as dissolution of carbonates and silicates, hydrolysis of metal ions, and degassing of CO 2 complicated water chemical evolution. The dissolution of silicates controlled the chemical composition of mine water, but more carbonates might be dissolved during the acidification of mine water. The sources of sulfate are quite different in water samples collected from the two selected mine. According to sulfur isotope analysis, the dissolution of gypsum is the primary source of sulfate in samples from Hongfa mine, whereas sulfide oxidation contributed a large amount of sulfate to the mine water in Fenghuangshan mine. The dissolution of carbonates should be an important source of DIC in mine water and CO 2 originating from organic mineralization might also have a certain contribution. This study elucidated the groundwater chemical evolution processes in high-sulfur coal-bearing strata and provided a foundation for further study of carbonates erosion and carbon emission during acidification of mine water.

Biodegradation of crude oil in Arctic subsurface water from the Disko Bay (Greenland) is limited.

PubMed

Scheibye, Katrine; Christensen, Jan H; Johnsen, Anders R

2017-04-01

Biological degradation is the main process for oil degradation in a subsurface oil plume. There is, however, little information on the biodegradation potential of Arctic, marine subsurface environments. We therefore investigated oil biodegradation in microcosms at 2 °C containing Arctic subsurface seawater from the Disko Bay (Greenland) and crude oil at three concentrations of 2.5-10 mg/L. Within 71 days, the total petroleum hydrocarbon concentration decreased only by 18 ± 18% for an initial concentration of 5 mg/L. The saturated alkanes nC13-nC30 and the isoprenoids iC18-iC21 were biodegraded at all concentrations indicating a substantial potential for biodegradation of these compound classes. Polycyclic aromatic compounds (PACs) disappeared from the oil phase, but dissolution was the main process of removal. Analysis of diagnostic ratios indicated almost no PAC biodegradation except for the C1-naphthalenes. To conclude, the marine subsurface microorganisms from the Disko Bay had the potential for biodegradation of n-alkanes and isoprenoids while the metabolically complex and toxic PACs and their alkylated homologs remained almost unchanged. Copyright © 2016 Elsevier Ltd. All rights reserved.

Geology of the Jewel Cave SW Quadrangle, Custer County, South Dakota

USGS Publications Warehouse

Braddock, William A.

1963-01-01

The Jewel Cave SW quadrangle is in the southwestern part of the Black Hills in Custer County, S. Dak., about midway between Edgemont, S. Dak., and Newcastle, Wyo. All the rocks that crop out within the quadrangle are of sedimentary origin and range in age from Pennsylvanian to Early Cretaceous. The Minnesota Formation of Pennsylvania and Permian age, which is about 1,000 feet thick, was studied in outcrop and from two diamond-drill cores. In the subsurface the upper part of the formation consists of gray sandstone, very fine grained dolomite, and anhydrite. The anhydrite has been leached from the formation near the outcrop, perhaps in the early part of the Cenozoic Era, and the resulting subsidence has produced collapse breccias in the Minnelusa and milder deformation in the overlying units. In the collapse breccias the rocks have been oxidized and are red, whereas in the subsurface they are gray. The anhydrite cement of the subsurface sandstone has been replaced by calcite, and the dolomite beds have been partially converted to limestone. The Opeche Formation of Permian age consists of 75 to 115 feet of red siltstone and shale and two thin gypsum beds. The Minnekahta Limestone of Permian age is about 40 feet thick. The Spearfish Formation of Permian and Triassic age is about 550 feet thick and consists of red siltstone red sandstone, dolomite, and gypsum. The dolomite and gypsum beds are restricted to the lower half of the formation. In the northeast corner of the quadrangle the gypsum beds have been dissolved by ground water. The Sundance Formation of Late Jurassic age is divided into five members that have a total thickness of about 360 feet. The Morrison Formation of Late Jurassic age ranges in thickness from 60 to 120 feet. It consists of blocky weathering noncarbonaceous mudstone and subordinate beds of limestone and sandstone. The Inyan Kara Group of Early Cretaceous age has been subdivided into the Lakota Formation and the Fall River Formation. The Lakota Formation consists of 200 to 300 feet of carbonaceous siltstone blocky-weathering claystone, and fine-grained to conglomeratic sandstone. These rocks were deposited in stream channels, flood plains, and ponds. The Fall River Formation is about 110 to 130 feet thick. Along the northeast side of the outcrop the formation consists of fine- to medium-grained sandstone, which forms an elongate body at least 1-1/2 miles wide and more than 25 miles long. To the southwest the formation consists of thinly stratified interbedded sandstone, carbonaceous siltstone, and varicolored mudstone. The Skull Creek and Mowry Shales of Early Cretaceous age consist of black fissile shale. The Mowry contains abundant fish scales and weathers to a silver gray. Alluvium fills the bottom of many intermittent streams, and small gravel-covered terraces mark the former high levels of these streams. Gravel, which caps hills at altitudes of 4,460 to 4,620 feet, is believed to have been deposited by a Pleistocene stream that drained southeastward toward the town of Minnekahta. Many landslides are present along the northward- and eastward-facing scarp of the Inyan Kara hogback. The Dewey fault, trending N. 75 deg E., crosses the quadrangle. It is probably a vertical dip-slip fault, and has an apparent displacement of 250 to 440 feet. Two northwest-trending anticlines are in the quadrangle - one extends from the Edgemont NE quadrangle to near the center of the Jewel Cave SW quadrangle, and the other is limited to the center of the Jewel Cave SW quadrangle. Collapse structures, which were produced by the solution of anhydrite, are (a) breccias in the Minnelusa Formation, (b) limestone-dolomite breccias in the Spearfish Formation, (c) undulations and normal faults in the formations overlying the Minnelusa and (d) breccia pipes that extend upward from the Minnelusa to at least as high as the Lakota Formation. The leaching probably occurred in early Cenozoic time. Minor deformationa

Environmental and taxonomic bacterial diversity of anaerobic uranium(IV) bio-oxidation.

PubMed

Weber, Karrie A; Thrash, J Cameron; Van Trump, J Ian; Achenbach, Laurie A; Coates, John D

2011-07-01

Microorganisms in diverse terrestrial surface and subsurface environments can anaerobically catalyze the oxidative dissolution of uraninite. While a limited quantity (∼5 to 12 μmol liter(-1)) of uranium is oxidatively dissolved in pure culture studies, the metabolism is coupled to electron transport, providing the potential of uraninite to support indigenous microbial populations and to solubilize uranium.

Bacterial and Archaeal Lipids Recovered from Subsurface Evaporites of Dalangtan Playa on the Tibetan Plateau and Their Astrobiological Implications

NASA Astrophysics Data System (ADS)

Cheng, Ziye; Xiao, Long; Wang, Hongmei; Yang, Huan; Li, Jingjing; Huang, Ting; Xu, Yi; Ma, Nina

2017-11-01

Qaidam Basin (Tibetan Plateau) is considered an applicable analogue to Mars with regard to sustained extreme aridity and abundant evaporites. To investigate the possibility of the preservation of microbial lipids under these Mars analog conditions, we conducted a mineralogical and organic geochemistry study on samples collected from two Quaternary sections in Dalangtan Playa, northwestern Qaidam Basin, which will enhance our understanding of the potential preservation of molecular biomarkers on Mars. Two sedimentary units were identified along two profiles: one salt unit characterized by a predominance of gypsum and halite, and one detrital unit with a decrease of gypsum and halite and enrichment in siliciclastic minerals. Bacterial fatty acids and archaeal acyclic diether and tetraether membrane lipids were detected, and they varied throughout the sections in concentration and abundance. Bacterial and archaeal biomolecules indicate a dominance of Gram-positive bacteria and halophilic archaea in this hypersaline ecosystem that is similar to those in other hypersaline environments. Furthermore, the abundance of bacterial lipids decreases with the increase of salinity, whereas archaeal lipids showed a reverse trend. The detection of microbial lipids in hypersaline environments would indicate, for example on Mars, a high potential for the detection of microbial biomarkers in evaporites over geological timescales.

A seismic search for the paleoshorelines of Lake Otero beneath White Sands Dune Field, New Mexico

NASA Astrophysics Data System (ADS)

Wagner, P. F.; Reece, R.; Ewing, R. C.

2014-12-01

The Tularosa Basin, which now houses White Sands Dune Field, was once occupied by Pleistocene Lake Otero. Several paleoshorelines of Lake Otero have been identified throughout the basin by field surveys and remote sensing using digital elevation models. Up to four shorelines may be buried beneath White Sands Dune Field and it has been posited that the current upwind margin of White Sands coincides with a one of these shorelines. Here we employ a novel geophysical instrument and method to image the subsurface: the seismic land streamer. The land streamer utilizes weighted base plates and one-component vertical geophones in a towed array. With a seisgun acoustic source, we imaged in the Alkali Flats area near the upwind margin, one potential location of paleoshorelines, as well as the Film Lot closer to the center of the dune field. Surfaces in both locations are indurated gypsum playa, which made seismic imaging possible and successful. We collected one SW-NE trending seismic line at each location, which matches the dominant wind and dune migration directions. Based on initial data analysis we find some subsurface structure that may coincide with the paleo lake bed of Lake Otero. The successful demonstration of this new method provides the foundation for an expanded regional subsurface study to image the strata and structure of the Tularosa Basin.

Control of topography gradients on residence time distributions, mixing dynamics and reactive hotspot development

NASA Astrophysics Data System (ADS)

Bandopadhyay, Aditya; Le Borgne, Tanguy; Davy, Philippe

2017-04-01

Topography-driven subsurface flows are thought to play a central role in determining solute turnover and biogeochemical processes at different scales in the critical zone, including river-hyporheic zone exchanges, hillslope solute transport and reactions, and catchment biogeochemical cycles. Hydraulic head gradients, induced by topography gradients at different scales, generate a distribution of streamlines at depth, dictating the spatial distribution of redox sensitive species, the magnitude of surface water - ground water exchanges and ultimately the source/sink function of the subsurface. Flow velocities generally decrease with depth, leading to broad residence time distributions, which have been shown to affect river chemistry and geochemical reactions in catchments. In this presentation, we discuss the impact of topography-driven flows on mixing processes and the formation of localized reactive hotspots. For this, we solve analytically the coupled flow, mixing and reaction equations in two-dimensional vertical cross-sections of subsurface domains with different topography gradients. For a given topography gradient, we derive the spatial distribution of subsurface velocities, the rates of solute mixing accross streamlines and the induced kinetics of redox, precipitation and dissolution reactions using a Lagrangian approach (Le Borgne et al. 2014). We demonstrate that vertical velocity profiles driven by topography variations, act effectively as shear flows, hence stretching continuously the mixing fronts between recently infiltrated and resident water (Bandopadhyay et al. 2017). We thus derive analytical expressions for residence time distributions, mixing rates and kinetics of chemical reactions as a function of the topography gradients. We show that the rates dissolution and precipitation reactions are significantly enhanced by the existence of vertical velocity gradients and that reaction rates reach a maximum in a localized subsurface reactive layer, whose location and intensity depends on topography gradients. As a consequence of these findings, we discuss the links between topography variations, subsurface velocity gradients and biogeochemical processes in the critical zone. References: Bandopadhyay A., T. Le Borgne, Y. Méheust and M. Dentz (2017) Enhanced reaction kinetics and reactive mixing scale dynamics in mixing fronts under shear flow for arbitrary Damkohler numbers, Adv. in Water Resour. Vol. 100, p. 78-95 Le Borgne T., T. Ginn and M. Dentz (2014) Impact of Fluid Deformation on Mixing-Induced Chemical Reactions in Heterogeneous Flows, Geophys. Res. Lett., Vol. 41, 22, p. 7898-790

Unravelling the mechanisms for plant survival on gypsum soils: an analysis of the chemical composition of gypsum plants from Turkey.

PubMed

Bolukbasi, A; Kurt, L; Palacio, S

2016-03-01

Depending on their specificity to gypsum, plants can be classified as gypsophiles (gypsum exclusive) and gypsovags (non-exclusive). The former may further be segregated into wide and narrow gypsophiles, depending on the breadth of their distribution area. Narrow gypsum endemics have a putative similar chemical composition to plants non-exclusive to gypsum (i.e. gypsovags), which may indicate their similar ecological strategy as stress-tolerant plant refugees on gypsum. However, this hypothesis awaits testing in different regions of the world. We compared the chemical composition of four narrow gypsum endemics, one widely distributed gypsophile and six gypsovags from Turkey. Further, we explored the plasticity in chemical composition of Turkish gypsovags growing on high- and low-gypsum content soils. Differences were explored with multivariate analyses (RDA) and mixed models (REML). Narrow gypsum endemics segregated from gypsovags in their chemical composition according to RDAs (mainly due to higher K and ash content in the former). Nevertheless, differences were small and disappeared when different nutrients were analysed individually. All the gypsovags studied accumulated more S and ash when growing on high-gypsum than on low-gypsum soils. Similar to narrow gypsum endemics from other regions of the world, most local gypsum endemics from Turkey show a similar chemical composition to gypsovags. This may indicate a shared ecological strategy as stress-tolerant plants not specifically adapted to gypsum. Nevertheless, the narrow gypsum endemic Gypsophila parva showed a chemical composition typical of gypsum specialists, indicating that various strategies are feasible within narrowly distributed gypsophiles. © 2015 German Botanical Society and The Royal Botanical Society of the Netherlands.

Hypogenic speleogenesis in quartzite: The case of Corona 'e Sa Craba Cave (SW Sardinia, Italy)

NASA Astrophysics Data System (ADS)

Sauro, Francesco; De Waele, Jo; Onac, Bogdan P.; Galli, Ermanno; Dublyansky, Yuri; Baldoni, Eleonora; Sanna, Laura

2014-04-01

The paper presents a detailed study demonstrating the hypogenic origin of the Corona 'e Sa Craba quartzite cave in SW Sardinia (Italy). Although the quartzite host-rock of this cave derived from silicification of Cambrian dolostones and dissolution of carbonate remnants could have had a role in the speleogenesis, detailed morphologic and petrographic investigation revealed clear evidence of quartz dissolution without signs of mechanical erosion by running waters. Thin section microscopy and scanning electron microscope (SEM) images show pervasive dissolution morphologies, such as pits and notches on quartz crystals causing the deep arenization of the cave walls, suggesting that the dissolution of quartz had a primary role in the formation of the void. The study of secondary cave minerals and the sulfur isotopic composition of sulfates and sulfides, coupled with data on fluid inclusions, allowed reconstruction of the peculiar speleogenetic history of this hypogenic hydrothermal quartzite cave. The cave formed by reduced hydrothermal fluids, probably under basic-neutral pH in phreatic conditions. The presence of abundant cations of Ba2 + in reduced Cl-rich fluids enhanced the quartz dissolution rate, allowing the formation of the voids in deep settings. During the Late Oligocene uplift of the area, the hydrothermal fluids in the cave reached oxygen-rich conditions, thus a minerogenetic phase started with the deposition of barite when the temperature of the fluid was ≤ 50 °C. The presence of cinnabar crusts in the lower part of the cave walls and on the boulders suggests a later volcanic phase with Hg-rich vapors ascending from below. Other minerals such as alunite, basaluminite, gypsum and halloysite (typical of an acid sulfate alteration environment), and phosphates were formed in a final, much more recent stage. The δ34S values of the cave sulfate minerals indicate that S is derived from the remobilization of original Precambrian Pb-Zn Mississippi Valley Type ores. These last two stages did not significantly affect the morphology of the cave. The Corona 'e Sa Craba appears to be the world's first example of a hypogenic cave in quartzite where the speleogenetic mechanisms have been studied and reconstructed in detail, using a variety of modern methods. This study confirms that dissolution of quartz by thermal alkaline fluids at depth can produce large dissolutional voids in the apparently poorly soluble quartzite rocks.

Surface denudation rate of gypsum in Sicily

NASA Astrophysics Data System (ADS)

Madonia, Giuliana; Vattano, Marco; Di Maggio, Cipriano; De Waele, Jo

2016-04-01

Studies on surface denudation rate of karst rocks were carried out for many years with different methods, although researches on limestones are much more numerous than those on gypsum. In Sicily the most large and complete Messinian evaporite succession of Gruppo Gessoso - Solfifero outcrops and since 1993-1994 surface denudation measurements were performed on different types of gypsum by the Micro-Erosion Meter (M.E.M.) method. MEM stations were placed on natural sites representing different lithological features of gypsum outcrops of the Island: 1) selenite gypsum with centimetre-sized crystals; 2) selenite gypsum with sub-centimetre crystals; 3) gypsum arenite; 4) microcrystalline gypsum; and 5) gypsum laminite (balatino type). The measuring stations are positioned in three localities in western and central Sicily: Santa Ninfa (Trapani), Ciminna (Palermo) and Campofranco (Caltanissetta). The average lowering rates vary in the different lithofacies: from 0.25 mm yr-1 in microcrystalline gypsum to 0.74 mm yr-1 in selenite gypsum with centimetre-sized crystals. The average surface denudation rates are 0.40 mm yr-1 in balatino gypsum and gypsum arenite, and 0.37 mm yr-1 in selenite gypsum with sub-centimetre crystals. These different values are connected to several factors such as: rock texture, dip of gypsum surfaces, climatic conditions, troubles on the measurement sites (e.g.: presence of lichens, soil, remains of vegetation, etc.). The aim of this paper is to show the results of roughly twenty years of experimental measurements, and to compare the surface denudation rate of gypsum in Sicily with those of other evaporite areas characterised by different climatic settings.

Episodic sediment-discharge events in Cascade Springs, southern Black Hills, South Dakota

USGS Publications Warehouse

Hayes, Timothy Scott

1999-01-01

Cascade Springs is a group of artesian springs in the southern Black Hills, South Dakota, with collective flow of about 19.6 cubic feet per second. Beginning on February 28, 1992, a large discharge of red suspended sediment was observed from two of the six known discharge points. Similar events during 1906-07 and 1969 were documented by local residents and newspaper accounts. Mineralogic and grain-size analyses were performed to identify probable subsurface sources of the sediment. Geochemical modeling was performed to evaluate the geochemical evolution of water discharged from Cascade Springs. Interpretations of results provide a perspective on the role of artesian springs in the regional geohydrologic framework. X-ray diffraction mineralogic analyses of the clay fraction of the suspended sediment were compared to analyses of clay-fraction samples taken from nine geologic units at and stratigraphically below the spring-discharge points. Ongoing development of a subsurface breccia pipe(s) in the upper Minnelusa Formation and/or Opeche Shale was identified as a likely source of the suspended sediment; thus, exposed breccia pipes in lower Hell Canyon were examined. Upper Minnelusa Formation breccia pipes in lower Hell Canyon occur in clusters similar to the discrete discharge points of Cascade Springs. Grain-size analyses showed that breccia masses lack clay fractions and have coarser distributions than the wall rocks, which indicates that the red, fine-grained fractions have been carried out as suspended sediment. These findings support the hypothesis that many breccia pipes were formed as throats of abandoned artesian springs. Geochemical modeling was used to test whether geochemical evolution of ground water is consistent with this hypothesis. The evolution of water at Cascade Springs could not be suitably simulated using only upgradient water from the Minnelusa aquifer. A suitable model involved dissolution of anhydrite accompanied by dedolomitization in the upper Minnelusa Formation, which is caused by upward leakage of relatively fresh water from the Madison aquifer. The anhydrite dissolution and dedolomitization account for the net removal of minerals that would lead to breccia pipe formation by gravitational collapse. Breccia pipes in the lower Minnelusa Formation are uncommon; however, networks of interconnected breccia layers and breccia dikes are common. These networks, along with vertical fractures and faults, are likely pathways for transmitting upward leakage from the Madison aquifer. It is concluded that suspended sediment discharged at Cascade Springs probably results from episodic collapse brecciation that is caused by subsurface dissolution of anhydrite beds and cements of the upper Minnelusa Formation, accompanied by replacement of dolomite by calcite. It is further concluded that many breccia pipes probably are the throats of artesian springs that have been abandoned and exposed by erosion. The locations of artesian spring-discharge points probably have been shifting outwards from the center of the Black Hills uplift, essentially keeping pace with regional erosion over geologic time. Thus, artesian springflow probably is a factor in controlling water levels in the Madison and Minnelusa aquifers, with hydraulic head declining over geologic time, in response to development of new discharge points. Development of breccia pipes as throats of artesian springs would greatly enhance vertical hydraulic conductivity in the immediate vicinity of spring-discharge points. Horizontal hydraulic conductivity in the Minnelusa Formation also may be enhanced by dissolution processes related to upward leakage from the Madison aquifer. Potential processes could include dissolution resulting from leakage in the vicinity of breccia pipes that are abandoned spring throats, active spring discharge, development of subsurface breccias with no visible surface expression or spring discharge, as well as general areal leakage

Dissolution of Permian salt and Mesozoic depositional trends, Powder River basin, Wyoming

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rasmussen, D.L.; Bean, D.W.

1983-08-01

Salt deposits in the Powder River basin of Wyoming occur in the Late Permian Ervay Member of the Goose Egg Formation which was deposited in a redbed-evaporite trend extending from the Williston basin of North Dakota to the Alliance basin of Nebraska and Wyoming. However, only remnants of the once extensive Ervay salt remain in the Powder River basin, with major salt dissolution events occurring during Late Jurassic and Early Cretaceous. Subsidence and deposition at the surface were contemporaneous with subsurface salt dissolution except in areas where uplift and erosion were occurring. Earliest dissolution of the Ervay salt occurred inmore » the Jurassic, during regional uplift and erosion of the overlying Triassic Chugwater Formation in the present Hartville uplift and southeastern Powder River basin areas. Thickness variations of the Canyon Springs and Stockade Beaver members of the early Late Jurassic Sundance Formation, which unconformably overlie the deeply eroded Chugwater Formation, may be related in part to dissolution of the Ervay salt. Extensive salt dissolution, synsubsidence, and syndeposition occurred throughout most of the Powder River basin during the latest Jurassic and Early Cretaceous. Many producing fields from the Mowry, Muddy, and Dakota formations exhibit either rapid stratigraphic changes syndepositional to salt collapse or fracture-enhanced reservoir quality due to postdepositional salt collapse. Major Muddy accumulations occurring in areas of local Ervay salt collapse include Kitty, Hilight, Fiddler Creek, and Clareton which have produced jointly over 172 million bbl of oil. The relationship of Ervay salt dissolution to Lower Cretaceous deposition can be exploited as an effective exploration tool.« less

Permian paleogeography of west-central Pangea: Reconstruction using sabkha-type gypsum-bearing deposits of Parnaíba Basin, Northern Brazil

NASA Astrophysics Data System (ADS)

Abrantes, Francisco R.; Nogueira, Afonso C. R.; Soares, Joelson L.

2016-07-01

Extreme aridity during Late Permian - Early Triassic period was the main factor for resetting the entire paleoclimate of the planet. Permian evaporite basins and lacustrine red beds were widely distributed along the supercontinent of Pangea. Sulphate deposits in Western Pangea, particularly in Northern Brazil, accumulated in an extensive playa lake system. Outcrop-based facies and stratigraphic analysis of up to 20 m thick evaporite-siliciclastic deposits reveal the predominance of laminated reddish mudstone with subordinate limestone, marl and lenses of gypsum. The succession was deposited in shallow lacustrine and inland sabkha environments associated with saline pans and mudflats. Gypsum deposits comprise six lithofacies: 1) bottom-growth gypsum, 2) nodular/micronodular gypsum, 3) mosaic gypsum, 4) fibrous/prismatic gypsum, 5) alabastrine gypsum, and 6) rosettes of gypsum. Gypsum types 1 and 2 are interpreted as primary deposition in saline pans. Bottom-growth gypsum forms grass-like crusts while nodular/micronodular gypsum indicates displacive precipitation of the crust in shallow water and the groundwater capillary zone. Types 3 and 4 are early diagenetic precipitates. Abundant inclusions of tiny lath-like anhydrite crystals suggest a primary origin of anhydrite. Alabastrine gypsum, fibrous gypsum (satinspar) and rosettes of gypsum probably derived from near-surface hydration of anhydrite. The gypsum-bearing deposits in the Parnaíba Basin contribute towards understanding paleogeographic changes in Western Pangea. A progressive uplift of East Pangea, culminated in the forced regression and retreat of epicontinental seas to the West. Restricted seas or large lakes were formed before the definitive onset of desert conditions in Pangea, leading to the development of extensive ergs.

Physicochemical Properties and Cellular Responses of Strontium-Doped Gypsum Biomaterials

PubMed Central

Pouria, Amir; Bandegani, Hadis; Pourbaghi-Masouleh, Milad; Hesaraki, Saeed; Alizadeh, Masoud

2012-01-01

This paper describes some physical, structural, and biological properties of gypsum bioceramics doped with various amounts of strontium ions (0.19–2.23 wt%) and compares these properties with those of a pure gypsum as control. Strontium-doped gypsum (gypsum:Sr) was obtained by mixing calcium sulfate hemihydrate powder and solutions of strontium nitrate followed by washing the specimens with distilled water to remove residual salts. Gypsum was the only phase found in the composition of both pure and gypsum:Sr, meanwhile a shift into lower diffraction angles was observed in the X-ray diffraction patterns of doped specimens. Microstructure of all gypsum specimens consisted of many rod-like small crystals entangled to each other with more elongation and higher thickness in the case of gypsum:Sr. The Sr-doped sample exhibited higher compressive strength and lower solubility than pure gypsum. A continuous release of strontium ions was observed from the gypsum:Sr during soaking it in simulated body fluid for 14 days. Compared to pure gypsum, the osteoblasts cultured on strontium-doped samples showed better proliferation rate and higher alkaline phosphatase activity, depending on Sr concentration. These observations can predict better in vivo behavior of strontium-doped gypsum compared to pure one. PMID:22719270

Hydrogeology and hydrogeochemistry at a site of strategic importance: the Pareja Limno-reservoir drainage basin (Guadalajara, central Spain)

NASA Astrophysics Data System (ADS)

Molina-Navarro, Eugenio; Sastre-Merlín, Antonio; Vicente, Rosa; Martínez-Pérez, Silvia

2014-08-01

A small calcareous basin in central Spain was studied to establish the role of groundwater in the Pareja Limno-reservoir. Limno-reservoirs aim to preserve a constant water level in the riverine zone of large reservoirs to mitigate the impacts arising from their construction. Groundwater flow contribution (mean 60 %) was derived by recharge estimation. In situ measurements (spring discharge, electrical conductivity and sulfate) were undertaken and spring discharge was compared with a drought index. Twenty-eight springs were monitored and three hydrogeological units (HGUs) were defined: a carbonate plateau (HGU1), the underlying aquitard (HGU2), and the gypsum-enriched HGU3. HGU1 is the main aquifer and may play a role in the preservation of the limno-reservoir water level. Hydrogeochemical sampling was conducted and the code PHREEQC used to describe the main geochemical processes. Weathering and dissolution of calcite and gypsum seem to control the hydrogeochemical processes in the basin. Water progresses from Ca2+-HCO3 - in the upper basin to Ca2+-SO4 2- in the lower basin, where HGU3 outcrops. A clear temporal pattern was observed in the limno-reservoir, with salinity decreasing in winter and increasing in summer. This variation was wider at the river outlet, but the mixing of the river discharge with limno-reservoir water buffered it.

Attenuation of seismic waves in rocks saturated with multiphase fluids: theory and experiments

NASA Astrophysics Data System (ADS)

Tisato, N.; Quintal, B.; Chapman, S.; Podladchikov, Y.; Burg, J. P.

2016-12-01

Albeit seismic tomography could provide a detailed image of subsurface fluid distribution, the interpretation of the tomographic signals is often controversial and fails in providing a conclusive map of the subsurface saturation. However, tomographic information is important because the upward migration of multiphase fluids through the crust of the Earth can cause hazardous events such as eruptions, explosions, soil-pollution and earthquakes. In addition, multiphase fluids, such as hydrocarbons, represent important resources for economy. Seismic tomography can be improved considering complex elastic moduli and the attenuation of seismic waves (1/Q) that quantifies the energy lost by propagating elastic waves. In particular, a significant portion of the energy carried by the propagating wave is dissipated in saturated media by the wave-induced-fluid-flow (WIFF) and the wave-induced-gas-exsolution-dissolution (WIGED) mechanism. The latter describes how a propagating wave modifies the thermodynamic equilibrium between different fluid phases causing exsolution and dissolution of gas bubbles in the liquid, which in turn causes a significant frequency-dependent 1/Q and moduli dispersion. The WIGED theory was initially postulated for bubbly magmas but was only recently demonstrated and extended to bubbly water. We report the theory and laboratory experiments that have been performed to confirm the WIGED theory. In particular, we present i) attenuation measurements performed by means of the Broad Band Attenuation Vessel on porous media saturated with water and different gases, and ii) numerical experiments validating the laboratory observations. Then, we extend the theory to fluids and pressure-temperature conditions which are typical of phreatomagmatic and hydrocarbon domains and we compare the propagation of seismic waves in bubble-free and bubble-bearing subsurface domains. This work etends the knowledge of attenuation in rocks saturated with multiphase fluid and emphasizes that the WIGED mechanism is very important to image subsurface gas plumes.

CO2 Driven Mineral Transformations in Fractured Reservoir

NASA Astrophysics Data System (ADS)

Schaef, T.

2015-12-01

Engineering fracture systems in low permeable formations to increase energy production, accelerate heat extraction, or to enhance injectivity for storing anthropogenic CO2, is a challenging endeavor. To complicate matters, caprocks, essential components of subsurface reservoirs, need to maintain their sealing integrity in this modified subsurface system. Supercritical CO2 (scCO2), a proposed non-aqueous based working fluid, is capable of driving mineral transformations in fracture environments. Water dissolution in scCO2 significantly impacts the reactivity of this fluid, largely due to the development of thin adsorbed H2O films on the surfaces of exposed rocks and minerals. Adsorbed H2O films are geochemically complex microenvironments that host mineral dissolution and precipitation processes that could be tailored to influence overall formation permeability. Furthermore, manipulating the composition of injected CO2 (e.g., moisture content and/or reactive gases such as O2, NOx, or SOx) could stimulate targeted mineral transformations that enhance or sustain reservoir performance. PNNL has developed specialized experimental techniques that can be used to characterize chemical reactions occurring between minerals and pressurized gases. For example, hydration of a natural shale sample (Woodford Shale) has been characterized by an in situ infrared spectroscopic technique as water partitions from the scCO2 onto the shale. Mineral dissolution and carbonate precipitation reactions were tracked by monitoring changes of Si-O and C-O stretching bands, respectively Structural changes indicated expandable clays in the shale such as montmorillonite are intercalated with scCO2, a process not observed with the non-expandable kaolinite component. Extreme scale ab initio molecular dynamics simulations were used in conjunction with model mineral systems to identify the driving force and mechanism of water films. They showed that the film nucleation and formation on minerals is driven by both enthalpic and entropic requirements. Collectively, the synergy between laboratory observations, state-of-the-art atomistic simulations and reservoir modeling has generated important insights for the design and engineering of subsurface reservoirs for CO2 storage and energy extraction.

Demonstration of Combined Zero-Valent Iron and Electrical Resistance Heating for In Situ Trichloroethene Remediation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Truex, Michael J.; Macbeth, Tamzen; Vermeul, Vincent R.

The effectiveness of in situ treatment using zero-valent iron to remediate sites with non-aqueous phase or significant sediment-associated contaminant mass can be limited by relatively low rates of mass transfer to bring contaminants in contact with the reactive media. For a field test in a trichloroethene source area, combining moderate-temperature (maximum 50oC) subsurface electrical resistance heating with in situ ZVI treatment was shown to accelerate dechlorination and dissolution rates by a factor of 4 to 6 based on organic daughter products and a factor 8-16 using a chloride concentrations. A mass-discharge-based analysis was used to evaluate reaction, dissolution, and volatilizationmore » at ambient groundwater temperature (~10oC) and as temperature was increased up to about 50oC. Increased reaction and contaminant dissolution were observed with increased temperature, but volatilization was minimal during the test because in situ reactions maintained low aqueous-phase TCE concentrations.« less

Electrolyte-induced surface transformation and transition-metal dissolution of fully delithiated LiNi 0.8Co 0.15Al 0.05O 2

DOE PAGES

Faenza, Nicholas V.; Lebens-Higgins, Zachary W.; Mukherjee, Pinaki; ...

2017-06-08

Here, enabling practical utilization of layered Rmore » $$\\bar{3}$$ m positive electrodes near full delithiation requires an enhanced understanding of the complex electrode–electrolyte interactions that often induce failure. Using Li[Ni 0.8Co 0.15Al 0.05]O 2 (NCA) as a model layered compound, the chemical and structural stability in a strenuous thermal and electrochemical environment was explored. Operando microcalorimetry and electrochemical impedance spectroscopy identified a fingerprint for a structural decomposition and transition-metal dissolution reaction that occurs on the positive electrode at full delithiation. Surface-sensitive characterization techniques, including X-ray absorption spectroscopy and high-resolution transmission electron microscopy, measured a structural and morphological transformation of the surface and subsurface regions of NCA. Despite the bulk structural integrity being maintained, NCA surface degradation at a high state of charge induces excessive transition-metal dissolution and significant positive electrode impedance development, resulting in a rapid decrease in electrochemical performance. Additionally, the impact of electrolyte salt, positive electrode surface area, and surface Li 2CO 3 content on the magnitude and character of the dissolution reaction was studied.« less

Electrolyte-Induced Surface Transformation and Transition-Metal Dissolution of Fully Delithiated LiNi0.8Co0.15Al0.05O2.

PubMed

Faenza, Nicholas V; Lebens-Higgins, Zachary W; Mukherjee, Pinaki; Sallis, Shawn; Pereira, Nathalie; Badway, Fadwa; Halajko, Anna; Ceder, Gerbrand; Cosandey, Frederic; Piper, Louis F J; Amatucci, Glenn G

2017-09-19

Enabling practical utilization of layered R3̅m positive electrodes near full delithiation requires an enhanced understanding of the complex electrode-electrolyte interactions that often induce failure. Using Li[Ni 0.8 Co 0.15 Al 0.05 ]O 2 (NCA) as a model layered compound, the chemical and structural stability in a strenuous thermal and electrochemical environment was explored. Operando microcalorimetry and electrochemical impedance spectroscopy identified a fingerprint for a structural decomposition and transition-metal dissolution reaction that occurs on the positive electrode at full delithiation. Surface-sensitive characterization techniques, including X-ray absorption spectroscopy and high-resolution transmission electron microscopy, measured a structural and morphological transformation of the surface and subsurface regions of NCA. Despite the bulk structural integrity being maintained, NCA surface degradation at a high state of charge induces excessive transition-metal dissolution and significant positive electrode impedance development, resulting in a rapid decrease in electrochemical performance. Additionally, the impact of electrolyte salt, positive electrode surface area, and surface Li 2 CO 3 content on the magnitude and character of the dissolution reaction was studied.

Hypogenic contribution to speleogenesis in a predominant epigenic karst system: A case study from the Venetian Alps, Italy

NASA Astrophysics Data System (ADS)

Tisato, Nicola; Sauro, Francesco; Bernasconi, Stefano M.; Bruijn, Rolf H. C.; De Waele, Jo

2012-05-01

Buso della Rana and Buso della Pisatela are two karstic caves located in north-east Italy. They are part of the same karst system and are developed in the Castelgomberto calcarenitic marine sediments, which were deposited in a shallow Caribbean-type sea during the Eocene. The Buso della Rana-Pisatela system developed mostly at the contact between the Castelgomberto calcarenite and underlying volcanic rocks. The system of caves is ~ 37 km long and has only three entrances, two of which are semi-artificial. The overlying karst plateau is not directly connected to the Buso della Rana-Pisatela system and, with the exception of one deep abyss, exhibits a rather poorly developed karst. This is unexpected considering the presence at depth of such a large and long cave. Gypsum (CaSO4·2H2O) has locally been observed on the walls of the Buso della Pisatela cave. Energy dispersive X-ray spectroscopy (EDS), performed with a scanning electron microscope (SEM), reveals the presence of sulfur-bearing minerals within the host rock. Gypsum was formed by oxidation of these minerals as indicated by negative δ34S values. The oxidation of sulfide minerals forms a sulfuric-acid solution that dissolves the Castelgomberto calcarenite and, once it is oversaturated in calcium, precipitates as gypsum. The lack of well-developed karst on top of the plateau and the analyses suggest that the formation mechanisms for the Buso della Rana-Pisatela system differ from classical epigenic speleogenesis. The "pyrite-effect" has been recognized in other caves and described in literature. In our case pyrite is responsible of two hypo-speleogenetic processes: i) the dissolution of a portion of the host rock and ii) the enlargement of the karst voids as a consequence of the haloclastic effect.

Weathering of the New Albany Shale, Kentucky, USA: I. Weathering zones defined by mineralogy and major-element composition

USGS Publications Warehouse

Tuttle, M.L.W.; Breit, G.N.

2009-01-01

Comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks. Here minerals that release and fix major elements during progressive weathering of a bed of Devonian New Albany Shale in eastern Kentucky are documented. Samples were collected from unweathered core (parent shale) and across an outcrop excavated into a hillside 40 year prior to sampling. Quantitative X-ray diffraction mineralogical data record progressive shale alteration across the outcrop. Mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange. Altered primary minerals include K-feldspars, plagioclase, calcite, pyrite, and chlorite. Secondary minerals include jarosite, gypsum, goethite, amorphous Fe(III) oxides and Fe(II)-Al sulfate salt (efflorescence). The mineralogy in weathered shale defines four weathered intervals on the outcrop-Zones A-C and soil. Alteration of the weakly weathered shale (Zone A) is attributed to the 40-a exposure of the shale. In this zone, pyrite oxidization produces acid that dissolves calcite and attacks chlorite, forming gypsum, jarosite, and minor efflorescent salt. The pre-excavation, active weathering front (Zone B) is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability. Acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt, jarosite and minor goethite. Intensely weathered shale (Zone C) is depleted in feldspars, chlorite, gypsum, jarosite and efflorescent salts, but has retained much of its primary quartz, illite and illite-smectite. Goethite and amorphous FE(III) oxides increase due to hydrolysis of jarosite. Enhanced permeability in this zone is due to a 14% loss of the original mass in parent shale. Denudation rates suggest that characteristics of Zone C were acquired over 1 Ma. Compositional differences between soil and Zone C are largely attributed to illuvial processes, formation of additional Fe(III) oxides and incorporation of modern organic matter.

Optimization of the gypsum-based materials by the sequential simplex method

NASA Astrophysics Data System (ADS)

Doleželová, Magdalena; Vimmrová, Alena

2017-11-01

The application of the sequential simplex optimization method for the design of gypsum based materials is described. The principles of simplex method are explained and several examples of the method usage for the optimization of lightweight gypsum and ternary gypsum based materials are given. By this method lightweight gypsum based materials with desired properties and ternary gypsum based material with higher strength (16 MPa) were successfully developed. Simplex method is a useful tool for optimizing of gypsum based materials, but the objective of the optimization has to be formulated appropriately.

Characterizing synthetic gypsum for wallboard manufacture

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henkels, P.J.; Gynor, J.C.

1996-12-31

United States Gypsum Company (USGC) has developed specifications and guidelines covering the chemical and physical aspects of synthetic gypsum to help predict end use acceptability in wallboard manufacture. These guidelines are based in part on past experiences with natural and synthetic gypsum. Similarly, most wallboard manufacturers in North America have developed their own guidelines based in part on its unique history and particular experiences with synthetic gypsum. While there are similarities between manufacturers` guidelines, differences do exist. This paper discusses the importance of selected parameters contained in the FGD gypsum guidelines. In most cases, the parameters are equally relevant tomore » other synthetic gypsums and the naturally occurring gypsum mineral as well.« less

The Gypsum: White gold of Rajasthan, introduction, uses and future prospective

NASA Astrophysics Data System (ADS)

Sharma, Gayatri

2013-06-01

Rajasthan is mineral based state and Bikaner and its surrounding district have been gifted with Gypsum. Mt of Gypsum is available in these districts. Gypsum has multiple uses including basic raw material for POP industry, addition in cement and a natural fertilizer. This mineral has changes the economic scenario in the remote areas of Bikaner, Nagaur, Hanumangarh, Sanchore, Shriganganagar etc. Gypsum and selenite are mined about 3.0 million tons per year. There is huge demand from cement industry as Gypsum is added for improving setting time of cement. Gypsum is a natural fertilizer for alkaline land and it role is vital in state like India where alkaline land is major role. Its high use as fertilizer has potential to change millions of poor farmer families and improving in crop production. Cement Industry has started importing Gypsum from Thailand, Bankong, Pakistan, Iran etc. The mining of gypsum of purity of 70% CaSO4.2H2O is cooperative effort between the land owners and Rajasthan State Mines and Minerals Limited. Gypsum fulfills the demand of POP and Cement industry in Rajasthan and powder gypsum used in agriculture for recon dining of alkaline soil. This paper deals with multiple uses, availability, and future prospective of Gypsum, a white gold of Rajasthan.

Using Terrestrial Sulfate Efflorescences as an Analogue of Hydrated Sulfate Formation in Valles Marineris on Mars

NASA Astrophysics Data System (ADS)

Smith, P. C.; Szynkiewicz, A.

2015-12-01

Hydrated sulfate minerals provide conclusive evidence that a hydrologic cycle was once active on the surface of Mars. Two classes of hydrated sulfate minerals have been detected by robotic instruments on Mars: monohydrated sulfate minerals comprised of kieserite and gypsum, and various polyhydrated sulfates with Fe-Ca-Na-Mg-rich compositions. These minerals are found in various locations on Mars, including large surface exposures in valley settings of Valles Marineris. However, the sulfate sources and formation mechanisms of these minerals are not yet well understood.Recently, it has been suggested that the sulfate minerals in Valles Marineris might have formed in a manner similar to sulfate efflorescences found in dry environments on Earth. In this study, we use sulfate effloresences from the Rio Puerco Watershed, New Mexico as a terrestrial analogue to assess major factors that might have led to deposition of sulfate minerals in Valles Marineris. In different seasons indicative of dry and wet conditions, we collected field photographs and sediment samples for chemical and stable isotopic analyses (sulfur content, δ34S) to determine major sources of sulfate ions for efflorescences and to assess how the seasonal changes in surface/groundwater activity affect their formation. Preliminary sulfur isotope results suggest that oxidation of bedrock sulfides (0.01-0.05 wt. S %) is a major source of sulfate ion for efflorescences formation because their δ34S varied in negative range (-28 to -20‰) similar to sulfides (average -32‰). Using field photographs collected in Oct 2006, Feb and Nov 2012, May 2013, Mar and Oct 2014, we infer that the highest surface accumulation of sulfate efflorescences in the studied analog site was observed after summer monsoon seasons when more water was available for surface and subsurface transport of solutes from chemical weathering. Conversely, spring snow melt led to enhanced dissolution of sulfate efflorescences.

Evaluation of FGD-gypsum to improve forage production and reduce phosphorus lossed from Piedmont soils

USDA-ARS?s Scientific Manuscript database

Flue gas desulfurization gypsum (FGD-gypsum), a byproduct from coal fired electricity generators, has the potential for beneficial use in agricultural systems as a soil amendment. Similar to mined gypsum it can improve soil chemical and physical properties and increase crop productivity. FGD-gypsum ...

Economics of Gypsum Production in Iran

NASA Astrophysics Data System (ADS)

Esmaeili, Abdoulkarim

The purpose of this research is to analyze the economics of gypsum production in Iran. The trend in production cost, selling price and profit are used to investigate economics of gypsum production. In addition, the multivariate time series method is used to determine factors affecting gypsum price in domestic market. The results indicated that due to increase in production and inflation, profitability of gypsum production has decreased during recent years. It is concluded that tariff and non-tariff barriers on mines machinery are among reasons for increasing production cost in Iranian gypsum mines. Decreasing such barriers could increase profitability of gypsum production in Iran.

Effects of gypsum on trace metals in soils and earthworms

USDA-ARS?s Scientific Manuscript database

Mined gypsum has been beneficially used for many years as an agricultural amendment. Currently a large amount of flue gas desulfurization (FGD) gypsum is produced by removal of SO2 from flue gas streams when fuels with high S content are burned. The FGD gypsum, similar to mined gypsum, can enhance c...

Microbial Life Driving Low-Temperature Basalt Alteration in the Subsurface: Decoupling Abiotic Processes from Biologically-Mediated Rock Alteration

NASA Astrophysics Data System (ADS)

Moore, R.; Lecoeuvre, A.; Stephant, S.; Dupraz, S.; Ranchou-Peyruse, M.; Ranchou-Peyruse, A.; Gérard, E.; Ménez, B.

2017-12-01

Microorganisms are involved with specific rock alteration processes in the deep subsurface. It is a challenge to link any contribution microbial life may have on rock alteration with specific functions or phyla because many alteration features and secondary minerals produced by metabolic processes can also produce abiotically. Here, two flow-through experiments were designed to mimic the circulation of a CO2-rich fluid through crystalline basalt. In order to identify microbially-mediated alteration and be able to link it with specific metabolisms represented in the subsurface, a relatively fresh crystalline basalt substrate was subsampled, sterilized and used as the substrate for both experiments. In one experiment, the substrate was left sterile, and in the other it was inoculated with an enrichment culture derived from the same aquifer as the rock substrate. Initial results show that the inoculum contained Proteobacteria and Firmicutes, which have diverse metabolic potentials. Fluid and rock analyses before, during, and after the experiments show that mineralogy, fluid chemistry, and dissolution processes differ between the sterile and inoculated systems. In the inoculated experiment iron-rich orthopyroxenes were preferentially dissolved while in the sterile system clinopyroxenes and plagioclases both exhibited a higher degree of dissolution. Additionally, the patterns of CO2 consumption and production over the duration of both experiments is different. This suggest that in a low-temperature basalt system with microorganisms CO2 is either consumed to produce biomass, or that carbonates are produced and then subsequently preserved. This suite of results combined with molecular ecology analyses can be used to conclude that in low-temperature basalts microorganisms play an intrinsic role in rock alteration.

Slanic Tuff and associated Miocene evaporite deposits, Eastern Carpathians, Romania

NASA Astrophysics Data System (ADS)

Bojar, Ana-Voica; Halas, Stanislaw; Barbu, Victor; Bojar, Hans-Peter; Wojtowicz, Artur; Duliu, Octavian

2017-04-01

Miocene tuffs of calcalkaline composition are widespread in the Carpathians, Pannonian and Eastern Alpine realm. Their occurrences are described in outcrops as well as in the subsurface. The presence of such tuffs may offer important criteria for stratigraphic correlations and help to establish the absolute age of deposits and associated climatic and environmental changes. The Green Stone Hill (Muntele Piatra Verde) is situated to the north of Slanic-Prahova salt mine, in the bend region of the Eastern Carpathians, Romania. From bottom to top the section is composed of: marls with Globigerina followed by the so called Slanic tuff, gypsum and salt breccia and, on the top, radiolarian bearing shales. The stratigraphic age of the section is Middle to Upper Badenian (nannoplankton zones NN5 to NN6). XRD investigations of the green Slanic tuff show that the main mineralogical component is clinoptilolite (zeolite) followed by quartz and plagioclase. For this type of tuff there is no crystalline phase, which may be used for radiometric dating. In the middle part of the green tuff interval, we found discrete layers of a much coarser white tuff, with mineralogy consisting of quartz, plagioclase, biotite and clinoptilolite. The white tuff forming distinct layers within the green tuff, has an andesitic composition. 40Ar/39Ar dating of biotite concentrates from the white tuff gives an age of 13.6±0.2Ma, the dated layer being situated below the gypsum and salt breccia. We consider that the age is well constraining the time when the green tuffs were formed at the border of the basin. From this level upwards discrete gypsum layers occurs within the green tuffs, the age may be considered as indicating the base of the evaporitic sequence. To the south-east, from this level upwards evaporites, mainly salt formed. The age suggests that evaporitic deposits formed after the Mid Badenian climatic optimum, evaporitic formation being related to restricted circulation due the drop of sea-level and tectonism.

Water chemistry at Snowshoe Mountain, Colorado: mixed processes in a common bedrock

USGS Publications Warehouse

Hoch, A.R.; Reddy, M.M.

2001-01-01

At Snowshoe Mountain the primary bedrock is quite homogeneous, but weathering processes vary as waters moves through the soils, vadose zone and phreatic zone of the subsurface. In the thin soil, physical degradation of tuff facilitates preferential dissolution of potassium ion from glass within the rock matrix, while other silicate minerals remain unaltered. In the vadose zone, in the upper few meters of fractured bedrock, dilute water infiltrates during spring snowmelt and summer storms, leading to preferential dissolution of augite exposed on fracture surfaces. Deeper yet, in the phreatic zone of the fractured bedrock, Pleistocene calcite fracture fillings dissolve, and dioctahedral and trioctahedral clays form as penetrative weathering alters feldspar and pyroxene. Alkalinity is generated and silica concentrations are buffered by mineral alteration reactions.

The role of mineral heterogeneity on the hydrogeochemical response of two fractured reservoir rocks in contact with dissolved CO2

NASA Astrophysics Data System (ADS)

Garcia Rios, Maria; Luquot, Linda; Soler, Josep M.; Cama, Jordi

2017-04-01

In this study we compare the hydrogeochemical response of two fractured reservoir rocks (limestone composed of 100 wt.% calcite and sandstone composed of 66 wt.% calcite, 28 wt.% quartz and 6 wt.% microcline) in contact with CO2-rich sulfate solutions. Flow-through percolation experiments were performed using artificially fractured limestone and sandstone cores and injecting a CO2-rich sulfate solution under a constant volumetric flow rate (from 0.2 to 60 mL/h) at P = 150 bar and T = 60 °C. Measurements of the pressure difference between the inlet and the outlet of the samples and of the aqueous chemistry enabled the determination of fracture permeability changes and net reaction rates. Additionally, X-ray computed microtomography (XCMT) was used to characterize and localized changes in fracture volume induced by dissolution and precipitation reactions. In all reacted cores an increase in fracture permeability and in fracture volume was always produced even when gypsum precipitation happened. The presence of inert silicate grains in sandstone samples favored the occurrence of largely distributed dissolution structures in contrast to localized dissolution in limestone samples. This phenomenon promoted greater dissolution and smaller precipitation in sandstone than in limestone experiments. As a result, in sandstone reservoirs, the larger increase in fracture volume as well as the more extended distribution of the created volume would favor the CO2 storage capacity. The different distribution of created volume between limestone and sandstone experiments led to a different variation in fracture permeability. The progressive stepped permeability increase for sandstone would be preferred to the sharp permeability increase for limestone to minimize risks related to CO2 injection, favor capillary trapping and reduce energetic storage costs. 2D reactive transport simulations that reproduce the variation in aqueous chemistry and the fracture geometry (dissolution pattern) were performed using CrunchFlow. The calcite reactive surface area had to be diminished with respect to the geometric surface area in order to account for the transport control of the calcite dissolution reaction at pH < 5. The fitted reactive surface area was higher under faster flow conditions, reflecting a decrease in transport control and a more distributed reaction in sandstone compared to limestone.

Regional Hydrogeochemistry of a Modern Coastal Mixing Zone

NASA Astrophysics Data System (ADS)

Wicks, Carol M.; Herman, Janet S.

1996-02-01

In west central Florida, groundwater samples were collected along flow paths in the unconfined upper Floridan aquifer that cross the inland, freshwater recharge area and the coastal discharge area. A groundwater flow and solute transport model was used to evaluate groundwater flow and mixing of fresh and saline groundwater along a cross section of the unconfined upper Floridan aquifer. Results show that between 8% and 15% of the fresh and 30-31% of the saline groundwater penetrates to the depth in the flow system where contact with and dissolution of gypsum is likely. The deeply circulating fresh and saline groundwater returns to the near-surface environment discharging CaSO4-rich water to the coastal area where it mixes with fresh CaHCO3 groundwater, resulting in a prediction of calcite precipitation in the modern mixing zone.

Gypsum

USGS Publications Warehouse

Crangle, R.D.

2012-01-01

The United States is the world's fourth leading producer and consumer of gypsum. Production of gypsum in the U.S. during 2011 was estimated to be 9.4 Mt (103 million st), an increase of 6 percent compared with 2010 production. The average price of mined crude gypsum was $7/t ($6.35/st). Synthetic gypsum, most of which is generated as a fluegas desulfurization process from coal-fired electric powerplants, was priced at approximately $1.50/t (1.36/st). Forty-seven companies produced gypsum in the U.S. at 54 mines and plants in 34 states. U.S. gypsum exports totaled about 300 kt (330,000 st). Imports were much higher at approximately 3.3 Mt (3.6 million st).

Gypsum crystals observed in experimental and natural sea ice

NASA Astrophysics Data System (ADS)

Geilfus, N.-X.; Galley, R. J.; Cooper, M.; Halden, N.; Hare, A.; Wang, F.; Søgaard, D. H.; Rysgaard, S.

2013-12-01

gypsum has been predicted to precipitate in sea ice, it has never been observed. Here we provide the first report on gypsum precipitation in both experimental and natural sea ice. Crystals were identified by X-ray diffraction analysis. Based on their apparent distinguishing characteristics, the gypsum crystals were identified as being authigenic. The FREeZing CHEMistry (FREZCHEM) model results support our observations of both gypsum and ikaite precipitation at typical in situ sea ice temperatures and confirms the "Gitterman pathway" where gypsum is predicted to precipitate. The occurrence of authigenic gypsum in sea ice during its formation represents a new observation of precipitate formation and potential marine deposition in polar seas.

Geochemical studies of northern taiga (gypsum) karst ecosystems and their high vulnerability to natural and anthropogenic hazards

NASA Astrophysics Data System (ADS)

Tuyukina, T. Yu.

2009-07-01

In the taiga gypsum karst ecosystems, gypsum soils formed on the hard gypsum substrates predominate in the soil cover. In these soils, the mineral horizons consist of 95-99% gypsum (CaSO4·2H2O) and the litter is the main horizon for nutrient accumulation. For this reason, the ecosystems are vulnerable to fire and erosion by walkers, from which they only recover slowly. Gypsum mining for industrial uses is also leading to the destruction of this unique ecosystem.

Experimental layering development by indenter technique and application to fault rheology differentiation

NASA Astrophysics Data System (ADS)

Gratier, J. P.; Noiriel, C. N.; Renard, F.

2014-12-01

Natural deformation of rocks is often associated with differentiation processes leading to irreversible transformations of their microstructural thus leading in turn to modifications of their rheological properties. The mechanisms of development of such processes at work during diagenesis, metamorphism or fault differentiation are poorly known as they are not easy to reproduce in the laboratory due to the long duration required for most of chemically controlled differentiation processes. Here we show that experimental compaction with layering development, similar to what happens in natural deformation, can be obtained in the laboratory by indenter techniques. Samples of plaster mixed with clay and samples of diatomite loosely interbedded with clays were loaded during several months at 40°C (plaster) and 150°C (diatomite) in presence of their saturated solutions. High-resolution X-ray tomography and SEM studies show that the layering development is a self-organized process. Stress driven dissolution of the soluble minerals (gypsum in plaster, silica in diatomite) is initiated in the zones initially richer in clays because the kinetics of diffusive mass transfer along the clay/soluble mineral interfaces is much faster than along the healed boundaries of the soluble minerals. The passive concentration of the clay minerals amplifies the localization of the dissolution along some layers oriented perpendicular to the maximum compressive stress component. Conversely, in the areas with initial low content in clay and clustered soluble minerals, dissolution is more difficult as the grain boundaries of the soluble species are healed together. These areas are less deformed and they act as rigid objects that concentrate the dissolution near their boundaries thus amplifying the differentiation. Applications to fault processes are discussed: i) localized pressure solution and sealing processes may lead to fault rheology differentiation with a partition between two end-member behaviors: seismic (in sealed zones) and aseismic (in dissolved zones); ii) tectonic layering may lead to highly anisotropic structures with a drastic decrease of the rock strength parallel to the layering.

Response of dissolved inorganic carbon (DIC) and δ13CDIC to changes in climate and land cover in SW China karst catchments

NASA Astrophysics Data System (ADS)

Zhao, Min; Liu, Zaihua; Li, Hong-Chun; Zeng, Cheng; Yang, Rui; Chen, Bo; Yan, Hao

2015-09-01

Monthly hydrochemical data and δ13C of dissolved inorganic carbon (DIC) in karst water samples from September 2007 to October 2012 were obtained to reveal the controlling mechanisms on DIC geochemistry and δ13CDIC under different conditions of climate and land cover in three karst catchments: Banzhai, Dengzhanhe and Chenqi, in Guizhou Province, SW China. DIC of karst water at the Banzhai site comes mainly from carbonate dissolution under open system conditions with soil CO2 produced by root respiration and organic carbon decomposition with lowest δ13C values under its dense virgin forest coverage. Weaker carbonate bedrock dissolution due to sparse and thin soil cover results in lower δ13CDIC, pCO2, DIC and EC, and lower cation and anion concentrations. At the Chenqi site, larger soil CO2 input from a thick layer of soil results in high pCO2 and DIC, and low pH, SIc and δ13CDIC in the karst water. At the Dengzhanhe site, a lesser soil CO2 input due to stronger karst rock desertification and strong gypsum dissolution contribute to higher δ13CDIC, high EC and high cation and anion concentrations. Soil CO2 inputs, controlled by biological activity and available soil moisture, carbonate bedrock dissolution, dilution and degassing effects, vary seasonally following rainfall and temperature changes. Consequently, there are seasonal cycles in hydrochemistry and δ13CDIC of the karst water, with high pCO2 and low pH, EC, SIc, and δ13CDIC values in the warm and rainy seasons, and vice versa during the cold and dry seasons. A strongly positive shift (>3‰) in δ13CDIC occurred in the drought year, 2011, indicating that δ13CDIC in groundwater systems can be an effective indicator of environmental and/or climate changes.

The crystallization water of gypsum rocks is a relevant water source for plants.

PubMed

Palacio, Sara; Azorín, José; Montserrat-Martí, Gabriel; Ferrio, Juan Pedro

2014-08-18

Some minerals, like gypsum, hold water in their crystalline structure. Although still unexplored, the use of such crystallization water by organisms would point to a completely new water source for life, critical under dry conditions. Here we use the fact that the isotopic composition of free water differs from gypsum crystallization water to show that plants can use crystallization water from the gypsum structure. The composition of the xylem sap of gypsum plants during summer shows closer values to gypsum crystallization water than to free soil water. Crystallization water represents a significant water source for organisms growing on gypsum, especially during summer, when it accounts for 70-90% of the water used by shallow-rooted plants. Given the widespread occurrence of gypsum in dry lands throughout the Earth and in Mars, these results may have important implications for arid land reclamation and exobiology.

Gypsum-bonded alumina dental investment for high-fusing casting.

PubMed

Yan, M; Takahashi, H

1998-09-01

In this study, we developed a new gypsum-bonded investment for high-fusing alloys. The investment was composed of gypsum as a binder and alumina as a refractory. Effects of type of alumina powder and gypsum content on characteristics of the gypsum-bonded alumina investment were investigated. Obtained characteristics of this experimental investment were as follows: fluidities ranged from 48.8 to 88.9 mm; setting times ranged from 21.2 to more than 120 minutes; setting expansions ranged from 0.4 to 1.3%; green strengths showed 0.5 to 4.5 MPa; fired strengths ranged from 0.2 to 1.7 MPa; thermal expansions after firing were -1.60 to 2.16%. Thermal expansion occurred because of the chemical reaction between Al2O3 and CaO decomposed from gypsum. These results suggest that this gypsum-bonded alumina investment with 20 or 25 mass% gypsum content possessed the fundamental properties for high-fusing alloy casting.

Mechanisms of Arsenic Mobilization and Attenuation in Subsurface Sediments

NASA Astrophysics Data System (ADS)

O'Day, P. A.; Illera, V.; Root, R.; Choi, S.; Vlassopoulos, D.

2007-12-01

This talk will review molecular mechanisms of As mobilization and attenuation in subsurface sediments using examples from recent field studies that represent a range in oxidation-redox (redox) potential. As a ubiquitous trace element in sediments, As speciation and fate is linked to the abundance and biogeochemical behavior of the generally more abundant redox-active elements Fe, S, and Mn. All four elements are subject to oxidation, reduction, and pH-dependent processes such as sorption, desorption, precipitation, and dissolution, and which may include both biotic and abiotic reaction steps. We have used spectroscopic interrogation and geochemical modeling to characterize As speciation in subsurface sediments in several contrasting environments, including high and low S and Fe settings. Aquifers most at risk for contamination by As include those that are rich in organic matter and nutrients, stimulating high rates of microbial reduction and creating anoxic conditions, but limited in labile or available S and/or Fe that remove As by precipitation or adsorption. In subsurface sediments with low labile S and Fe, laboratory experiments and spectroscopic studies suggest that sediment Mn minerals are important in the oxidation of sorbed As(III) to As(V), but that they have a limited oxidation capacity. Arsenic attenuation and mobilization in the subsurface are affected by seasonal variations when hydraulic conditions are influenced by surface infiltration, which may induce transitions from oxidized to reduced conditions (or vice versa) in porewater.

Can a fractured caprock self-heal?

NASA Astrophysics Data System (ADS)

Elkhoury, Jean E.; Detwiler, Russell L.; Ameli, Pasha

2015-05-01

The ability of geologic seals to prevent leakage of fluids injected into the deep subsurface is critical for mitigating risks associated with greenhouse-gas sequestration and natural-gas production. Fractures caused by tectonic or injection-induced stresses create potential leakage pathways that may be further enhanced by mineral dissolution. We present results from reactive-flow experiments in fractured caprock (dolomitic anhydrite), where additional dissolution occurs in the rock matrix adjacent to the fracture surfaces. Preferential dissolution of anhydrite left a compacted layer of dolomite in the fractures. At lower flow rate, rock-fluid reactions proceeded to near equilibrium within the fracture with preferential flow paths persisting over the 6-month duration of the experiment and a negligible change in permeability. At higher flow rate, permeability decreased by a dramatic two orders of magnitude. This laboratory-scale observation of self-healing argues against the likelihood of runaway permeability growth in fractured porous caprock composed of minerals with different solubilities and reaction kinetics. However, scaling arguments suggest that at larger length scales this self-healing process may be offset by the formation of dissolution channels. Our results have relevance beyond the greenhouse-gas sequestration problem. Chemical disequilibrium at waste injection sites and in hydrothermal reservoirs will lead to reactive flows that may also significantly alter formation permeability.

Radium-226 content of agricultural gypsums

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lindeken, C.L.; Coles, D.G.

1977-01-01

Gypsum (CaSO/sub 4/ . 2H/sub 2/O), used as a soil amendment for saline-alkali soils, is obtained either by quarrying or as a by-product in the phosphate fertilizer industry. The latter, termed phospho gypsum, contains variable amounts of /sup 226/Ra, depending on the uranium content of the phosphate rock. Radium-226 contents of both quarried and phospho gypsum were determined by gamma counting in a low-background Ge(Li) spectrometer equipped with Compton suppression. Quarried samples from Nova Scotia, Iowa, Texas, and California were compared with phospho gypsum derived from Florida land pebble phosphates. Quarried gypsums showed an average radium content of 0.21 pCi/g.more » The average radium in phospho gypsum was 14.6 pCi/g. Uranium-238 measurements showed that near secular equilibrium existed between the uranium and radium in the quarried samples. Disequilibrium in the phospho gypsums occurred because of the preferential separation of radium during chemical processing. At the levels observed, no health hazard is implied from uptake of radium by plants grown in phospho gypsum treated soil.« less

Mathematical models as tools for probing long-term safety of CO2 storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pruess, Karsten; Birkholzer, Jens; Zhou, Quanlin

Subsurface reservoirs being considered for storing CO{sub 2} include saline aquifers, oil and gas reservoirs, and unmineable coal seams (Baines and Worden, 2004; IPCC, 2005). By far the greatest storage capacity is in saline aquifers (Dooley et al., 2004), and our discussion will focus primarily on CO{sub 2} storage in saline formations. Most issues for safety and security of CO{sub 2} storage arise from the fact that, at typical temperature and pressure conditions encountered in terrestrial crust, CO{sub 2} is less dense than aqueous fluids. Accordingly, CO{sub 2} will experience an upward buoyancy force in most subsurface environments, and willmore » tend to migrate upwards whenever (sub-)vertical permeable pathways are available, such as fracture zones, faults, or improperly abandoned wells (Bachu, 2008; Pruess, 2008a, b; Tsang et al., 2008). CO{sub 2} injection will increase fluid pressures in the target formation, thereby altering effective stress distributions, and potentially triggering movement along fractures and faults that could increase their permeability and reduce the effectiveness of a caprock in containing CO{sub 2} (Rutqvist et al., 2008; Chiaramonte et al., 2008). Induced seismicity as a consequence of fluid injection is also a concern (Healy et al., 1968; Raleigh et al., 1976; Majer et al., 2007). Dissolution of CO{sub 2} in the aqueous phase generates carbonic acid, which may induce chemical corrosion (dissolution) of minerals with associated increase in formation porosity and permeability, and may also mediate sequestration of CO{sub 2} as solid carbonate (Gaus et al., 2008). Chemical dissolution of caprock minerals could promote leakage of CO{sub 2} from a storage reservoir (Gherardi et al., 2007). Chemical dissolution and geomechanical effects could reinforce one another in compromising CO{sub 2} containment. Additional issues arise from the potential of CO{sub 2} to mobilize hazardous chemical species (Kharaka et al., 2006), and from migration of the large amounts of brine that would be mobilized by industrial-scale CO{sub 2} injection (Nicot et al., 2008; Birkholzer et al., 2008a, b).« less

Long-term geochemical evolution of the near field repository: Insights from reactive transport modelling and experimental evidences

NASA Astrophysics Data System (ADS)

Arcos, David; Grandia, Fidel; Domènech, Cristina; Fernández, Ana M.; Villar, María V.; Muurinen, Arto; Carlsson, Torbjörn; Sellin, Patrik; Hernán, Pedro

2008-12-01

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept. In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution-precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.

Long-term geochemical evolution of the near field repository: insights from reactive transport modelling and experimental evidences.

PubMed

Arcos, David; Grandia, Fidel; Domènech, Cristina; Fernández, Ana M; Villar, María V; Muurinen, Arto; Carlsson, Torbjörn; Sellin, Patrik; Hernán, Pedro

2008-12-12

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept. In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution-precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.

MICROBIAL RESISTANT GYPSUM PRODUCTS

EPA Science Inventory

Gypsum building materials often become wet, resulting in mold growth that leads to health and productivity impacts. A major source of mold growth is gypsum wallboard since nearly 90% of the interior finished surfaces of buildings are covered with gypsum products. It has been est...

Gypsum accumulation on carbonate stone

USGS Publications Warehouse

McGee, E.S.; Mossotti, V.G.

1992-01-01

The accumulation of gypsum on carbonate stone has been investigated through exposure of fresh samples of limestone and marble at monitored sites, through examination of alteration crusts from old buildings and through laboratory experiments. Several factors contribute to gypsum accumulation on carbonate stone. Marble or limestone that is sheltered from direct washing by rain in an urban environment with elevated pollution levels is likely to accumulate a gypsum crust. Crust development may be enhanced if the stone is porous or has an irregular surface area. Gypsum crusts are a surficial alteration feature; gypsum crystals form at the pore opening-air interface, where evaporation is greatest.

Groundwater hydrochemistry in the active layer of the proglacial zone, Finsterwalderbreen, Svalbard

USGS Publications Warehouse

Cooper, R.J.; Wadham, J.L.; Tranter, M.; Hodgkins, R.; Peters, N.E.

2002-01-01

Glacial bulk meltwaters and active-layer groundwaters were sampled from the proglacial zone of Finsterwalderbreen during a single melt season in 1999, in order to determine the geochemical processes that maintain high chemical weathering rates in the proglacial zone of this glacier. Results demonstrate that the principle means of solute acquisition is the weathering of highly reactive moraine and fluvial active-layer sediments by supra-permafrost groundwaters. Active-layer groundwater derives from the thaw of the proglacial snowpack, buried ice and glacial bulk meltwaters. Groundwater evolves by sulphide oxidation and carbonate dissolution. Evaporation- and freeze-concentration of groundwater in summer and winter, respectively produce Mg-Ca-sulphate salts on the proglacial surface. Re-dissolution of these salts in early summer produces groundwaters that are supersaturated with respect to calcite. There is a pronounced spatial pattern to the geochemical evolution of groundwater. Close to the main proglacial channel, active layer sediments are flushed diurnally by bulk meltwaters. Here, Mg-Ca-sulphate deposits become exhausted in the early season and geochemical evolution proceeds by a combination of sulphide oxidation and carbonate dissolution. At greater distances from the channel, the dissolution of Mg-Ca-sulphate salts is a major influence and dilution by the bulk meltwaters is relatively minor. The influence of sulphate salt dissolution decreases during the sampling season, as these salts are exhausted and waters become increasingly routed by subsurface flowpaths. ?? 2002 Elsevier Science B.V. All rights reserved.

Gypsum

USGS Publications Warehouse

Crangle, R.D.

2013-01-01

The United States is the world’s fifth ranked producer and consumer of gypsum. Production of crude gypsum in the United States during 2012 was estimated to be 9.9 Mt (10.9 million st), an increase of 11 percent compared with 2011 production. The average price of mined crude gypsum was $7/t ($6.35/st). Synthetic gypsum production in 2012, most of which is generated as a flue-gas desulphurization product from coal-fired electric powerplants, was estimated to be 11.8 Mt (13 million st) and priced at approximately $1.50/t ($1.36/st). Forty-seven companies produced gypsum in the United States at 54 mines and plants in 34 states. U.S. gypsum exports totaled 408 kt (450,000 st). Imports were much higher at 3.2 Mt (3.5 million st).

Growth of indoor fungi on gypsum.

PubMed

Segers, F J J; van Laarhoven, K A; Wösten, H A B; Dijksterhuis, J

2017-08-01

To have a better understanding of fungal growth on gypsum building materials to prevent indoor fungal growth. Gypsum is acquired by mining or as a by-product of flue-gas desulphurization or treatment of phosphate ore for the production of fertilizer. Natural gypsum, flue-gas gypsum and phosphogypsum therefore have different mineral compositions. Here, growth of fungi on these types of gypsum was assessed. Conidia of the indoor fungi Aspergillus niger, Cladosporium halotolerans and Penicillium rubens were inoculated and observed using microscopic techniques including low-temperature scanning electron microscopy. Elemental analysis of gypsum was done using inductively coupled plasma atomic emission spectroscopy and segmented flow analysis. Moisture content of the gypsum was determined using a dynamic vapour sorption apparatus. Aspergillus niger, C. halotolerans and P. rubens hardly germinated on natural gypsum and flue-gas gypsum. The latter two fungi did show germination, outgrowth, and conidiation on phosphogypsum, while A. niger hardly germinated on this substrate. Other experiments show that C. halotolerans and P. rubens can develop in pure water, but A. niger does not. The observations show that the lack of germination of three indoor fungi is explained by the low amount of phosphor in natural, flue-gas and laboratory-grade gypsum. Additionally, C. halotolerans and P. rubens can develop in pure water, while conidia of A. niger do not show any germination, which is explained by the need for organic molecules of this species to induce germination. Indoor fungal growth is a potential threat to human health and causes damage to building materials. This study possibly helps in the application of the right type of gypsum in buildings. © 2017 The Society for Applied Microbiology.

Origin of secondary sulfate minerals on active andesitic stratovolcanoes

USGS Publications Warehouse

Zimbelman, D.R.; Rye, R.O.; Breit, G.N.

2005-01-01

Sulfate minerals in altered rocks on the upper flanks and summits of active andesitic stratovolcanoes result from multiple processes. The origin of these sulfates at five active volcanoes, Citlalte??petl (Mexico), and Mount Adams, Hood, Rainier, and Shasta (Cascade Range, USA), was investigated using field observations, petrography, mineralogy, chemical modeling, and stable-isotope data. The four general groups of sulfate minerals identified are: (1) alunite group, (2) jarosite group, (3) readily soluble Fe- and Al-hydroxysulfates, and (4) simple alkaline-earth sulfates such as anhydrite, gypsum, and barite. Generalized assemblages of spatially associated secondary minerals were recognized: (1) alunite+silica??pyrite??kaolinite?? gypsum??sulfur, (2) jarosite+alunite+silica; (3) jarosite+smectite+silica??pyrite, (4) Fe- and Al-hydroxysulfates+silica, and (5) simple sulfates+silica??Al-hydroxysulfates??alunite. Isotopic data verify that all sulfate and sulfide minerals and their associated alteration assemblages result largely from the introduction of sulfur-bearing magmatic gases into meteoric water in the upper levels of the volcanoes. The sulfur and oxygen isotopic data for all minerals indicate the general mixing of aqueous sulfate derived from deep (largely disproportionation of SO2 in magmatic vapor) and shallow (oxidation of pyrite or H2S) sources. The hydrogen and oxygen isotopic data of alunite indicate the mixing of magmatic and meteoric fluids. Some alunite-group minerals, along with kaolinite, formed from sulfuric acid created by the disproportionation of SO2 in a condensing magmatic vapor. Such alunite, observed only in those volcanoes whose interiors are exposed by erosion or edifice collapse, may have ??34S values that reflect equilibrium (350??50 ??C) between aqueous sulfate and H2S. Alunite with ??34S values indicating disequilibrium between parent aqueous sulfate and H2S may form from aqueous sulfate created in higher level low-temperature environments in which SO2 is scrubbed out by groundwater or where H2S is oxidized. Jarosite-group minerals associated with smectite in only slightly altered volcanic rock are formed largely from aqueous sulfate derived from supergene oxidation of hydrothermal pyrite above the water table. Soluble Al- and Fehydroxysulfates form in low-pH surface environments, especially around fumaroles, and from the oxidation of hydrothermal pyrite. Anhydrite/gypsum, often associated with native sulfur and occasionally with small amounts of barite, also commonly form around fumaroles. Some occurrences of anhydrite/gypsum may be secondary, derived from the dissolution and reprecipitation of soluble sulfate. Edifice collapse may also reveal deep veins of anhydrite/gypsum??barite that formed from the mixing of saline fluids with magmatic sulfate and dilute meteoric water. Alteration along structures associated with both hydrothermal and supergene sulfates, as well as the position of paleo-water tables, may be important factors in edifice collapse and resulting debris flows at some volcanoes. ?? 2004 Elsevier B.V. All rights reserved.

Theoretical study of the influence of chemical reactions and physical parameters on the convective dissolution of CO2 in aqueous solutions

NASA Astrophysics Data System (ADS)

Loodts, Vanessa; Rongy, Laurence; De Wit, Anne

2014-05-01

Subsurface carbon sequestration has emerged as a promising solution to the problem of increasing atmospheric carbon dioxide (CO2) levels. How does the efficiency of such a sequestration process depend on the physical and chemical characteristics of the storage site? This question is emblematic of the need to better understand the dynamics of CO2 in subsurface formations, and in particular, the properties of the convective dissolution of CO2 in the salt water of aquifers. This dissolution is known to improve the safety of the sequestration by reducing the risks of leaks of CO2 to the atmosphere. Buoyancy-driven convection makes this dissolution faster by transporting dissolved CO2 further away from the interface. Indeed, upon injection, the less dense CO2 phase rises above the aqueous layer where it starts to dissolve. The dissolved CO2 increases the density of the aqueous solution, thereby creating a layer of denser CO2-rich solution above less dense solution. This unstable density gradient in the gravity field is at the origin of convection. In this framework, we theoretically investigate the effect of CO2 pressure, salt concentration, temperature, and chemical reactions on the dissolution-driven convection of CO2 in aqueous solutions. On the basis of a linear stability analysis, we assess the stability of the time-dependent density profiles developing when CO2 dissolves in an aqueous layer below it. We predict that increasing CO2 pressure destabilizes the system with regard to buoyancy-driven convection, because it increases the density gradient at the origin of the instability. By contrast, increasing salt concentration or temperature stabilizes the system via effects on CO2 solubility, solutal expansion coefficient, diffusion coefficient and on the viscosity and density of the solution. We also show that a reaction of CO2 with chemical species dissolved in the aqueous solution can either enhance or decrease the amplitude of the convective dissolution compared to the non reactive one. On the basis of a reaction-diffusion-convection model, we classify the various possible cases and show that the difference between the solutal expansion coefficients of the reactant and of the product governs the type of density profile building up in the aqueous solution and thus the stability of the system. By contrast to non reactive density profiles, reactive density profiles can feature a minimum that induces a delay of the buoyancy-driven convection. This work identifies the parameters that could influence the dissolution-driven convection in the aquifers, and thus impact the safety of the sequestration. In other words, this theoretical study shows that it is crucial to analyse the composition and reactivity of potential storage sites to choose those that will be most efficient for long-term CO2 sequestration.

Hydrothermal Alteration of Glass from Underground Nuclear Tests: Formation and Transport of Pu-clay Colloids at the Nevada National Security Site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zavarin, M.; Zhao, P.; Joseph, C.

2015-05-27

The testing of nuclear weapons at the Nevada National Security Site (NNSS), formerly the Nevada Test Site (NTS), has led to the deposition of substantial quantities of plutonium into the environment. Approximately 2.8 metric tons (3.1×10 4 TBq) of Pu were deposited in the NNSS subsurface as a result of underground nuclear testing. While 3H is the most abundant anthropogenic radionuclide deposited in the NNSS subsurface (4.7×10 6 TBq), plutonium is the most abundant from a molar standpoint. The only radioactive elements in greater molar abundance are the naturally occurring K, Th, and U isotopes. 239Pu and 240Pu represent themore » majority of alpha-emitting Pu isotopes. The extreme temperatures associated with underground nuclear tests and the refractory nature of Pu results in most of the Pu (98%) being sequestered in melted rock, referred to as nuclear melt glass (Iaea, 1998). As a result, Pu release to groundwater is controlled, in large part, by the leaching (or dissolution) of nuclear melt glass over time. The factors affecting glass dissolution rates have been studied extensively. The dissolution of Pu-containing borosilicate nuclear waste glasses at 90ºC has been shown to lead to the formation of dioctahedral smectite colloids. Colloid-facilitated transport of Pu at the NNSS has been observed. Recent groundwater samples collected from a number of contaminated wells have yielded a wide range of Pu concentrations from 0.00022 to 2.0 Bq/L. While Pu concentrations tend to fall below the Maximum Contaminant Level (MCL) established by the Environmental Protection Agency (EPA) for drinking water (0.56 Bq/L), we do not yet understand what factors limit the Pu concentration or its transport behavior. To quantify the upper limit of Pu concentrations produced as a result of melt glass dissolution and determine the nature of colloids and Pu associations, we performed a 3 year nuclear melt glass dissolution experiment across a range of temperatures (25-200 °C) that represent hydrothermal conditions representative of the underground nuclear test cavities (when groundwater has re-saturated the nuclear melt glass and glass dissolution occurs). Colloid loads and Pu concentrations were monitored along with the mineralogy of both the colloids and the secondary mineral phases. The intent was to establish an upper limit for Pu concentrations at the NNSS, provide context regarding the Pu concentrations observed at the NNSS to date and the Pu concentrations that may be observed in the future. The results provide a conceptual model for the risks posed by Pu migration at the NNSS.« less

Flue gas desulfurization gypsum agricultural network alabama (cotton)

USDA-ARS?s Scientific Manuscript database

Flue gas desulfurization gypsum (FGDG) is an excellent source of gypsum (CaSO4•2H2O) that can be beneficially used in agriculture. Research was conducted as part of the Flue Gas Desulfurization Gypsum Agricultural Network program sponsored by the Electric Power Research Institute in collaboration wi...

Flue gas desulfurization gypsum agricultural network alabama (bermudagrass)

USDA-ARS?s Scientific Manuscript database

Synthetic gypsum is being produced in large quantities each year as a byproduct of SO2 removal from flue gas stream at coal-fired utility plants. This synthetic gypsum which is believed to be comparable or better than mined gypsum may enhance crop production. However, there is a paucity of informati...

The role of evapotranspiration in the groundwater hydrochemistry of an arid coastal wetland (Península Valdés, Argentina).

PubMed

Alvarez, María Del Pilar; Carol, Eleonora; Dapeña, Cristina

2015-02-15

Coastal wetlands are complex hydrogeological systems, in which saline groundwater usually occurs. Salinity can be attributed to many origins, such as dissolution of minerals in the sediments, marine contribution and evapotranspiration, among others. The aim of this paper is to evaluate the processes that condition the hydrochemistry of an arid marsh, Playa Fracasso, located in Patagonia, Argentina. A study of the dynamics and geochemistry of the groundwater was carried out in each hydrogeomorphological unit, using major ion and isotope ((18)O and (2)H) data, soil profiles descriptions and measurements, and recording of water tables in relation to the tidal flow. Water balances and analytical models based on isotope data were used to quantify the evaporation processes and to define the role of evaporation in the chemical composition of water. The results obtained show that the groundwater salinity of the marsh comes mainly from the tidal inflow, to which the halite and gypsum dissolution is added. These mineral facies are the result of the total evaporation of the marine water flooding that occurs mostly at the spring high tides. The isotope relationships in the fan and bajada samples show the occurrence of evaporation processes. Such processes, however, are not mainly responsible for the saline content of groundwater, which is actually generated by the dissolution of the typical evaporite facies of the arid environment sediments. It is concluded that the evapotranspiration processes condition groundwater quality. This is not only due to the saline enrichment caused by the evapotranspiration of shallow water, but also because such processes are the main drivers of the formation of soluble salts, which are then incorporated into the water by groundwater or tidal flow. Copyright © 2014 Elsevier B.V. All rights reserved.

FGD gypsum issues

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buecker, B.

2007-11-15

The article first explains how gypsum by-product is produced in flue gas desulfurization systems in coal-fired power plants. It goes on to talk about the main markets for gypsum - wallboard manufacture (Plaster of Paris), cement production and soil stabilization. In the USA in 2006 41.6 million tons of gypsum was used by manufacturers of wallboard and plaster products, 3.0 mt for cement production and 1.1 mt for agricultural purposes. A method of determining the by-product gypsum content by thermogravimetric analysis is outlined. 4 refs., 1 fig.

Combined electromagnetic geophysical mapping at Arctic perennial saline springs: Possible applications for the detection of water in the shallow subsurface of Mars

NASA Astrophysics Data System (ADS)

Samson, C.; Mah, J.; Haltigin, T.; Holladay, S.; Ralchenko, M.; Pollard, W.; Monteiro Santos, F. A.

2017-05-01

Perennial springs at the Gypsum Hill site on Axel Heiberg Island in the Canadian Arctic (79°24‧N, 90°44‧W) represent a high-fidelity analogue to hydrothermal systems that might exist on Mars. The springs were surveyed using an electromagnetic induction sounder (EMIS) and ground penetrating radar (GPR). Both instruments probed the subsurface to a depth of approximately 3 m. Lateral EMIS soundings were performed every metre along a 400 m long reconnaissance line roughly oriented SW-NE and extending through 23 active springs and 1 dry outlet to measure electrical conductivity. Two distinct zones were identified within the survey area on the basis of these data: in the southwest portion, sharp conductivity peaks correspond to isolated springs with well-defined outlets, flowing over dry rocky soil; in the northeast portion, the springs are fed by a pervasive network of saline fluids, resulting in high background readings and muddy surface conditions. These observations are consistent with vertical EMIS sounding data which showed that the brine body feeding the saline springs can be found closer to the ground surface towards the northeast portion of the survey site. In areas of high electrical conductivity, the GPR data exhibits strong scattering. The noisy areas are sharply defined and interpreted to correspond to narrow vertical conduits feeding individual spring outlets. The EMIS is a rugged instrument that could be included as payload in future rover-based Mars exploration missions aiming at probing the shallow subsurface for the presence of brine pockets.

Effects of FGD-gypsum, used-wallboard and calcium sulfate on corn and soybean root growth

USDA-ARS?s Scientific Manuscript database

Flue gas desulfurization (FGD)-gypsum production has increased 44 percent from 2007 to 2008. The major use of FGD-gypsum today is in the wallboard industry. Reduction in the construction, however, reduces the demand for wallboard. Agriculture could become the second largest user of FGD-gypsum. F...

Gypsum and organic matter distribution in a mixed construction and demolition waste sorting process and their possible removal from outputs.

PubMed

Montero, A; Tojo, Y; Matsuo, T; Matsuto, T; Yamada, M; Asakura, H; Ono, Y

2010-03-15

With insufficient source separation, construction and demolition (C&D) waste becomes a mixed material that is difficult to recycle. Treatment of mixed C&D waste generates residue that contains gypsum and organic matter and poses a risk of H(2)S formation in landfills. Therefore, removing gypsum and organic matter from the residue is vital. This study investigated the distribution of gypsum and organic matter in a sorting process. Heavy liquid separation was used to determine the density ranges in which gypsum and organic matter were most concentrated. The fine residue that was separated before shredding accounted for 27.9% of the waste mass and contained the greatest quantity of gypsum; therefore, most of the gypsum (52.4%) was distributed in this fraction. When this fine fraction was subjected to heavy liquid separation, 93% of the gypsum was concentrated in the density range of 1.59-2.28, which contained 24% of the total waste mass. Therefore, removing this density range after segregating fine particles should reduce the amount of gypsum sent to landfills. Organic matter tends to float as density increases; nevertheless, separation at 1.0 density could be more efficient. (c) 2009 Elsevier B.V. All rights reserved.

Raman spectroscopy of shocked gypsum from a meteorite impact crater

NASA Astrophysics Data System (ADS)

Brolly, Connor; Parnell, John; Bowden, Stephen

2017-07-01

Impact craters and associated hydrothermal systems are regarded as sites within which life could originate on Earth, and on Mars. The Haughton impact crater, one of the most well preserved craters on Earth, is abundant in Ca-sulphates. Selenite, a transparent form of gypsum, has been colonized by viable cyanobacteria. Basement rocks, which have been shocked, are more abundant in endolithic organisms, when compared with un-shocked basement. We infer that selenitic and shocked gypsum are more suitable for microbial colonization and have enhanced habitability. This is analogous to many Martian craters, such as Gale Crater, which has sulphate deposits in a central layered mound, thought to be formed by post-impact hydrothermal springs. In preparation for the 2020 ExoMars mission, experiments were conducted to determine whether Raman spectroscopy can distinguish between gypsum with different degrees of habitability. Ca-sulphates were analysed using Raman spectroscopy and results show no significant statistical difference between gypsum that has experienced shock by meteorite impact and gypsum, which has been dissolved and re-precipitated as an evaporitic crust. Raman spectroscopy is able to distinguish between selenite and unaltered gypsum. This shows that Raman spectroscopy can identify more habitable forms of gypsum, and demonstrates the current capabilities of Raman spectroscopy for the interpretation of gypsum habitability.

Sustainable Uses of FGD Gypsum in Agricultural Systems: Introduction.

PubMed

Watts, Dexter B; Dick, Warren A

2014-01-01

Interest in using gypsum as a management tool to improve crop yields and soil and water quality has recently increased. Abundant supply and availability of flue gas desulfurization (FGD) gypsum, a by-product of scrubbing sulfur from combustion gases at coal-fired power plants, in major agricultural producing regions within the last two decades has attributed to this interest. Currently, published data on the long-term sustainability of FGD gypsum use in agricultural systems is limited. This has led to organization of the American Society of Agronomy's Community "By-product Gypsum Uses in Agriculture" and a special collection of nine technical research articles on various issues related to FGD gypsum uses in agricultural systems. A brief review of FGD gypsum, rationale for the special collection, overviews of articles, knowledge gaps, and future research directions are presented in this introductory paper. The nine articles are focused in three general areas: (i) mercury and other trace element impacts, (ii) water quality impacts, and (iii) agronomic responses and soil physical changes. While this is not an exhaustive review of the topic, results indicate that FGD gypsum use in sustainable agricultural production systems is promising. The environmental impacts of FGD gypsum are mostly positive, with only a few negative results observed, even when applied at rates representing cumulative 80-year applications. Thus, FGD gypsum, if properly managed, seems to represent an important potential input into agricultural systems. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Carbonate replacement of lacustrine gypsum deposits in two Neogene continental basins, eastern Spain

NASA Astrophysics Data System (ADS)

Anadón, P.; Rosell, L.; Talbot, M. R.

1992-07-01

Bedded nonmarine gypsum deposits in the Miocene Teruel and Cabriel basins, eastern Spain, are partly replaced by carbonate. The Libros gypsum (Teruel Graben) is associated with fossiliferous carbonate wackestones and finely laminated, organic matter-rich mudstones which accumulated under anoxic conditions in a meromictic, permanent lake. The gypsum is locally pseudomorphed by aragonite or, less commonly, replaced by calcite. Low δ 13C values indicate that sulphate replacement resulted from bacterial sulphate reduction processes that were favoured by anacrobic conditions and abundant labile organic matter in the sediments. Petrographic evidence and oxygen isotopic composition suggest that gypsum replacement by aragonite occurred soon after deposition. A subsequent return to oxidising conditions caused some aragonite to be replaced by diagenetic gypsum. Native sulphur is associated with some of these secondary gypsum occurrences. The Los Ruices sulphate deposits (Cabriel Basin) contain beds of clastic and selenitic gypsum which are associated with limestones and red beds indicating accumulation in a shallow lake. Calcite is the principal replacement mineral. Bacterial sulphate reduction was insignificant in this basin because of a scarcity of organic matter. Stable isotope composition of diagenetic carbonate indicates that gypsum replacement occurred at shallow burial depths due to contact with dilute groundwaters of meteoric origin. Depositional environment evidently has a major influence upon the diagenetic history of primary sulphate deposits. The quantity of preserved organic matter degradable by sulphate-reducing bacteria is of particular importance and, along with groundwater composition, is the main factor controlling the mechanism of gypsum replacement by carbonate.

Biosignatures in modern sulfates: texture, composition and depositional environments of gypsum deposits at Guerrero Negro, Baja, Mexico

NASA Astrophysics Data System (ADS)

Vogel, M. B.; Des Marais, D. J.; Jahnke, L. L.; Turk, K.; Kubo, M.

2007-12-01

Gypsum (CaSO4·H2O) is an important phase in biogeochemistry and sedimentology as a mineral sink for sulfur, a paleoclimatic indicator, and an endolithic niche for phototrophic and chemotrophic bacteria. Sulfate deposits are also important targets of exploration for evidence of habitable environments and life on Mars. Gypsum deposits from a range of sedimentary environments at the Guerrero Negro crystallizer ponds and sabkha settings were investigated for microscale structure and composition to differentiate fabrics formed under microbial influence from those formed under abiogenic conditions. Sub-sedimentary gypsum forms in sabkha environments as mm to cm scale selenite discs (termed bird beak gypsum; Warren, 2006) and selenite disc aggregates. Selenite discs and other sub-sedimentary gypsum are characterized by a sinuous axial microtexture and poikilitically enclosed detrital particles. Sub-aqueous gypsum forms as cements, granules (termed gypsooids), and massive botryoidal crusts that line the sediment water interface and margins of managed crystallizer ponds and natural anchialine pools. Sub-aqueous gypsum exhibits a wide range of textures and mineral/biofilm associations that include amorphous to euhedral, tabular, needle and lensoidal morphologies. Elemental sulfur forms rinds on prismatic, growth aligned gypsum twins and reticulate magnesian carbonate is interspersed with both twinned crystals and rosette aggregates in stratified sub-aqueous environments. Intracrystalline biofilms and cell material was observed in association with nearly all sub-aqueous morphologies but only scarce evidence has been found for intercrystalline microbial communities. Columnar microbial communities living in anchialine pools were found to host precipitation of mm scale gypsum granules in their EPS matrix. Fine scale gypsum textures are unlikely to persist through diagenetic alteration, but understanding their primary associations with sulfur and carbonates is necessary for interpreting sulfates or their replacement phases in the ancient record.

Diagenetic gypsum related to sulfur deposits in evaporites (Libros Gypsum, Miocene, NE Spain)

NASA Astrophysics Data System (ADS)

Ortí, Federico; Rosell, Laura; Anadón, Pere

2010-07-01

The Libros Gypsum is the thickest evaporite unit of the Miocene infill of the Teruel Basin in NE Spain. During the deposition of this unit, intense bacterial sulfate-reducing (BSR) activity in the lake depocenter generated a native sulfur deposit. Diagenetic gypsum resulted from subsequent sulfur oxidation. The different processes involved in these transformations were first investigated by Anadón et al. (1992). The present paper is concerned with this diagenetic gypsum from the stratigraphic, petrographic, isotopic and genetic points of view. Diagenetic gypsum occurs mainly as continuous or discontinuous layers, individual levels or lenses, irregular masses, nodules and micronodules, and veins. Its main textures are coarse-crystalline anhedral and fine-grained (alabastrine), both of which can replace any former lithology (carbonate, gypsum, and sulfur). The following sequence of processes and mineral/textural transformations is deduced: primary gypsum deposition — BSR and biodiagenetic carbonate/H 2S production — growth of native sulfur — growth of diagenetic gypsum — partial recrystallization of the diagenetic gypsum textures. The gypsification of the native sulfur generated two types of banded structures in the diagenetic gypsum: (1) concentric structures of centripetal growth, and (2) expansive, roughly concentric structures. In the first type, the gypsification operated from the outer boundaries towards the inner parts. In the second type, part of the carbonate hosting the sulfur was also gypsified (replaced/cemented). In the diagenetic gypsum, the δ34S values are in agreement with a native sulfur and H 2S provenance. The δ18O sulfate values, however, enable us to differentiate two main groups of values: one with positive values and the other with negative values. In the group of positive values, interstitial (evaporated) solutions participated in the sulfur oxidation; this process presumably occurred in a first oxidation stage during shallow-to-deeper burial of the Libros Gypsum unit. In the group of negative values, however, only meteoric waters participated in the oxidation, which presumably occurred in a second oxidation stage during the final exhumation of the unit. A third group of values is characterized by very high sulfur and oxygen values, suggesting that BSR residual solutions also participated in the oxidation processes locally. During the two oxidation stages, both the textural characteristics and the isotopic composition of the diagenetic gypsum indicate that gypsification operated as a multistadic process.

Hypogeal geological survey in the "Grotta del Re Tiberio" natural cave (Apennines, Italy): a valid tool for reconstructing the structural setting

NASA Astrophysics Data System (ADS)

Ghiselli, Alice; Merazzi, Marzio; Strini, Andrea; Margutti, Roberto; Mercuriali, Michele

2011-06-01

As karst systems are natural windows to the underground, speleology, combined with geological surveys, can be useful tools for helping understand the geological evolution of karst areas. In order to enhance the reconstruction of the structural setting in a gypsum karst area (Vena del Gesso, Romagna Apennines), a detailed analysis has been carried out on hypogeal data. Structural features (faults, fractures, tectonic foliations, bedding) have been mapped in the "Grotta del Re Tiberio" cave, in the nearby gypsum quarry tunnels and open pit benches. Five fracture systems and six fault systems have been identified. The fault systems have been further analyzed through stereographic projections and geometric-kinematic evaluations in order to reconstruct the relative chronology of these structures. This analysis led to the detection of two deformation phases. The results permitted linking of the hypogeal data with the surface data both at a local and regional scale. At the local scale, fracture data collected in the underground have been compared with previous authors' surface data coming from the quarry area. The two data sets show a very good correspondence, as every underground fracture system matches with one of the surface fracture system. Moreover, in the cave, a larger number of fractures belonging to each system could be mapped. At the regional scale, the two deformation phases detected can be integrated in the structural setting of the study area, thereby enhancing the tectonic interpretation of the area ( e.g., structures belonging to a new deformation phase, not reported before, have been identified underground). The structural detailed hypogeal survey has, thus, provided very useful data, both by integrating the existing information and revealing new data not detected at the surface. In particular, some small structures ( e.g., displacement markers and short fractures) are better preserved in the hypogeal environment than on the surface where the outcropping gypsum is more exposed to dissolution and recrystallization. The hypogeal geological survey, therefore, can be considered a powerful tool for integrating the surface and log data in order to enhance the reconstruction of the deformational history and to get a three-dimensional model of the bedrock in karst areas.

Gypsum effects on crop yield and chemistry of soil, crop tissue, and vadose zone water: A meta-analysis.

USDA-ARS?s Scientific Manuscript database

Gypsum has various potential benefits as a soil amendment, but data are lacking on gypsum effects on crop yields and on environmental impacts across diverse field sites. Gypsum studies were conducted in six states using a common design with three rates each of mined and flue gas desulfurization (FGD...

Mechanical properties of gypsum board at elevated temperatures

Treesearch

S.M. Cramer; O.M. Friday; R.H. White; G. Sriprutkiat

2003-01-01

Gypsum board is a common fire barrier used in house and general building construction. Recently, evaluation of the collapses of the World Trade Center Towers highlighted the potential role and failure of gypsum board in containing the fires and resisting damage. The use of gypsum board as primary fire protection of light-flame wood or steel construction is ubiquitous....

Integrated Research Methods for Applied Urban Hydrogeology of Karst Sites

NASA Astrophysics Data System (ADS)

Epting, J.; Romanov, D. K.; Kaufmann, G.; Huggenberger, P.

2008-12-01

Integrated and adaptive surface- and groundwater monitoring and management in urban areas require innovative process-oriented approaches. To accomplish this, it is necessary to develop and combine interdisciplinary instruments that facilitate adequately quantifying cumulative effects on groundwater flow regimes. While the characterization and modeling of flow in heterogeneous and fractured media has been investigated intensively, there are no well-developed long-term hydrogeological research sites for gypsum karst. Considering that infrastructures in karst regions, particularly in gypsum, are prone to subsidence, severe problems can arise in urban areas. In the 1880's, a river dam was constructed on gypsum-containing rock, Southeast of Basel, Switzerland. Over the last 30 years, subsidence of the dam and an adjacent highway has been observed. Surface water infiltrates upstream of the dam, circulates in the gravel deposits and in the weathered bedrock around and beneath the dam and exfiltrates downstream into the river. These processes enhance karstification processes in the soluble units of the gypsum. As a result an extended weathering zone within the bedrock and the development of preferential flow paths within voids and conduits can be observed. To prevent further subsidence, construction measures were conducted in two major project phases in 2006 and 2007. The highway was supported by a large number of pillars embedded in the non- weathered rock and by a sealing pile wall, to prevent infiltrating river water circulating around the dam and beneath the foundation of the highway. To safeguard surface and subsurface water resources during the construction measures, an extensive observation network was set up. Protection schemes and geotechnical investigations that are necessary for engineering projects often provide "windows of opportunity", bearing the possibility to change perceptions concerning the sustainable development of water resources and coordinate future measures. Theories describing the evolution of karst systems are mainly based on conceptual models. Although these models are based on fundamental and well established physical and chemical principles that allow studying important processes from initial small scale fracture networks to the mature karst, systems for monitoring the evolution of karst phenomena are rare. Integrated process-oriented investigation methods are presented, comprising the combination of multiple data sources (lithostratigraphic information of boreholes, extensive groundwater monitoring, dye tracer tests, geophysics) with high-resolution numerical groundwater modeling and model simulations of karstification below the dam. Subsequently, different scenarios evaluated the future development of the groundwater flow regime, the karstification processes as well as possible remediation measures. The approach presented assists in optimizing investigation methods, including measurement and monitoring technologies with predictive character for similar subsidence problems within karst environments in urban areas.

Contaminants from Cretaceous Black Shale Part 1: Natural weathering processes controlling contaminant cycling in Mancos Shale, southwestern United States, with emphasis on salinity and selenium

USGS Publications Warehouse

Tuttle, Michele L.W.; Fahy, Juli W.; Elliott, John G.; Grauch, Richard I.; Stillings, Lisa L.

2013-01-01

Soils derived from black shale can accumulate high concentrations of elements of environmental concern, especially in regions with semiarid to arid climates. One such region is the Colorado River basin in the southwestern United States where contaminants pose a threat to agriculture, municipal water supplies, endangered aquatic species, and water-quality commitments to Mexico. Exposures of Cretaceous Mancos Shale (MS) in the upper basin are a major contributor of salinity and selenium in the Colorado River. Here, we examine the roles of geology, climate, and alluviation on contaminant cycling (emphasis on salinity and Se) during weathering of MS in a Colorado River tributary watershed. Stage I (incipient weathering) began perhaps as long ago as 20 ka when lowering of groundwater resulted in oxidation of pyrite and organic matter. This process formed gypsum and soluble organic matter that persist in the unsaturated, weathered shale today. Enrichment of Se observed in laterally persistent ferric oxide layers likely is due to selenite adsorption onto the oxides that formed during fluctuating redox conditions at the water table. Stage II weathering (pedogenesis) is marked by a significant decrease in bulk density and increase in porosity as shale disaggregates to soil. Rainfall dissolves calcite and thenardite (Na2SO4) at the surface, infiltrates to about 1 m, and precipitates gypsum during evaporation. Gypsum formation (estimated 390 kg m−2) enriches soil moisture in Na and residual SO4. Transpiration of this moisture to the surface or exposure of subsurface soil (slumping) produces more thenardite. Most Se remains in the soil as selenite adsorbed to ferric oxides, however, some oxidizes to selenate and, during wetter conditions is transported with soil moisture to depths below 3 m. Coupled with little rainfall, relatively insoluble gypsum, and the translocation of soluble Se downward, MS landscapes will be a significant nonpoint source of salinity and Se to the Colorado River well into the future. Other trace elements weathering from MS that are often of environmental concern include U and Mo, which mimic Se in their behavior; As, Co, Cr, Cu, Ni, and Pb, which show little redistribution; and Cd, Sb, V, and Zn, which accumulate in Stage I shale, but are lost to varying degrees from upper soil intervals. None of these trace elements have been reported previously as contaminants in the study area.

Imaging near-subsurface subrosion structures and faults using SH-wave reflection seismics

NASA Astrophysics Data System (ADS)

Wadas, Sonja; Polom, Ulrich; Buness, Hermann; Krawczyk, Charlotte

2016-04-01

Subrosion is a term for underground leaching of soluble rocks and is a global phenomenon. It involves dissolution of evaporites due to the presence of unsaturated water, fractures and faults. Fractures and faults are pathways for water to circulate and to generate subsurface cavities. Depending on the leached material and the parameters of the generation process, especially the dissolution rate, different kinds of subrosion structures evolve in the subsurface. The two end members are collapse and depression structures. Subrosion is a natural process, but it can be enhanced by anthropogenic factors like manipulation of the aquifer system and groundwater flow and by e.g. extraction of saline water. The formation of sinkholes and depressions are a dangerous geohazard, especially if they occur in urban areas, which often leads to building and infrastructural damage and life-threatening situations. For this reason investigations of the processes that induce subrosion and a detailed analysis of the resulting structures are of importance. To develop a comprehensive model of near-subsurface subrosion structures, reflection seismics is one of the methods used by the Leibniz Institute for Applied Geophysics. The study area is located in the city of Bad Frankenhausen in northern Thuringia, Germany. Most of the geological underground of Thuringia is characterized by Permian deposits. Bad Frankenhausen is situated directly south of the Kyffhäuser mountain range at the Kyffhäuser Southern Margin Fault. This major fault is one of the main pathways for the circulating ground- and meteoric waters that leach the Permian deposits, especially the Leine-, Staßfurt- and Werra Formations. 2014 and 2015 eight shear wave reflection seismic profiles were carried out in the urban area of Bad Frankenhausen and three profiles in the countrified surroundings. Altogether ca. 3.6 km were surveyed using a landstreamer as receiver and an electro-dynamic vibrator as source. The surveys were adjusted in able to measure in the medieval center of Bad Frankenhausen. This required special equipment and configuration due to the densely built-up area, the differing ground conditions and the varying topography. The analysis of the seismic sections revealed structures associated with the continuing subrosion of the Permian deposits. The reflection patterns indicate heterogeneous near-surface geology of lateral and vertical variations in forms of discontinuous reflectors, small-scale fractures and faults. The fractures and faults also serve as additional pathways for the circulating water and the deposits are subsiding along these features, resulting in the formation of depression structures in the near-subsurface. Diffractions in the unmigrated sections indicate voids in the subsurface that develop due to the longtime subrosion processes. Besides these structures, variations of the traveltime, absorption and scattering of the seismic waves induced by the subrosion processes are visible.

Modeling NAPL dissolution from pendular rings in idealized porous media

NASA Astrophysics Data System (ADS)

Huang, Junqi; Christ, John A.; Goltz, Mark N.; Demond, Avery H.

2015-10-01

The dissolution rate of nonaqueous phase liquid (NAPL) often governs the remediation time frame at subsurface hazardous waste sites. Most formulations for estimating this rate are empirical and assume that the NAPL is the nonwetting fluid. However, field evidence suggests that some waste sites might be organic wet. Thus, formulations that assume the NAPL is nonwetting may be inappropriate for estimating the rates of NAPL dissolution. An exact solution to the Young-Laplace equation, assuming NAPL resides as pendular rings around the contact points of porous media idealized as spherical particles in a hexagonal close packing arrangement, is presented in this work to provide a theoretical prediction for NAPL-water interfacial area. This analytic expression for interfacial area is then coupled with an exact solution to the advection-diffusion equation in a capillary tube assuming Hagen-Poiseuille flow to provide a theoretical means of calculating the mass transfer rate coefficient for dissolution at the NAPL-water interface in an organic-wet system. A comparison of the predictions from this theoretical model with predictions from empirically derived formulations from the literature for water-wet systems showed a consistent range of values for the mass transfer rate coefficient, despite the significant differences in model foundations (water wetting versus NAPL wetting, theoretical versus empirical). This finding implies that, under these system conditions, the important parameter is interfacial area, with a lesser role played by NAPL configuration.

Drivers of Water Column Calcium Carbonate Fluxes and Dissolution in the Gulf of Maine: Impacts on the Carbon Cycle

NASA Astrophysics Data System (ADS)

Pilskaln, C. H.; Wang, A. Z.; Lawson, G. L.; Hayashi, K.; Salisbury, J.

2016-02-01

Recent studies indicate that the U.S. Northeast coastal region, particularly the Gulf of Maine (GoME), may be more susceptible to ocean acidification (OA) than previously thought due to the low buffer capacity, low pH, and low calcium carbonate saturation measured in the region. In particular, sub-surface waters of the GoME already experience under-saturation with respect to aragonite in spring and summer and recent data suggest that water-column aragonite dissolution may occur throughout the year, even when aragonite is slightly over-saturated. This dissolution process appears associated with organic carbon remineralization in the extensive benthic nepheloid layers and may thus represent a major control over the calcium carbonate (CaCO3) budget of deep, near-bottom waters of the GoME. These findings are surprising for shallow, non-upwelling shelf systems and have important implications for the CaCO3 cycle, shell-building organisms, and the GoME planktonic ecosystem. Additionally, freshening of the GoME over the past several decades due to an increase in low-salinity water input originating in the Labrador Sea may further decrease seawater pH and aragonite saturation in the gulf. We present a variety of biogeochemical data that suggest linkages between potential water column CaCO3 dissolution and their impacts on the GoME carbon cycle.

Frontiers of Karst Research: Proceedings and recommendations of the workshop held in San Antonio, Texas on 3-5 May 2007. Karst Waters Institute Special Publication 13

DTIC Science & Technology

2009-01-08

a rich and abundant food source provided by chemolithoautotrophy may reduce nutritional stress to subsurface fauna because members of the...sulfide oxidation on coastal limestone dissolution in Yucatan cenotes: Ground Water, v. 31, p. 566-575. Symk, B., and Drzal, M., 1964, Research on...the nutritional status and availability (i.e. quality and quantity of carbon substrates) and the energetic base of cave ecosystems. The base of

Hydrogeological study of the aquifer system of the northern Sahara in the Algero-Tunisian border: A case study of Oued Souf region

NASA Astrophysics Data System (ADS)

Halassa, Younes; Zeddouri, Aziez; Mouhamadou, Ould Babasy; Kechiched, Rabah; Benhamida, Abdeldjebbar Slimane

2018-05-01

The aquifer system in The Algero-Tunisian border and Chotts region is mainly composed of two aquifers: The first is the Complex Terminal (CT) and the second is the Intercalary aquifer (CI). This study aims the identification and spatial evolution of factors that controlling the water quality in the Complex Terminal aquifer (CT) in the Chotts region (Oued Souf region - Southeastern of Algeria). The concentration of major elements, temperature, pH and salinity were monitored during 2015 in 34 wells from the CT aquifer. The geological, geophysical, hydrogeological and hydrochemical methods were applied in order to carried out a model for the investigated aquifer system and to characterize the hydrogeological and the geochemical behavior, as well as the geometrical and the lithological configuration. Multivariate statistical analyses such as Principal Component Analysis (PCA) were also used for the treatment of several data. Results show that the salinity follows the same regional distribution of Chloride, Sodium, Magnesium, Sulfate and Calcium. Note that the salinity shows low contents in the upstream part of investigated region suggesting restricted dissolution of salts. Hydro-chemical study and saturation indexes highlight the dominance of the dissolution and the precipitation of calcite, dolomite, anhydrite, gypsum and halite. The PCA analysis indicates that Na+, Cl-, Ca2+, Mg2+, SO42- and K+ variables that influence the water mineralization.

Influence of Flue Gas Desulfurization Gypsum Amendments on Heavy Metal Distribution in Reclaimed Sodic Soils

PubMed Central

Chen, Qun; Wang, Shujuan; Li, Yan; Zhang, Ning; Zhao, Bo; Zhuo, Yuqun; Chen, Changhe

2015-01-01

Abstract Although flue gas desulfurization (FGD) gypsum has become an effective soil amendment for sodic soil reclamation, it carries extra heavy metal contamination into the soil environment. The fate of heavy metals introduced by FGD gypsum in sodic or saline–alkali soils is still unclear. This work aims to investigate the effects of FGD gypsum addition on the heavy metal distributions in a sodic soil. Original soil samples were collected from typical sodic land in north China. Soil column leaching tests were conducted to investigate the influence of FGD gypsum addition on the soil properties, especially on distribution profiles of the heavy metals (Pb, Cd, Cr, As, and Hg) in the soil layers. Results showed that pH, electrical conductivity, and exchangeable sodium percentage in amended soils were significantly reduced from 10.2 to 8.46, 1.8 to 0.2 dS/m, and 18.14% to 1.28%, respectively. As and Hg concentrations in the soils were found to be positively correlated with FGD gypsum added. The amount of Hg in the leachate was positively correlated with FGD gypsum application ratio, whereas a negative correlation was observed between the Pb concentration in the leachate and the FGD gypsum ratio. Results revealed that heavy metal concentrations in soils complied well with Environmental Quality Standard for Soils in China (GB15618-1995). This work helps to understand the fate of FGD gypsum-introduced heavy metals in sodic soils and provides a baseline for further environmental risk assessment associated with applying FGD gypsum for sodic soil remediation. PMID:26064038

Alfalfa Responses to Gypsum Application Measured Using Undisturbed Soil Columns

PubMed Central

Tirado-Corbalá, Rebecca; Slater, Brian K.; Dick, Warren A.; Barker, Dave

2017-01-01

Gypsum is an excellent source of Ca and S, both of which are required for crop growth. Large amounts of by-product gypsum [Flue gas desulfurization gypsum-(FGDG)] are produced from coal combustion in the United States, but only 4% is used for agricultural purposes. The objective of this study was to evaluate the effects of (1) untreated, (2) short-term (4-year annual applications of gypsum totaling 6720 kg ha−1), and (3) long-term (12-year annual applications of gypsum totaling 20,200 kg ha−1) on alfalfa (Medicago sativa L.) growth and nutrient uptake, and gypsum movement through soil. The study was conducted in a greenhouse using undisturbed soil columns of two non-sodic soils (Celina silt loam and Brookston loam). Aboveground growth of alfalfa was not affected by gypsum treatments when compared with untreated (p > 0.05). Total root biomass (0–75 cm) for both soils series was significantly increased by gypsum application (p = 0.04), however, increased root growth was restricted to 0–10 cm depth. Soil and plant analyses indicated no unfavorable environmental impact from of the 4-year and 12-year annual application of FGDG. We concluded that under sufficient water supply, by-product gypsum is a viable source of Ca and S for land application that might benefit alfalfa root growth, but has less effect on aboveground alfalfa biomass production. Undisturbed soil columns were a useful adaptation of the lysimeter method that allowed detailed measurements of alfalfa nutrient uptake, root biomass, and yield and nutrient movement in soil. PMID:28696383

Influence of Flue Gas Desulfurization Gypsum Amendments on Heavy Metal Distribution in Reclaimed Sodic Soils.

PubMed

Chen, Qun; Wang, Shujuan; Li, Yan; Zhang, Ning; Zhao, Bo; Zhuo, Yuqun; Chen, Changhe

2015-06-01

Although flue gas desulfurization (FGD) gypsum has become an effective soil amendment for sodic soil reclamation, it carries extra heavy metal contamination into the soil environment. The fate of heavy metals introduced by FGD gypsum in sodic or saline-alkali soils is still unclear. This work aims to investigate the effects of FGD gypsum addition on the heavy metal distributions in a sodic soil. Original soil samples were collected from typical sodic land in north China. Soil column leaching tests were conducted to investigate the influence of FGD gypsum addition on the soil properties, especially on distribution profiles of the heavy metals (Pb, Cd, Cr, As, and Hg) in the soil layers. Results showed that pH, electrical conductivity, and exchangeable sodium percentage in amended soils were significantly reduced from 10.2 to 8.46, 1.8 to 0.2 dS/m, and 18.14% to 1.28%, respectively. As and Hg concentrations in the soils were found to be positively correlated with FGD gypsum added. The amount of Hg in the leachate was positively correlated with FGD gypsum application ratio, whereas a negative correlation was observed between the Pb concentration in the leachate and the FGD gypsum ratio. Results revealed that heavy metal concentrations in soils complied well with Environmental Quality Standard for Soils in China (GB15618-1995). This work helps to understand the fate of FGD gypsum-introduced heavy metals in sodic soils and provides a baseline for further environmental risk assessment associated with applying FGD gypsum for sodic soil remediation.

The Contributions Regarding the Use of Microwave to Obtain Modeling Gypsum for Phonic-Absorbent Construction and Orthopedic Materials

NASA Astrophysics Data System (ADS)

Pop, P. A.; Ungur, P. A.; Caraban, A.; Marcu, F.

2009-11-01

The paper has presented some experiments realized at "Congips" Co. Oradea and University of Oradea, regarding of increase machining efficiency and quality for modeling gypsum plaster by using of microwave energy to gypsum ore roast. The elaboration process of microwave energy for modeling gypsum plaster has done on electromagnetic waves properties and specific properties for dielectric materials. Microwaves are radiations of electromagnetic waveform nature, determine by pulsations of electrical-E) and magnetically-H components of electromagnetic wave in interdependence with Maxwell equations. The gypsum ore is calcium sulphate dehydrate (CaSO4ṡ2H2O) using at modeling gypsum plaster fabrication, which is calcium sulphate hemihydrate (CaSO4ṡ1/2H2O), that has behavior of dielectric with losses. The gypsum ore getting in microwave field, in conditions of predictable pressure and temperature has transformed in modeling gypsum plaster, by quick lost of a part from crystallization water. The processing time is very short, which due to a great productivity and machining efficiency, finally of low process cost. All of these recommend continuing the research at pilot station level.

Measuring the gypsum content of C&D debris fines.

PubMed

Musson, Stephen E; Xu, Qiyong; Townsend, Timothy G

2008-11-01

Construction and demolition (C&D) debris recycling facilities often produce a screened material intended for use as alternative daily cover (ADC) at active landfills or for shaping and grading at closed landfills. This product contains soil and small pieces of wood, concrete, gypsum drywall, shingles and other components of C&D debris. Concerns have been raised over the contribution of gypsum drywall in C&D debris fines to odor problems at landfills where the product is used. To address such concerns, limitations may be placed on the percentage of gypsum (or sulfate) that can occur, and standardized testing procedures are required to permit valid compliance testing. A test procedure was developed for measuring the gypsum content in C&D debris fines. The concentration of sulfate leached in an aqueous solution was used to estimate the initial gypsum content of the sample. The impact of sample size and leaching time were evaluated. Precision and accuracy increased with increasing gypsum content. Results from replicate samples had an average relative standard deviation of 9%. The gypsum content of fines obtained from different facilities in the US varied widely from 1% to over 25%. These variations not only occurred between differing facilities, but within batches produced within a single facility.

Effects of selective handling of pyritic, acid-forming materials on the chemistry of pore gas and ground water at a reclaimed surface coal mine in Clarion County, PA, USA

USGS Publications Warehouse

Cravotta,, Charles A.; Dugas, Diana L.; Brady, Keith; Kovalchuck, Thomas E.

1994-01-01

A change from dragline to “selective handling” mining methods at a reclaimed surface coal mine in western Pennsylvania did not significantly affect concentrations of metals in ground water because oxidation of pyrite and dissolution of siderite were not abated. Throughout the mine, placement of pyritic material near the land surface facilitated the oxidation of pyrite, causing the consumption of oxygen (O2) and release of acid, iron, and sulfate ions. Locally in the unsaturated zone, water sampled within or near pyritic zones was acidic, with concentrations of sulfate exceeding 3,000 milligrams per liter (mg/L). However, acidic conditions generally did not persist below the water table because of neutralization by carbonate minerals. Dissolution of calcite, dolomite, and siderite in unsaturated and saturated zones produced elevated concentrations of carbon dioxide (CO2), alkalinity, calcium, magnesium, iron, and manganese. Alkalinity concentrations of 600 to 800 mg/L as CaCO3 were common in water samples from the unsaturated zone in spoil, and alkalinities of 100 to 400 mg/L as CaCO3 were common in ground-water samples from the underlying saturated zone in spoil and bedrock. Saturation indices indicated that siderite could dissolve in water throughout the spoil, but that calcite dissolution or precipitation could occur locally. Calcite dissolution could be promoted as a result of pyrite oxidation, gypsum precipitation, and calcium ion exchange for sodium. Calcite precipitation could be promoted by evapotranspiration and siderite dissolution, and corresponding increases in concentrations of alkalinity and other solutes. Partial pressures of O2 (Po2) and CO2 (Pco2) in spoil pore gas indicated that oxidation of pyrite and precipitation of ferric hydroxide, coupled with dissolution of calcite, dolomite, and siderite were the primary reactions affecting water quality. Highest vertical gradients in Po2, particularly in the near-surface zone (0-1 m), did not correlate with concentrations of total sulfur in spoil. This lack of correlation could indicate that total sulfur concentrations in spoil do not reflect the amount of reactive pyrite or that oxidation rates can be controlled more by rates of O2 diffusion than the amount of pyrite. Hence, if placed in O2-rich zones near the land surface, even small amounts of disseminated pyritic material can be relatively significant sources of acid and mineralized water.

An Investigation of Mineral Dynamics in Sea Ice by Solubility Measurements

NASA Astrophysics Data System (ADS)

Butler, B.; Kennedy, H.; Papadimitriou, S.

2016-02-01

Sea ice is a composite material with a sponge-like structure. The framework of the structure is composed of pure ice, and within the pores exists a concentrated seawater brine. When the temperature is reduced, the volume of this residual brine decreases, while its salinity increases. As a result of the paired changes to temperature and salinity, the brine becomes supersaturated with respect to a mineral at several points when cooling sea ice towards -30°C, creating a sequence of minerals that precipitate. The presence of countless microscopic salt crystals encapsulated within the ice, coupled with changes in brine volume associated with their precipitation/dissolution, results in changes to the optical and structural properties of the medium that contribute to the surface energy balance in sea ice environments. Furthermore, attainment of mineral equilibrium can result in abrupt changes in brine composition and osmotic conditions in the isolated brine pockets, imposing challenging conditions upon the biota that habitat the sea ice environment. Mirabilite (Na2SO4.10H2O), gypsum (CaSO4.2H2O) and hydrohalite (NaCl.2H2O) each represent minerals that are understood to exist within sea ice. Previous research has focused upon mineral extraction/detection, and the specific temperature for the onset of each minerals precipitation in sea ice; rather than the overarching dynamics. For this reason, solubility measurements of mirabilite, gypsum and hydrohalite in conditions representative of equilibrium sea ice brines were carried between 0 and -28°C, covering a range of undersaturated and supersaturated conditions for each mineral. Results provide accurate data for the onset of each minerals formation in sea ice, as well as important information on the way in which precipitation and dissolution reactions are affected when sea ice warms or cools. By incorporating the solubility data into a model that simluates the temperature-salinity profiles of first-year sea ice, the spatial and temporal distrubtion of each mineral throughout periods of ice growth and melt have been estimated for the first time. This information highlights the ubiquitous presence of minerals in the sea ice system, which have remained relatively elusive due to the nature of the complex structure and extreme environment that they exist in.

Fate of Mercury in Synthetic Gypsum Used for Wallboard Production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jessica Marshall Sanderson

2006-06-01

This report presents and discusses results from Task 5 of the study ''Fate of Mercury in Synthetic Gypsum Used for Wallboard Production,'' performed at a full-scale commercial wallboard plant. Synthetic gypsum produced by wet flue gas desulfurization (FGD) systems on coal-fired power plants is commonly used in the manufacture of wallboard. The FGD process is used to control the sulfur dioxide emissions which would result in acid rain if not controlled. This practice has long benefited the environment by recycling the FGD gypsum byproduct, which is becoming available in increasing quantities, decreasing the need to landfill this material, and increasingmore » the sustainable design of the wallboard product. However, new concerns have arisen as recent mercury control strategies developed for power plants involve the capture of mercury in FGD systems. The objective of this study is to determine whether any mercury is released into the atmosphere when the synthetic gypsum material is used as a feedstock for wallboard production. The project is being co-funded by the U.S. DOE National Energy Technology Laboratory (Cooperative Agreement DE-FC26-04NT42080), USG Corporation, and EPRI. USG Corporation is the prime contractor, and URS Group is a subcontractor. The project scope includes five discrete tasks, each conducted at various USG wallboard plants using synthetic gypsum from different FGD systems. The five tasks were to include (1) a baseline test, then variations representing differing power plant (2) emissions control configurations, (3) treatment of fine gypsum particles, (4) coal types, and (5) FGD reagent types. However, Task 5, which was to evaluate gypsum produced from an alternate FGD reagent, could not be conducted as planned. Instead, Task 5 was conducted at conditions similar to a previous task, Task 3, although with gypsum from an alternate FGD system. In this project, process stacks in the wallboard plant have been sampled using the Ontario Hydro method. The stack locations sampled for each task include a dryer for the wet gypsum as it enters the plant and a gypsum calciner. The stack of the dryer for the wet wallboard product was also tested as part of this task, and was tested as part of Tasks 1 and 4. Also at each site, in-stream process samples were collected and analyzed for mercury concentration before and after each significant step in wallboard production. The Ontario Hydro results, process sample mercury concentration data, and process data were used to construct mercury mass balances across the wallboard plants. Task 5 was conducted at a wallboard plant processing synthetic gypsum from a power plant that fires Eastern bituminous coal. The power plant is equipped with a selective catalytic reduction (SCR) system for NOX emissions control, but the SCR was bypassed during the time period the gypsum tested was produced. The power plant has a single-loop, open spray tower, limestone reagent FGD system, with forced oxidation conducted in a reaction tank integral with the FGD absorber. The FGD system has gypsum fines blow down as part of the dewatering step. Gypsum fines blow down is believed to be an important variable that impacts the amount of mercury in the gypsum byproduct and possibly its stability during the wallboard process. The results of the Task 5 stack testing, as measured by the Ontario Hydro method, detected that an average of 51% of the incoming mercury in the FGD gypsum was emitted during wallboard production. These losses were distributed as 2% or less each across the wet gypsum dryer and product wallboard dryer, and about 50% across the gypsum calciner. Emissions were similar to what Task 3 results showed, on both a percentage and a mass basis, for gypsum produced by a power plant firing bituminous coal and also having gypsum fines blow down as part of the FGD dewatering scheme. As was seen in the Task 1 through 4 results, most of the mercury detected in the stack testing on the wet gypsum dryer and kettle calciner was in the form of elemental mercury. In the wallboard dryer kiln, a more significant percentage of the mercury detected was in the oxidized form, particularly from the stack near the product discharge end of the kiln. However, this represented a very small percentage of the overall mercury loss.« less

The origin of brines and salts in Chilean salars: a hydrochemical review

NASA Astrophysics Data System (ADS)

Risacher, François; Alonso, Hugo; Salazar, Carlos

2003-11-01

Northern Chile is characterized by a succession of north-south-trending ranges and basins occupied by numerous saline lakes and salt crusts, collectively called salars. Fossil salt crusts are found to the west in the extremely arid Central Valley, while active salars receiving permanent inflows fill many intravolcanic basins to the east in the semiarid Cordillera. Sea salts and desert dust are blown eastward over the Cordillera, where they constitute an appreciable fraction of the solute load of very dilute waters (salt content<0.1 g/l). The weathering of volcanic rocks contributes most components to inflow waters with salt content ranging from 0.1 to 0.6 g/l. However, the average salt content of all inflows is much higher: about 3.2 g/l. Chemical composition, Cl/Br ratio, and 18O- 2H isotope contents point to the mixing of very dilute meteoric waters with present lake brines for the origin of saline inflows. Ancient gypsum in deep sedimentary formations seems to be the only evaporitic mineral recycled in present salars. Saline lakes and subsurface brines are under steady-state regime. The average residence time of conservative components ranges from a few years to some thousands years, which indicates a permanent leakage of the brines through bottom sediments. The infiltrating brines are recycled in the hydrologic system where they mix with dilute meteoric waters. High heat flow is the likely driving force that moves the deep waters in this magmatic arc region. Active Chilean salars cannot be considered as terminal lakes nor, strictly speaking, as closed basin lakes. Almost all incoming salts leave the basin and are transported elsewhere. Moreover, the dissolution of fossil salt crusts in some active salars also carries away important fluxes of components in percolating brines. Evaporative concentration of inflow waters leads to sulfate-rich or calcium-rich, near-neutral brines. Alkaline brines are almost completely lacking. The alkalinity/calcium ratio of inflow waters is lowered by the oxidation of native sulfur (reducing alkalinity) and the deposition of eolian gypsum (increasing Ca concentration). Theoretically, SO 4-rich inflow waters and their derived SO 4-rich brines should be found in the intravolcanic basins of the Cordillera because of the ubiquity of native sulfur, while Ca-rich brines should prevail in sedimentary basins where Ca-rich minerals are abundant. This relation is perfectly observed in the salar de Atacama, the largest in Chile. However, several salars located within the volcanic Cordillera belong to the Ca-rich group. Inflows and brines may have acquired their Ca-rich composition in Pleistocene time when their drainage basins were mainly sedimentary. Later on, recent lava flows and ignimbrites covered the sedimentary formations. Underground waters may have kept their early sedimentary signature by continuous recycling. However, the weathering of volcanic rocks tend to slowly shift the water compositions from the Ca-rich to the SO 4-rich type.

Gypsum under pressure: A first-principles study

NASA Astrophysics Data System (ADS)

Giacomazzi, Luigi; Scandolo, Sandro

2010-02-01

We investigate by means of first-principles methods the structural response of gypsum (CaSO4ṡ2H2O) to pressures within and above the stability range of gypsum-I (P≤4GPa) . Structural and vibrational properties calculated for gypsum-I are in excellent agreement with experimental data. Compression within gypsum-I takes place predominantly through a reduction in the volume of the CaO8 polyhedra and through a distortion of the hydrogen bonds. The distance between CaSO4 layers becomes increasingly incompressible, indicating a mechanical limit to the packing of water molecules between the layers. We find that a structure with collapsed interlayer distances becomes more stable than gypsum-I above about 5 GPa. The collapse is concomitant with a rearrangement of the hydrogen-bond network of the water molecules. Comparison of the vibrational spectra calculated for this structure with experimental data taken above 5 GPa supports the validity of our model for the high-pressure phase of gypsum.

Effect of gypsum application on enzymatic browning activity in lettuce.

PubMed

Chutichudet, Prasit; Chutichudet, B; Kaewsit, S

2009-09-15

A comprehensive study to evaluate calcium, in terms of gypsum (CaSO4.2H2O) by soil dressing application, on enzymatic browning activity of Polyphenol oxidase (PPO) and internal qualities was tested on lettuce var. Grand Rapids under field conditions. A factorial in completely randomized design was arranged with four replications. The results showed that plants-treated with 50 mg kg(-1) gypsum applied at 40 DAP had the maximal fresh weight of 25.83 g plant(-1). The internal qualities of the lettuce at harvest showed that plants treated with 50 mg kg(-1) gypsum had the maximal chlorophyll content (26.80 mg m(-2)), while all gypsum concentrations applied in this study, had less content of ascorbic acid than the control plants. Plants-treated with 100 mg kg(-1) gypsum affected to the lowest level of PPO activity at week 3 after transplanting. Furthermore, gypsum application had no effect to biomass, leaf colour, the contents of phenolic and quinone in lettuce at harvesting stage.

Primary Evaporites for the Messinian Salinity Crisis: the shallow gypsum vs. deep dolomite formation paradox solved

NASA Astrophysics Data System (ADS)

De Lange, Gert J.; Krijgsman, Wout

2014-05-01

The Messinian Salinity Crisis (MSC) is a dramatic event that took place ~ 5.9 Ma ago, and resulted in the deposition of 0.3-3 km thick evaporites at the Mediterranean seafloor. A considerable and long-lasting controversy existed on the modes of their formation. During the CIESM Almeria Workshop a consensus was reached on several aspects. In addition, remaining issues to be solved were identified, such as for the observed shallow gypsum versus deep dolostone deposits for the early phase of MSC. The onset of MSC is marked by deposition of gypsum/sapropel-like alternations, thought to relate to arid/humid climate conditions. Gypsum precipitation only occurred at marginal settings, while dolomite containing rocks have been reported from deeper settings. A range of potential explanations have been reported, most of which cannot satisfactorily explain all observations. Biogeochemical processes during MSC are poorly understood and commonly neglected. These may, however, explain that different deposits formed in shallow versus deep environments without needing exceptional physical boundary conditions for each. We present here a unifying mechanism in which gypsum formation occurs at all shallow water depths but its preservation is mostly limited to shallow sedimentary settings. In contrast, ongoing anoxic organic matter (OM) degradation processes in the deep basin result in the formation of dolomite. Gypsum precipitation in evaporating seawater takes place at 3-7 times concentrated seawater; seawater is always largely oversaturated relative to dolomite but its formation is thought to be inhibited by the presence of dissolved sulphate. Thus the conditions for formation of gypsum exclude those for the formation of dolomite and vice versa. Another process that links the saturation states of gypsum and dolomite is that of OM degradation by sulphate reduction. In stagnant deep water, oxygen is rapidly depleted through OM degradation, then sulphate becomes the main oxidant for OM mineralization, thus reducing the deep-water sulphate content. In addition, considerable amounts of dissolved carbonate are formed. This means that low-sulphate conditions as for MSC deepwater, i.e. unfavorable conditions for gypsum formation, always coincide with anoxic, i.e. oxygen-free conditions. Thus one would expect a bath-tub rim of gypsum at all shallow depths, but gypsum appears mainly at silled marginal basins. However, a thick package of heavy gypsum on top of more liquid mud in a marginal/slope setting is highly unstable, thus any physical disturbance such as tectonic activity or sea-level change, would easily lead to downslope transport of such marginal gypsum deposits. The absence of gypsum and the presence of erosional unconformities at the sill-less Mediterranean passive margins concord to such removal mechanism. In addition, large-scale re-sedimentation of gypsum has also been found for deep Messinian settings in the Northern Apennines and Sicily. Only at those marginal settings that were silled, the marginal gypsum deposits have been preserved. Including the dynamic biogeochemical processes in the thusfar static interpretations of evaporite formation mechanisms can thus account for the paradoxal, isochronous formation of shallow gypsum and deep-dolomite during the early MSC (1). (1) De Lange G.J. and Krijgsman W. (2010) Mar. Geol. 275, 273-277.

The calcium isotope evolution of Lake Lisan, the Dead Sea glacial precursor

NASA Astrophysics Data System (ADS)

Bradbury, H. J.; Turchyn, A. V.; Wong, K.; Torfstein, A.

2016-12-01

Calcium is a stoichiometric component of carbonate minerals whose calcium isotopic composition reflects changes in the calcium isotope composition of the water from which it precipitates as well as the calcium isotope fractionation factor during precipitation. The lacustrine deposits of the last glacial Dead Sea (Lisan Formation) are dominated by carbonate minerals (aragonite) that record the geochemical history of the lake. The sediment sequence comprises alternating laminae of aragonite and clay-rich marls, interspersed with primary gypsum beds and disseminated secondary gypsum crystals. The aragonite precipitated annually during high lake stands associated with wet periods, while the primary gypsum precipitated during low lake conditions (arid periods). We report the calcium isotopic composition (δ44Ca in ‰ relative to bulk silicate earth) of primary aragonite laminae, primary gypsum and secondary gypsum at 1-5kyr resolution throughout the Lisan Formation sampled at the Masada section (70 - 14.5 ka). The δ44Ca of the primary gypsum averages +0.29‰, and displays smaller temporal variations than the aragonite, which averages -0.35‰ but ranges between +0.18‰ and -0.68‰. The aragonite δ44Ca changes temporally in sync with the previously reconstructed lake level suggesting the aragonite δ44Ca reflects changes in the lake calcium balance during lake level changes. The secondary gypsum composition (-0.3‰) corresponds to coeval aragonite samples. For the secondary gypsum to have a similar δ44Ca to the aragonite it is likely that the calcium derived from the aragonite in a near quantitative fashion through recrystallization of the aragonite to gypsum. A numerical box model is used to explore the effect of changing lake water levels on the calcium isotope composition of the aragonite and gypsum over the time interval studied.

Gypsum-karst problems in constructing dams in the USA

USGS Publications Warehouse

Johnson, K.S.

2008-01-01

Gypsum is a highly soluble rock and is dissolved readily to form caves, sinkholes, disappearing streams, and other karst features that typically are also present in limestones and dolomites. Gypsum karst is widespread in the USA and has caused problems at several sites where dams were built, or where dam construction was considered. Gypsum karst is present (at least locally) in most areas where gypsum crops out, or is less than 30-60 m below the land surface. These karst features can compromise on the ability of a dam to hold water in a reservoir, and can even cause collapse of a dam. Gypsum karst in the abutments or foundation of a dam can allow water to pass through, around, or under a dam, and solution channels can enlarge quickly, once water starts flowing through such a karst system. The common procedure for controlling gypsum karst beneath the dam is a deep cut-off trench, backfilled with impermeable material, or a close-spaced grout curtain that hopefully will fill all cavities. In Oklahoma, the proposed Upper Mangum Dam was abandoned before construction, because of extensive gypsum karst in the abutments and impoundment area. Catastrophic failure of the Quail Creek Dike in southwest Utah in 1989 was due to flow of water through an undetected karstified gypsum unit beneath the earth-fill embankment. The dike was rebuilt, at a cost of US $12 million, with construction of a cut-off trench 600 m long and 25 m deep. Other dams in the USA with severe gypsum-karst leakage problems in recent years are Horsetooth and Carter Lake Dams, in Colorado, and Anchor Dam, in Wyoming. ?? 2007 Springer-Verlag.

The early diagenetic and PETROphysical behaviour of recent cold-water CARbonate mounds in Deep Environments (PETROCARDE)

NASA Astrophysics Data System (ADS)

Foubert, Anneleen; Pirlet, Hans; Thierens, Mieke; de Mol, Ben; Henriet, Jean-Pierre; Swennen, Rudy

2010-05-01

Sub-recent cold-water carbonate mounds localized in deeper slope settings on the Atlantic continental margins cannot be any longer neglected in the study of carbonate systems. They clearly play a major role in the dynamics of mixed siliciclastic-carbonate and/or carbonate-dominated continental slopes. Carbonate accumulation rates of cold-water carbonate mounds are about 4 to 12 % of the carbonate accumulation rates of tropical shallow-water reefs but exceed the carbonate accumulation rates of their slope settings by a factor of 4 to 12 (Titschack et al., 2009). These findings emphasize the importance of these carbonate factories as carbonate niches on the continental margins. The primary environmental architecture of such carbonate bodies is well-characterized. However, despite proven evidences of early diagenesis overprinting the primary environmental record (e.g. aragonite dissolution) (Foubert & Henriet, 2009), the extent of early diagenetic and biogeochemical processes shaping the petrophysical nature of mounds is until now not yet fully understood. Understanding (1) the functioning of a carbonate mound as biogeochemical reactor triggering early diagenetic processes and (2) the impact of early diagenesis on the petrophysical behaviour of a carbonate mound in space and through time are necessary (vital) for the reliable prediction of potential late diagenetic processes. Approaching the fossil carbonate mound record, through a profound study of recent carbonate bodies is innovative and will help to better understand processes observed in the fossil mound world (such as cementation, brecciation, fracturing, etc…). In this study, the 155-m high Challenger mound (Porcupine Seabight, SW of Ireland), drilled during IODP Expedition 307 aboard the R/V Joides Resolution (Foubert & Henriet, 2009), and mounds from the Gulf of Cadiz (Moroccan margin) will be discussed in terms of early diagenetic processes and petrophysical behaviour. Early differential diagenesis overprints the primary environmental signals in Challenger mound, with extensive coral dissolution and the genesis of small-scaled semi-lithified layers in the Ca-rich intervals. The low cementation rates compared to the extensive dissolution patterns can be explained by an open-system diagenetic model. Moreover, Pirlet et al. (2009) emphasizes the occurrence of gypsum and dolomite in another mound system (Mound Perseverance) in Porcupine Seabight, which might be also related with fluid oxidation events in a semi-open diagenetic system. Along the Moroccan margins, fluid seepage and fluxes in pore water transport affect the development of mound structures, enhancing extensive cold-water coral dissolution and precipitation of diagenetic minerals such as dolomite, calcite, pyrite, etc. (Foubert et al., 2008). Recent carbonate mounds provide indeed an excellent opportunity to study early diagenetic processes in carbonate systems without the complications of burial and/or later meteoric diagenesis. References Foubert, A. and Henriet, J.P. (2009) Nature and Significance of the Recent Carbonate Mound Record: The Mound Challenger Code. Lecture Notes in Earth Sciences, Vol. 126. Springer, 298 pp. ISBN: 978-3-642-00289-2. Pirlet, H., Wehrmann, L., Brunner, B., Frank, N., Dewanckele, J., Van Rooij, D., Foubert, A., Swennen, R., Naudts, L., Boone, M., Cnudde, V. and Henriet, J.P. (2009) Diagenetic formation of gypsum and dolomite in a cold-water coral mound in the Porcupine Seabight, off Ireland. Sedimentology. doi: 10.1111/j.1365-3091.2009.01119.x. Titschack, J., Thierens, M., Dorschel, B., Schulbert, C., Freiwald, A., Kano, A., Takashima, C., Kawagoe, N., Li, X. and the IODP Expedition 307 Scientific Party (2009) Carbonate budget of a cold-water coral mound (Challenger Mound, IODP Exp. 307). Marine Geology, 259, 36-46.

Pre-contamination of new gypsum wallboard with potentially harmful fungal species.

PubMed

Andersen, B; Dosen, I; Lewinska, A M; Nielsen, K F

2017-01-01

Gypsum wallboard is a popular building material, but is also very frequently overgrown by Stachybotrys chartarum after severe and/or undetected water damage. The purpose of this study was to determine whether Stachybotrys and other fungi frequently isolated from wet gypsum wallboard are already present in the panels directly from the factory. Surface-disinfected gypsum disks were wetted with sterile water, sealed, and incubated for 70 days. The results showed that Neosartorya hiratsukae (≡ Aspergillus hiratsukae) was the most dominant fungus on the gypsum wallboard followed by Chaetomium globosum and Stachybotrys chartarum. Our results suggest that these three fungal species are already embedded in the materials, presumably in the paper/carton layer surrounding the gypsum core, before the panels reach the retailers/building site. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Building on previous OSL dating techniques for gypsum: a case study from Salt Basin playa, New Mexico and Texas

USGS Publications Warehouse

Mahan, Shannon; Kay, John

2012-01-01

The long term stability and reliability of the luminescence signal for gypsum has not been well documented or systematically measured until just recently. A review of the current literature for luminescence dating of gypsum is compiled here along with original efforts at dating an intact and in-situ bed of selenite gypsum at Salt Basin Playa, New Mexico and Texas. This effort differs from other documented luminescence dating efforts because the gypsum is not powdery or redistributed from its original growth patterns within the playa basin but is instead of a crystalline form. Sixteen ages from eight cores were ultimately produced with seven of the ages coming from rare detrital quartz encased in or with the gypsum crystals while the remaining ages are from the crystalline gypsum. As far as can be ascertained, the quartz was measured separately from the gypsum and no contaminants were noted in any of the aliquots. Some basic and preliminary tests of signal stability were measured and found to be mitigated by lessening of pre-heat protocols. Ages ranged from 8 ka to 10 ka in the shallow cores and 16 ka to 22 ka in the deeper cores. These ages will be useful in determining rates of gypsum growth within a sequence of evaporates which, in turn, will help to better document historic rates of evaporation and thus estimate, with more precision, the corresponding annual evaporation rates.

Establishing a Geologic Baseline Of Cape Canaveral's Natural Landscape: Black Point Drive

NASA Technical Reports Server (NTRS)

Parkinson, Randall W.

2001-01-01

The goal of this project is to identify the process responsible for the formation of geomorphic features in the Black Point Drive area of Merritt Island National Wildlife Refuge/Kennedy Space Center (MINWR/KSC), northwest Cape Canaveral. This study confirms the principal landscape components (geomorphology) of Black Point Drive reflect interaction between surficial sediments deposited in association with late-Quaternary sea-level highstands and the chemical evolution of late-Cenozoic subsurface limestone formations. The Black Point Drive landscape consists of an undulatory mesic terrain which dips westward into myriad circular and channel-like depression marshes and lakes. This geomorphic gradient may reflect: (1) spatial distinctions in the elevation, character or age of buried (pre-Miocene) limestone formations, (2) dissolution history of late-Quaternary coquina and/or (3) thickness of unconsolidated surface sediment. More detailed evaluation of subsurface data will be necessary before this uncertainty can be resolved.

Establishing A Geologic Baseline of Cape Canaveral''s Natural Landscape: Black Point Drive

NASA Technical Reports Server (NTRS)

Parkinson, Randall W.

2002-01-01

The goal of this project is to identify the process responsible for the formation of geomorphic features in the Black Point Drive area of Merritt Island National Wildlife Refuge/Kennedy Space Center (MINWR/KSC), northwest Cape Canaveral. This study confirms the principal landscape components (geomorphology) of Black Point Drive reflect interaction between surficial sediments deposited in association with late-Quaternary sea-level highstands and the chemical evolution of late-Cenozoic sub-surface limestone formations. The Black Point Drive landscape consists of an undulatory mesic terrain which dips westward into myriad circular and channel-like depression marshes and lakes. This geomorphic gradient may reflect: (1) spatial distinctions in the elevation, character or age of buried (pre-Miocene) limestone formations, (2) dissolution history of late-Quaternary coquina and/or (3) thickness of unconsolidated surface sediment. More detailed evaluation of subsurface data will be necessary before this uncertain0 can be resolved.

Multiple sulphur and oxygen isotopes reveal microbial sulphur cycling in spring waters in the Lower Engadin, Switzerland.

PubMed

Strauss, Harald; Chmiel, Hannah; Christ, Andreas; Fugmann, Artur; Hanselmann, Kurt; Kappler, Andreas; Königer, Paul; Lutter, Andreas; Siedenberg, Katharina; Teichert, Barbara M A

2016-01-01

Highly mineralized springs in the Scuol-Tarasp area of the Lower Engadin and in the Albula Valley near Alvaneu, Switzerland, display distinct differences with respect to the source and fate of their dissolved sulphur species. High sulphate concentrations and positive sulphur (δ(34)S) and oxygen (δ(18)O) isotopic compositions argue for the subsurface dissolution of Mesozoic evaporitic sulphate. In contrast, low sulphate concentrations and less positive or even negative δ(34)S and δ(18)O values indicate a substantial contribution of sulphate sulphur from the oxidation of sulphides in the crystalline basement rocks or the Jurassic sedimentary cover rocks. Furthermore, multiple sulphur (δ(34)S, Δ(33)S) isotopes support the identification of microbial sulphate reduction and sulphide oxidation in the subsurface, the latter is also evident through the presence of thick aggregates of sulphide-oxidizing Thiothrix bacteria.

Age and speleogenesis of epigenic gypsum caves in the northern Apennines (Italy)

NASA Astrophysics Data System (ADS)

Columbu, Andrea; Chiarini, Veronica; De Waele, Jo; Drysdale, Russell; Forti, Paolo; Hellstrom, John; Woodhead, Jon

2016-04-01

Triassic and Messinian gypsum beds host the majority of the caves in the eastern flank of the northern Apennines. To date, more than six hundreds voids have been mapped, including the longest known epigenic gypsum cave system in the world (Spipola-Acquafredda, ~11 km of tunnels) (De Waele et al., 2013). Superimposed caves are typically sub-horizontal (Klimchouk, 2000) and connected through vertical shafts, reflecting the palaeo base-level variations. When preserved, river terraces at the surface lie at the same palaeo altitude of the base level and horizontal cave passages. Notwithstanding the well-known geology of the area known (Vai and Martini, 2001), the age of these caves has been greatly underestimated in the past. Considering the rapid dissolution of the gypsum and uplifting of the area, the start of speleogenesis activity was considered to have occurred during the last glacial age. The age of karst voids can be only indirectly estimated by the dating of the infilling sediments. U-Th dating on carbonate speleothems provides high-precision and accurate ages (Hellstrom, 2003; Scholz and Hoffmann, 2008). We thus applied this methodology to 20 speleothems coming from 14 different caves belonging to the Monte Tondo, Spipola Acquafredda, Castelnuovo, Stella-Rio Basino and Brisighella systems. The results show that: i) caves were forming since at least ~300 ka; ii) the peak of speleogenesis was reached during relatively cold climate stages, when rivers formed terraces at the surface and aggradation caused paragenesis in the stable cave levels (Columbu et al., 2015). Besides the significant contribution to the understanding of the Apennines evaporite karst evolution, this study (and its further advancement) may also refine knowledge of the local vs regional uplifting rates and base-level variations since the late Pleistocene (Wegmann and Pazzaglia, 2009). References Columbu, A., De Waele, J., Forti, P., Montagna, P., Picotti, V., Pons-Branchu, E., Hellstrom, J., Bajo, P., and Drysdale, R., 2015, Gypsum caves as indicators of climate-driven river incision and aggradation in a rapidly uplifting region: Geology. De Waele, J., Fabbri, F., Forti, P., Lucci, P., and Marabini, S., 2013, Evoluzione speleogenetica del sistema carsico del re Tiberio (Vena del gesso Romagnola): I gessi e la cava di Monte Tondo. Memorie dell'istituto Italiano di speleologia. Hellstrom, J., 2003, Rapid and accurate U/Th dating using parallel ion-counting multi-collector ICP-MS.: Journal of Analytical Atomic Spectrometry, v. 18. Klimchouk, A. B., 2000, Speleogenesis in noncarbonate lithologies: In: Klimchouk, A.B., Ford, D.C., Palmer, A.N., Dreybrodt, W. (Eds.) Speleogenesis, evolution of karst aquifers, p. 430-442. Scholz, D., and Hoffmann, D., 2008, 230Th/U-dating of fossil corals and speleothems: Quat. Sci. J, v. 57, p. 52. Vai, G. B., and Martini, I. P., 2001, Anatomy of an orogen: The Apennines and adjacent Mediterranean:: Dordrecht, Netherlands, Kluwer Academic Publishers,, p. 631. Wegmann, K. W., and Pazzaglia, F. J., 2009, Late Quaternary fluvial terraces of the Romagna and Marche Apennines, Italy: climatic, lithologic, and tectonic controls on terrace genesis in an active orogen: Quaternary Science Reviews, v. 28, no. 1, p. 137-165.

The microbe-mineral environment and gypsum neogenesis in a weathered polar evaporite.

PubMed

Cockell, C S; Osinski, G R; Banerjee, N R; Howard, K T; Gilmour, I; Watson, J S

2010-09-01

Evaporitic deposits are a globally widespread habitat for micro-organisms. The microbe-mineral environment in weathered and remobilized gypsum from exposed mid-Ordovician marine evaporite beds in the polar desert of Devon Island, Nunavut, Canadian High Arctic was examined. The gypsum is characterized by internal green zones of cyanobacterial colonization (dominated by Gloeocapsa/Aphanothece and Chroococcidiopsis spp. morphotypes) and abundant black zones, visible from the surface, that contain pigmented cyanobacteria and fungi. Bioessential elements in the gypsum are primarily provided by allochthonous material from the present-day polar desert. The disruption, uplift and rotation of the evaporite beds by the Haughton meteorite impact 39 Ma have facilitated gypsum weathering and its accessibility as a habitat. No cultured cyanobacteria, bacteria and fungi were halophilic consistent with the expectation that halophily is not required to persist in gypsum habitats. Heterotrophic bacteria from the evaporite were slightly or moderately halotolerant, as were heterotrophs isolated from soil near the gypsum outcrop showing that halotolerance is common in arctic bacteria in this location. Psychrotolerant Arthrobacter species were isolated. No psychrophilic organisms were isolated. Two Arthrobacter isolates from the evaporite were used to mediate gypsum neogenesis in the laboratory, demonstrating a potential role for microbial biomineralization processes in polar environments.

Simplified models of rates of CO2 mineralization in Geologic Carbon Storage

NASA Astrophysics Data System (ADS)

DePaolo, D. J.; Zhang, S.

2017-12-01

Geologic carbon storage (GCS) reverses the flow of carbon to the atmosphere, returning the carbon to long-term geologic storage. Models suggest that most of the injected CO2 will be "trapped" in the subsurface by physical means, but the most risk-free and permanent form of carbon storage is as carbonate minerals (Ca,Mg,Fe)CO3. The transformation of CO2 to carbonate minerals requires supply of divalent cations by dissolution of silicate minerals. Available data suggest that rates of transformation are difficult to predict. We show that the chemical kinetic observations and experimental results, when reduced to a single timescale that describes the fractional rate at which cations are released to solution by mineral dissolution, show sufficiently systematic behavior that the rates of mineralization can be estimated with reasonable certainty. Rate of mineralization depends on both the abundance (determined by the reservoir rock mineralogy) and the rate at which cations are released by dissolution into pore fluid that has been acidified with dissolved CO2. Laboratory-measured rates and field observations give values spanning 8 to 10 orders of magnitude, but when evaluated in the context of reservoir-scale reactive transport simulations, this range becomes much smaller. Reservoir scale simulations indicate that silicate mineral dissolution and subsequent carbonate mineral precipitation occur at pH 4.5 to 6, fluid flow velocity less than 5m/yr, and 50-100 years or more after the start of injection. These constraints lead to estimates of 200 to 2000 years for conversion of 60-90% of injected CO2 when the reservoir rock has a sufficient volume fraction of divalent cation-bearing silicate minerals (ca. 20%), and confirms that when reservoir rock mineralogy is not favorable the fraction of CO2 converted to carbonate minerals is minimal over 104 years. A sufficient amount of reactive minerals represents the condition by which the available cations per volume of rock plus pore space exceeds the locally trapped CO2 by a factor of two or more. Our approach may allow for rapid evaluation of mineralization potential of subsurface storage reservoirs, and illustrates how reservoir scale modeling can be integrated with other observations to address key issues for engineering geologic systems.

The future of FGD gypsum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, E.C.

2005-09-30

According to ACAA's 'Coal combustion production and user survey' covering 2003, FGD gypsum utilization in the USA has risen to 70% but with 12 m tons being produced annually there is great opportunity to expand its use in producing wallboard (its primary use) and also in cement and concrete products and agriculture. In 2003 less than 1 mt of FGD gypsum was sold into these latter markets. Although nearly all the 12 newest wallboard plants announced since 1995 have been designed to use this material, only 27% of total gypsum wallboard production in the USA utilizes FGD gypsum. 1 ref.,more » 2 figs., 2 photos.« less

40 CFR 60.734 - Monitoring of emissions and operations.

Code of Federal Regulations, 2014 CFR

2014-07-01

... fuller's earth rotary dryer, a gypsum rotary dryer, a gypsum flash calciner, gypsum kettle calciner, an... water column gauge pressure at the level of operation. The liquid flow rate monitoring device must be...

40 CFR 60.734 - Monitoring of emissions and operations.

Code of Federal Regulations, 2013 CFR

2013-07-01

... fuller's earth rotary dryer, a gypsum rotary dryer, a gypsum flash calciner, gypsum kettle calciner, an... water column gauge pressure at the level of operation. The liquid flow rate monitoring device must be...

40 CFR 60.734 - Monitoring of emissions and operations.

Code of Federal Regulations, 2012 CFR

2012-07-01

... fuller's earth rotary dryer, a gypsum rotary dryer, a gypsum flash calciner, gypsum kettle calciner, an... water column gauge pressure at the level of operation. The liquid flow rate monitoring device must be...

40 CFR 60.734 - Monitoring of emissions and operations.

Code of Federal Regulations, 2011 CFR

2011-07-01

... fuller's earth rotary dryer, a gypsum rotary dryer, a gypsum flash calciner, gypsum kettle calciner, an... water column gauge pressure at the level of operation. The liquid flow rate monitoring device must be...

[Study on microwave digestion of gypsum for the determination of multielement by ICP-OES and ICP-MS].

PubMed

Wang, Hui; Song, Qiang; Yang, Rui-ming; Yao, Qiang; Chen, Chang-he

2010-09-01

Three acids (HNO3, HNO3/HF and HNO3 /HF+ H3BO3) were used to decompose gypsum with microwave digestion system. The contents of 10 mineral elements (Al, Ca, Mg, Fe, K, Na, S, Ti, Si and Sr) in gypsum were determined by inductively coupled plasma-optical emission spectrometry (ICP-OES) while 6 heavy metals (V, Cr, Mn, Zn, Se and Ce) were determined by inductively coupled plasma-mass spectrometry (ICP-MS). GBW03109a, GBW03110 and FGD-2 were used as gypsum standard reference materials. The results showed that two-step microwave digestion with HNO3/HF at 210 degrees C and then adding H3BO3 for the removal of HF and fluorides completely decomposed the gypsums, while this method achieved good recoveries for all elements in the three gypsum standard reference materials. The recovery was from 88% to 112% and the RSD of tests was below 3%. The method was applied to the elemental analysis for flue gas desulfurization gypsums from three coal-fired power plants.

Permeability structure of a highly heterogeneous transgressive-marine complex: Tocito Sandstone, New Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lambert, M.L.; Cole, R.D.

1996-01-01

The Tocito Sandstone Member of the Mancos Shale is an Upper Cretaceous shallow-marine sandstone and mudrock complex deposited along the western margin of the Western Interior seaway. The Tocito is a major hydrocarbon producer in the San Juan Basin (approximately 117 million barrels of oil and 79 billion cubic feet of gas). Because of reservoir heterogeneity, ultimate Tocito oil recovery factors are low, generally between 10 and 20 percent. To enhance understanding of permeability heterogeneity in the Tocito, we have undertaken a detailed surface and subsurface investigation. A total of 2,697 permeability measurements have been made using minipermeameters. Permeability variationmore » within the Tocito is controlled by two principal factors: lithofacies and burial/diagenetic history. Coarser grained and better sorted lithofacies have the highest permeability. The permeability values from outcrop and shallow subsurface cores are dramatically higher than those from deep subsurface cores. This is due to dissolution of grains and calcite cement, and decompaction that preferentially affected the outcrop and shallow subsurface. Correlation lengths for permeability values along horizontal transacts are typically less than 3 m, whereas those for vertical transacts are usually less than 0.6 m. These data suggest that small grid block sizes should be used during reservoir simulations if the investigator wishes to accurately capture the reservoir heterogeneity.« less

Permeability structure of a highly heterogeneous transgressive-marine complex: Tocito Sandstone, New Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lambert, M.L.; Cole, R.D.

1996-12-31

The Tocito Sandstone Member of the Mancos Shale is an Upper Cretaceous shallow-marine sandstone and mudrock complex deposited along the western margin of the Western Interior seaway. The Tocito is a major hydrocarbon producer in the San Juan Basin (approximately 117 million barrels of oil and 79 billion cubic feet of gas). Because of reservoir heterogeneity, ultimate Tocito oil recovery factors are low, generally between 10 and 20 percent. To enhance understanding of permeability heterogeneity in the Tocito, we have undertaken a detailed surface and subsurface investigation. A total of 2,697 permeability measurements have been made using minipermeameters. Permeability variationmore » within the Tocito is controlled by two principal factors: lithofacies and burial/diagenetic history. Coarser grained and better sorted lithofacies have the highest permeability. The permeability values from outcrop and shallow subsurface cores are dramatically higher than those from deep subsurface cores. This is due to dissolution of grains and calcite cement, and decompaction that preferentially affected the outcrop and shallow subsurface. Correlation lengths for permeability values along horizontal transacts are typically less than 3 m, whereas those for vertical transacts are usually less than 0.6 m. These data suggest that small grid block sizes should be used during reservoir simulations if the investigator wishes to accurately capture the reservoir heterogeneity.« less

Gossan Hill, Victoria Island, Northwest Territories: An analogue for mine waste reactions within permafrost and implication for the subsurface mineralogy of Mars

NASA Astrophysics Data System (ADS)

Peterson, Ronald C.; Williamson, Marie-Claude; Rainbird, Robert H.

2014-08-01

Gossan Hill is located within the Minto Inlier in central Victoria Island, Northwest Territories (N 71.36697°, W 114.95155°). A study of the mineralogical associations and geological setting of this deposit indicates that it is an arrested hydrothermal system frozen in permafrost. From above, the hill stands out because of the topographic relief of 75 m and the orange-brown color of the surficial material. The surface of the hill is marked by areas of concentric color zonation up to 3 m across, with light gray centers surrounded by a yellow-orange ring that is surrounded by an orange-brown color that covers the rest of the surface of the hill. Trenches dug into these areas reveal that the central zone contains quartz and pyrite +/- native sulfur in a loose aggregate of sand-sized grains. This central area is surrounded by a zone dominated by gypsum and quartz with some jarosite. Beyond this, the surrounding surface consists of quartz, hematite, and amorphous iron oxides. The radial arrangement of the mineral assemblage indicates an increase in oxidation of sulfur from the center outward. Analysis of isotopic composition of the sulfur indicates the source of sulfur could be the underlying strata. The hill is underlain by inter-bedded carbonate and sulfate-evaporite sedimentary rocks of the Kilian formation in the upper part of the Neoproterozoic Shaler Super group. The sedimentary rocks were intruded by diabase sills of the 720 Ma Franklin igneous event, which crop out 2 km to the south of Gossan Hill. The soft friable nature of the deposit and the topographic relief of the hill indicate a post-glacial (Pleistocene) age of formation. Permafrost has maintained the disequilibrium mineral assemblage since the cessation of fluid flow. Extraction of the permafrost ice from the central zone yields a liquid with a pH of 2.3. The observed long-term persistence of pyrite encased within the acidic permafrost indicates that oxidation and dissolution reactions common in mine waste are slowed, if not stopped, in such an environment. The predicted rise of Arctic temperatures will cause the active layer to move deeper and result in the release of the acidic solutions frozen in the permafrost. Water ice or frozen CO2 just below the Martian surface would also preserve such mineral disequilibrium for very long periods of time. No region exists on Earth where ice has existed continuously for millions of years, but the Gossan Hill deposit is an excellent terrestrial analogue. On Mars, the subsurface ice may be very old. Ancient reactive Martian mineral assemblages and the fluids associated with them will reflect conditions that existed in the past.

A reactive transport model for Marcellus shale weathering

NASA Astrophysics Data System (ADS)

Heidari, Peyman; Li, Li; Jin, Lixin; Williams, Jennifer Z.; Brantley, Susan L.

2017-11-01

Shale formations account for 25% of the land surface globally and contribute a large proportion of the natural gas used in the United States. One of the most productive shale-gas formations is the Marcellus, a black shale that is rich in organic matter and pyrite. As a first step toward understanding how Marcellus shale interacts with water in the surface or deep subsurface, we developed a reactive transport model to simulate shale weathering under ambient temperature and pressure conditions, constrained by soil and water chemistry data. The simulation was carried out for 10,000 years since deglaciation, assuming bedrock weathering and soil genesis began after the last glacial maximum. Results indicate weathering was initiated by pyrite dissolution for the first 1000 years, leading to low pH and enhanced dissolution of chlorite and precipitation of iron hydroxides. After pyrite depletion, chlorite dissolved slowly, primarily facilitated by the presence of CO2 and organic acids, forming vermiculite as a secondary mineral. A sensitivity analysis indicated that the most important controls on weathering include the presence of reactive gases (CO2 and O2), specific surface area, and flow velocity of infiltrating meteoric water. The soil chemistry and mineralogy data could not be reproduced without including the reactive gases. For example, pyrite remained in the soil even after 10,000 years if O2 was not continuously present in the soil column; likewise, chlorite remained abundant and porosity remained small if CO2 was not present in the soil gas. The field observations were only simulated successfully when the modeled specific surface areas of the reactive minerals were 1-3 orders of magnitude smaller than surface area values measured for powdered minerals. Small surface areas could be consistent with the lack of accessibility of some fluids to mineral surfaces due to surface coatings. In addition, some mineral surface is likely interacting only with equilibrated pore fluids. An increase in the water infiltration rate enhanced weathering by removing dissolution products and maintaining far-from-equilibrium conditions. We conclude from these observations that availability of reactive surface area and transport of H2O and gases are the most important factors affecting rates of Marcellus shale weathering of the in the shallow subsurface. This weathering study documents the utility of reactive transport modeling for complex subsurface processes. Such modelling could be extended to understand interactions between injected fluids and Marcellus shale gas reservoirs at higher temperature, pressure, and salinity conditions.

Hydrogeologic data for the McKay Creek subsurface waste-injection test site, Pinellas County, Florida

USGS Publications Warehouse

Hickey, John D.

1977-01-01

Lithologic, hydraulic, geophysical, and water-quality data collected at the McKay Creek subsurface waste-injection test site in Pinellas County, Florida, are reported. Data were collected to determine the possibility of subsurface injection of waste-treatment plant effluent. One exploratory hole, one test injection well, and eight observation wells were constructed between May 1973 and February 1976. The exploratory hole was drilled to a depth of 1,750 feet below land surface; the test injection well is open in dolomite between 952 and 1 ,040 feet; and the observation wells are open to intervals above , in, and below the test injection zone. The lithology of the upper 100 feet is predominantly clay. From 100 to 1,750 feet below land surface, limestone and dolomite predominate. Gypsum is present 1,210 feet below land surface. Laboratory analyses of cores taken during drilling are given for vertical intrinsic permeability, porosity, interval transit time, and compressibility. Specific capacities tested during drilling range from 4 to 2,500 gallons per minute per foot of drawdown. An 83-hour withdrawal test at 4,180 gallons per minute and a 2-month injection test at 650 gallons per minute were run. Small water-quality changes were observed in one observation well immediately above the test injection zone during and after the injection test. Formation water in all of the wells with the exception of the shallowest observation wells is saline. The vertical position of saltwater is estimated to be at about 280 feet below land surface. Thirteen wells within a 1-mile radius of the test site were located and sampled for water quality. (USGS)

Enhancement of archaeological heritage. El Risco de las Cuevas at Perales de Tajuña, Madrid (Spain)

NASA Astrophysics Data System (ADS)

Freire-Lista, David Martin; Alvarez de Buergo, Mónica; Fort, Rafael

2016-04-01

Heritage conservation has a great impact on the economy of a country. The enhancement of archaeological sites is an investment that promotes tourism and culture. The interdisciplinary knowledge of heritage should be the basis of its management. Preventive actions, non-destructive analytical techniques and monitoring for the conservation of these assets should be promoted. "El Risco de las Cuevas" is a highly decayed and nearly vertical gypsum escarpment which contains a series of dwellings excavated during the Chalcolithic and much more recent times. It is located at Perales de Tajuña, 40 km southeast of Madrid, Spain. This monument is approximately 70 metres high and 500 metres wide. It was listed as a cultural and monumental heritage site by the regional government of Madrid in 1998. The gypsum escarpment housing the dwellings forms part of a lower Miocene unit (Madrid Basin). Debris cones with a mixture of debris from the lower, medium and upper units are found at the bottom of the rockwall. The vulnerability of this monument to atmospheric agents has been studied using "in situ" monitoring techniques of humidity, temperature and rate of rockfalls. Drones have been used for aerial photography in the highest areas of the escarpment and have provided an information network of fractures likely to cause rockfall. Gypsum artificial accelerated ageing has been carried out in the laboratory, including freeze/thaw, wet/dry, thermal shock and dissolution tests. To determine the response of these accelerated ageing processes, density, micro-roughness, ultrasound velocities (Vp and Vs), air permeability and microscopy measurements were made before, during and after ageing tests. Geomorphological studies, rates of decay, material characteristics and durability tests indicate that the decay is controlled by the mineralogy, clay content and porosity of the gypsum rock, as well as microclimate, temperature changes and rock fractures. Rockfalls are particularly relevant in the safety of the monument and visitors. The enhancement of El Risco de las Cuevas has involved both local government (City council of Perales de Tajuña) and regional one (General Directorate of Historical Heritage of the Community of Madrid), besides the Institute of Geosciences IGEO (CSIC-UCM). Thanks to the collaboration of these agencies an interpretation centre has been created, preserving El Risco de las Cuevas in an educational and user-friendly manner. By conducting tours during the Science week of Madrid this promotes citizen participation, dissemination and social transfer, which are essential to preserve heritage. A project has been designed to monitor and ensure control and stability of the monument Acknowledgements: Community of Madrid for financing Geomateriales2 program (P2013/MIT2914), CEI-Moncloa UCM-UPM, Applied Petrology for Heritage Stone Materials Conservation Research Group and local government of Perales de Tajuña.

High-resolution seismic-reflection imaging 25 years of change in I-70 sinkhole, Russell County, Kansas

USGS Publications Warehouse

Miller, R.D.; Steeples, D.W.; Lambrecht, J.L.; Croxton, N.

2006-01-01

Time-lapse seismic reflection imaging improved our understanding of the consistent, gradual surface subsidence ongoing at two sinkholes in the Gorham Oilfield discovered beneath a stretch of Interstate Highway 70 through Russell and Ellis Counties in Kansas in 1966. With subsidence occurring at a rate of around 10 cm per year since discovery, monitoring has been beneficial to ensure public safety and optimize maintenance. A miniSOSIE reflection survey conducted in 1980 delineated the affected subsurface and successfully predicted development of a third sinkhole at this site. In 2004 and 2005 a high-resolution vibroseis survey was completed to ascertain current conditions of the subsurface, rate and pattern of growth since 1980, and potential for continued growth. With time and improved understanding of the salt dissolution affected subsurface in this area it appears that these features represent little risk to the public from catastrophic failure. However, from an operational perspective the Kansas Department of Transportation should expect continued subsidence, with future increases in surface area likely at a slightly reduced vertical rate. Seismic characteristics appear empirically consistent with gradual earth material compaction/settling. ?? 2005 Society of Exploration Geophysicists.

Controlled study of mold growth and cleaning procedure on treated and untreated wet gypsum wallboard in an indoor environment.

PubMed

Krause, Michael; Geer, William; Swenson, Lonie; Fallah, Payam; Robbins, Coreen

2006-08-01

The basis for some common gypsum wallboard mold remediation practices was examined. The bottom inch of several gypsum wallboard panels was immersed in bottled drinking water; some panels were coated and others were untreated. The panels were examined and tested for a period of 8 weeks. This study investigated: (a) whether mold growth, detectable visually or with tape lift samples, occurs within 1 week on wet gypsum wallboard; (b) the types, timing, and extent of mold growth on wet gypsum wallboard; (c) whether mold growth is present on gypsum wallboard surfaces 6 inches from visible mold growth; (d) whether some commonly used surface treatments affect the timing of occurrence and rate of mold growth; and (e) if moldy but dried gypsum wallboard can be cleaned with simple methods and then sealed with common surface treatments so that residual mold particles are undetectable with typical surface sampling techniques. Mold growth was not detected visually or with tape lift samples after 1 week on any of the wallboard panels, regardless of treatment, well beyond the 24-48 hours often mentioned as the incubation period. Growth was detected at 2 weeks on untreated gypsum. Penicillium, Cladosporium, and Acremonium were early colonizers of untreated panels. Aspergillus, Epicoccum, Alternaria, and Ulocladium appeared later. Stachybotrys was not found. Mold growth was not detected more than 6 inches beyond the margin of visible mold growth, suggesting that recommendations to remove gypsum wallboard more than 1 foot beyond visible mold are excessive. The surface treatments resulted in delayed mold growth and reduced the area of mold growth compared with untreated gypsum wallboard. Results showed that simple cleaning of moldy gypsum wallboard was possible to the extent that mold particles beyond "normal trapping" were not found on tape lift samples. Thus, cleaning is an option in some situations where removal is not feasible or desirable. In cases where conditions are not similar to those of this study, or where large areas may be affected, a sample area could be cleaned and tested to verify that the cleaning technique is sufficient to reduce levels to background or normal trapping. These results are generally in agreement with laboratory studies of mold growth on, and cleaning of, gypsum wallboard.

Initiation and growth of gypsum piercement structures in the Zechstein Basin

USGS Publications Warehouse

Williams-Stroud, S. C.; Paul, J.

1997-01-01

The importance of tectonic processes in initiating halite diapirs has become much better understood in recent years. Less well understood is the development of diapiric structures involving rocks composed predominantly of gypsum. Below about 1000 m, gypsum dehydrates to anhydrite, which often obscures primary sedimentary textures. If the strain associated with diapiric rise in the rock induces the transition to anhydrite, obliteration of primary features in the gypsum can be expected. In our study, we infer that the diapiric movement in the Werra Anhydrite member of cycle 1 of the Zechstein Formation of Europe occurred before the initial transition of gypsum to anhydrite based on the presence of pseudomorphs of bedded primary gypsum crystals, the overburden lithologies and depositional environment, and the mechanical properties of gypsum, anhydrite and carbonate rocks. Faulting and differential loading of a shallow overburden were the key components in initiating the gypsum diapirism. The transition to anhydrite occurred after burial and after cessation of diapirism. In comparison, the diapirism of calcium sulfate of the Leine Anhydrite into the Leine Halite members of cycle 3 of the Zechstein Formation probably occurred much later after burial and appears to have been triggered by halite diapirism, which in turn triggered the dehydration reaction, causing the calcium sulfate to become the incompetent phase relative to the halite. Published by Elsevier Science Ltd.

Shell Condition and Survival of Puget Sound Pteropods Are Impaired by Ocean Acidification Conditions

PubMed Central

Busch, D. Shallin; Maher, Michael; Thibodeau, Patricia; McElhany, Paul

2014-01-01

We tested whether the thecosome pteropod Limacina helicina from Puget Sound, an urbanized estuary in the northwest continental US, experiences shell dissolution and altered mortality rates when exposed to the high CO2, low aragonite saturation state (Ωa) conditions that occur in Puget Sound and the northeast Pacific Ocean. Five, week-long experiments were conducted in which we incubated pteropods collected from Puget Sound in four carbon chemistry conditions: current summer surface (∼460–500 µatm CO2, Ωa≈1.59), current deep water or surface conditions during upwelling (∼760 and ∼1600–1700 µatm CO2, Ωa≈1.17 and 0.56), and future deep water or surface conditions during upwelling (∼2800–3400 µatm CO2, Ωa≈0.28). We measured shell condition using a scoring regime of five shell characteristics that capture different aspects of shell dissolution. We characterized carbon chemistry conditions in statistical analyses with Ωa, and conducted analyses considering Ωa both as a continuous dataset and as discrete treatments. Shell dissolution increased linearly as aragonite saturation state decreased. Discrete treatment comparisons indicate that shell dissolution was greater in undersaturated treatments compared to oversaturated treatments. Survival increased linearly with aragonite saturation state, though discrete treatment comparisons indicated that survival was similar in all but the lowest saturation state treatment. These results indicate that, under starvation conditions, pteropod survival may not be greatly affected by current and expected near-future aragonite saturation state in the NE Pacific, but shell dissolution may. Given that subsurface waters in Puget Sound’s main basin are undersaturated with respect to aragonite in the winter and can be undersaturated in the summer, the condition and persistence of the species in this estuary warrants further study. PMID:25162395

Shell condition and survival of Puget Sound pteropods are impaired by ocean acidification conditions.

PubMed

Busch, D Shallin; Maher, Michael; Thibodeau, Patricia; McElhany, Paul

2014-01-01

We tested whether the thecosome pteropod Limacina helicina from Puget Sound, an urbanized estuary in the northwest continental US, experiences shell dissolution and altered mortality rates when exposed to the high CO2, low aragonite saturation state (Ωa) conditions that occur in Puget Sound and the northeast Pacific Ocean. Five, week-long experiments were conducted in which we incubated pteropods collected from Puget Sound in four carbon chemistry conditions: current summer surface (∼460-500 µatm CO2, Ωa≈1.59), current deep water or surface conditions during upwelling (∼760 and ∼1600-1700 µatm CO2, Ωa≈1.17 and 0.56), and future deep water or surface conditions during upwelling (∼2800-3400 µatm CO2, Ωa≈0.28). We measured shell condition using a scoring regime of five shell characteristics that capture different aspects of shell dissolution. We characterized carbon chemistry conditions in statistical analyses with Ωa, and conducted analyses considering Ωa both as a continuous dataset and as discrete treatments. Shell dissolution increased linearly as aragonite saturation state decreased. Discrete treatment comparisons indicate that shell dissolution was greater in undersaturated treatments compared to oversaturated treatments. Survival increased linearly with aragonite saturation state, though discrete treatment comparisons indicated that survival was similar in all but the lowest saturation state treatment. These results indicate that, under starvation conditions, pteropod survival may not be greatly affected by current and expected near-future aragonite saturation state in the NE Pacific, but shell dissolution may. Given that subsurface waters in Puget Sound's main basin are undersaturated with respect to aragonite in the winter and can be undersaturated in the summer, the condition and persistence of the species in this estuary warrants further study.

Evaluation of potential for mercury volatilization from natural and FGD gypsum products using flux-chamber tests.

PubMed

Shock, Scott S; Noggle, Jessica J; Bloom, Nicholas; Yost, Lisa J

2009-04-01

Synthetic gypsum produced by flue-gas desulfurization (FGD) in coal-fired power plants (FGD gypsum) is put to productive use in manufacturing wallboard. FGD gypsum wallboard is widely used, accounting for nearly 30% of wallboard sold in the United States. Mercury is captured in flue gas and thus is one of the trace metals present in FGD gypsum; raising questions about the potential for mercury exposure from wallboard. Mercury is also one of the trace metals present in "natural" mined gypsum used to make wall board. Data available in the literature were not adequate to assess whether mercury in wallboard from either FGD or natural gypsum could volatilize into indoor air. In this study, mercury volatilization was evaluated using small-scale (5 L) glass and Teflon flux chambers, with samples collected using both iodated carbon and gold-coated sand traps. Mercury flux measurements made using iodated carbon traps (n=6) were below the detection limit of 11.5 ng/m2-day for all natural and synthetic gypsum wallboard samples. Mercury flux measurements made using gold-coated sand traps (n=6) were 0.92 +/- 0.11 ng/m2-day for natural gypsum wallboard and 5.9 +/- 2.4 ng/m2-day for synthetic gypsum wallboard. Room air mercury concentrations between 0.028 and 0.28 ng/m3 and between 0.13 and 2.2 ng/m3 were estimated based on the flux-rate data for natural and synthetic gypsum wallboard samples, respectively, and were calculated assuming a 3 m x 4 m x 5 m room, and 10th and 90th percentile air exchange rates of 0.18/hour and 1.26/hour. The resulting concentration estimates are well below the U.S. Environmental Protection Agency (EPA) reference concentration for indoor air elemental mercury of 300 ng/m3 and the Agency for Toxic Substances and Disease Registry minimal risk level (MRL) of 200 ng/m3. Further, these estimates are below background mercury concentrations in indoor air and within or below the range of typical background mercury concentrations in outdoor air.

Steeply dipping heaving bedrock, Colorado: Part 2 - Mineralogical and engineering properties

USGS Publications Warehouse

Noe, D.C.; Higgins, J.D.; Olsen, H.W.

2007-01-01

This paper describes the mineralogical and engineering properties of steeply dipping, differentially heaving bedrock, which has caused severe damage near the Denver area. Several field sites in heave-prone areas have been characterized using high sample densities, numerous testing methodologies, and thousands of sample tests. Hydrometer testing shows that the strata range from siltstone to claystone (33 to 66 percent clay) with occasional bentonite seams (53 to 98 percent clay mixed with calcite). From X-ray diffraction analyses, the claystone contains varying proportions of illite-smectite and discrete (pure) smectite, and the bentonite contains discrete smectite. Accessory minerals include pyrite, gypsum, calcite, and oxidized iron compounds. The dominant exchangeable cation is Ca2+, except where gypsum is prevalent, and Mg2+ and Na1+ are elevated. Scanning electron microscope analyses show that the clay fabric is deformed and porous and that pyrite is absent within the weathered zone. Unified Soil Classification for the claystone varies from CL to CH, and the bentonite is CH to MH. Average moisture content values are 17 percent for claystone and 32 percent for bentonite, and these are typically 0 to 5 percent lower than the plastic limit. Swell-consolidation and suction testing shows a full range of swelling potentials from low to very high. These findings confirm that type I (bed-parallel, symmetrical to asymmetrical) heave features are strongly associated with changes in bedrock composition and mineralogy. Composition changes are not necessarily a factor for type II (bed-parallel to bed-oblique, strongly asymmetrical) heave features, which are associated with movements along subsurface shear zones.

Method Analysis of Microbial Resistant Gypsum Products

EPA Science Inventory

Abstract: Several commercially available gypsum products are marketed as microbial-resistant. During previous test method research on a microbial resistant gypsum wallboard study, a common theme from both stakeholders and product vendors was the need for a unified and accepted m...

Dissolution-Enlarged Fractures Imaging Using Electrical Resistivity Tomography (ERT)

NASA Astrophysics Data System (ADS)

Siami-Irdemoosa, Elnaz

In recent years the electrical imaging techniques have been largely applied to geotechnical and environmental investigations. These techniques have proven to be the best geophysical methods for site investigations in karst terrain, particularly when the overburden soil is clay-dominated. Karst is terrain with a special landscape and distinctive hydrological system developed by dissolution of rocks, particularly carbonate rocks such as limestone and dolomite, made by enlarging fractures into underground conduits that can enlarge into caverns, and in some cases collapse to form sinkholes. Bedding planes, joints, and faults are the principal structural guides for underground flow and dissolution in almost all karstified rocks. Despite the important role of fractures in karst development, the geometry of dissolution-enlarged fractures remain poorly unknown. These features are characterized by an strong contrast with the surrounding formations in terms of physical properties, such as electrical resistivity. Electrical resistivity tomography (ERT) was used as the primary geophysical tool to image the subsurface in a karst terrain in Greene County, Missouri. Pattern, orientation and density of the joint sets were interpreted from ERT data in the investigation site. The Multi-channel Analysis of Surface Wave (MASW) method and coring were employed to validate the interpretation results. Two sets of orthogonal visually prominent joints have been identified in the investigation site: north-south trending joint sets and west-east trending joint sets. However, most of the visually prominent joint sets are associated with either cultural features that concentrate runoff, natural surface drainage features or natural surface drainage.

Uptake and speciation of uranium in synthetic gypsum (CaSO4•2H2O): Applications to radioactive mine tailings.

PubMed

Lin, Jinru; Sun, Wei; Desmarais, Jacques; Chen, Ning; Feng, Renfei; Zhang, Patrick; Li, Dien; Lieu, Arthur; Tse, John S; Pan, Yuanming

2018-01-01

Phosphogypsum formed from the production of phosphoric acid represents by far the biggest accumulation of gypsum-rich wastes in the world and commonly contains elevated radionuclides, including uranium, as well as other heavy metals and metalloids. Therefore, billions-of-tons of phosphogypsum stockpiled worldwide not only possess serious environmental problems but also represent a potential uranium resource. Gypsum is also a major solid constituent in many other types of radioactive mine tailings, which stems from the common usage of sulfuric acid in extraction processes. Therefore, management and remediation of radioactive mine tailings as well as future beneficiation of uranium from phosphogysum all require detailed knowledge about the nature and behavior of uranium in gypsum. However, little is known about the uptake mechanism or speciation of uranium in gypsum. In this study, synthesis experiments suggest an apparent pH control on the uptake of uranium in gypsum at ambient conditions: increase in U from 16 μg/g at pH = 6.5 to 339 μg/g at pH = 9.5. Uranium L 3 -edge synchrotron X-ray absorption spectroscopic analyses of synthetic gypsum show that uranyl (UO 2 ) 2+ at the Ca site is the dominant species. The EXAFS fitting results also indicate that uranyl in synthetic gypsum occurs most likely as carbonate complexes and yields an average U-O distance ∼0.25 Å shorter than the average Ca-O distance, signifying a marked local structural distortion. Applications to phosphogypsum from the New Wales phosphoric acid plant (Florida, USA) and uranium mine tailings from the Key Lake mill (Saskatchewan, Canada) show that gypsum is an important carrier of uranium over a wide range of pH and controls the fate of this radionuclide in mine tailings. Also, development of new technologies for recovering U from phosphogypsum in the future must consider lattice-bound uranyl in gypsum. Copyright © 2017 Elsevier Ltd. All rights reserved.

Petrographic and Facies Properties of the Evaporites in the Cihanbeyli-Yeniceoba Basin (Central Anatolia, Turkey)

NASA Astrophysics Data System (ADS)

Sami Us, Muhammed; Tekin, Erdoǧan

2016-04-01

The Cihanbeyli-Yeniceoba Tertiary basin and other neighbouring basins such as Haymana on the NW and Tuzgölü on the east were formed after ophiolite emplacement and then evolved as tectonic controlled basins bordered with normal and oblique-slip fault systems NW-SE in extending. Where sedimentation commenced with Late Cretaceous-Early Paleocene marine transgression and ended by late Middle Eocene-Early Oligocene regression that involved thick evaporite sedimentation just before the onset of the terrestrial regime through the early Late Oligocene-Pliocene time. This study mainly was focused on the evaporitic sediments of the Late Oligocene-Middle Miocene aged Gökdaǧ Formation which unconformably overlain by fluvial and alluvial units of the Cihanbeyli Formation (Late Miocene-Early Pliocene). Typical outcrops have been seen around the Yeniceoba-Kütükuşaǧı-Kuşca region located in the western part of Tuz Gölü (Salt Lake). The study includes several targets. These are stratigraphical contact and relationship between evaporite and non-evaporite units, evaporite environments and mineralogical, petrographical and microtextural features of the evaporites. The following five evaporite facies were described: a) massive gypsum (F1), b) laminated-banded gypsum (F2), c) nodular gypsum (F3), d) clastic gypsum (F4), e) satin-spar gypsum (F5). On the other hand polarized microscope and scanning electron microscope (SEM) show that secondary gypsums are represented by alabastrine and porfiroblastic textures. Primary anhydrite relicts, euhedral celestine crystals accompanied with the secondary gypsum. Clastic gypsum is rich in fragment fossils (mostly nummulites) and kaolinite clay minerals. All data suggest that evaporites were widely deposited as basin margin evaporite that temporally underwent atmospheric conditions gave rise to detrital gypsum ranging from gypsarenite to gypsum conglomerate. Acknowledgement:This presentation was prepared MS thesis to financially supported by the Scientific and Technological Research Council of Turkey (TUBITAK-CAYDAG) with 113 Y 090 numbered project.

Ballasting by cryogenic gypsum enhances carbon export in a Phaeocystis under-ice bloom.

PubMed

Wollenburg, J E; Katlein, C; Nehrke, G; Nöthig, E-M; Matthiessen, J; Wolf-Gladrow, D A; Nikolopoulos, A; Gázquez-Sanchez, F; Rossmann, L; Assmy, P; Babin, M; Bruyant, F; Beaulieu, M; Dybwad, C; Peeken, I

2018-05-16

Mineral ballasting enhances carbon export from the surface to the deep ocean; however, little is known about the role of this process in the ice-covered Arctic Ocean. Here, we propose gypsum ballasting as a new mechanism that likely facilitated enhanced vertical carbon export from an under-ice phytoplankton bloom dominated by the haptophyte Phaeocystis. In the spring 2015 abundant gypsum crystals embedded in Phaeocystis aggregates were collected throughout the water column and on the sea floor at a depth below 2 km. Model predictions supported by isotopic signatures indicate that 2.7 g m -2 gypsum crystals were formed in sea ice at temperatures below -6.5 °C and released into the water column during sea ice melting. Our finding indicates that sea ice derived (cryogenic) gypsum is stable enough to survive export to the deep ocean and serves as an effective ballast mineral. Our findings also suggest a potentially important and previously unknown role of Phaeocystis in deep carbon export due to cryogenic gypsum ballasting. The rapidly changing Arctic sea ice regime might favour this gypsum gravity chute with potential consequences for carbon export and food partitioning between pelagic and benthic ecosystems.

Investigation on Microbial Dissolution of Uranium (VI) from Autunite Mineral - 13421

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sepulveda, Paola; Katsenovich, Yelena; Lagos, Leonel

2013-07-01

Precipitating autunite minerals by polyphosphate injection was identified as a feasible remediation strategy for sequestering uranium in contaminated groundwater and soil in situ at the Hanford Site. Autunite stability under vadose and saturated zone environmental conditions can help to determine the long-term effectiveness of this remediation strategy. The Arthrobacter bacteria are one of the most common groups in soils and are found in large numbers in Hanford soil as well as other subsurface environments contaminated with radionuclides. Ubiquitous in subsurface microbial communities, these bacteria can play a significant role in the dissolution of minerals and the formation of secondary minerals.more » The main objective of this investigation was to study the bacterial interactions under oxidizing conditions with uranium (VI); study the potential role of bicarbonate, which is an integral complexing ligand for U(VI) and a major ion in groundwater compositions; and present data from autunite dissolution experiments using Arthrobacter strain G968, a less U(VI)-tolerant strain. Sterile 100 mL glass mixed reactors served as the major bioreactor for initial experimentation. These autunite-containing bioreactors were injected with bacterial cells after the autunite equilibrated with the media solution amended with 0 mM, 3 mM 5 mM and 10 mM concentrations of bicarbonate. G968 Arthrobacter cells in the amount of 10{sup 6} cells/mL were injected into the reactors after 27 days, giving time for the autunite to reach steady state. Abiotic non-carbonate controls were kept without bacterial inoculation to provide a control for the biotic samples. Samples of the solution were analyzed for dissolved U(VI) by means of kinetic phosphorescence analyzer KPA-11 (Chemcheck Instruments, Richland, WA). Analysis showed that as [HCO{sub 3}{sup -}] increases, a diminishing trend on the effect of bacteria on autunite leaching is observed. Viability of cells was conducted after 24 hours of cell incubation with the appropriate uranium and bicarbonate concentration treatment. As expected, the cells started to reduce after day 41 due to the nutritional exhaustion of the media. Moreover, viable bacteria accounted for more than 94% in the presence of 10 mM bicarbonate. Experiments showed that despite differences between the G975 and the G968 bacterial strains resistance to U(VI), in the presence of bicarbonate ions they are able to dissolute uranium from autunite mineral at the same capacity. The effect of both bacterial strains on autunite dissolution is reduced as the concentration of bicarbonate increases while the increase in soluble U(VI) concentration induced by G968 and G975 is dwarfed, for larger [HCO{sub 3}{sup -}]. (authors)« less

Surface Coating of Gypsum-Based Molds for Maxillofacial Prosthetic Silicone Elastomeric Material: The Surface Topography.

PubMed

Khalaf, Salah; Ariffin, Zaihan; Husein, Adam; Reza, Fazal

2015-07-01

This study aimed to compare the surface roughness of maxillofacial silicone elastomers fabricated in noncoated and coated gypsum materials. This study was also conducted to characterize the silicone elastomer specimens after surfaces were modified. A gypsum mold was coated with clear acrylic spray. The coated mold was then used to produce modified silicone experimental specimens (n = 35). The surface roughness of the modified silicone elastomers was compared with that of the control specimens, which were prepared by conventional flasking methods (n = 35). An atomic force microscope (AFM) was used for surface roughness measurement of silicone elastomer (unmodified and modified), and a scanning electron microscope (SEM) was used to evaluate the topographic conditions of coated and noncoated gypsum and silicone elastomer specimens (unmodified and modified) groups. After the gypsum molds were characterized, the fabricated silicone elastomers molded on noncoated and coated gypsum materials were evaluated further. Energy-dispersive X-ray spectroscopy (EDX) analysis of gypsum materials (noncoated and coated) and silicone elastomer specimens (unmodified and modified) was performed to evaluate the elemental changes after coating was conducted. Independent t test was used to analyze the differences in the surface roughness of unmodified and modified silicone at a significance level of p < 0.05. Roughness was significantly reduced in the silicone elastomers processed against coated gypsum materials (p < 0.001). The AFM and SEM analysis results showed evident differences in surface smoothness. EDX data further revealed the presence of the desired chemical components on the surface layer of unmodified and modified silicone elastomers. Silicone elastomers with lower surface roughness of maxillofacial prostheses can be obtained simply by coating a gypsum mold. © 2014 by the American College of Prosthodontists.

A study of the effectiveness of the use of gypsum and volcanic ash against the stability of clay soil in terms of UCT and CBR values

NASA Astrophysics Data System (ADS)

Roesyanto; Iskandar, R.; Hastuty, IP; Lubis, AIU

2018-02-01

Soil stabilization is an effort to improve engineering properties of soil. The conventional soil stabilization is by adding additives to the soil such as Portland cement, lime, and bitumen. The clay stabilization research was done by adding gypsum and volcanic ash. The research purposes were to find out the value of engineering properties of clay due to the addition of 2% gypsum and 2% - 15% volcanic ash. The soil was classified as Clay - Low Plasticity (CL) based on USCS and was classified as A-7-6 (10) based on AASHTO classification system. The UCT values of original soil and original soil plus 2% gypsum were 1.40 kg/cm2 and 1.66 kg/cm2 respectively. The CBR soaked and unsoaked values of original soil were 4.44% and 6.28% correspondingly. Meanwhile, CBR soaked and CBR unsoaked values of original soil plus 2% gypsum were 6.74% and 8.02% respectively. The research results showed that the additives materials of gypsum and volcanic ash improved the engineering properties of clay. The UCT result from the stabilized soil by 2% gypsum and 10% volcanic ash gave value of 2.79 kg/cm2 (increased 99.28% from original soil). For CBR test, the most effective mixture were in variation of 2% gypsum and 9% volcanic ash which gave value of 9.07% (104.27% increase from original soil) for CBR soaked and 10.29% (63.85% increase from original soil) for CBR unsoaked. The stabilized soil with 2% gypsum and 9% volcanic ash was classified as CL based on USCS and was classified as A-6 (4) based on AASHTO classification system.

Aluminosilicate Dissolution and Silicate Carbonation during Geologic CO2 Sequestration

NASA Astrophysics Data System (ADS)

Min, Yujia

Geologic CO2 sequestration (GCS) is considered a promising method to reduce anthropogenic CO2 emission. Assessing the supercritical CO2 (scCO2) gas or liquid phase water (g, l)-mineral interactions is critical to evaluating the viability of GCS processes. This work contributes to our understanding of geochemical reactions at CO 2-water (g, l)-mineral interfaces, by investigating the dissolution of aluminosilicates in CO2-acidified water (l). Plagioclase and biotite were chosen as model minerals in reservoir rock and caprock, respectively. To elucidate the effects of brine chemistry, first, the influences of cations in brine including Na, Ca, and K, have been investigated. In addition to the cations, the effects of abundant anions including sulfate and oxalate were also examined. Besides the reactions in aqueous phase, we also examine the carbonation of silicates in water (g)-bearing supercritical CO2 (scCO2) under conditions relevant to GCS. For the metal carbonation, in particular, the effects of particle sizes, water, temperature, and pressure on the carbonation of wollastonite were systematically examined. For understanding the cations effects in brine, the impacts of Na concentrations up to 4 M on the dissolution of plagioclase and biotite were examined. High concentrations of Na significantly inhibited plagioclase dissolution by competing adsorption with proton and suppressing proton-promoted dissolution. Ca has a similar effect to Na, and their effects did not suppress each other when Na and Ca co-existed. For biotite, the inhibition effects of Na coupled with an enhancing effect due to ion exchange reaction between Na and interlayer K, which cracked the basal surfaces of biotite. The K in aqueous phase significantly inhibited the dissolution. If the biotite is equilibrated with NaCl solutions initially, the biotite dissolved faster than the original biotite and the dissolution was inhibited by Na and K in brine. The outcomes improve our current knowledge of silicates dissolution to the high salinity conditions in subsurface environments. In addition to cations, the role of anions in geochemical reactions in subsurfaces are important. This study investigated the anion effects by studying sulfate and oxalate. Sulfate formed monodentate surface complexes with the Al sites on plagioclase surface and enhanced the dissolution. Oxalate was also found to enhance the plagioclase dissolution. Co-existing oxalate and sulfate suppressed the effects of sulfate on plagioclase dissolution. This information provides useful insights for understanding the roles of sulfate and organic compounds on the CO2 water-mineral interactions during scCO2 enhanced oil recovery. The results also aid in formulating a scientific guideline of the proper amount of SO2 co-injection with CO2. Water in GCS sites can exist in water-bearing scCO2 in addition to the aqueous phase in brine. Thus, it is important to understand the effects of water-bearing scCO2 on the carbonation of silicates. To address the gap between the nano- and micro-sized particles used in the laboratory to the large grains in field sites, we utilized wollastonite and investigated the effects of particle sizes on the wollastonite carbonation in water-bearing scCO2. The thickness of the reacted layer on the particle surfaces was found to be constant for different sized particles. The amorphous silica layer formed act as a diffusion barrier for water-bearing scCO2. In addition, the reaction extent was higher with more water, lower temperature, and higher pressure. Further, higher water saturation percentage and lower temperature can lead to the formation of more permeable amorphous silica layers. This thesis included the investigations of both liquid phase and vapor phase water that contacted with scCO2, and the effects of cations and anions on both formation and caprock minerals. The findings from this work improve our knowledge of the geochemical reactions at CO2-water-mineral interfaces, which will help us design a safer GCS operation and assess the impacts of GCS on the environmental safety and quality.

Not just fractal surfaces, but surface fractal aggregates: Derivation of the expression for the structure factor and its applications

NASA Astrophysics Data System (ADS)

Besselink, R.; Stawski, T. M.; Van Driessche, A. E. S.; Benning, L. G.

2016-12-01

Densely packed surface fractal aggregates form in systems with high local volume fractions of particles with very short diffusion lengths, which effectively means that particles have little space to move. However, there are no prior mathematical models, which would describe scattering from such surface fractal aggregates and which would allow the subdivision between inter- and intraparticle interferences of such aggregates. Here, we show that by including a form factor function of the primary particles building the aggregate, a finite size of the surface fractal interfacial sub-surfaces can be derived from a structure factor term. This formalism allows us to define both a finite specific surface area for fractal aggregates and the fraction of particle interfacial sub-surfaces at the perimeter of an aggregate. The derived surface fractal model is validated by comparing it with an ab initio approach that involves the generation of a "brick-in-a-wall" von Koch type contour fractals. Moreover, we show that this approach explains observed scattering intensities from in situ experiments that followed gypsum (CaSO4 ṡ 2H2O) precipitation from highly supersaturated solutions. Our model of densely packed "brick-in-a-wall" surface fractal aggregates may well be the key precursor step in the formation of several types of mosaic- and meso-crystals.

Raman spectroscopy of the Dukhan sabkha: identification of geological and biogeological molecules in an extreme environment.

PubMed

Edwards, Howell G M; Sadooni, Fadhil; Vítek, Petr; Jehlicka, Jan

2010-07-13

The characterization of minerals and biogeological deposits in a terrestrial Arabian sabkha has a direct relevance for the exploration of Mars since the discovery by the NASA rovers Spirit and Opportunity of evaporate minerals on Mars that could have arisen from aquifers and subsurface water movement. The recognition of carbonates and sulphates in Gusev Crater has afforded an additional impetus to these studies, as relict or extant microbial extremophilic organisms could have colonized these geological matrices, as has been recorded on Earth. Here, we describe the Raman spectroscopic analysis of specimens of evaporitic materials sampled from the Dukhan sabkha, the largest inland sabkha in the Persian Gulf. With daily temperatures reaching in excess of 60 degrees C and extreme salinity, we have identified the characteristic Raman signatures of key biomolecular compounds in association with evaporitic minerals and geological carbonate and sulphate matrices, which indicate that extremophilic cyanobacterial colonies are existent there. This evidence, the first to be acquired spectroscopically from such a region, establishes a platform for further studies using remote, portable Raman instrumentation that will inform the potential of detection of similar systems on the Martian surface or subsurface in future space missions. A comparison is made between the results from this study and the previous analysis of a gypsum/halite sabkha where the extremophilic molecular signatures were better preserved.

Hydrogen sulfide release from dairy manure storages containing gypsum bedding

USDA-ARS?s Scientific Manuscript database

Recycled gypsum products can provide a cost-effective bedding alternative for dairy producers. Manufacturers report reduced odors, moisture and bacteria in the stall environment when compared to traditional bedding. Gypsum provides a sulfate source that can be converted to hydrogen sulfide under ana...

MARKETING OF BYPRODUCT GYPSUM FROM FLUE GAS DESULFURIZATION

EPA Science Inventory

The report gives results of an evaluation of the 1985 marketing potential of byproduct gypsum from utility flue gas desulfurization (FGD), for the area east of the Rocky Mountains, using the calculated gypsum production rates of 14 selected power plants. The 114 cement plants and...

Calcium sulfoaluminate (Ye'elimite) hydration in the presence of gypsum, calcite, and vaterite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hargis, Craig W.; Telesca, Antonio; Monteiro, Paulo J.M., E-mail: monteiro@ce.berkeley.edu

Six calcium sulfoaluminate-based cementitious systems composed of calcium sulfoaluminate, calcite, vaterite, and gypsum were cured as pastes and mortars for 1, 7, 28 and 84 days. Pastes were analyzed with X-ray diffraction, thermogravimetric and differential thermal analyses. Mortars were tested for compressive strength, dimensional stability and setting time. Furthermore, pastes with a water/cementitious material mass ratio of 0.80 were tested for heat evolution during the first 48 h by means of isothermal conduction calorimetry. It has been found that: (1) both calcite and vaterite reacted with monosulfoaluminate to give monocarboaluminate and ettringite, with vaterite being more reactive; (2) gypsum loweredmore » the reactivity of both carbonates; (3) expansion was reduced by calcite and vaterite, irrespective of the presence of gypsum; and (4) both carbonates increased compressive strength in the absence of gypsum and decreased compressive strength less in the presence of gypsum, with vaterite's action more effective than that of calcite.« less

Fate of Mercury in Synthetic Gypsum Used for Wallboard Production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jessica Sanderson

2007-12-31

This report presents and discusses results from the project 'Fate of Mercury in Synthetic Gypsum Used for Wallboard Production', performed at five different full-scale commercial wallboard plants. Synthetic gypsum produced by wet flue gas desulfurization (FGD) systems on coal-fired power plants is commonly used in the manufacture of wallboard. This practice has long benefited the environment by recycling the FGD gypsum byproduct, which is becoming available in increasing quantities, decreasing the need to landfill this material, and increasing the sustainable design of the wallboard product. However, new concerns have arisen as recent mercury control strategies involve the capture of mercurymore » in FGD systems. The objective of this study has been to determine whether any mercury is released into the atmosphere at wallboard manufacturing plants when the synthetic gypsum material is used as a feedstock for wallboard production. The project has been co-funded by the U.S. DOE National Energy Technology Laboratory (Cooperative Agreement DE-FC26-04NT42080), USG Corporation, and EPRI. USG Corporation is the prime contractor, and URS Group is a subcontractor. The project scope included seven discrete tasks, each including a test conducted at various USG wallboard plants using synthetic gypsum from different wet FGD systems. The project was originally composed of five tasks, which were to include (1) a base-case test, then variations representing differing power plant: (2) emissions control configurations, (3) treatment of fine gypsum particles, (4) coal types, and (5) FGD reagent types. However, Task 5,could not be conducted as planned and instead was conducted at conditions similar to Task 3. Subsequently an opportunity arose to test gypsum produced from the Task 5 FGD system, but with an additive expected to impact the stability of mercury, so Task 6 was added to the project. Finally, Task 7 was added to evaluate synthetic gypsum produced at a power plant from an additional coal type. In the project, process stacks in the wallboard plant were sampled using the Ontario Hydro method. In every task, the stack locations sampled included a gypsum dryer and a gypsum calciner. In Tasks 1 and 4 through 7, the stack of the dryer for the wet wallboard product was also tested. Also at each site, in-stream process samples were collected and analyzed for mercury concentration before and after each significant step in wallboard production. These results and process data were used to construct mercury mass balances across the wallboard plants. The results from the project showed a wide range of percentage mercury losses from the synthetic gypsum feedstocks as measured by the Ontario Hydro method at the process stacks, ranging from 2% to 55% of the mercury in the gypsum feedstock. For the tasks exceeding 10% mercury loss across the wallboard plant, most of the loss occurred across the gypsum calciner. When total wallboard emissions remained below 10%, the primary emission location varied with a much less pronounced difference in emission between the gypsum dryer, calciner and board dryer. For all seven tasks, the majority of the mercury emissions were measured to be in the elemental form (Hg{sup 0}). Overall, the measured mercury loss mass rates ranged from 0.01 to 0.17 grams of mercury per dry ton of synthetic gypsum processed, or 0.01 to 0.4 pounds of mercury released per million square feet of wallboard produced from synthetic gypsum. The Coal Combustion Product Production and Use Survey from the American Coal Ash Association (ACAA) indicate that 7,579,187 short tons of synthetic gypsum were used for wallboard production in 2006. Extrapolating the results of this study to the ACAA industry usage rate, we estimate that mercury releases from wallboard production plants in 2006 ranged between 150 to 3000 pounds for the entire U.S. wallboard industry. With only seven sets of wallboard plant measurements, it is difficult to draw firm conclusions about what variables impact the mercury loss percentages across the wallboard plants. One significant observation from this study was that higher purge rates of chlorides and fine solid particles from the wet FGD systems appear to produce gypsum with lower mercury concentrations. Any chemical interaction between mercury and chlorides is not well understood; however, based on the information available the lower mercury content in the gypsum product is likely due to the blow down of fine, mercury-rich particles as opposed to a decreased chloride concentration. One possible explanation is that a decrease of fine particles in the FGD slurry allows for less adsorption of mercury onto those particles, thus the mercury remains with the FGD liquor rather than the gypsum product. A more detailed discussion on synthetic gypsum sources and FGD chemistry data can be found in the Experimental section of this report and Table 4.« less

Impact of welan gum on tricalcium aluminate-gypsum hydration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma Lei, E-mail: malei198713@163.com; Zhao Qinglin, E-mail: zhaoqinglin@whut.edu.cn; Yao Chukang

The retarding effect of welan gum on tricalcium aluminate-gypsum hydration, as a partial system of ordinary Portland cement (OPC) hydration, was investigated with several methods. The tricalcium aluminate-gypsum hydration behavior in the presence or absence of welan gum was researched by field emission gun scanning electron microscopy, X-ray diffraction and zeta potential analysis. Meanwhile, we studied the surface electrochemical properties and adsorption characteristics of welan gum by utilizing a zeta potential analyzer and UV-VIS absorption spectrophotometer. By adding welan gum, the morphology change of ettringite and retardation of hydration stages in tricalcium aluminate-gypsum system was observed. Moreover, we detected themore » adsorption behavior and zeta potential inversion of tricalcium aluminate and ettringite, as well as a rapid decrease in the zeta potential of tricalcium aluminate-gypsum system. The reduction on nucleation rate of ettringite and hydration activity of C{sub 3}A was also demonstrated. Thus, through the adsorption effect, welan gum induces a retarding behavior in tricalcium aluminate-gypsum hydration. Highlights: Black-Right-Pointing-Pointer Adsorption characteristics of welan gum on C{sub 3}A and ettringite have been studied. Black-Right-Pointing-Pointer C{sub 3}A-gypsum hydration behavior and the hydration products are examined in L/S = 3. Black-Right-Pointing-Pointer Welan gum retards the process of C{sub 3}A-gypsum hydration. Black-Right-Pointing-Pointer The addition of welan gum changes the nucleation growth of ettringite.« less

Sustainable uses of FGD gypsum in agricultural systems

USDA-ARS?s Scientific Manuscript database

Interest in using gypsum as a management tool to improve crop yields and soil/water quality has recently increased. Abundant supply and availability of flue gas desulfurization (FGD) gypsum, a by-product of scrubbing sulfur (S) from combustion gases at coal-fired power plants, in major agricultural...

Mineral precipitation and dissolution at two slag-disposal sites in northwestern Indiana, USA

USGS Publications Warehouse

Bayless, E.R.; Schulz, M.S.

2003-01-01

Slag is a ubiquitous byproduct of the iron- and steel-refining industries. In northwestern Indiana and northeastern Illinois, slag has been deposited over more than 52 km2 of land surface. Despite the widespread use of slag for fill and construction purposes, little is known about its chemical effects on the environment. Two slagdisposal sites were examined in northwestern Indiana where slag was deposited over the native glacial deposits. At a third site, where slag was not present, background conditions were defined. Samples were collected from cores and drill cuttings and described with scanning electron microscopy and electron microprobe analysis. Ground-water samples were collected and used to assess thermodynamic equilibria between authigenic minerals and existing conditions. Differences in the mineralogy at background and slag-affected sites were apparent. Calcite, dolomite, gypsum, iron oxides, and clay minerals were abundant in native sediments immediately beneath the slag. Mineral features indicated that these minerals precipitated rapidly from slag drainage and co-precipitated minor amounts of non-calcium metals and trace elements. Quartz fragments immediately beneath the slag showed extensive pitting that was not apparent in sediments from the background site, indicating chemical weathering by the hyperalkaline slag drainage. The environmental impacts of slag-related mineral precipitation include disruption of natural ground-water flow patterns and bed-sediment armoring in adjacent surface-water systems. Dissolution of native quartz by the hyperalkaline drainage may cause instability in structures situated over slag fill or in roadways comprised of slag aggregates.

Hydrochemical processes and evolution of karst groundwater in the northeastern Huaibei Plain, China

NASA Astrophysics Data System (ADS)

Qian, Jiazhong; Peng, Yinxue; Zhao, Weidong; Ma, Lei; He, Xiaorui; Lu, YueHan

2018-06-01

Major ion geochemistry reveals that the hydrochemical evolutionary process of karst groundwater in the northeastern Huaibei Plain, China, consists of three sub-processes: the dissolution of dolomite, gypsum dissolution with dedolomitization, and mixing with overlying pore water. Understanding hydrochemical evolution has been an important topic in understanding the history, status, and dynamics of the groundwater flow system. The presented study found a hydrochemical boundary roughly corresponding to the thickness of overlying strata equating to 50 m depth, indicating two flow compartments participating in different hydrological cycles—a local shallow rapidly replenished compartment showing lower and more stable main ion concentrations, and a regional deep-flow compartment showing higher and sporadic concentrations of Na+, K+, Ca2+, Mg2+, Cl- and SO4 2-, as well as high total dissolved solids (TDS), total hardness, and sodium adsorption ratio (SAR). In areas with aquifers with low water transmitting ability, groundwater samples show a high chloride ratio and elevated TDS values, indicating salinization of groundwater due to stagnant water flows. Analyses of the data on the saturation indexes and mineral solutions, in tandem with trilinear diagram analysis and petrological observations, indicate that dedolomitization is the dominant process controlling the chemical characteristics of karst groundwater in the study area. Groundwater and pore-water mixing was also observed at the later evolutionary stage of groundwater flow, demonstrating frequent groundwater/pore-water interactions where groundwater is recharged by pore water due to lower groundwater level in the study area.

Strontium isotopes as an indicator for groundwater salinity sources in the Kirkuk region, Iraq.

PubMed

Sahib, Layth Y; Marandi, Andres; Schüth, Christoph

2016-08-15

The Kirkuk region in northern Iraq hosts some of the largest oil fields in the Middle East. Several anticline structures enabled vertical migration and entrapment of the oil. Frequently, complex fracture systems and faults cut across the Eocene and middle Oligocene reservoirs and the cap rock, the Fatha Formation of Miocene age. Seepage of crude oil and oil field brines are therefore a common observation in the anticline axes and contamination of shallow groundwater resources is a major concern. In this study, 65 water samples were collected in the Kirkuk region to analyze and distinguish mixing processes between shallow groundwater resources, uprising oil field brines, and dissolution of gypsum and halite from the Fatha Formation. Hydrochemical analyses of the water samples included general hydrochemistry, stable water isotopes, as well as strontium concentrations and for 22 of the samples strontium isotopes ((87)Sr/(86)Sr). Strontium concentrations increased close to the anticline axes with highest concentrations in the oil field brines (300mg/l). Strontium isotopes proved to be a valuable tool to distinguish mixing processes as isotope signatures of the oil field brines and of waters from the Fatha Formation are significantly different. It could be shown, that mixing of shallow groundwater with oil field brines is occurring close to the major fault zones in the anticlines but high concentrations of strontium in the water samples are mainly due to dissolution from the Fatha Formation. Copyright © 2016 Elsevier B.V. All rights reserved.

The chemical evolution of Kurnub Group palcowater in the Sinai-Negev province - A mass balance approach

USGS Publications Warehouse

Rosenthal, E.; Jones, B.F.; Weinberger, G.

1998-01-01

The chemical evolution of the Kurnub Group paleowater was studied starting from rainwater in recharge areas of the Sinai and along groundwater flowpaths leading to the natural outlets of this regional aquifer. This was achieved by investigating the chemical composition of groundwater, ionic ratios, degrees of saturation with common mineral species, normative analysis of dissolved salts and by modeling of rock/water interaction and mixing processes occurring along groundwater flow paths. The initial groundwater composition used is from the Nakhel well in Sinai. It evolves from desert rainwater percolating through typical Kurnub Group lithology in Sinai. This rainwater dissolves mainly gypsum, halite and dolomite together with smaller amounts of marine aerosol and K-feldspar. At the same time it precipitates calcite, SiO2, smectite and degasses CO2. Between the area of Nakhel and the northern Negev the chemistry of Kurnub Group waters is influenced by dissolution of halite and lesser amounts of gypsum of surficial origin in recharge areas, small amounts of feldspars and of dolomite cement in sandstones eroded from the Arabo-Nubian igneous massif of Sinai and organic degradation-derived CO2. Concomitantly, there is precipitation of calcite, smectite, SiO2 and probably analcime characteristic of sediments in continental closed basins. North of the Negev, the Kurnub Group fluids are diluted and altered by mixing with Judea Group aquifer groundwaters. On the E there is mixing with residual brines from the water body ancestral to the Dead Sea, prior to discharge into the Arava valley. Rock/water interaction indicated by NETPATH and PHREEQC modeling is in agreement with lithology and facies changes previously observed in the Kurnub Group sequence.

Dynamic three-dimensional pore-scale imaging of reaction in a carbonate at reservoir conditions.

PubMed

Menke, Hannah P; Bijeljic, Branko; Andrew, Matthew G; Blunt, Martin J

2015-04-07

Quantifying CO2 transport and average effective reaction rates in the subsurface is essential to assess the risks associated with underground carbon capture and storage. We use X-ray microtomography to investigate dynamic pore structure evolution in situ at temperatures and pressures representative of underground reservoirs and aquifers. A 4 mm diameter Ketton carbonate core is injected with CO2-saturated brine at 50 °C and 10 MPa while tomographic images are taken at 15 min intervals with a 3.8 μm spatial resolution over a period of 2(1/2) h. An approximate doubling of porosity with only a 3.6% increase in surface area to volume ratio is measured from the images. Pore-scale direct simulation and network modeling on the images quantify an order of magnitude increase in permeability and an appreciable alteration of the velocity field. We study the uniform reaction regime, with dissolution throughout the core. However, at the pore scale, we see variations in the degree of dissolution with an overall reaction rate which is approximately 14 times lower than estimated from batch measurements. This work implies that in heterogeneous rocks, pore-scale transport of reactants limits dissolution and can reduce the average effective reaction rate by an order of magnitude.

Gypsum as a bedding source for broiler chickens

USDA-ARS?s Scientific Manuscript database

Three trials examined the feasibility of flue gas desulfurization gypsum as a bedding material for raising broilers. Gypsum was used alone, under or on top of pine shavings and pine bark. Test materials were placed as bedding in pens to simulate commercial broiler production through three growout cy...

An important tool with no instruction manual: A review of gypsum use in agriculture

USDA-ARS?s Scientific Manuscript database

Land application of gypsum has been studied and utilized in agriculture and environmental remediation for many years. Most of the published literature has focused on gypsum application impacts on soil properties rather than crop yields. This literature review was conducted to (i) gather results from...

Impact of FGD gypsum on soil fertility and plant nutrient uptake

USDA-ARS?s Scientific Manuscript database

Use of FGD gypsum is thought to improve soil productivity and increase plant production. Thus, a study was conducted to evaluate the effects of FGD gypsum on yield, plant nutrient uptake and soil productivity. The study was conducted on an established bermudagrass pasture. Poultry litter was applied...

Analyzing the rules of fracture and damage, and the characteristics of the acoustic emission signal of a gypsum specimen under uniaxial loading

NASA Astrophysics Data System (ADS)

Chen, Dong; Wang, En-yuan; Li, Nan

2017-08-01

In order to study the mechanism of rock bursts in a mined-out area of a gypsum mine, in this paper acoustic emission testing of the uniaxial compression of gypsum and sandstone samples is carried out. The case of rupture of the specimen is observed, and the load axial deformation curve and acoustic emission parameters are obtained for the whole process of specimen rupture. The similarities and differences between the gypsum and sandstone samples are determined in terms of their mechanical properties, their damage evolution laws and frequency band energy distributions, and the instantaneous energy characteristics of their acoustic emission. The results show that the main fracture morphology of gypsum is ‘eight’-type, and the macroscopic fracture morphology of sandstone is mainly of partial ‘Y’-type and inverted Y-type. The intensity and uniformity of the gypsum and sandstone of the medium are different; because the gypsum is more uniform, it does not show as much variation as sandstone, instead suddenly increasing and decreasing. The maximum value of the damage variable D of gypsum reached 1, but the maximum value of D of the sandstone only reached 0.9. The frequency band of the maximum energy of gypsum and sandstone gradually decreased across the the four stages of rupture, while the maximum energy percentage increased gradually. From the stage where damage gradually increases to the stage of integral fracture of the specimen, the instantaneous energy showed a certain degree of increase. With an increase in the strength of the sample, the maximum energy percentage of the two materials corresponding to each phase gradually increases, and from the stage where damage gradually increases to the stage of integral fracture of the specimen, the value of instantaneous energy obviously increases. The results indicate that gypsum mines will also experience rock bursts, as coal mines do, but the intensity will be different. Therefore, using the three indicators, the frequency band of the maximum energy, the maximum energy percentage, and the maximum instantaneous energy, the rupture of the sample can be predicted, which can be used to improve the accuracy and efficiency of early warning systems for rock bursts in gypsum mines.

Inverse geochemical modeling of groundwater evolution with emphasis on arsenic in the Mississippi River Valley alluvial aquifer, Arkansas (USA)

USGS Publications Warehouse

Sharif, M.U.; Davis, R.K.; Steele, K.F.; Kim, B.; Kresse, T.M.; Fazio, J.A.

2008-01-01

Inverse geochemical modeling (PHREEQC) was used to identify the evolution of groundwater with emphasis on arsenic (As) release under reducing conditions in the shallow (25-30 m) Mississippi River Valley Alluvial aquifer, Arkansas, USA. The modeling was based on flow paths defined by high-precision (??2 cm) water level contour map; X-ray diffraction (XRD), scanning electron microscopic (SEM), and chemical analysis of boring-sediments for minerals; and detailed chemical analysis of groundwater along the flow paths. Potential phases were constrained using general trends in chemical analyses data of groundwater and sediments, and saturation indices data (MINTEQA2) of minerals in groundwater. Modeling results show that calcite, halite, fluorite, Fe oxyhydroxide, organic matter, H2S (gas) were dissolving with mole transfers of 1.40E - 03, 2.13E - 04, 4.15E - 06, 1.25E + 01, 3.11, and 9.34, respectively along the dominant flow line. Along the same flow line, FeS, siderite, and vivianite were precipitating with mole transfers of 9.34, 3.11, and 2.64E - 07, respectively. Cation exchange reactions of Ca2+ (4.93E - 04 mol) for Na+ (2.51E - 04 mol) on exchange sites occurred along the dominant flow line. Gypsum dissolution reactions were dominant over calcite dissolution in some of the flow lines due to the common ion effect. The concentration of As in groundwater ranged from <0.5 to 77 ??g/L. Twenty percent total As was complexed with Fe and Mn oxyhydroxides. The redox environment, chemical data of sediments and groundwater, and the results of inverse geochemical modeling indicate that reductive dissolution of Fe oxyhydroxide is the dominant process of As release in the groundwater. The relative rate of reduction of Fe oxyhydroxide over SO42 - with co-precipitation of As into sulfide is the limiting factor controlling dissolved As in groundwater. ?? 2007 Elsevier B.V. All rights reserved.

Operator Exposure to Hydrogen Sulfide from Dairy Manure Storages Containing Gypsum Bedding.

PubMed

Fabian-Wheeler, Eileen E; Hile, Michael L; Murphy, Dennis J; Hill, Davis E; Meinen, Robert; Brandt, Robin C; Elliott, Hershel A; Hofstetter, Daniel

2017-01-26

Dairy manure storages containing gypsum-based bedding have been linked anecdotally with injury and death due to presumed dangerous levels of gases released. Recycled gypsum products are used as a cost-effective bedding alternative to improve animal welfare and provide agronomic benefits to manure recycled back to the land. Sulfur contained in gypsum (calcium sulfate) can contribute to hydrogen sulfide (H2S) gas formation under the anaerobic storage conditions typical of dairy manure slurry. Disturbance of stored manure during agitation releases a burst of volatile gases. On-farm monitoring was conducted to document conditions during manure storage agitation relative to gas concentration and operator safety. One objective was to document operator exposure to H2S levels; therefore, each operator wore a personal gas monitor while performing tasks associated with manure storage agitation. Data from three dairy bedding management categories on ten farms were compared: (1) traditional organic bedding, (2) gypsum bedding, and (3) gypsum bedding plus a manure additive thought to reduce H2S formation and/or release. Portable meters placed around the perimeter of dairy manure storages recorded H2S concentrations prior to and during 19 agitation events. Results show that farms using gypsum bedding produced higher H2S concentrations during manure storage agitation than farms using traditional bedding. In most cases, gypsum-containing manure storages produced H2S levels above recognized safe thresholds for both livestock and humans. Farm operators were most at risk during activities in close proximity to the manure storage during agitation, and conditions 10 m away from the storage were above the 20 ppm H2S threshold on some farms using gypsum bedding. Although H2S concentrations rose to dangerous levels, only two of 18 operators were exposed to >50 ppm H2S during the first 60 min of manure storage agitation. Operators who are aware of the risk of high H2S concentrations near gypsum-laden manure storages can reduce their exposure risk by working upwind and away from the H2S plume within a closed tractor cab. Copyright© by the American Society of Agricultural Engineers.

Messinian Salinity Crisis' Primary Evaporites: the shallow gypsum vs. deep dolomite formation paradox solved

NASA Astrophysics Data System (ADS)

De Lange, G. J.; Krijgsman, W.

2015-12-01

The Messinian Salinity Crisis (MSC) is a dramatic event that took place ~ 5.9 Ma ago, resulting in deposition of 1-3 km thick evaporites at the Mediterranean seafloor. A considerable, long-lasting controversy existed on the modes of their formation, including the observed shallow gypsum versus deep dolostone deposits for the early phase of MSC. The onset of MSC is marked by deposition of gypsum/sapropel-like alternations, thought to relate to arid/humid climate conditions at a precessional rhythm. Gypsum precipitation only occurred at marginal- and dolomite formation at deeper settings. A range of potential explanations was given, most of which cannot satisfactorily explain all observations. Biogeochemical processes during MSC are commonly neglected but may explain that different deposits formed in shallow vs deep environments without exceptional physical boundary conditions for each. A unifying mechanism is presented in which gypsum formation occurs at all shallow water depths but its preservation is limited to shallow sedimentary settings. In contrast, ongoing deep-basin anoxic organic matter (OM) degradation processes result in dolomite formation. Gypsum precipitation in evaporating seawater takes place at 3-7 times concentrated seawater; seawater is always oversaturated relative to dolomite but its formation is inhibited by the presence of dissolved sulphate. Thus conditions for formation of gypsum exclude those for formation of dolomite and vice versa. Another process linking the saturation states of gypsum and dolomite is that of OM degradation by sulphate reduction. In stagnant deep water, ongoing OM-degradation may result in reducing the sulphate and enhancing the dissolved carbonate content. Such low-sulphate / high carbonate conditions in MSC deepwater are. unfavorable for gypsum preservation and favorable for dolomite formation, and always coincide with anoxic, i.e. oxygen-free conditions. Including dynamic biogeochemical processes in the thusfar static interpretations of evaporite formation mechanisms can thus account for the paradoxal, isochronous formation of shallow gypsum and deep-dolomite during the early MSC (1). (1) De Lange G.J. and Krijgsman W. (2010) Mar. Geol. 275, 273-277

Stratigraphy and depositional environments of Jurassic Gypsum Spring and Sundance Formations, Sheep Mountain anticline area, Big Horn County, Wyoming

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doyle, A.B.

1986-08-01

The Sheep Mountain anticlinal complex between Lovell and Greybull, Wyoming, in the Bighorn basin provides exposure suitable for three-dimensional stratigraphic studies of Mesozoic rocks. The lower unit of the Gypsum Spring Formation is interbedded shale and gypsum. The middle unit is a cyclic sequence of variegated shales, mudstones, and wackestones. The upper unit is red shale. The contact between the underlying Upper Triassic Chugwater Group and the Gypsum Spring Formation is unconformable, as evidenced by an erosional surface. The Sundance Formation is divided into Sundance A and Sundance B, based on fossil data. Sundance A is predominantly green shale withmore » some limestone-shale interbeds. Sundance B lithology is similar to Sundance A with belemnoid guards. Toward the top of Sundance B are beds of glauconitic sandstones that grade upward into fossiliferous limestone. The contact between the Gypsum Spring, Sundance, and Morrison Formations appears to be gradational. The Western Interior sedimentary basin experienced four major transgressions during the Jurassic, resulting in the deposition of the Gypsum Spring and Sundance. Gypsum Spring deposition was influenced by paleohighs, specifically the Belt Island and Sheridan arch, and a warm, arid climate with rare storms. The lower Gypsum Spring unit was deposited in a restricted basin, with the middle and upper units reflecting subsequent deepening and freshening of the Jurassic sea. Most of the Sundance Formation was deposited in a relatively quiet, open-marine environment. Individual units represent shoaling conditions during minor regressions. Storms cut channels into sand bars, which were filled with coquinoid deposits.« less

Use of FGD gypsum on a bermudagrass pasture in the Appalachian Plateau Region

USDA-ARS?s Scientific Manuscript database

Addition of industrial by-products from coal fired power plants (FGD gypsum and FGD gypsum + fly ash) are thought to increase plant production. Thus, a study was conducted to evaluate the effects of industrial by-products as a soil amendment on bermudagrass (Cynodon dactylon L.) yield. The study was...

Effect of gypsum application on mineral composition in peanut pod walls and seeds

USDA-ARS?s Scientific Manuscript database

Alleviation of soil-Ca deficiency through gypsum amendment increases the yield potential and ensures high seed quality in peanut (Arachis hypogaea L.). The effects of gypsum treatment, plant life cycle stage, and the fruit development stages on the accrual of several essential minerals (Ca, S, Mg, P...

Potential of a gypsum-free composting process of wheat straw for mushroom production.

PubMed

Mouthier, Thibaut M B; Kilic, Baris; Vervoort, Pieter; Gruppen, Harry; Kabel, Mirjam A

2017-01-01

Wheat straw based composting generates a selective substrate for mushroom production. The first phase of this process requires 5 days, and a reduction in time is wished. Here, we aim at understanding the effect of gypsum on the duration of the first phase and the mechanism behind it. Hereto, the regular process with gypsum addition and the same process without gypsum were studied during a 5-day period. The compost quality was evaluated based on compost lignin composition analysed by py-GC/MS and its degradability by a commercial (hemi-)cellulolytic enzyme cocktail. The composting phase lead to the decrease of the pyrolysis products 4-vinylphenol and 4-vinylguaiacol that can be associated with p-coumarates and ferulates linking xylan and lignin. In the regular compost, the enzymatic conversion reached 32 and 39% for cellulose, and 23 and 32% for xylan after 3 and 5 days, respectively. In absence of gypsum similar values were reached after 2 and 4 days, respectively. Thus, our data show that in absence of gypsum the desired compost quality was reached 20% earlier compared to the control process.

Potential of a gypsum-free composting process of wheat straw for mushroom production

PubMed Central

Mouthier, Thibaut M. B.; Kilic, Baris; Vervoort, Pieter; Gruppen, Harry

2017-01-01

Wheat straw based composting generates a selective substrate for mushroom production. The first phase of this process requires 5 days, and a reduction in time is wished. Here, we aim at understanding the effect of gypsum on the duration of the first phase and the mechanism behind it. Hereto, the regular process with gypsum addition and the same process without gypsum were studied during a 5-day period. The compost quality was evaluated based on compost lignin composition analysed by py-GC/MS and its degradability by a commercial (hemi-)cellulolytic enzyme cocktail. The composting phase lead to the decrease of the pyrolysis products 4-vinylphenol and 4-vinylguaiacol that can be associated with p-coumarates and ferulates linking xylan and lignin. In the regular compost, the enzymatic conversion reached 32 and 39% for cellulose, and 23 and 32% for xylan after 3 and 5 days, respectively. In absence of gypsum similar values were reached after 2 and 4 days, respectively. Thus, our data show that in absence of gypsum the desired compost quality was reached 20% earlier compared to the control process. PMID:28982119

Fate of Mercury in Synthetic Gypsum Used for Wallboard Production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jessica Sanderson; Gary M. Blythe; Mandi Richardson

2006-12-01

This report presents and discusses results from Task 6 of the study 'Fate of Mercury in Synthetic Gypsum Used for Wallboard Production,' performed at a full-scale commercial wallboard plant. Synthetic gypsum produced by wet flue gas desulfurization (FGD) systems on coal-fired power plants is commonly used in the manufacture of wallboard. This practice has long benefited the environment by recycling the FGD gypsum byproduct, which is becoming available in increasing quantities, decreasing the need to landfill this material, and increasing the sustainable design of the wallboard product. However, new concerns have arisen as recent mercury control strategies involve the capturemore » of mercury in FGD systems. The objective of this study is to determine whether any mercury is released into the atmosphere when the synthetic gypsum material is used as a feedstock for wallboard production. The project is being co-funded by the U.S. DOE National Energy Technology Laboratory (Cooperative Agreement DE-FC26-04NT42080), USG Corporation, and EPRI. USG Corporation is the prime contractor, and URS Group is a subcontractor. The project scope now includes six discrete tasks, each conducted at various USG wallboard plants using synthetic gypsum from different FGD systems. The project was originally composed of five tasks, which were to include (1) a baseline test, then variations representing differing power plant: (2) emissions control configurations, (3) treatment of fine gypsum particles, (4) coal types, and (5) FGD reagent types. However, Task 5, which was to include testing with an alternate FGD reagent, could not be conducted as planned. Instead, Task 5 was conducted at conditions similar to Task 3, although with gypsum from an alternate FGD system. Subsequent to conducting Task 5 under these revised conditions, an opportunity arose to test gypsum produced at the same FGD system, but with an additive (Degussa Corporation's TMT-15) being used in the FGD system. TMT-15 was expected to impact the stability of mercury in synthetic gypsum used to produce wallboard, so Task 6 was added to the project to test this theory. In this project, process stacks in the wallboard plant have been sampled using the Ontario Hydro method. For every task, the stack locations sampled have included a dryer for the wet gypsum as it enters the plant and a gypsum calciner. For Tasks 1, 4, 5 and 6, the stack of the dryer for the wet wallboard product was also tested. Also at each site, in-stream process samples were collected and analyzed for mercury concentration before and after each significant step in wallboard production. The Ontario Hydro results, process sample mercury concentration data, and process data were used to construct mercury mass balances across the wallboard plants. Task 6 was conducted at a wallboard plant processing synthetic gypsum from a power plant that fires Eastern bituminous coal. The power plant has a single-loop, open spray tower limestone forced oxidation FGD system, with the forced oxidation conducted in the reaction tank integral with the FGD absorber. The FGD system has gypsum fines blow down as part of the dewatering step. The power plant is equipped with a selective catalytic reduction (SCR) system for NOX emissions control, and the SCR was in service during the time period the gypsum tested was produced. Also, as mentioned above, Degussa additive TMT-15 was being added to the FGD system when this gypsum was produced. The results of the Task 6 stack testing, as measured by the Ontario Hydro method, detected that an average of 55% of the incoming mercury was emitted during wallboard production. These losses were distributed as about 4% across the dryer mill, 6% across the board dryer kiln, and 45% across the kettle calciner. Emissions were similar to what Task 5 results showed on a percentage basis, but about 30% lower on a mass basis. The same power plant FGD system produced the synthetic gypsum used in Task 5 (with no use of TMT-15) and in Task 6 (with TMT-15 added to the FGD system). The lower emissions on a mass basis appeared to be due to lower average mercury content in the gypsum being processed. It is not certain whether the lower average mercury content in the gypsum was an effect of TMT-15 addition to the FGD system. As was seen in the Task 1 through 5 results, most of the mercury detected in the Ontario Hydro method stack testing was in the form of elemental mercury.« less

Electrochemical characterization of cerium-based conversion coatings on aluminum alloy 7075-T6

NASA Astrophysics Data System (ADS)

Joshi, Simon

This research used electrochemical techniques to characterize the deposition and corrosion protection behavior of cerium-based conversion coatings on Al 7075-T6. Alkaline activation decreased native oxide impedance (5.9 kO-cm2) by ˜25% promoting deposition of 250--500 nm coatings. Activation in NaOH solutions deposited coatings with large cracks and craters, whereas Na2CO3 activation resulted in uniform coatings, i.e., fewer cracks and almost no craters. Uniformly deposited coatings exhibited better cathodic inhibition and higher impedance (˜200 kO-cm 2) than on NaOH activated substrates (˜100 kO-cm 2). Subsurface crevices, caused by Cl- and H 2O2 in the deposition solution, were found under large cracks and craters. Thus, Na2CO3 activation produced fewer subsurface crevices. To reduce subsurface crevice formation, Ce(NO3) 3 and CeCl3 were used in different ratios. Coatings made using 100% Ce(NO3)3 solutions were ˜60 nm thick without subsurface crevices, but the coatings offered little corrosion protection. Despite formation of subsurface crevices, Cl- was necessary as impedance increased linearly with Cl- concentration in the deposition solution. To characterize the different non-uniform features of the coatings, microelectrochemical testing was performed and it showed three distinct regions: active, intermediate, and passive. Humidity experiments were performed to understand the effect of moisture during salt spray testing and showed an increase in coating impedance by making the exposed substrate oxide more passive. However, this passive oxide could not provide corrosion resistance in a chloride environment. Dissolution studies showed that cerium migration was only possible at pH ≤2. Overall, deposition of uniform 250--500 nm thick outings was essential to make it an effective barrier to Cl - attach and prevent subsurface crevices on Al 7075-T6.

XRD and mineralogical analysis of gypsum dunes at White Sands National Monument, New Mexico and applications to gypsum detection on Mars

NASA Astrophysics Data System (ADS)

Lafuente, B.; Bishop, J. L.; Fenton, L. K.; King, S. J.; Blake, D.; Sarrazin, P.; Downs, R.; Horgan, B. H.

2013-12-01

A field portable X-ray Diffraction (XRD) instrument was used at White Sands National Monument to perform in-situ measurements followed by laboratory analyses of the gypsum-rich dunes and to determine its modal mineralogy. The field instrument is a Terra XRD (Olympus NDT) based on the technology of the CheMin (Chemistry and Mineralogy) instrument onboard the Mars Science Laboratory (MSL) rover Curiosity which is providing the mineralogical and chemical composition of scooped soil samples and drilled rock powders collected at Gale Crater [1]. Using Terra at White Sands will contribute to 'ground truth' for gypsum-bearing environments on Mars. Together with data provided by VNIR spectra [2], this study clarifies our understanding of the origin and history of gypsum-rich sand dunes discovered near the northern polar region of Mars [3]. The results obtained from the field analyses performed by XRD and VNIR spectroscopy in four dunes at White Sands revealed the presence of quartz and dolomite. Their relative abundance has been estimated using the Reference Intensity Ratio (RIR) method. For this study, particulate samples of pure natural gypsum, quartz and dolomite were used to prepare calibration mixtures of gypsum-quartz and gypsum-dolomite with the 90-150μm size fractions. All single phases and mixtures were analyzed by XRD and RIR factors were calculated. Using this method, the relative abundance of quartz and dolomite has been estimated from the data collected in the field. Quartz appears to be present in low amounts (2-5 wt.%) while dolomite is present at percentages up to 80 wt.%. Samples from four dunes were collected and prepared for subsequent XRD analysis in the lab to estimate their composition and illustrate the changes in mineralogy with respect to location and grain size. Gypsum-dolomite mixtures: The dolomite XRD pattern is dominated by an intense diffraction peak at 2θ≈36 deg. which overlaps a peak of gypsum, This makes low concentrations of dolomite difficult to quantify in mixtures with high concentration of gypsum. Dolomite has been detected in some locations at dune 3 as high as 80 wt.%. Gypsum-quartz mixtures: The intensity of the main diffraction peak of quartz at 2θ≈31 deg. decreases progressively with the decrease of the amount of quartz in the mixtures. Samples from dune 1 and 2 show quartz abundance at 5.6 and 2.6 wt.% respectively . [1] Blake et al. Space Sci. Rev. (2012). doi:10.1007/s11214-012-9905-1. [2] King et al. (2013) AGU, submitted. [3] Langevin et al. (2005). Science 307, 1584-1586.

Hydrogeochemical characteristics and assessment of water quality in the Al-Saad Lake, Abha Saudi Arabia

NASA Astrophysics Data System (ADS)

Mallick, Javed

2017-10-01

Hydrogeochemical characteristics and assessment of water quality investigations have been carried out at Abha, located in Saudi Arabia, where Al-Saad Lake represents a rare example of natural endorheic lake. The ecosystem within and around the Al-Saad Lake including catchment area is of great social, cultural, aesthetic, environmental and economic values to Abha. Sampling and experiments of lake water has been carried out with the aim of characterizing the main physico-chemical parameters, such as DO, EC, TDS, Mg2+, Ca2+, Na+, K+, SO4 2-, Cl-, HCO3, NO3 - and F- concentration. The ordinary kriging (OK) method was used to produce the spatial patterns of water quality. The Result of DO (mean 5.38 mg/L) trend in Al-Saad Lake is not very encouraging as majority of the lake area is under DO stress or marginally above it. So, proper management strategies are needed to be formulated to protect flora and fauna of the lake. Furthermore, the chemical analysis results show the abundance of the major cations in the order Mg2+ > Ca2+ > Na+ > K+ whereas the abundance of anions are in the order SO4 2- > Cl- > HCO3 > NO3 - > F-. The result obtained in this investigation inferred that the cations in water i.e. sodium and iron are within the permissible limits but magnesium and potassium have exceeded the permissible limit. Whereas anions such as nitrate and fluoride are within the permissible range but chloride and sulphate have exceeded the permissible limits. The concentration of cation, magnesium (Mg) and potassium (K) in the lake water has exceeded the desirable range (30, 10 mg/L, respectively). This may be due to weathering and transported from rocks and particularly from sulphate deposits such as gypsum and anhydride and subsequently ends up in water. The concentration of anion, Sulphate (SO4) and chloride are above the desirable limit. The major source of bicarbonate are the carbonate rocks containing calcite (CaCO3) and dolomite (CaMg (CO3)2), Calcium (Ca) and Magnesium (Mg) can also be transported from Ca-silicates and Mg-silicates. The piper trilinear plot suggests the increase of Ca and SO4 contents is attributed to dissolution of gypsum and anhydrite, which are commonly found in the quaternary formations of watershed (wadi). Ion exchange, dissolution of calcite, semi-arid climate, alkaline condition and weathering are responsible for high concentration of ions exceeding the desirable limit of the study area.

A Reactive Transport Model for Marcellus Shale Weathering

NASA Astrophysics Data System (ADS)

Li, L.; Heidari, P.; Jin, L.; Williams, J.; Brantley, S.

2017-12-01

Shale formations account for 25% of the land surface globally. One of the most productive shale-gas formations is the Marcellus, a black shale that is rich in organic matter and pyrite. As a first step toward understanding how Marcellus shale interacts with water, we developed a reactive transport model to simulate shale weathering under ambient temperature and pressure conditions, constrained by soil chemistry and water data. The simulation was carried out for 10,000 years, assuming bedrock weathering and soil genesis began right after the last glacial maximum. Results indicate weathering was initiated by pyrite dissolution for the first 1,000 years, leading to low pH and enhanced dissolution of chlorite and precipitation of iron hydroxides. After pyrite depletion, chlorite dissolved slowly, primarily facilitated by the presence of CO2 and organic acids, forming vermiculite as a secondary mineral. A sensitivity analysis indicated that the most important controls on weathering include the presence of reactive gases (CO2 and O2), specific surface area, and flow velocity of infiltrating meteoric water. The soil chemistry and mineralogy data could not be reproduced without including the reactive gases. For example, pyrite remained in the soil even after 10,000 years if O2 was not continuously present in the soil column; likewise, chlorite remained abundant and porosity remained small with the presence of soil CO2. The field observations were only simulated successfully when the specific surface areas of the reactive minerals were 1-3 orders of magnitude smaller than surface area values measured for powdered minerals, reflecting the lack of accessibility of fluids to mineral surfaces and potential surface coating. An increase in the water infiltration rate enhanced weathering by removing dissolution products and maintaining far-from-equilibrium conditions. We conclude that availability of reactive surface area and transport of H2O and gases are the most important factors affecting chemical weathering of the Marcellus shale in the shallow subsurface. This study documents the utility of reactive transport modeling for complex subsurface processes. Such modelling could be extended to understand interactions between injected fluids and Marcellus shale gas reservoirs at higher temperature and pressure.

Fayalite Dissolution and Siderite Formation in Water-Saturated Supercritical CO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qafoku, Odeta; Kovarik, Libor; Kukkadapu, Ravi K.

2012-11-25

Olivines, a significant constituent of basaltic rocks, have the potential to immobilize permanently CO2 after it is injected in the deep subsurface, due to carbonation reactions occurring between CO2 and the host rock. To investigate the reactions of fayalitic olivine with supercritical CO2 (scCO2) and formation of mineral carbonates, experiments were conducted at temperatures of 35 °C to 80 °C, 90 atm pressure and anoxic conditions. For every temperature, the dissolution of fayalite was examined both in the presence of liquid water and H2O-saturated scCO2. The experiments were conducted in a high pressure batch reactor at reaction time extending upmore » to 85 days. The newly formed products were characterized using a comprehensive suite of bulk and surface characterization techniques X-ray diffraction, Transmission/Emission Mössbauer Spectroscopy, Scanning Electron Microscopy coupled with Focused Ion Beam, and High Resolution Transmission Electron Microscopy. Siderite with rhombohedral morphology was formed at 35 °C, 50 °C, and 80 °C in the presence of liquid water and scCO2. In H2O-saturated scCO2, the formation of siderite was confirmed only at high temperature (80 °C). Characterization of reacted samples in H2O-saturated scCO2 with high resolution TEM indicated that siderite formation initiated inside voids created during the initial steps of fayalite dissolution. Later stages of fayalite dissolution result in the formation of siderite in layered vertical structures, columns or pyramids with a rhombus base morphology.« less

An upscaled rate law for magnesite dissolution in heterogeneous porous media

NASA Astrophysics Data System (ADS)

Wen, Hang; Li, Li

2017-08-01

Spatial heterogeneity in natural subsurface systems governs water fluxes and residence time in reactive zones and therefore determines effective rates of mineral dissolution. Extensive studies have documented mineral dissolution rates in natural systems, although a general rate law has remain elusive. Here we fill this gap by answering two questions: (1) how and to what extent does spatial heterogeneity affect water residence time and effectively-dissolving surface area? (2) what is the upscaled rate law that quantifies effective dissolution rates in natural, heterogeneous media? With data constraints from experimental work, 240 Monte-Carlo numerical experiments of magnesite dissolution within quartz matrix were run with spatial distributions characterized by a range of permeability variance σ2lnκ (0.5-6.0) and correlation length (2-50 cm). Although the total surface area and global residence time (τa) are the same in all experiments, the water fluxes through reactive magnesite zones varies between 0.7 and 72.8% of the total water fluxes. Highly heterogeneous media with large σ2lnκ and long λ divert water mostly into non-reactive preferential flow paths, therefore bypassing and minimizing flow in low permeability magnesite zones. As a result, the water residence time in magnesite zones (i.e., reactive residence time τa,r) is long and magnesite dissolution quickly reaches local equilibrium, which leads to small effective surface area and low dissolution rates. Magnesite dissolution rates in heterogeneous media vary from 2.7 to 100% of the rates in the equivalent homogeneous media, with effectively-dissolving surface area varying from 0.18 to 6.83 m2 (out of 51.71 m2 total magnesite surface area). Based on 240 numerical experiments and 45 column experiments, a general upscaled rate law in heterogeneous media, RMgCO3,ht =kAe,hm(1 - exp(-τa/τa,r))α, was derived to quantify effective dissolution rates. The dissolution rates in heterogeneous media are a function of the rate constants k being those measured under well-mixed conditions, effective surface area in equivalent homogeneous media Ae,hm, and the heterogeneity factor (1 - exp(-τa/τa,r))α. The heterogeneity factor quantify heterogeneity effects and depends on the relative magnitude of global residence time (τa) and reactive residence time (τa,r), as well as the shape factor α(= 5 σlnκ2) of the gamma distribution for reactive residence times. Exponential forms of rate laws have been used at the micro-scale describing direct interactions among water and mineral surface, and at the catchment scale describing weathering rates and concentration-discharge relationships. These observations highlight the key role of mineral-water contact time in determining dissolution rates at different scales. This work also emphasizes the importance of critical interfaces between reactive and non-reactive zones as determined by the details of spatial patterns and effective surface area as a scaling factor that quantifies dissolution rates in heterogeneous media across scales.

Implications of diapir-derived detritus and gypsic paleosols in Lower Triassic strata near the Castle Valley salt wall, Paradox Basin, Utah

NASA Astrophysics Data System (ADS)

Lawton, Timothy F.; Buck, Brenda J.

2006-10-01

Gypsum-bearing growth strata and sedimentary facies of the Moenkopi Formation on the crest and NE flank of the Castle Valley salt wall in the Paradox Basin record salt rise, evaporite exposure, and salt-withdrawal subsidence during the Early Triassic. Detrital gypsum and dolomite clasts derived from the middle Pennsylvanian Paradox Formation were deposited in strata within a few kilometers of the salt wall and indicate that salt rise rates roughly balanced sediment accumulation, resulting in long-term exposure of mobile evaporite. Deposition took place primarily in flood-basin or inland sabkha settings that alternated between shallow subaqueous and subaerial conditions in a hyperarid climate. Matrix-supported and clast-supported conglomerates with gypsum fragments represent debris-flow deposits and reworked debris-flow deposits, respectively, interbedded with flood-basin sandstone and siltstone during development of diapiric topography. Mudstone-rich flood-basin deposits with numerous stage I to III gypsic paleosols capped by eolian gypsum sand sheets accumulated during waning salt-withdrawal subsidence. Association of detrital gypsum, eolian gypsum, and gypsic paleosols suggests that the salt wall provided a common source for gypsum in the surrounding strata. This study documents a previously unrecognized salt weld with associated growth strata containing diapir-derived detritus and gypsic palesols that can be used to interpret halokinesis.

Modeling dissolution and volatilization of LNAPL sources migrating on the groundwater table.

PubMed

Kim, Jeongkon; Corapcioglu, M Yavuz

2003-08-01

A vertically averaged two-dimensional model was developed to describe areal spreading and migration of light nonaqueous-phase liquids (LNAPLs) introduced into the subsurface by spills or leaks from underground storage tanks. The NAPL transport model was coupled with two-dimensional contaminant transport models to predict contamination of soil gas and groundwater resulting from a LNAPL migrating on the water table. Numerical solutions were obtained by using the finite-difference method. Simulations and sensitivity analyses were conducted with a LNAPL of pure benzene to study LNAPL migration and groundwater contamination. The model was applied to subsurface contamination by jet fuel. Results indicated that LNAPL migration were affected mostly by volatilization. The generation and movement of the dissolved plume was affected by the geology of the site and the free-product plume. Most of the spilled mass remained as a free LNAPL phase 20 years after the spill. The migration of LNAPL for such a long period resulted in the contamination of both groundwater and a large volume of soil.

Rates of CO2 Mineralization in Geological Carbon Storage.

PubMed

Zhang, Shuo; DePaolo, Donald J

2017-09-19

Geologic carbon storage (GCS) involves capture and purification of CO 2 at industrial emission sources, compression into a supercritical state, and subsequent injection into geologic formations. This process reverses the flow of carbon to the atmosphere with the intention of returning the carbon to long-term geologic storage. Models suggest that most of the injected CO 2 will be "trapped" in the subsurface by physical means, but the most risk-free and permanent form of carbon storage is as carbonate minerals (Ca,Mg,Fe)CO 3 . The transformation of CO 2 to carbonate minerals requires supply of the necessary divalent cations by dissolution of silicate minerals. Available data suggest that rates of transformation are highly uncertain and difficult to predict by standard approaches. Here we show that the chemical kinetic observations and experimental results, when they can be reduced to a single cation-release time scale that describes the fractional rate at which cations are released to solution by mineral dissolution, show sufficiently systematic behavior as a function of pH, fluid flow rate, and time that the rates of mineralization can be estimated with reasonable certainty. The rate of mineralization depends on both the abundance (determined by the reservoir rock mineralogy) and the rate at which cations are released from silicate minerals by dissolution into pore fluid that has been acidified with dissolved CO 2 . Laboratory-measured rates and field observations give values spanning 8 to 10 orders of magnitude, but when they are evaluated in the context of a reservoir-scale reactive transport simulation, this range becomes much smaller. The reservoir scale simulations provide limits on the applicable conditions under which silicate mineral dissolution and subsequent carbonate mineral precipitation are likely to occur (pH 4.5 to 6, fluid flow velocity less than 5 m/year, and 50-100 years or more after the start of injection). These constraints lead to estimates of 200 to 2000 years for conversion of 60-90% of injected CO 2 when the reservoir rock has a sufficient volume fraction of divalent cation-bearing silicate minerals and confirms that when reservoir rock mineralogy is not favorable the fraction of CO 2 converted to carbonate minerals is minimal over 10 4 years. A sufficient amount of reactive minerals is typically about 20% by volume. Our approach may allow for rapid evaluation of mineralization potential of subsurface storage reservoirs and illustrates how reservoir scale modeling can be integrated with other observations to address key issues relating to engineering of geologic systems.

Long-term evolution of Wink sinkholes in West Texas observed by high-resolution satellite imagery

NASA Astrophysics Data System (ADS)

Kim, J. W.; Lu, Z.

2016-12-01

Sinkhole is ground depression and/or collapse over the subsurface cavity in the karst terrain underlain by the carbonates, evaporites, and other soluble soils and rocks. The geohazards have been considered as a "hidden threat" to human life, infrastructures, and properties. The Delaware Basin of West Texas in the southwest part of the Permian Basin contains one of the greatest accumulations of evaporites in the United States. Sinkholes in West Texas have been developed by the dissolution of the subsurface evaporite deposits that come in contact with groundwater. Two Wink sinkholes in Wink, Texas, were developed in 1980 and 2002, respectively. However, monitoring the sinkholes in no man's lands has been challenging due to the lack of availability of high-resolution and temporally dense acquisitions. We employ aerial photography and radar satellite imagery to measure the long-term deformation from early 2000 and characterize the inherent hydrogeology that is closely related to sinkhole collapse and subsidence. Furthermore, data on oil/gas production and water injection into the subsurface as well as ground water level are analyzed to study their effects on the concurrent unstable ground surface in Wink sinkholes. Our study will provide invaluable information to understand the mechanism of sinkhole development and mitigate the catastrophic outcomes of the geohazards.

Populations of some molds in water-damaged homes may differ if the home was constructed with gypsum drywall compared to plaster

EPA Science Inventory

Starting in the 1940s, gypsum drywall began replacing plaster and lathe in the U.S. home construction industry. Our goal was to evaluate whether some mold populations differ in water- damaged homes primarily constructed with gypsum drywall compared to plaster. The dust samples fr...

Utilization of FGD gypsum in agriculture for environmental benefits

USDA-ARS?s Scientific Manuscript database

This paper will discuss the utilization of FGD gypsum in agriculture for environmental benefits. Gypsum (CaSO4 .2H2O) has been used as an agricultural soil amendment for over 250 years. It is a soluble source of calcium and sulfur for crops and has been shown to improve soil physical and chemical pr...

Gypsum's influence on corn yield and p loss from an eroded southern piedmont soil

USDA-ARS?s Scientific Manuscript database

Gypsum (CaSO4) has been shown to reduce dissolved P in surface water runoff from pastures fertilized with poultry litter (PL). However, limited research has evaluated gypsum’s influence on P loss under row crops. Moreover, can gypsum effectively reduce P loss when applied only to grass buffer strips...

FEASIBILITY OF PRODUCING AND MARKETING BYPRODUCT GYPSUM FROM SO2 EMISSION CONTROL AT FOSSIL-FUEL-FIRED POWER PLANTS

EPA Science Inventory

The report gives results of a study to identify fossil-fuel-fired power plants that might, in competition with existing crude gypsum sources and other power plants, lower the cost of compliance with SO2 regulations by producing and marketing abatement gypsum. In the Eastern U.S.,...

The origin of sulphur in gypsum and dissolved sulphate in the Central Namib Desert, Namibia

NASA Astrophysics Data System (ADS)

Eckardt, F. D.; Spiro, B.

1999-02-01

This study investigates the sulphur source of gypsum sulphate and dissolved groundwater sulphate in the Central Namib Desert, home to one of Africa's most extensive gypsum (CaSO 4·2H 2O) accumulations. It investigates previously suggested sulphate precursors such as bedrock sulphides and decompositional marine biogenic H 2S and studies the importance of other potential sources in order to determine the origin of gypsum and dissolved sulphate in the region. An attempt has been made to sample all possible sulphur sources, pathways and types of gypsum accumulations in the Central Namib Desert. We have subjected those samples to sulphur isotopic analyses and have compiled existing results. In addition, ionic ratios of Cl/SO 4 are used to determine the presence of non-sea-salt (NSS) sulphur in groundwater and to investigate processes affecting groundwater sulphate. In contrast to previous work, this study proposes that the sulphur cycle, and the formation of gypsum, in the Namib Desert appears to be dominated by the deposition of atmospheric sulphates of phytoplanktonic origin, part of the primary marine production of the Benguela upwelling cells. The aerosol sulphates are subjected to terrestrial storage within the gypsum deposits on the hyper-arid gravel plain and are traceable in groundwater including coastal sabkhas. The hypothesis of decompositional marine biogenic H 2S or bedrock sulphide sources, as considered previously for the Namib Desert, cannot account for the widespread accumulation of gypsum in the region. The study area in the Central Namib Desert, between the Kuiseb and Omaruru rivers, features extensive gypsum accumulations in a ca. 50-70 km wide band, parallel to the shore. They consist of surficial or shallow pedogenic gypsum crusts in the desert pavement, hydromorphic playa or sabkha gypsum, as thin isolated pockets on bedrock ridges and as discrete masses of gypsum selenite along some faults. The sulphur isotopic values (δ 34S ‰CDT) of these occurrences are between δ 34S +13.0 and +18.8‰, with lower values in proximity to sulphuric ore bodies (δ 34S +3.1 and +3.4‰). Damaran bedrock sulphides have a wide range from δ 34S -4.1 to +13.8‰ but seem to be significant sources on a local scale at the most. Dissolved sulphate at playas, sabkhas, springs, boreholes and ephemeral rivers have an overall range between δ 34S +9.8 and +20.8‰. However, they do not show a systematic geographical trend. The Kalahari waters have lower values, between δ 34S +5.9 and +12.3‰. Authigenic gypsum from submarine sediments in the upwelling zone of the Benguela Current between Oranjemund and Walvis Bay ranges between δ 34S -34.6 to -4.6‰. A single dry atmospheric deposition sample produced a value of δ 34S +15.9‰. These sulphur isotopic results, complemented by meteorological, hydrological and geological information, suggest that sulphate in the Namib Desert is mainly derived from NSS sulphur, in particular oxidation products of marine dimethyl sulphide CH 3SCH 3 (DMS). The hyper-arid conditions prevailing along the Namibian coast since Miocene times favour the overall preservation of the sulphate minerals. However, sporadic and relatively wetter periods have promoted gypsum formation: the segregation of sulphates from the more soluble halite, and the gradual seaward redistribution of sulphate. This study suggests that the extreme productivity of the Benguela Current contributes towards the sulphur budget in the adjacent Namib Desert.

Residual effects of monoammonium phosphate, gypsum and elemental sulfur on cadmium phytoavailability and translocation from soil to wheat in an effluent irrigated field.

PubMed

Qayyum, Muhammad Farooq; Rehman, Muhammad Zia Ur; Ali, Shafaqat; Rizwan, Muhammad; Naeem, Asif; Maqsood, Muhammad Aamer; Khalid, Hinnan; Rinklebe, Jörg; Ok, Yong Sik

2017-05-01

Cadmium (Cd) accumulation in agricultural soils is one of the major threats to food security. The application of inorganic amendments such as mono-ammonium phosphate (MAP), gypsum and elemental sulfur (S) could alleviate the negative effects of Cd in crops. However, their long-term residual effects on decreasing Cd uptake in latter crops remain unclear. A field that had previously been applied with treatments including control and 0.2, 0.4 and 0.8% by weight of each MAP, gypsum and S, and grown with wheat and rice and thereafter wheat in the rotation was selected for this study. Wheat (Triticum aestivum L.) was grown in the same field as the third crop without further application of amendments to evaluate the residual effects of the amendments on Cd uptake by wheat. Plants were harvested at maturity and grain, and straw yield along with Cd concentration in soil, straw, and grains was determined. The addition of MAP and gypsum significantly increased wheat growth and yield and decreased Cd accumulation in straw and grains compared to control while the reverse was found in S application. Both MAP and gypsum decreased AB-DTPA extractable Cd in soil while S increased the bioavailable Cd in soil. Both MAP and gypsum increased the Cd immobilization in the soil and S decreased Cd immobilization in a dose-additive manner. We conclude that MAP and gypsum had a significant residual effect on decreasing Cd uptake in wheat. The cost-benefit ratio revealed that gypsum is an effective amendment for decreasing Cd concentration in plants. Copyright © 2017 Elsevier Ltd. All rights reserved.

The potential leaching and mobilization of trace elements from FGD-gypsum of a coal-fired power plant under water re-circulation conditions.

PubMed

Córdoba, Patricia; Castro, Iria; Maroto-Valer, Mercedes; Querol, Xavier

2015-06-01

Experimental and geochemical modelling studies were carried out to identify mineral and solid phases containing major, minor, and trace elements and the mechanism of the retention of these elements in Flue Gas Desulphurisation (FGD)-gypsum samples from a coal-fired power plant under filtered water recirculation to the scrubber and forced oxidation conditions. The role of the pH and related environmental factors on the mobility of Li, Ni, Zn, As, Se, Mo, and U from FGD-gypsums for a comprehensive assessment of element leaching behaviour were also carried out. Results show that the extraction rate of the studied elements generally increases with decreasing the pH value of the FGD-gypsum leachates. The increase of the mobility of elements such as U, Se, and As in the FGD-gypsum entails the modification of their aqueous speciation in the leachates; UO2SO4, H2Se, and HAsO2 are the aqueous complexes with the highest activities under acidic conditions. The speciation of Zn, Li, and Ni is not affected in spite of pH changes; these elements occur as free cations and associated to SO4(2) in the FGD-gypsum leachates. The mobility of Cu and Mo decreases by decreasing the pH of the FGD-gypsum leachates, which might be associated to the precipitation of CuSe2 and MoSe2, respectively. Time-of-Flight mass spectrometry of the solid phase combined with geochemical modelling of the aqueous phase has proved useful in understanding the mobility and geochemical behaviour of elements and their partitioning into FGD-gypsum samples. Copyright © 2015. Published by Elsevier B.V.

Influence of sodium borate on the early age hydration of calcium sulfoaluminate cement

DOE Office of Scientific and Technical Information (OSTI.GOV)

Champenois, Jean-Baptiste; Dhoury, Mélanie; Cau Dit Coumes, Céline, E-mail: celine.cau-dit-coumes@cea.fr

Calcium sulfoaluminate (CSA) cements are potential candidates for the conditioning of radioactive wastes with high sodium borate concentrations. This work thus investigates early age hydration of two CSA cements with different gypsum contents (0 to 20%) as a function of the mixing solution composition (borate and NaOH concentrations). Gypsum plays a key role in controlling the reactivity of cement. When the mixing solution is pure water, increasing the gypsum concentration accelerates cement hydration. However, the reverse is observed when the mixing solution contains sodium borate. Until gypsum exhaustion, the pore solution pH remains constant at ~ 10.8, and a poorlymore » crystallized borate compound (ulexite) precipitates. A correlation is established between this transient precipitation and the hydration delay. Decreasing the gypsum content in the binder, or increasing the sodium content in the mixing solution, are two ways of reducing the stability of ulexite, thus decreasing the hydration delay.« less

Movement and fate of crude-oil in contaminants in the subsurface environment at Bemidji, Minnesota: Chapter C in U.S. Geological Survey program on toxic waste--ground-water contamination: Proceedings of the Third technical meeting, Pensacola, Florida, March 23-27, 1987

USGS Publications Warehouse

Hult, Marc F.

1987-01-01

Predictions of the evolution and ultimate geometry of contaminant plumes resulting from spills require quantitative descriptions of the rate of mass transfer from the organic fluid to ground water. Pfannkuch presents laboratory and field work that describe how the the rate of oil dissolution, and therefore the strength of the contaminant source, is controlled by fluctuations in ground-water velocity and water-table fluctuations.

Morphology and evolution of sulphuric acid caves in South Italy

NASA Astrophysics Data System (ADS)

D'Angeli, Ilenia M.; De Waele, Jo; Galdenzi, Sandro; Madonia, Giuliana; Parise, Mario; Vattano, Marco

2016-04-01

Sulphuric acid speleogenesis (SAS) related to the upwelling of acid water enriched in H2S and CO2 represents an unusual way of cave development. Since meteoric infiltration waters are not necessarily involved in speleogenesis, caves can form without the typical associated karst expressions (i.e. dolines) at the surface. The main mechanism of sulphuric acid dissolution is the oxidation of H2S (Jones et al., 2015) which can be amplified by bacterial mediation (Engel et al., 2004). In these conditions, carbonate dissolution associated with gypsum replacement, is generally believed to be faster than the normal epigenic one (De Waele et al., 2016). In Italy several SAS caves have been identified, but only few systems have been studied in detail: Frasassi and Acquasanta Terme (Marche)(Galdenzi et al., 2010), Monte Cucco (Umbria) (Galdenzi & Menichetti, 1995), and Montecchio (Tuscany) (Piccini et al., 2015). Other preliminary studies have been carried out in Calabria (Galdenzi, 2007) and Sicily (De Waele et al., 2016). Several less studied SAS cave systems located in South Italy, and in particular in Apulia (Santa Cesarea Terme), Sicily (Acqua Fitusa, Acqua Mintina) and Calabria (Mt. Sellaro and Cassano allo Ionio) have been selected in the framework of a PhD thesis on SAS caves and their speleogenesis. Using both limestone tablet weight loss (Galdenzi et al., 2012) and micro erosion meter (MEM) (Furlani et al., 2010) methods the dissolution rate above and under water in the caves will be quantified. Geomorphological observations, landscape analysis using GIS tools, and the analysis of gypsum and other secondary minerals (alunite and jarosite) (stable isotopes and dating) will help to reconstruct the speleogenetic stages of cave formation. Preliminary microbiological analysis will determine the microbial diversity and ecology in the biofilms. References Engel S.A., Stern L.A., Bennett P.C., 2004 - Microbial contributions to cave formation: New insight into sulfuric acid speleogenesis. Geology, 32: 369-372. De Waele J., Audra P., Madonia G., Vattano M., Plan L., D'Angeli I.M., Bigot J.-Y., Nobécourt J.-C., 2016 - Sulfuric acid speleogenesis (SAS) close to the water table: examples from southern France, Austria, and Sicily. Geomorphology, 253: 452-467. Furlani S., Cucchi F., Odorico R., 2010 - A new method to study micro-topographical changes in the intertidal zone: one year of TMEM measurements on a limestone removable slab (RRS). Z. Geomorph., 54(2): 137-151. Galdenzi S., 1997 - Initial geological observations in caves bordering the Sibari plain (southern Italy). J. Cave Karst Stud., 59: 81-86. Galdenzi S., 2012 - Corrosion of limestone tablets in sulfidic ground-water: measurements and speleogenetic implications. Int. J. Spel., 41(2): 149-159. Galdenzi S., Menichetti M., 1995 - Occurrence of hypogenic caves in a karst region: examples from central Italy. Environmental Geology, 26: 39-47. Galdenzi S., Cocchioni F., Filipponi G., Selvaggio R., Scuri S., Morichetti L., Cocchioni M., 2010 - The sulfidic thermal caves of Acquasanta Terme (central Italy). J. Cave Karst Stud. 72(1): 43-58. Jones, D.S., Polerecky, L., Galdenzi, S., Dempsey, B.A., Macalady, J.L., 2015 - Fate of sulfide in the Frasassi cave system and implications for sulfuric acid speleogenesis. Chemical Geology, 410: 21-27.

Properties study of cotton stalk fiber/gypsum composite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li Guozhong; Yu Yanzhen; Zhao Zhongjian

This manuscript addresses treating cotton stalk fiber surface with styrene acrylic emulsion, which improves the interfacial combined state of cotton stalk fiber/gypsum composite effectively and improves its mechanical properties notably. Mixes less slag, ordinary Portland cement, etc., to modify gypsum base. The electron microscope was utilized to analyze and research on the effect on composite properties of the abovementioned mixtures.

Impact of FGD gypsum soil amendment applications on soil and environmental quality

USDA-ARS?s Scientific Manuscript database

This paper will discuss the utilization of FGD gypsum in agriculture for improving soil quality and other environmental benefits. Gypsum (CaSO4 .2H2O) has been used as an agricultural soil amendment for over 250 years. It is a soluble source of calcium and sulfur- for crops and has been shown to i...

Evaluating the fate of mercury and other metals across the life-cycle stages from the use of FGD gypsum for wallboard production

EPA Science Inventory

In 2007, 12.3 million tons of flue gas desulfurization (FGD) gypsum was produced due to air emission controls at coal-fired power plants. With increasing use of wet scrubbers in response to more stringent air pollution control requirements, FGD gypsum production is expected to in...

[The effect of disinfectant soaking on dental gypsum model size].

PubMed

Zhu, Cao-yun; Xu, Yun-wen; Xu, Kan

2012-12-01

To study the influence of disinfectant soaking on the dimensional stability of three kinds of dental gypsum model. Three commonly used gypsums ( type III,IV,Vtype) in clinic were used to make 24 specimens for 50 mm×15 mm×10 mm in size. One hour after release, the specimens were placed for 24 h. A digital caliper was used to measure the size of the gypsum model. Distilled water immersion was as used control, glutaraldehyde disinfectant and Metrix CaviCide disinfectant soaking were used for the experimental group. After soaking for 0.5h, the gypsum models were removed and placed for 0.5 h, 1 h, 2 h, 24 h. The size of the models was measured again using the same method. The data was analyzed with SPSS10.0 software package. The initial gypsum model length was (50.07±0.017) mm, (50.048±0.015) mm and (50.027±0.015) mm. After soaking for different times, the size of the model changed little, and the dimensions changed less than 0.01%. The results show that disinfectant soaking has no significant effect on dental model dimensions.

Gypsum: a review of its role in the deterioration of building materials

NASA Astrophysics Data System (ADS)

Charola, A. Elena; Pühringer, Josef; Steiger, Michael

2007-03-01

The deterioration of buildings and monuments by gypsum is the result of crystallization cycles of this salt. Although gypsum can dehydrate to a hemihydrate, the mineral bassanite, and to an anhydrate, the mineral anhydrite, this reaction occurs in nature on a geological time scale and therefore it is unlikely to occur when gypsum is found on and in building materials. The CaSO4-H2O system appears deceptively simple, however there are still discrepancies between the experimental and thermodynamically calculated data. The reason for the latter can be attributed to the slow crystallization kinetics of anhydrite. Apart from this, the large numbers of studies carried out on this system have focused on industrially important metastable phases, such as the hemihydrate and soluble anhydrite. The paper presents a review of the studies dealing with the phase equilibria of the CaSO4-H2O system as well as the influence of other salts on the solubility of gypsum. It tries to glean out the relevant information that will serve to explain the deterioration observed on building materials by the crystallization of gypsum and thus allows developing improved conservation methods.

Gypsum crystal size distribution in four continuous flow stirred slurry boric acid reactors in series compared with the batch

NASA Astrophysics Data System (ADS)

Çakal, G. Ö.; Eroğlu, İ.; Özkar, S.

2006-04-01

Colemanite, one of the important boron minerals, is dissolved in aqueous sulfuric acid to produce boric acid. In this reaction, gypsum is obtained as a by-product. Gypsum crystals are in the shape of thin needles. These crystals should be grown to an easily filterable size in order to increase the production yield and purity of boric acid. In this paper, the particle size distributions and the volume-weighted mean diameters of the gypsum crystals obtained in batch and continuous flow systems were compared. Experiments in both batch and continuous reactors were performed at a temperature of 85 °C, a stirring rate of 400 rpm, and the inlet CaO to SO42- molar ratio of 1.0 using colemanite mineral in particle size smaller than 150 μm. The average diameter of the gypsum crystals obtained at 3.5 h from the batch reactor was found to be 37-41 μm. This value for the continuous system at steady state was observed to change between 44-163 μm. The particle size of the gypsum crystals was found to increase with the residence time of the solid in the continuous system.

Dissolution of a Tetrachloroethene (PCE) pool in an Anaerobic Sand Tank Aquifer System: Bioenhancement, Ecology, and Hydrodynamics

NASA Astrophysics Data System (ADS)

Klemm, Sara; Becker, Jennifer; Seagren, Eric

2017-04-01

Dehalorespiring bacteria that reductively dechlorinate and grow on chlorinated ethenes in the aqueous phase can also achieve treatment of dense nonaqueous phase liquid (DNAPL) contaminants in the subsurface via bioenhanced dissolution, i.e., enhanced mass transfer from the DNAPL to the aqueous phase. Theoretical and experimental analyses predict that a number of interrelated physicochemical processes (e.g., advection and dispersion) and biological factors (e.g., biokinetics and competition) may influence the degree of bioenhancement. This research focused on understanding the interrelated roles that hydrodynamics and ecological interactions among dehalorespiring populations play in determining the distribution of dehalorespiring populations and the impact on bioenhanced dissolution and detoxification. The hypotheses driving this research are that: (1) ecological interactions between different dehalorespiring strains can significantly impact the dissolution rate bioenhancement and extent of dechlorination; and (2) hydrodynamics near the DNAPL pool will affect the outcome of ecological interactions and the potential for bioenhancement and detoxification. These hypotheses were evaluated via a multi-objective modeling and experimental framework focused on quantifying the impact of microbial interactions and hydrodynamics on the dissolution rate bioenhancement and plume detoxification using a model co-culture of Desulfuromonas michiganensis BB1 and Dehalococcoides mccartyi 195. The experiments were performed in a saturated intermediate-scale flow cell (1.2 m), with flow parallel to a tetrachloroethene (PCE) pool. Bioenhancement of PCE dissolution by the two dehalorespirers was evaluated using a steady-state mass balance, and initially resulted in a two- to three-fold increase in the dissolution rate, with cis-dichloroethene (cDCE) as the primary dechlorination product. Quantitative analysis of microbial population distribution and abundance using a 16S rRNA gene-based qPCR approach indicated that Dsm. michiganensis BB1 was the dominant population in the effluent. This was expected based on our previous work characterizing the PCE utilization kinetics of the two populations, and suggests that Dsm. michiganensis BB1 was the dominant population in the aquifer system and controlled PCE dissolution and its bioenhancement. This conclusion is consistent with our numerical modeling predictions for the same conditions, which suggested Dhc. mccartyi 195 had little effect on dissolution and dehalorespiration, but aided detoxification by growing on the cDCE produced by Dsm. michiganensis BB1. Subsequently, the PCE dissolution enhancement increased to six- to seven-fold relative to the abiotic dissolution rate. Quantitative analysis of population distribution and abundance in the porous media and nonreactive tracer studies suggested that microbial growth-induced bioclogging, coupled with inhibition of microbial activity near the DNAPL, resulted in increased flow immediately adjacent to the DNAPL-aqueous interface. The increased flow rate past the DNAPL could explain the observed increase in the PCE dissolution rate and is consistent with our numerical modeling of the system. The research described here is part of a larger project working to improve the fundamental understanding of the impact of hydrodynamics and ecological interactions on DNAPL dissolution rate bioenhancement and plume detoxification. These biotic data build on the baseline abiotic experiments reported in another abstract submitted to Session HS8.1.6.

Large depressions, thickened terraces, and gravitational deformation in the Ebro River valley (Zaragoza area, NE Spain): Evidence of glauberite and halite interstratal karstification

NASA Astrophysics Data System (ADS)

Guerrero, Jesús; Gutiérrez, Francisco; Galve, Jorge P.

2013-08-01

In the studied reach of the Ebro Valley, the terrace and pediment sediments deposited over glauberite- and halite-bearing evaporites show local thickenings (> 50 m) recording dissolution-induced synsedimentary subsidence. Recent data on the lithostratigraphy of the evaporite sequence allow relating the alluvium thickenings with either halite or glauberite dissolution. The alluvium-filled dissolution basin underlying the youngest terraces (T8-T11) is ascribed to halite karstification; the top of a halite unit approximately 75 m thick is situated 40-15 m below the valley bottom. The thickenings of terrace (T1-T7) and pediment sediments are attributed to interstratal glauberite karstification: (1) Coincidence between the elevation range of the terraces and that of the glauberite-rich unit. Glauberite beds reach 30 and 100 m in single-bed and cumulative thickness, respectively. (2) The exposed bedrock underlying thickened alluvium shows abundant subsidence features indicative of interstratal karstification. The most common structure corresponds to hectometer-scale sag basins with superimposed collapses in the central sector of each basin. The subsided bedrock is frequently transformed into dissolution-collapse breccias showing a complete textural gradation, from crackle packbreccias to chaotic floatbreccias and karstic residues. (3) Paleokarst exposures show evidence of karstification confined to specific beds made up of secondary gypsum after precursory glauberite, partly dissolved and partly replaced. Despite the magnitude of the subsidence recorded by the thickened alluvium and unlike nearby tributaries, the terraces show a continuous and parallel arrangement indicating that the fluvial system was able to counterbalance subsidence by aggradation. A number of kilometer-size flat-bottom depressions have been developed in the valley margin, typically next to and inset into thickened terrace and pediment deposits. The subsidence structures exposed in artificial excavations excavated in the bottom of some depressions and the correlation between the altitudinal distribution of these basins and that of the glauberite-rich unit reveal that subsidence related to interstratal glauberite karstification is the main process involved in their genesis. This research ascribes for the first time the thickenings and deformation of specific terrace levels and pediment levels and the development of large karstic depressions to interstratal karstification of exceptionally thick glauberite units.

U-isotopes and (226)Ra as tracers of hydrogeochemical processes in carbonated karst aquifers from arid areas.

PubMed

Guerrero, José Luis; Vallejos, Ángela; Cerón, Juan Carlos; Sánchez-Martos, Francisco; Pulido-Bosch, Antonio; Bolívar, Juan Pedro

2016-07-01

Sierra de Gádor is a karst macrosystem with a highly complex geometry, located in southeastern Spain. In this arid environment, the main economic activities, agriculture and tourism, are supported by water resources from the Sierra de Gádor aquifer system. The aim of this work was to study the levels and behaviour of some of the most significant natural radionuclides in order to improve the knowledge of the hydrogeochemical processes involved in this groundwater system. For this study, 28 groundwater and 7 surface water samples were collected, and the activity concentrations of the natural U-isotopes ((238)U, (235)U and (234)U) and (226)Ra by alpha spectrometry were determined. The activity concentration of (238)U presented a large variation from around 1.1 to 65 mBq L(-1). Elevated groundwater U concentrations were the result of oxidising conditions that likely promoted U dissolution. The PHREEQC modelling code showed that dissolved U mainly existed as uranyl carbonate complexes. The (234)U/(238)U activity ratios were higher than unity for all samples (1.1-3.8). Additionally, these ratios were in greater disequilibrium in groundwater than surface water samples, the likely result of greater water-rock contact time. (226)Ra presented a wide range of activity concentrations, (0.8 up to about 4 × 10(2) mBq L(-1)); greatest concentrations were detected in the thermal area of Alhama. Most of the samples showed (226)Ra/(234)U activity ratios lower than unity (median = 0.3), likely the result of the greater mobility of U than Ra in the aquifer system. The natural U-isotopes concentrations were strongly correlated with dissolution of sulphate evaporites (mainly gypsum). (226)Ra had a more complex behaviour, showing a strong correlation with water salinity, which was particularly evident in locations where thermal anomalies were detected. The most saline samples showed the lowest (234)U/(238)U activity ratios, probably due to fast uniform bulk mineral dissolution, which would minimize the impact of solubility-controlled fractionation processes. Furthermore, the high bulk dissolution rates promoted greater groundwater (226)Ra/(234)U ratios because the Ra has a comparatively much greater mobility than U in saline conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mineral of the month: gypsum

USGS Publications Warehouse

Founie, Alan

2004-01-01

The earliest known use of gypsum as a building material was in Anatolia (in what is now Turkey) around 6000 B.C. It has been found on the interiors of the great pyramids in Egypt, which were erected in about 3700 B.C. Now an average new American home contains more than 7 metric tons of gypsum in the form of more than 6,000 square feet of wallboard.

Incorporation of gypsum waste in ceramic block production: Proposal for a minimal battery of tests to evaluate technical and environmental viability of this recycling process.

PubMed

Godinho-Castro, Alcione P; Testolin, Renan C; Janke, Leandro; Corrêa, Albertina X R; Radetski, Claudemir M

2012-01-01

Civil engineering-related construction and demolition debris is an important source of waste disposed of in municipal solid waste landfills. After clay materials, gypsum waste is the second largest contributor to the residential construction waste stream. As demand for sustainable building practices grows, interest in recovering gypsum waste from construction and demolition debris is increasing, but there is a lack of standardized tests to evaluate the technical and environmental viability of this solid waste recycling process. By recycling gypsum waste, natural deposits of gypsum might be conserved and high amounts of the waste by-product could be reused in the civil construction industry. In this context, this paper investigates a physical property (i.e., resistance to axial compression), the chemical composition and the ecotoxicological potential of ceramic blocks constructed with different proportions of clay, cement and gypsum waste, and assesses the feasibility of using a minimal battery of tests to evaluate the viability of this recycling process. Consideration of the results for the resistance to axial compression tests together with production costs revealed that the best formulation was 35% of plastic clay, 35% of non-plastic clay, 10% of Portland cement and 20% of gypsum waste, which showed a mean resistance of 4.64MPa. Energy dispersive X-ray spectrometry showed calcium and sulfur to be the main elements, while quartz, gypsum, ettringite and nacrite were the main crystalline compounds found in this formulation. Ecotoxicity tests showed that leachate from this formulation is weakly toxic toward daphnids and bacteria (EC(20%)=69.0 and 75.0, respectively), while for algae and fish the leachate samples were not toxic at the EC(50%) level. Overall, these results show that the addition of 20% of gypsum waste to the ceramic blocks could provide a viable substitute for clay in the ceramics industry and the tests applied in this study proved to be a useful tool for the technical and environmental evaluation of this recycling process, bacterial and daphnid tests being more sensitive than algae and fish tests. Copyright © 2011 Elsevier Ltd. All rights reserved.

Characterizing 3-D flow velocity in evolving pore networks driven by CaCO3 precipitation and dissolution

NASA Astrophysics Data System (ADS)

Chojnicki, K. N.; Yoon, H.; Martinez, M. J.

2015-12-01

Understanding reactive flow in geomaterials is important for optimizing geologic carbon storage practices, such as using pore space efficiently. Flow paths can be complex in large degrees of geologic heterogeneities across scales. In addition, local heterogeneity can evolve as reactive transport processes alter the pore-scale morphology. For example, dissolved carbon dioxide may react with minerals in fractured rocks, confined aquifers, or faults, resulting in heterogeneous cementation (and/or dissolution) and evolving flow conditions. Both path and flow complexities are important and poorly characterized, making it difficult to determine their evolution with traditional 2-D transport models. Here we characterize the development of 3-D pore-scale flow with an evolving pore configuration due to calcium carbonate (CaCO3) precipitation and dissolution. A simple pattern of a microfluidic pore network is used initially and pore structures will become more complex due to precipitation and dissolution processes. At several stages of precipitation and dissolution, we directly visualize 3-D velocity vectors using micro particle image velocimetry and a laser scanning confocal microscope. Measured 3-D velocity vectors are then compared to 3-D simulated flow fields which will be used to simulate reactive transport. Our findings will highlight the importance of the 3-D flow dynamics and its impact on estimating reactive surface area over time. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000. This material is based upon work supported as part of the Center for Frontiers of Subsurface Energy Security, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001114.

Effects of nitrate on the stability of uranium in a bioreduced region of the subsurface.

PubMed

Wu, Wei-Min; Carley, Jack; Green, Stefan J; Luo, Jian; Kelly, Shelly D; Van Nostrand, Joy; Lowe, Kenneth; Mehlhorn, Tonia; Carroll, Sue; Boonchayanant, Benjaporn; Löfller, Frank E; Watson, David; Kemner, Kenneth M; Zhou, Jizhong; Kitanidis, Peter K; Kostka, Joel E; Jardine, Philip M; Criddle, Craig S

2010-07-01

The effects of nitrate on the stability of reduced, immobilized uranium were evaluated in field experiments at a U.S. Department of Energy site in Oak Ridge, TN. Nitrate (2.0 mM) was injected into a reduced region of the subsurface containing high levels of previously immobilized U(IV). The nitrate was reduced to nitrite, ammonium, and nitrogen gas; sulfide levels decreased; and Fe(II) levels increased then deceased. Uranium remobilization occurred concomitant with nitrite formation, suggesting nitrate-dependent, iron-accelerated oxidation of U(IV). Bromide tracer results indicated changes in subsurface flowpaths likely due to gas formation and/or precipitate. Desorption-adsorption of uranium by the iron-rich sediment impacted uranium mobilization and sequestration. After rereduction of the subsurface through ethanol additions, background groundwater containing high levels of nitrate was allowed to enter the reduced test zone. Aqueous uranium concentrations increased then decreased. Clone library analyses of sediment samples revealed the presence of denitrifying bacteria that can oxidize elemental sulfur, H(2)S, Fe(II), and U(IV) (e.g., Thiobacillus spp.), and a decrease in relative abundance of bacteria that can reduce Fe(III) and sulfate. XANES analyses of sediment samples confirmed changes in uranium oxidation state. Addition of ethanol restored reduced conditions and triggered a short-term increase in Fe(II) and aqueous uranium, likely due to reductive dissolution of Fe(III) oxides and release of sorbed U(VI). After two months of intermittent ethanol addition, sulfide levels increased, and aqueous uranium concentrations gradually decreased to <0.1 microM.

Assessment of the potential for karst in the Rustler Formation at the WIPP site.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lorenz, John Clay

2006-01-01

This report is an independent assessment of the potential for karst dissolution in evaporitic strata of the Rustler Formation at the Waste Isolation Pilot Plant (WIPP) site. Review of the available data suggests that the Rustler strata thicken and thin across the area in depositional patterns related to lateral variations in sedimentary accommodation space and normal facies changes. Most of the evidence that has been offered for the presence of karst in the subsurface has been used out of context, and the different pieces are not mutually supporting. Outside of Nash Draw, definitive evidence for the development of karst inmore » the Rustler Formation near the WIPP site is limited to the horizon of the Magenta Member in drillhole WIPP-33. Most of the other evidence cited by the proponents of karst is more easily interpreted as primary sedimentary structures and the localized dissolution of evaporitic strata adjacent to the Magenta and Culebra water-bearing units. Some of the cited evidence is invalid, an inherited baggage from studies made prior to the widespread knowledge of modern evaporite depositional environments and prior to the existence of definitive exposures of the Rustler Formation in the WIPP shafts. Some of the evidence is spurious, has been taken out of context, or is misquoted. Lateral lithologic variations from halite to mudstone within the Rustler Formation under the WIPP site have been taken as evidence for the dissolution of halite such as that seen in Nash Draw, but are more rationally explained as sedimentary facies changes. Extrapolation of the known karst features in Nash Draw eastward to the WIPP site, where conditions are and have been significantly different for half a million years, is unwarranted. The volumes of insoluble material that would remain after dissolution of halite would be significantly less than the observed bed thicknesses, thus dissolution is an unlikely explanation for the lateral variations from halite to mudstone and siltstone. Several surficial depressions at WIPP, suggested to be sinkholes, do not have enough catchment area to form a sinkhole, and holes drilled to investigate the subsurface strata do not support a sinkhole interpretation. Surface drainage across the WIPP site is poorly developed because it has been disrupted by migrating sand dunes and because precipitation is not focused by defined catchment areas in this region of low precipitation and low-dip bedding, not because it has been captured by sinkholes. There are no known points of discharge from the Rustler Formation at WIPP that would indicate the presence of a subsurface karst drainage system. The existing drillholes across the WIPP site, though small in diameter, are sufficient to assess the probability of karst development along the horizontal fractures that are common in the Rustler Formation, and the area of investigation has been augmented significantly by the mapping of four large-diameter shafts excavated into the WIPP repository. The general absence of dissolution, karsting, and related conduits is corroborated by the pumping tests which have interrogated large volumes of the Rustler Formation between drillholes. Diffusion calculations suggest that separate isotopic signatures for the water found in the fractures and the water found in the pores of the matrix rock between fractures are unlikely, thus the isotopic evidence for ancient Rustler formation waters is valid. Geophysical techniques show a number of anomalies, but the anomalies do not overlap to portray consistent and mutually supporting patterns that can be definitively related to karst void space at any given location. The coincidence of the Culebra and Magenta potentiometric heads between Nash Draw and the WIPP site is the inevitable intersection of two non-parallel surfaces rather than an indication of karst-related hydraulic communication between the two units. The proponents of karst in the Rustler Formation at the WIPP site tend to mix data, to take data out of context, and to offer theory as fact. They do not analyze the data or synthesize it into a rigorous, mutually supporting framework. They assume that the existence of an anomaly rather than the specific characteristics of that anomaly proves the existence of intra-stratal karst in the Rustler Formation. In most cases, the interpretations of karst offered are non-unique interpretations of data for which more plausible interpretations exist.« less

Hydrogeochemical characteristics and sources of salinity of the springs near Wenquanzhen in the eastern Sichuan Basin, China

NASA Astrophysics Data System (ADS)

Guo, Juan; Zhou, Xun; Wang, Lidong; Zhang, Yuqi; Shen, Xiaowei; Zhou, Haiyan; Ye, Shen; Fang, Bin

2018-06-01

Natural springs have the potential to provide important information on hydrogeochemical processes within aquifers. This study used traditional and classic technical methods and procedures to determine the characteristics and evolution of springs to gain further knowledge on the differences between hot saline springs and cold fresh springs. In a short river segment near Wenquanzhen in the eastern Sichuan Basin, southwest China, several natural springs coexist with total dissolved solids (TDS) ranging from less than 1 to 15 g/L and temperatures from 15 to 40 °C. The springs emanate from the outcropping Lower and Middle Triassic carbonates in the river valley cutting the core of an anticline. The cold springs are of Cl·HCO3-Na·Ca and Cl·SO4-Na types, and the hot saline springs are mainly of Cl-Na type. The chemistry of the springs has undergone some changes with time. The stable hydrogen and oxygen isotopes indicate that the spring waters are of a meteoric origin. The salinity of the springs originates from dissolution of minerals, including halite, gypsum, calcite and dolomite. The evolution of the springs involves the following mechanisms: the groundwater receives recharge from infiltration of precipitation, then undergoes deep circulation in the core of the anticline (incongruent dissolution of the salt-bearing strata occurs), and emerges in the river valley in the form of hot springs with high TDS. Groundwater also undergoes shallow circulation in the northern and southern flanks of the anticline and appears in the river valley in the form of cold springs with low TDS.

Hydrogeochemical characteristics and sources of salinity of the springs near Wenquanzhen in the eastern Sichuan Basin, China

NASA Astrophysics Data System (ADS)

Guo, Juan; Zhou, Xun; Wang, Lidong; Zhang, Yuqi; Shen, Xiaowei; Zhou, Haiyan; Ye, Shen; Fang, Bin

2017-12-01

Natural springs have the potential to provide important information on hydrogeochemical processes within aquifers. This study used traditional and classic technical methods and procedures to determine the characteristics and evolution of springs to gain further knowledge on the differences between hot saline springs and cold fresh springs. In a short river segment near Wenquanzhen in the eastern Sichuan Basin, southwest China, several natural springs coexist with total dissolved solids (TDS) ranging from less than 1 to 15 g/L and temperatures from 15 to 40 °C. The springs emanate from the outcropping Lower and Middle Triassic carbonates in the river valley cutting the core of an anticline. The cold springs are of Cl·HCO3-Na·Ca and Cl·SO4-Na types, and the hot saline springs are mainly of Cl-Na type. The chemistry of the springs has undergone some changes with time. The stable hydrogen and oxygen isotopes indicate that the spring waters are of a meteoric origin. The salinity of the springs originates from dissolution of minerals, including halite, gypsum, calcite and dolomite. The evolution of the springs involves the following mechanisms: the groundwater receives recharge from infiltration of precipitation, then undergoes deep circulation in the core of the anticline (incongruent dissolution of the salt-bearing strata occurs), and emerges in the river valley in the form of hot springs with high TDS. Groundwater also undergoes shallow circulation in the northern and southern flanks of the anticline and appears in the river valley in the form of cold springs with low TDS.

Geochemical evolution of groundwater in the Mud Lake area, eastern Idaho, USA

USGS Publications Warehouse

Rattray, Gordon W.

2015-01-01

Groundwater with elevated dissolved-solids concentrations—containing large concentrations of chloride, sodium, sulfate, and calcium—is present in the Mud Lake area of Eastern Idaho. The source of these solutes is unknown; however, an understanding of the geochemical sources and processes controlling their presence in groundwater in the Mud Lake area is needed to better understand the geochemical sources and processes controlling the water quality of groundwater at the Idaho National Laboratory. The geochemical sources and processes controlling the water quality of groundwater in the Mud Lake area were determined by investigating the geology, hydrology, land use, and groundwater geochemistry in the Mud Lake area, proposing sources for solutes, and testing the proposed sources through geochemical modeling with PHREEQC. Modeling indicated that sources of water to the eastern Snake River Plain aquifer were groundwater from the Beaverhead Mountains and the Camas Creek drainage basin; surface water from Medicine Lodge and Camas Creeks, Mud Lake, and irrigation water; and upward flow of geothermal water from beneath the aquifer. Mixing of groundwater with surface water or other groundwater occurred throughout the aquifer. Carbonate reactions, silicate weathering, and dissolution of evaporite minerals and fertilizer explain most of the changes in chemistry in the aquifer. Redox reactions, cation exchange, and evaporation were locally important. The source of large concentrations of chloride, sodium, sulfate, and calcium was evaporite deposits in the unsaturated zone associated with Pleistocene Lake Terreton. Large amounts of chloride, sodium, sulfate, and calcium are added to groundwater from irrigation water infiltrating through lake bed sediments containing evaporite deposits and the resultant dissolution of gypsum, halite, sylvite, and bischofite.

Mineralogy and fluid inclusions study of carbonate-hosted Mississippi valley-type Ain Allega Pb-Zn-Sr-Ba ore deposit, Northern Tunisia

NASA Astrophysics Data System (ADS)

Abidi, R.; Slim-Shimi, N.; Somarin, A.; Henchiri, M.

2010-05-01

The Ain Allega Pb-Zn-Sr-Ba ore deposit is located in the flysch zone on the Eastern edge of the Triassic diapir of Jebel Hamra. It is part of the extrusive Triassic evaporate formation along the Ghardimaou-Cape Serrat faults. The ore body consists of argilic-dolomite breccias surrounded by argilo-gypsum Triassic formation, which forms the hanging wall of the deposit, and rimmed by the Paleocene marls. The ore minerals show a cap-rock type mineralization with different styles particularly impregnation in dolomite, cement of breccias, replacement ore and open space filling in the dissolution cavities and fractures. Ore minerals include sphalerite, galena, marcasite and pyrite. Principal gangue minerals are composed of barite, celestite, calcite, dolomite and quartz. The ore minerals are hosted by the Triassic carbonate rocks which show hydrothermal alteration, dissolution and brecciation. X-ray - crystallographic study of barite-celestite mineral series shows that pure barite and celestite are the abundant species, whereas strontianiferous barite (85-96.5% BaSO 4) and barian-celestite (95% SrSO 4) are minor. Primary and secondary mono-phase (liquid only) fluid inclusions are common in celestite. Microthermometric analyses in two-phases (liquid and vapour) fluid inclusions suggest that gangue and ore minerals were precipitated by a low-temperature (180 °C) saline (16.37 wt.% NaCl equivalent) solution originated possibly from a basinal brine with some input from magmatic or metamorphic fluid. Based on geology, mineralogy, texture and fluid characteristics, the Ain Allega deposit is classified as a carbonate-hosted Mississippi valley-type deposit.

An innovative coupling between column leaching and oxygen consumption tests to assess behavior of contaminated marine dredged sediments.

PubMed

Couvidat, Julien; Benzaazoua, Mostafa; Chatain, Vincent; Zhang, Fan; Bouzahzah, Hassan

2015-07-01

Contaminated dredged sediments are often considered hazardous wastes, so they have to be adequately managed to avoid leaching of pollutants. The mobility of inorganic contaminants is a major concern. Metal sulfides (mainly framboïdal pyrite, copper, and zinc sulfides) have been investigated in this study as an important reactive metal-bearing phase sensitive to atmospheric oxygen action. An oxygen consumption test (OC-Test) has been adapted to assess the reactivity of dredged sediments when exposed to atmospheric oxygen. An experimental column set-up has been developed allowing the coupling between leaching and oxygen consumption test to investigate the reactivity of the sediment. This reactivity, which consisted of sulfide oxidation, was found to occur for saturation degree between 60 and 90 % and until the 20th testing week, through significant sulfates releases. These latter were assumed to come from sulfide oxidation in the first step of the test, then probably from gypsum dissolution. Confrontation results of OC-Test and leachate quality shows that Cu was well correlated to sulfates releases, which in turn, leads to Ca and Mg dissolution (buffer effect). Cu, and mostly Zn, was associated to organic matter, phyllosilicates, and other minerals through organo-clay complexes. This research confirmed that the OC-Test, originally developed for mine tailings, could be a useful tool in the dredged sediment field which can allow for intrinsic characterization of reactivity of a material suspected to readily reacting with oxygen and for better understanding of geochemical processes that affect pollutants behavior, conversion, and transfer in the environment.

The role of fluids in rock layering development: a pressure solution self-organized process revealed by laboratory experiments

NASA Astrophysics Data System (ADS)

Gratier, Jean-Pierre; Noiriel, Catherine; Renard, Francois

2015-04-01

Natural deformation of rocks is often associated with stress-driven differentiation processes leading to irreversible transformations of their microstructures. The development mechanisms of such processes during diagenesis, tectonic, metamorphism or fault differentiation are poorly known as they are difficult to reproduce experimentally due to the very slow kinetics of stress-driven chemical processes. Here, we show that experimental compaction with development of differentiated layering, similar to what happens in natural deformation, can be obtained by indenter techniques in laboratory conditions. Samples of plaster mixed with clay and of diatomite loosely interbedded with volcanic dust were loaded in presence of their saturated aqueous solutions during several months at 40°C and 150°C, respectively. High-resolution X-ray microtomography and scanning electron microscopy observations show that the layering development is a pressure solution self-organized process. Stress-driven dissolution of the soluble minerals (either gypsum or silica) is initiated in the areas initially richer in insoluble minerals (clays or volcanic dust) because the kinetics of diffusive mass transfer along the soluble/insoluble mineral interfaces is much faster than along the healed boundaries of the soluble minerals. The passive concentration of insoluble minerals amplifies the localization of dissolution along some layers oriented perpendicular to the maximum compressive stress. Conversely, in the areas with initial low content in insoluble minerals and clustered soluble minerals, dissolution is slower. Consequently, these areas are less deformed, they host the re-deposition of the soluble species and they act as rigid objects that concentrate the dissolution near their boundaries thus amplifying the differentiation. A crucial parameter required for self-organized process of pressure solution is the presence of a fluid that is a good solvent of at least some of the rock-forming minerals. Another general requirement for the development of such differentiated layering is the heterogeneous mixing of variously soluble and insoluble species. From a general point of view, the development of diagenetic or tectonic layering has crucial consequences in geological processes. The main one is to modify the composition and microstructure of rocks by dissolution of the most soluble species, passive concentration of the insoluble species and re-deposition of the dissolved species at a distance that depends on the transport efficiency (diffusion or advection). Consequently, layering development modifies both the rheological and the transfer properties of rocks. It is the most common strain localization process in the upper crust when a reactive fluid phase is present, complementary to other strain localization processes in the lithosphere. A specific effect is the development of anisotropic properties that may favor local sliding on weak surfaces. This is particularly important in fault zones where pressure solution processes are at work. Modeling of differentiated layering during natural deformation must be rooted in the stress-driven dissolution and transport properties of the various minerals forming the rocks, and on the evolution of their rheological properties. The strength evolution can be taken into account through a weakening factor in the zone of dissolution and a strengthening factor in the zone of deposition. The kinetics evolution is controlled by the critical parameters of pressure solution.

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

NASA Astrophysics Data System (ADS)

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong; Chorover, Jon; O'Day, Peggy A.

2017-06-01

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium (U) concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this work, the dissolution rates of K- and Na-compreignacite (K2(UO2)6O4(OH)6·8H2O and Na2(UO2)6O4(OH)6·8H2O, respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved carbonate concentration (ca. 0.2 and 2.8 mmol L-1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area, and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total U mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved U was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57 · 10-10 vs. 1.28 · 10-13 mol m-2 s-1 [log R = -9.81 and -12.89] and 5.79 · 10-10 vs. 3.71 · 10-13 mol m-2 s-1 [log R = -9.24 and -12.43] for K- and Na-compreignacite, respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for U mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. This study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as U in porous geomedia.

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this paper, the dissolution rates of K- and Na-compreignacite (K 2(UO 2) 6O 4(OH) 6·8H 2O and Na 2(UO 2) 6O 4(OH) 6·8H 2O respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved total carbonate content (ca. 0.2 and 2.8 mmolmore » L -1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total uranium mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved uranium was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were about 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57·10 -10 vs. 1.28·10 -13 mol m -2 s -1 [log R = -9.81 and -12.89] and 5.79·10 -10 vs. 3.71·10 -13 mol m -2 s -1 [log R = -9.24 and -12.43] for K- and Na-compreignacite respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for uranium mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. Finally, this study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as uranium in porous geomedia.« less

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

DOE PAGES

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong; ...

2017-06-01

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this paper, the dissolution rates of K- and Na-compreignacite (K 2(UO 2) 6O 4(OH) 6·8H 2O and Na 2(UO 2) 6O 4(OH) 6·8H 2O respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved total carbonate content (ca. 0.2 and 2.8 mmolmore » L -1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total uranium mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved uranium was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were about 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57·10 -10 vs. 1.28·10 -13 mol m -2 s -1 [log R = -9.81 and -12.89] and 5.79·10 -10 vs. 3.71·10 -13 mol m -2 s -1 [log R = -9.24 and -12.43] for K- and Na-compreignacite respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for uranium mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. Finally, this study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as uranium in porous geomedia.« less

Sedimentary differentiation of aeolian grains at the White Sands National Monument, New Mexico, USA

NASA Astrophysics Data System (ADS)

Fenton, Lori K.; Bishop, Janice L.; King, Sara; Lafuente, Barbara; Horgan, Briony; Bustos, David; Sarrazin, Philippe

2017-06-01

Gypsum (CaSO4·2H2O) has been identified as a major component of part of Olympia Undae in the northern polar region of Mars, along with the mafic minerals more typical of Martian dune fields. The source and age of the gypsum is disputed, with the proposed explanations having vastly different implications for Mars' geological history. Furthermore, the transport of low density gypsum grains relative to and concurrently with denser grains has yet to be investigated in an aeolian setting. To address this knowledge gap, we performed a field study at White Sands National Monument (WSNM) in New Mexico, USA. Although gypsum dominates the bulk of the dune field, a dolomite-rich [CaMg(CO3)2] transport pathway along the northern border of WSNM provides a suitable analog site to study the transport of gypsum grains relative to the somewhat harder and denser carbonate grains. We collected samples along the stoss slope of a dune and on two coarse-grained ripples at the upwind margin of the dune field where minerals other than gypsum were most common. For comparison, additional samples were taken along the stoss slope of a dune outside the dolomite transport pathway, in the center of the dune field. Visible and near-infrared (VNIR), X-ray powder diffraction (XRD), and Raman analyses of different sample size fractions reveal that dolomite is only prevalent in grains larger than ∼1 mm. Other minerals, most notably calcite, are also present in smaller quantities among the coarse grains. The abundance of these coarse grains, relative to gypsum grains of the same size, drops off sharply at the upwind margin of the dune field. In contrast, gypsum dominated the finer fraction (<∼1 mm) at all sample sites, displaying no spatial variation. Estimates of sediment fluxes indicate that, although mineralogical differentiation of wind-transported grains occurs gradually in creep, the process is much more rapid when winds are strong enough to saltate the ⩾1 mm grains. The observed grain segregation is consistent with the WSNM dune field formative friction velocity (0.39 m/s) proposed by Jerolmack et al. (2011): winds significantly weaker than this value would not lift the large grains into differentiation-inducing saltation, whereas the observed differentiated trend would be obliterated by significantly stronger winds. When applied to Olympia Undae, a similar sediment flux analysis suggests that the strongest winds modeled by the Mars Climate Database (MCD) are consistent with the observed concentration of gypsum at dune crests. Density-driven differentiation in transport should not influence sediment fluxes of finer grains (<1 mm) as strongly on Earth, suggesting that the high ratio of fine gypsum grains to other minerals at WSNM is caused by a relatively high production and/or abrasion rate of gypsum sand. The observed preferential transport of coarse-grained gypsum in the dune field conceals a broader range of coarse-grained minerals present on Alkali Flat, contributing to the problem that mineralogy determined through both remote sensing of dune fields and analysis of dune foresets does not fully represent that of the source regions. Unlike quartz, the concentration of gypsum in WSNM occurs not because it is more resistant to weathering and erosion than other minerals, but rather because it is more readily produced (in the case of finer grains) and transported (in the case of coarser grains) than other minerals present in the region.

Gypsum Formation during the Messinian Salinity Crisis: an Alternative Model

NASA Astrophysics Data System (ADS)

Grothe, A.; Krijgsman, W.; Sangiorgi, F.; Vasiliev, I.; Baak, C. V.; Wolthers, M.; Stoica, M.; Reichart, G. J.; Davies, G.

2016-12-01

During the Messinian Salinity Crisis (MSC; 5.97 - 5.33 Myr ago), thick packages of evaporites (gypsum and halite) were deposited in the Mediterranean Basin. Traditionally, the occurrence of these evaporites is explained by the so-called "desiccation-model", in which evaporites are considered to result from a (partly) desiccated basin. In the last decade, it was thought that changes in the Mediterranean-Atlantic connectivity could explain the formation of gypsum. Stable isotope studies, however, show that the gypsum formed under influence of large freshwater input. Here we present new strontium isotope data from two well-dated Messinian sections in the Black and Caspian Seas. Our Sr isotope records suggest a persistent Mediterranean-Black Sea connection throughout the salinity crisis, which implies a large additional freshwater source to the Mediterranean. We claim that low saline waters from the Black Sea region are a prerequisite for gypsum formation in the Mediterranean and speculate about the mechanisms explaining this apparent paradox.

Development of gypsum alteration on marble and limestone

USGS Publications Warehouse

McGee, E.S.

1996-01-01

Blackened alteration crusts of gypsum plus particulates that form on sheltered areas on marble and limestone buildings pose a challenge for rehabilitation and cleaning. Fresh marble and limestone samples exposed at monitored exposure sites present conditions of simple geometry and well-documented exposures but have short exposure histories (one to five years). The gypsum alteration crusts that develop on these samples provide insight into the early stages and rate of alteration crust formation. Alteration crusts from buildings give a longer, but less well known exposure history and present much more complex surfaces for gypsum accumulation. Integrated observations and measurements of alteration crusts from exposure samples and from buildings identify four factors that are important in the formation and development of alteration crusts on marble and limestone: (1) pollution levels, (2) exposure to rain or washing, (3) geometry of exposure of the stone surface, and (4) permeability of the stone. The combination of these factors contributes to both the distribution and the physical characteristics of the gypsum crusts which may affect cleaning decisions.

Factors influencing gypsum crystal morphology within a flue gas desulfurization vessel

NASA Astrophysics Data System (ADS)

Lewis, Kinsey M.

Flue gas desulfurization (FGD) is utilized by the coal--powered generating industry to safely eliminate sulfur dioxide. A FGD vessel (scrubber) synthetically creates gypsum crystals by combining limestone (CaCO3), SO2 flue gas, water and oxygen resulting in crystalline gypsum (CaSO4 · 2H2O), which can be sold for an economic return. Flat disk--like crystals, opposed to rod--like crystals, are hard to dewater, lowering economic return. The objectives were to investigate the cause of varying morphologies, understand the environment of precipitation, as well as identify correlations between operating conditions and resulting unfavorable gypsum crystal growth. Results show evidence supporting airborne impurities due to the onsite coal pile, the abundance and size of CaCO 3 and high Ca:SO4 ratios within the scrubber as possible factors controlling gypsum crystal morphology. In conclusion, regularly purging the system and incorporating a filter on the air intake valve will provide an economic byproduct avoiding costly landfill deposits.

Gypsum-permineralized microfossils and their relevance to the search for life on Mars.

PubMed

Schopf, J William; Farmer, Jack D; Foster, Ian S; Kudryavtsev, Anatoliy B; Gallardo, Victor A; Espinoza, Carola

2012-07-01

Orbital and in situ analyses establish that aerially extensive deposits of evaporitic sulfates, including gypsum, are present on the surface of Mars. Although comparable gypsiferous sediments on Earth have been largely ignored by paleontologists, we here report the finding of diverse fossil microscopic organisms permineralized in bottom-nucleated gypsums of seven deposits: two from the Permian (∼260 Ma) of New Mexico, USA; one from the Miocene (∼6 Ma) of Italy; and four from Recent lacustrine and saltern deposits of Australia, Mexico, and Peru. In addition to presenting the first report of the widespread occurrence of microscopic fossils in bottom-nucleated primary gypsum, we show the striking morphological similarity of the majority of the benthic filamentous fossils of these units to the microorganisms of a modern sulfuretum biocoenose. Based on such similarity, in morphology as well as habitat, these findings suggest that anaerobic sulfur-metabolizing microbial assemblages have changed relatively little over hundreds of millions of years. Their discovery as fossilized components of the seven gypsiferous units reported suggests that primary bottom-nucleated gypsum represents a promising target in the search for evidence of past life on Mars. Key Words: Confocal laser scanning microscopy-Gypsum fossils-Mars sample return missions-Raman spectroscopy-Sample Analysis at Mars (SAM) instrument-Sulfuretum.

Investigation of a mercury speciation technique for flue gas desulfurization materials.

PubMed

Lee, Joo-Youp; Cho, Kyungmin; Cheng, Lei; Keener, Tim C; Jegadeesan, Gautham; Al-Abed, Souhail R

2009-08-01

Most of the synthetic gypsum generated from wet flue gas desulfurization (FGD) scrubbers is currently being used for wallboard production. Because oxidized mercury is readily captured by the wet FGD scrubber, and coal-fired power plants equipped with wet scrubbers desire to benefit from the partial mercury control that these systems provide, some mercury is likely to be bound in with the FGD gypsum and wallboard. In this study, the feasibility of identifying mercury species in the FGD gypsum and wallboard samples was investigated using a large sample size thermal desorption method. Potential candidates of pure mercury standards including mercuric chloride (HgCl2), mercurous chloride (Hg2Cl2), mercury oxide (HgO), mercury sulfide (HgS), and mercuric sulfate (HgSO4) were analyzed to compare their results with those obtained from FGD gypsum and dry wallboard samples. Although any of the thermal evolutionary curves obtained from these pure mercury standards did not exactly match with those of the FGD gypsum and wallboard samples, it was identified that Hg2Cl2 and HgCl2 could be candidates. An additional chlorine analysis from the gypsum and wallboard samples indicated that the chlorine concentrations were approximately 2 orders of magnitude higher than the mercury concentrations, suggesting possible chlorine association with mercury.

Investigation of a mercury speciation technique for flue gas desulfurization materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, J.Y.; Cho K.; Cheng L.

2009-08-15

Most of the synthetic gypsum generated from wet flue gas desulfurization (FGD) scrubbers is currently being used for wallboard production. Because oxidized mercury is readily captured by the wet FGD scrubber, and coal-fired power plants equipped with wet scrubbers desire to benefit from the partial mercury control that these systems provide, some mercury is likely to be bound in with the FGD gypsum and wallboard. In this study, the feasibility of identifying mercury species in the FGD gypsum and wallboard samples was investigated using a large sample size thermal desorption method and samples from power plants in Pennsylvania. Potential candidatesmore » of pure mercury standards including mercuric chloride, mercurous chloride, mercury oxide, mercury sulfide, and mercuric sulfate were analyzed to compare their results with those obtained from FGD gypsum and dry wallboard samples. Although any of the thermal evolutionary curves obtained from these pure mercury standards did not exactly match with those of the FGD gypsum and wallboard samples, it was identified that Hg{sub 2}Cl{sub 2} and HgCl{sub 2} could be candidates. An additional chlorine analysis from the gypsum and wallboard samples indicated that the chlorine concentrations were approximately 2 orders of magnitude higher than the mercury concentrations, suggesting possible chlorine association with mercury. 21 refs., 5 figs., 3 tabs.« less

Bacterial Communities and the Nitrogen Cycle in the Gypsum Soils of Cuatro Ciénegas Basin, Coahuila: A Mars Analogue

PubMed Central

López-Lozano, Nguyen E.; Eguiarte, Luis E.; Bonilla-Rosso, Germán; García-Oliva, Felipe; Martínez-Piedragil, Celeste; Rooks, Christine

2012-01-01

Abstract The OMEGA/Mars Express hyperspectral imager identified gypsum at several sites on Mars in 2005. These minerals constitute a direct record of past aqueous activity and are important with regard to the search of extraterrestrial life. Gale Crater was chosen as Mars Science Laboratory Curiosity's landing site because it is rich in gypsum, as are some desert soils of the Cuatro Ciénegas Basin (CCB) (Chihuahuan Desert, Mexico). The gypsum of the CCB, which is overlain by minimal carbonate deposits, was the product of magmatic activity that occurred under the Tethys Sea. To examine this Mars analogue, we retrieved gypsum-rich soil samples from two contrasting sites with different humidity in the CCB. To characterize the site, we obtained nutrient data and analyzed the genes related to the N cycle (nifH, nirS, and nirK) and the bacterial community composition by using 16S rRNA clone libraries. As expected, the soil content for almost all measured forms of carbon, nitrogen, and phosphorus were higher at the more humid site than at the drier site. What was unexpected is the presence of a rich and divergent community at both sites, with higher taxonomic diversity at the humid site and almost no taxonomic overlap. Our results suggest that the gypsum-rich soils of the CCB host a unique microbial ecosystem that includes novel microbial assemblies. Key Words: Cuatro Ciénegas Basin—Gale Crater—Gypsum soil microbial diversity—Molecular ecology—Nitrogen cycle. Astrobiology 12, 699–709. PMID:22920518

Application of small panel damping measurements to larger walls

NASA Astrophysics Data System (ADS)

Hastings, Mardi C.; Godfrey, Richard; Babcock, G. Madison

1996-05-01

Damping properties of a viscoelastic material were determined using a standard resonant beam technique. The damping material was then applied to 1 by 2 foot gypsum panels in a constrained layer construction. Damping loss factors in panels with and without the constrained layer were determined based on reverberation times after excitation at third-octave band center frequencies. The constrained damping layer had been designed to increase damping by an order of magnitude above that of a single gypsum panel at 2000 Hz; however, relative to a gypsum panel of the same overall thickness as the panel with the constrained layer, loss factors increased only by a factor of three to five. Next modal damping loss factors in 9 by 14 foot gypsum single and double walls were calculated from the experimentally determined quality factor for each modal resonance. Results showed that below 2500 Hz, modes in 1 by 2 foot gypsum panels had nearly the same damping loss factors as modes in a 9 by 14 foot gypsum wall of the same thickness; however, loss factors for the wall were an order of magnitude lower than those of the 1 by 2 foot panels at frequencies above 2500 Hz, the coincidence frequency for 5/8-inch thick gypsum plates. Thus it was inconclusive whether or not damping loss factors measured using small panels could be used to estimate the effect of a constrained damping layer on transmission loss through a 9 by 14 foot wall unless boundary conditions and modal frequencies were the same for each size.

Why does carbon increase in highly weathered soil under no-till upon lime and gypsum use?

PubMed

Inagaki, Thiago Massao; de Moraes Sá, João Carlos; Caires, Eduardo Fávero; Gonçalves, Daniel Ruiz Potma

2017-12-01

Field experiments have been used to explain how soil organic carbon (SOC) dynamics is affected by lime and gypsum applications, however, how SOC storage occurs is still debatable. We hypothesized that although many studies conclude that Ca-based soil amendments such as lime and gypsum may lead to SOC depletion due to the enhancement of microbial activity, the same does not occur under conservation agriculture conditions. Thus, the objective of this study was to elucidate the effects of lime and gypsum applications on soil microbial activity and SOC stocks in a no-till field and in a laboratory incubation study simulating no-till conditions. The field experiment was established in 1998 in a clayey Oxisol in southern Brazil following a completely randomized blocks design with a split-plot arrangement and three replications. Lime and gypsum were surface applied in 1998 and reapplied in 2013. Undisturbed soil samples were collected before the treatments reapplications, and one year after. The incubation experiment was carried out during 16months using these samples adding crop residues on the soil surface to simulate no-till field conditions. Lime and gypsum applications significantly increased the labile SOC stocks, microbial activity and soil fertility attributes in both field and laboratory experiments. Although the microbial activity was increased, no depletion of SOC stocks was observed in both experiments. Positive correlations were observed between microbial activity increase and SOC gains. Labile SOC and Ca 2+ content increase leads to forming complex with mineral soil fractions. Gypsum applications performed a higher influence on labile SOC pools in the field than in the laboratory experiment, which may be related to the presence of active root system in the soil profile. We conclude that incubation experiments using lime and gypsum in undisturbed samples confirm that soil microbial activity increase does not deplete SOC stocks under conservation agriculture. Copyright © 2017 Elsevier B.V. All rights reserved.

Barium isotope fractionation during witherite (BaCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; van Zuilen, Kirsten; Purgstaller, Bettina; Baldermann, Andre; Nägler, Thomas F.; Dietzel, Martin

2016-10-01

This study examines the behavior of Ba isotope fractionation between witherite and fluid during mineral dissolution, precipitation and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 10-2 M NaCl solution where the pH was adjusted by continuous bubbling of a water saturated gas phase of CO2 or atmospheric air. During witherite dissolution no Ba isotope fractionation was observed between solid and fluid. In contrast, during witherite precipitation, caused by a pH increase, a preferential uptake of the lighter 134Ba isotopomer in the solid phase was observed. In this case, the isotope fractionation factor αwitherite-fluid is calculated to be 0.99993 ± 0.00004 (or Δ137/134Bawitherite-fluid ≈ -0.07 ± 0.04‰, 2 sd). The most interesting feature of this study, however, is that after the attainment of chemical equilibrium, the Ba isotope composition of the aqueous phase is progressively becoming lighter, indicating a continuous exchange of Ba2+ ions between witherite and fluid. Mass balance calculations indicate that the detachment of Ba from the solid is not only restricted to the outer surface layer of the solid, but affects several (∼7 unit cells) subsurface layers of the crystal. This observation comes in excellent agreement with the concept of a dynamic system at chemical equilibrium in a mineral-fluid system, denoting that the time required for the achievement of isotopic equilibrium in the witherite-fluid system is longer compared to that observed for chemical equilibrium. Overall, these results indicate that the isotopic composition of Ba bearing carbonates in natural environments may be altered due to changes in fluid composition without a net dissolution/precipitation to be observed.

Gypsum karst in Italy: a review

NASA Astrophysics Data System (ADS)

De Waele, Jo; Chiarini, Veronica; Columbu, Andrea; D'Angeli, Ilenia M.; Madonia, Giuliana; Parise, Mario; Piccini, Leonardo; Vattano, Marco; Vigna, Bartolomeo; Zini, Luca; Forti, Paolo

2016-04-01

Although outcropping only rarely in Italy, gypsum karst has been described in detail since the early XXth century (Marinelli, 1917). Gypsum caves are now known from almost all Italian regions (Madonia & Forti, 2003), but are mainly localised along the northern border of the Apennine chain (Emilia Romagna and Marche regions), Calabria, and Sicily, where the major outcrops occur. Recently, important caves have also been discovered in the underground gypsum quarries in Piedmont (Vigna et al., 2010). During the late 80s and 90s several multidisciplinary studies have been carried out in many gypsum areas. All this work converged into a comprehensive overview in 2003 (Madonia & Forti, 2003). Further detailed studies focused on the gypsum areas of Emilia Romagna (Chiesi et al., 2010; Forti & Lucci, 2010; Demaria et al., 2012; De Waele & Pasini, 2013; Ercolani et al., 2013; Columbu et al., 2015; Lucci & Piastra, 2015; Tedeschi et al., 2015) and of Sicily (Madonia & Vattano, 2011). Sinkholes related to Permo-Triassic gypsum have been studied in Friuli Venezia Giulia (Zini et al., 2015). This presentation will review the state of the art regarding different aspects of evaporite karst in Italy focusing on the main new results. References Chiesi M., et al. (2010) - Origin and evolution of a salty gypsum/anhydrite karst spring: the case of Poiano (Northern Apennines, Italy). Hydrogeology Journal, 18, pp. 1111-1124. Columbu A. et al. (2015) - Gypsum caves as indicators of climate-driven river incision and aggradation in a rapidly uplifting region. Geology, 43(6), 539-542. Demaria D. et al. (Eds.) (2012), Le Grotte Bolognesi, GSB-USB, 431 p. De Waele J., Pasini G. (2013) - Intra-messinian gypsum palaeokarst in the northern Apennines and its palaeogeographic implications. Terra Nova 25, pp. 199-205. Ercolani M., et al. (Eds.) (2013), I Gessi e la Cave i Monte Tondo. Studio multidisciplinare di un'area carsica nella Vena del Gesso Romagnola. Memorie Ist. It. Spel. II(26), 559 p. Forti P., Lucci P. (Eds.) (2010) - Il Progetto Stella-Basino. Studio multidisciplinare di un sistema carsico nella Vena del Gesso Romagnola. Memorie Ist. It. Spel. II(14), 260 p. Lucci P., Piastra S. (Eds.) (2015), I Gessi di Brisighella e Rontana: studio multidisciplinare di un'area carsica nella Vena del Gesso Romagnola. Memorie Ist. It. Spel. II(28), 751 p. Madonia G., Forti P. (2003) - Le aree carsiche gessose d'Italia. Memorie Ist. It. Spel. II(14), 285 p. Madonia G., Vattano M. (2011) - New knowledge on the Monte Conca gypsum karst system (central-western Sicily, Italy). Acta Carsologica, 40, (1), pp. 53-64. Marinelli O. (1917) - Fenomeni carsici nelle regioni gessose d'Italia. Mem. Geografiche di Giotto Dainelli, 34, pp. 263-416, suppl. to Riv. Geografica It Tedeschi L. et al. (2015) - Comportamento idrogeologico di alcune risorgenti carsiche nei gessi dell'Emilia-Romagna. Memorie Ist. It. Spel. II(29), pp. 399-404. Vigna B. et al. (2010) - Evolution of karst in Messinian gypsum (Monferrato, Northern Italy). Geodinamica Acta, 23(1-3), pp. 29-40. Zini L. et al. (2015) - a multidisciplinary approach in sinkhole analysis: the Quinis village case study (NE-Italy). Engineering Geology, 197, pp.132-144.

Archaeometrical analyses demonstrates that humans excavated clay from mardels on the Luxembourger Gutland plateau to produce ceramics.

NASA Astrophysics Data System (ADS)

Vanmourik, Jan; Braekmans, Dennis

2017-04-01

Mardels, small closed depressions, are distinctive landforms on the Luxembourger Gutland plateau. In the present landscape most mardels are shallow fens, filled with colluvial sediments. Slotboom (1963) investigated 108 mardels in the Luxembourger Gutland and ascribed the mardels in the Luxembourger Keuper marl formations to subsurface solution of gypsum inclusions, followed by collapse and subsidence of the overlying beds. The colluvial deposits in the mardels were palynologically dated as Post Roman. Schmalen (2001) published an actualized inventory of mardels in the Gutland. This inventory includes also mardels on the Lias marls, a formation without gypsum inclusions. Etienne et al. (2011) considered beside natural processes also anthropogenic factors as explanation for CD's in the Lorraine landscape. The sediments in the majority of the CD's were palynologically dated as Post Roman. Combined with the open character of the local vegetation this suggest that the majority of the mardels are probably abandoned Roman quarries. Slotboom and van Mourik (2015) showed that the fillings of the mardels on the Lias marls are Post-Roman, just as on the Keuper marls. To answer the question "are mardels natural subsidence basins or abandoned quarries" we need additional information from the soil archives. Firstly we must identify the process, responsible for the deposition of clay in the mardels. The majority of the mardels in the Gutland occur in clusters in deciduous forests. Earthworm activity in the forest soils promote lateral clay leaching and soil erosion and mardels function as sediment traps. Due to this process clay with the best properties for the production of ceramics occurred in mardels. This process was active during the whole Holocene. It is striking that we did not find Pre-Roman but only Post-Roman mardel fillings. Secondly we need information about the practice of clay, excavated from mardels. If mardels are really abandoned quarries, the excavated sediments must have been used, most probably for the production of ceramics. If we can find relicts of ceramics in the vicinity of mardels we can compare the composition of these ceramics with mardel clay. We could collect finds of Roman tile-works on the Lias marls (Kalefeld) and of Roman pottery on the Keuper marls (Biischtert) in the vicinity of mardels. Provenance analysis (XRF) demonstrated the similarity of chemical composition of mardel clay and ceramics. This indicates that the mardels on the Gutland plateau developed initially as natural depressions (sediment traps), on Strassen marls related to soil subsidence, caused by joints in the underlying Luxembourger sandstone, on Keuper marls to subsidence after soil subsurface dissolving of gypsum veins. The colluvial clay was used by the Romans for the production of ceramics. Due to the excavation reached the actual seizes. Colluvial clay accumulation restarted in the abandoned quarries. • Slotboom, R.T. (1963) Comparative geomorphological and palynological investigation of the pingos (Viviers) in the Haute Fagnes (Belgium) and the Mardellen in the Gutland (Luxembourg). Zeitschrift für Geomorphologie 7: 193-231. • Schmalen, C. (2002) Einige Mardellen Luxemburgs auf den Keuper-und Liasschichten des Forstamtbezirks Zentrum. Diplomarbeit in Studiengang Umweltplannung an der Fachhochschule Trier, Standort Birkenfeld, 2002. • Etienne, D., Ruffaldi, P., Goepp, S., Ritz, F., Georges-Leroy, M., Pollier, B., Dambrine, E. (2011) The origin of closed depressions in Northeastern France: A new assessment. Geomorphology 126: 121-131. • Slotboom, R.T., van Mourik, J.M. (2015) Pollen records of mardel deposits; the effects of climatic oscillations and land management on soil erosion in Gutland, Luxembourg. Catena 132 (2015) 72-88.

Utilization of Phase Change Materials (PCM) to Reduce Energy Consumption in Buildings

DTIC Science & Technology

2011-09-14

incorporating PCM for use in building applications. Ongoing research in thermal storage in which the PCM were encapsulated in concrete, gypsum wallboard ... wallboards were made from commercial panels after a first attempt to use gypsum walls. Three types of wallboards were studied: (i) a polycarbonate panel...and compared with ordinary gypsum wallboard . Within this comparison, the PCM composite solidification temperature was 22 °C (i.e. 2 K higher than the

A Review of Multidimensional, Multifluid Intermediate-scale Experiments: Flow Behavior, Saturation Imaging, and Tracer Detection and Quantification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oostrom, Mart; Dane, J. H.; Wietsma, Thomas W.

2007-08-01

A review is presented of original multidimensional, intermediate-scale experiments involving non-aqueous phase liquid (NAPL) flow behavior, imaging, and detection/quantification with solute tracers. In a companion paper (Oostrom, M., J.H. Dane, and T.W. Wietsma. 2006. A review of multidimensional, multifluid intermediate-scale experiments: Nonaqueous phase dissolution and enhanced remediation. Vadose Zone Journal 5:570-598) experiments related to aqueous dissolution and enhanced remediation were discussed. The experiments investigating flow behavior include infiltration and redistribution experiments with both light and dense NAPLs in homogeneous and heterogeneous porous medium systems. The techniques used for NAPL saturation mapping for intermediate-scale experiments include photon-attenuation methods such as gammamore » and X-ray techniques, and photographic methods such as the light reflection, light transmission, and multispectral image analysis techniques. Solute tracer methods used for detection and quantification of NAPL in the subsurface are primarily limited to variations of techniques comparing the behavior of conservative and partitioning tracers. Besides a discussion of the experimental efforts, recommendations for future research at this laboratory scale are provided.« less

3-D Resistivity Tomography for Cliff Stability Study at the D-Day Pointe du Hoc Historic Site in Normandy, France

NASA Astrophysics Data System (ADS)

Udphuay, S.; Everett, M. E.; Guenther, T.; Warden, R. R.

2007-12-01

The D-Day invasion site at Pointe du Hoc in Normandy, France is one of the most important World War II battlefields. The site remains today a valuable historic cultural resource. However the site is vulnerable to cliff collapses that could endanger the observation post building and U.S. Ranger memorial located just landward of the sea stack, and an anti-aircraft gun emplacement, Col. Rudder's command post, located on the cliff edge about 200 m east of the observation post. A 3-D resistivity tomography incorporating extreme topography is used in this study to provide a detailed site stability assessment with special attention to these two buildings. Multi-electrode resistivity measurements were made across the cliff face and along the top of the cliff around the two at-risk buildings to map major subsurface fracture zones and void spaces that could indicate possible accumulations and pathways of groundwater. The ingress of acidic groundwater through the underlying carbonate formations enlarges pre-existing tectonic fractures via limestone dissolution and weakens the overall structural integrity of the cliff. The achieved 3-D resistivity tomograms provide diagnostic subsurface resistivity distributions. Resistive zones associated with subsurface void spaces have been located. These void spaces constitute a stability geohazard as they become significant drainage routes during and after periods of heavy rainfalls.

Dry Stream Reaches in Carbonate Terranes: Surface Indicators of Ground-Water Reservoirs

USGS Publications Warehouse

Brahana, J.V.; Hollyday, E.F.

1988-01-01

In areas where dry stream reaches occur, subsurface drainage successfully competes with surface drainage, and sheet-like dissolution openings have developed parallel to bedding creating the ground-water reservoir. Union Hollow in south-central Tennessee is the setting for a case study that illustrates the application of the dry stream reach technique. In this technique, dry stream reach identification is based on two types of readily acquired information: remotely sensed black and white infrared aerial photography; and surface reconnaissance of stream channel characteristics. Test drilling in Union Hollow subsequent to identification of the dry reach proved that a localized ground-water reservoir was present.

Production development and utilization of Zimmer Station wet FGD by-products. Final report. Volume 5, A laboratory greenhouse study conducted in fulfillment of Phase 2, Objective 2 titled. Use of FGD by-product gypsum enriched with magnesium hydroxide as a soil amendment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yibirin, H.; Stehouwer, R. C.; Bigham, J. M.

The Clean Air Act, as revised in 1992, has spurred the development of flue gas desulfurization (FGD) technologies that have resulted in large volumes of wet scrubber sludges. In general, these sludges must be dewatered, chemically treated, and disposed of in landfills. Disposal is an expensive and environmentally questionable process for which suitable alternatives must be found. Wet scrubbing with magnesium (Mg)-enhanced lime has emerged as an efficient, cost effective technology for SO 2 removal. When combined with an appropriate oxidation system, the wet scrubber sludge can be used to produce gypsum (CaSO 4-2H 2O) and magnesium hydroxide [Mg(OH) 2]more » of sufficient purity for beneficial re-use. Product value generally increases with purity of the by-product(s). The pilot plant at the CINERGY Zimmer Station near Cincinnati produces gypsum by products that can be formulated to contain varying amounts of Mg(OH) 2. Such materials may have agricultural value as soil conditioners, liming agents and sources of plant nutrients (Ca, Mg, S). This report describes a greenhouse study designed to evaluate by-product gypsum and Mg gypsum from the Zimmer Station pilot plant as amendments for improving the quality of agricultural soils and mine spoils that are currently unproductive because of phytotoxic conditions related to acidity and high levels of toxic dissolved aluminum (Al). In particular, the technical literature contains evidence to suggest that gypsum may be more effective than agricultural limestone in modifying soil chemical conditions below the immediate zone of application. Representative samples of by-product gypsum and Mg(OH) 2 from the Zimmer Station were initially characterized. The gypsum was of high chemical purity and consisted of well crystalline, lath-shaped particles of low specific surface area. By contrast, the by-product Mg(OH) 2 was a high surface area material (50 m 2 g -1) that contained 20% CaSO 4 with variable hydration state. Artificial blends of these materials containing 4% and 8% Mg(OH) 2 were prepared for comparison with other liming agents in the form of agricultural limestone and gypsum amended with laboratory Ca(OH) 2.« less

Competition between reaction-induced expansion and creep compaction during gypsum formation: Experimental and numerical investigation

NASA Astrophysics Data System (ADS)

Skarbek, R. M.; Savage, H. M.; Spiegelman, M. W.; Kelemen, P. B.; Yancopoulos, D.

2017-12-01

Deformation and cracking caused by reaction-driven volume increase is an important process in many geological settings, however the conditions controlling these processes are poorly understood. The interaction of rocks with reactive fluids can change permeability and reactive surface area, leading to a large variety of feedbacks. Gypsum is an ideal material to study these processes. It forms rapidly at room temperature via bassanite hydration, and is commonly used as an analogue for rocks in high-temperature, high-pressure conditions. We conducted uniaxial strain experiments to study the effects of applied axial load on deformation and fluid flow during the formation of gypsum from bassanite. While hydration of bassanite to gypsum involves a solid volume increase, gypsum exhibits significant creep compaction when in contact with water. These two volume changing processes occur simultaneously during fluid flow through bassanite. We cold-pressed bassanite powder to form cylinders 2.5 cm in height and 1.2 cm in diameter. Samples were compressed with a static axial load of 0.01 to 4 MPa. Water infiltrated initially unsaturated samples through the bottom face and the height of the samples was recorded as a measure of the total volume change. We also performed experiments on pure gypsum samples to constrain the amount of creep observed in tests on bassanite hydration. At axial loads < 0.15 MPa, volume increase due to the reaction dominates and samples exhibit monotonic expansion. At loads > 1 MPa, creep in the gypsum dominates and samples exhibit monotonic compaction. At intermediate loads, samples exhibit alternating phases of compaction and expansion due to the interplay of the two volume changing processes. We observed a change from net compaction to net expansion at an axial load of 0.250 MPa. We explain this behavior with a simple model that predicts the strain evolution, but does not take fluid flow into account. We also implement a 1D poro-visco-elastic model of the imbibition process that includes the reaction and gypsum creep. We use the results of these models, with models of the creep rate in gypsum, to estimate the temperature dependence of the axial load where total strain transitions from compaction to expansion. Our results have implications for the depth dependence of reaction induced volume changes in the Earth.

Towards the establishment of a general rate law for gypsum nucleation

NASA Astrophysics Data System (ADS)

Reznik, Itay J.; Ganor, Jiwchar; Gruber, Chen; Gavrieli, Ittai

2012-05-01

Gypsum nucleation kinetics from a wide range of chemical compositions (1.45 < Ca2+/SO42- < 115), ionic strengths (I = 2.5-10 m) and saturation state with respect to gypsum (Ωgyp = 1.07-8.4) were examined in batch experiments containing mixtures of Ca2+-rich Dead Sea brine and SO42-rich seawater with or without addition of extra Na2SO4 and CaCl2·2H2O. The induction times attained in the present study were compiled together with literature values from experiments carried out under significantly different conditions (synthetic NaCl solutions; I = 0.09-6.3 m; Ca2+/SO42- = 1; Ωgyp:1.59-7.76). Despite the variability in the experimental solutions, a single rate law based on classic nucleation theory was formulated to describe the induction times from more than 80 experiments: logT=log{1}/{3.17·Cs·exp{-}7.08ln2Ω}+0.072·Cs·exp-{1.426}/{ln2Ω} where Tind is the induction time, Cs is the solubility of gypsum and Ω is the saturation state with respect to gypsum. The rate law provides Tind for gypsum precipitation from aqueous solutions at 25 °C, containing no synthetic antiscalants or catalysts, within a 95% confidence interval within a factor of 5. Based on this rate law, we show that at present most of the precipitation of gypsum from the Dead Sea brine occurs following significant evaporation in the industrial evaporation ponds and not in the Dead Sea itself. Whereas Tind in Dead Sea brines is very long (on the order of 3 years), the evaporation of brine in the industrial ponds leads to increased Ω values, and thus to short Tind in the order of a few days. However, if seawater or reject brine from seawater desalinization will be introduced to the Dead Sea to restore its declining level, Tind will be significantly reduced and gypsum nucleation and precipitation will occur. For evaporated seawater, the proposed rate law predicts that even though saturation is obtained when seawater is evaporated by a factor of 2.8, gypsum will nucleate at reasonable times (few years) only when seawater are evaporated by a factor of ˜3.3.

Experimental Shock Transformation of Gypsum to Anhydrite: A New Low Pressure Regime Shock Indicator

NASA Technical Reports Server (NTRS)

Bell, Mary S.; Zolensky, Michael E.

2011-01-01

The shock behavior of gypsum is important in understanding the Cretaceous/Paleogene event and other terrestrial impacts that contain evaporite sediments in their targets (e.g., Mars Exploration Rover Spirit detected sulfate at Gusev crater, [1]). Most interest focuses on issues of devolatilization to quantify the production of SO2 to better understand its role in generating a temporary atmosphere and its effects on climate and biota [2,3]. Kondo and Ahrens [4] measured induced radiation emitted from single crystal gypsum shocked to 30 and 40 GPa. They observed greybody emission spectra corresponding to temperatures in the range of 3,000 to 4,000 K that are a factor of 2 to 10 times greater than calculated pressure-density energy equation of state temperatures (Hugoniot) and are high enough to melt gypsum. Chen et al. [5] reported results of shock experiments on anhydrite, gypsum, and mixtures of these phases with silica. Their observations indicated little or no devolatilization of anhydrite shocked to 42 GPa and that the fraction of sulfur, by mass, that degassed is approx.10(exp -2) of theoretical prediction. In another report of shock experiments on calcite, anhydrite, and gypsum, Badjukov et al. [6] observed only intensive plastic deformation in anhydrite shock loaded at 63 GPa, and gypsum converted to anhydrite when shock loaded at 56 GPa but have not experimentally shocked gypsum in a step-wise manner to constrain possible incipient transformation effects. Schmitt and Hornemann [7] shock loaded anhydrite and quartz to a peak pressure of 60 GPa and report the platy anhydrite grains were completely pseudomorphed by small crystallized anhydrite grains. However, no evidence of interaction between the two phases could be observed and they suggested that recrystallization of anhydrite grains is the result of a solid-state transformation. They concluded that significant decomposition of anhydrite requires shock pressures higher than 60 GPa. Gupta et al. [8] reanalyzed the calcite and anhydrite shock wave experiments of Yang [9] using improved equations of state of porous materials and vaporized products. They determined the pressures for incipient and complete vaporization to be 32.5 and 122 GPa for anhydrite GPa which is a factor of 2 to 3 lower than reported earlier by Yang [9]. These studies are not in agreement regarding the onset of sulfate decomposition and documentation of shock effects in gypsum is incomplete.

A kinetics database and scripts for PHREEQC

NASA Astrophysics Data System (ADS)

Hu, B.; Zhang, Y.; Teng, Y.; Zhu, C.

2017-12-01

Kinetics of geochemical reactions has been increasingly used in numerical models to simulate coupled flow, mass transport, and chemical reactions. However, the kinetic data are scattered in the literature. To assemble a kinetic dataset for a modeling project is an intimidating task for most. In order to facilitate the application of kinetics in geochemical modeling, we assembled kinetics parameters into a database for the geochemical simulation program, PHREEQC (version 3.0). Kinetics data were collected from the literature. Our database includes kinetic data for over 70 minerals. The rate equations are also programmed into scripts with the Basic language. Using the new kinetic database, we simulated reaction path during the albite dissolution process using various rate equations in the literature. The simulation results with three different rate equations gave difference reaction paths at different time scale. Another application involves a coupled reactive transport model simulating the advancement of an acid plume in an acid mine drainage site associated with Bear Creek Uranium tailings pond. Geochemical reactions including calcite, gypsum, and illite were simulated with PHREEQC using the new kinetic database. The simulation results successfully demonstrated the utility of new kinetic database.

Effect of calcium formate as an additive on desulfurization in power plants.

PubMed

Li, Zhenhua; Xie, Chunfang; Lv, Jing; Zhai, Ruiguo

2018-05-01

SO 2 in flue gas needs to be eliminated to alleviate air pollution. As the quality of coal decreases and environmental standard requirements become more stringent, the high-efficiency desulfurization of flue gas faces more and more challenges. As an economical and environmentally friendly solution, the effect of calcium formate as an additive on desulfurization efficiency in the wet flue gas desulfurization (WFGD) process was studied for the first time. Improvement of the desulfurization efficiency was achieved with limited change in pH after calcium formate was added into the reactor, and it was found to work better than other additives tested. The positive effects were further verified in a power plant, which showed that adding calcium formate could promote the dissolution of calcium carbonate, accelerate the growth of gypsum crystals and improve the efficiency of desulfurization. Thus, calcium formate was proved to be an effective additive and can potentially be used to reduce the amount of limestone slurry required, as well as the energy consumption and operating costs in industrial desulfurization. Copyright © 2017. Published by Elsevier B.V.

Modeling the long-term durability of concrete barriers in the context of low-activity waste storage

NASA Astrophysics Data System (ADS)

Protière, Y.; Samson, E.; Henocq, P.

2013-07-01

The paper investigates the long-term durability of concrete barriers in contact with a cementitious wasteform designed to immobilize low-activity nuclear waste. The high-pH pore solution of the wasteform contains high concentration level of sulfate, nitrate, nitrite and alkalis. The multilayer concrete/wasteform system was modeled using a multiionic reactive transport model accounting for coupling between species, dissolution/ precipitation reactions, and feedback effect. One of the primary objectives was to investigate the risk associated with the presence of sulfate in the wasteform on the durability of concrete. Simulation results showed that formation of expansive phases, such as gypsum and ettringite, into the concrete barrier was not extensive. Based on those results, it was not possible to conclude that concrete would be severely damaged, even after 5,000 years. Lab work was performed to provide data to validate the modeling results. Paste samples were immersed in sulfate contact solutions and analyzed to measure the impact of the aggressive environment on the material. The results obtained so far tend to confirm the numerical simulations.

Triple oxygen isotope systematics of structurally bonded water in gypsum

NASA Astrophysics Data System (ADS)

Herwartz, Daniel; Surma, Jakub; Voigt, Claudia; Assonov, Sergey; Staubwasser, Michael

2017-07-01

The triple oxygen isotopic composition of gypsum mother water (gmw) is recorded in structurally bonded water in gypsum (gsbw). Respective fractionation factors have been determined experimentally for 18O/16O and 17O/16O. By taking previous experiments into account we suggest using 18αgsbw-gmw = 1.0037; 17αgsbw-gmw = 1.00195 and θgsbw-gmw = 0.5285 as fractionation factors in triple oxygen isotope space. Recent gypsum was sampled from a series of 10 ponds located in the Salar de Llamara in the Atacama Desert, Chile. Total dissolved solids (TDS) in these ponds show a gradual increase from 23 g/l to 182 g/l that is accompanied by an increase in pond water 18O/16O. Gsbw falls on a parallel curve to the ambient water from the saline ponds. The offset is mainly due to the equilibrium fractionation between gsbw and gmw. However, gsbw represents a time integrated signal biased towards times of strong evaporation, hence the estimated gmw comprises elevated 18O/16O compositions when compared to pond water samples taken on site. Gypsum precipitation is associated with algae mats in the ponds with lower salinity. No evidence for respective vital effects on the triple oxygen isotopic composition of gypsum hydration water is observed, nor are such effects expected. In principle, the array of δ18Ogsbw vs. 17Oexcess can be used to: (1) provide information on the degree of evaporation during gypsum formation; (2) estimate pristine meteoric water compositions; and (3) estimate local relative humidity which is the controlling parameter of the slope of the array for simple hydrological situations. In our case study, local mining activities may have decreased deep groundwater recharge, causing a recent change of the local hydrology.

Prediction Model for Impulsive Noise on Structures

DTIC Science & Technology

2012-09-01

construction usually have an interior wall finish of: a) gypsum wallboard (also called plasterboard or drywall), b) plaster or c) wood paneling... Gypsum Plaster , Wall Board 11,67 0.04 NA For simply-supported beams vibrating in their fundamental mode, the value of KS is needed for...Dev of log10(f0) for wood panel interior to be average for wood walls with plaster or gypsum board interior. (8) L(w) based on estimated standard

Bacterial communities and the nitrogen cycle in the gypsum soils of Cuatro Ciénegas Basin, coahuila: a Mars analogue.

PubMed

López-Lozano, Nguyen E; Eguiarte, Luis E; Bonilla-Rosso, Germán; García-Oliva, Felipe; Martínez-Piedragil, Celeste; Rooks, Christine; Souza, Valeria

2012-07-01

The OMEGA/Mars Express hyperspectral imager identified gypsum at several sites on Mars in 2005. These minerals constitute a direct record of past aqueous activity and are important with regard to the search of extraterrestrial life. Gale Crater was chosen as Mars Science Laboratory Curiosity's landing site because it is rich in gypsum, as are some desert soils of the Cuatro Ciénegas Basin (CCB) (Chihuahuan Desert, Mexico). The gypsum of the CCB, which is overlain by minimal carbonate deposits, was the product of magmatic activity that occurred under the Tethys Sea. To examine this Mars analogue, we retrieved gypsum-rich soil samples from two contrasting sites with different humidity in the CCB. To characterize the site, we obtained nutrient data and analyzed the genes related to the N cycle (nifH, nirS, and nirK) and the bacterial community composition by using 16S rRNA clone libraries. As expected, the soil content for almost all measured forms of carbon, nitrogen, and phosphorus were higher at the more humid site than at the drier site. What was unexpected is the presence of a rich and divergent community at both sites, with higher taxonomic diversity at the humid site and almost no taxonomic overlap. Our results suggest that the gypsum-rich soils of the CCB host a unique microbial ecosystem that includes novel microbial assemblies.

Visualization of the structural changes in plywood and gypsum board during the growth of Chaetomium globosum and Stachybotrys chartarum.

PubMed

Lewinska, Anna M; Hoof, Jakob B; Peuhkuri, Ruut H; Rode, Carsten; Lilje, Osu; Foley, Matthew; Trimby, Patrick; Andersen, Birgitte

2016-10-01

Fungal growth in indoor environments is associated with many negative health effects. Many studies focus on brown- and white-rot fungi and their effect on wood, but there is none that reveals the influence of soft-rot fungi, such as Stachybotrys spp. and Chaetomium spp., on the structure of building materials such as plywood and gypsum wallboard. This study focuses on using micro-computed tomography (microCT) to investigate changes of the structure of plywood and gypsum wallboard during fungal degradation by S. chartarum and C. globosum. Changes in the materials as a result of dampness and fungal growth were determined by measuring porosity and pore shape via microCT. The results show that the composition of the building material influenced the level of penetration by fungi as shown by scanning electron microscopy (SEM). Plywood appeared to be the most affected, with the penetration of moisture and fungi throughout the whole thickness of the sample. Conversely, fungi grew only on the top cardboard in the gypsum wallboard and they did not have significant influence on the gypsum wallboard structure. The majority of the observed changes in gypsum wallboard occurred due to moisture. This paper suggests that the mycelium distribution within building materials and the structural changes, caused by dampness and fungal growth, depend on the type of the material. Copyright © 2016 Elsevier B.V. All rights reserved.

Investigations of subsurface flow constructed wetlands and associated geomaterial resources in the Akumal and Reforma regions, Quintana Roo, Mexico

NASA Astrophysics Data System (ADS)

Krekeler, Mark P. S.; Probst, Pete; Samsonov, Misha; Tselepis, Cynthia M.; Bates, William; Kearns, Lance E.; Maynard, J. Barry

2007-12-01

Subsurface flow constructed wetlands in the village of Akumal, Quintana Roo, Mexico were surveyed to determine the general status of the wetland systems and provide baseline information for long term monitoring and further study. Twenty subsurface flow wetlands were surveyed and common problems observed in the systems were overloading, poor plant cover, odor, and no secondary containment. Bulk mineral composition of aggregate from two subsurface flow constructed wetlands was determined to consist solely of calcite using bulk powder X-ray diffraction. Some soil structure is developed in the aggregate and aggregate levels in wetlands drop at an estimated rate between 3 and 10 cm/year for overloaded wetlands owing to dissolution. Mineral composition from fresh aggregate samples commonly is a mixture of calcite and aragonite. Trace amounts of Pb, Zn, Co, and Cr were observed in fresh aggregate. Coefficients of permeability ( k) varied from 0.006 to 0.027 cm/s with an average values being 0.016 cm/s. Grain size analysis of fresh aggregate samples indicates there are unimodal and multimodal size distributions in the samples with modes in the coarse and fine sand being common. Investigations of other geologic media from the Reforma region indicate that a dolomite with minor amounts of Fe-oxide and palygorskite is abundant and may be a better aggregate source that the current materials used. A Ca-montmorillonite bed was identified in the Reforma region as well and this unit is suitable to serve as a clay liner to prevent leaks for new and existing wetland systems. These newly discovered geologic resources should aid in the improvement of subsurface flow constructed wetlands in the region. Although problems do exist in these wetlands with respect to design, these systems represent a successful implementation of constructed wetlands at a community level in developing regions.

Fire and Brimstone: The Microbially Mediated Formation of Elemental Sulfur Nodules from an Isotope and Major Element Study in the Paleo-Dead Sea

PubMed Central

Bishop, Tom; Turchyn, Alexandra V.; Sivan, Orit

2013-01-01

We present coupled sulfur and oxygen isotope data from sulfur nodules and surrounding gypsum, as well as iron and manganese concentration data, from the Lisan Formation near the Dead Sea (Israel). The sulfur isotope composition in the nodules ranges between -9 and -11‰, 27 to 29‰ lighter than the surrounding gypsum, while the oxygen isotope composition of the gypsum is constant around 24‰. The constant sulfur isotope composition of the nodule is consistent with formation in an ‘open system’. Iron concentrations in the gypsum increase toward the nodule, while manganese concentrations decrease, suggesting a redox boundary at the nodule-gypsum interface during aqueous phase diagenesis. We propose that sulfur nodules in the Lisan Formation are generated through bacterial sulfate reduction, which terminates at elemental sulfur. We speculate that the sulfate-saturated pore fluids, coupled with the low availability of an electron donor, terminates the trithionate pathway before the final two-electron reduction, producing thionites, which then disproportionate to form abundant elemental sulfur. PMID:24098403

Salt lake Laguna de Fuente de Piedra (S-Spain) as Late Quaternary palaeoenvironmental archive

NASA Astrophysics Data System (ADS)

Höbig, Nicole; Melles, Martin; Reicherter, Klaus

2014-05-01

This study deals with Late Quaternary palaeoenvironmental variability in Iberia reconstructed from terrestrial archives. In southern Iberia, endorheic basins of the Betic Cordilleras are relatively common and contain salt or fresh-water lakes due to subsurface dissolution of Triassic evaporites. Such precipitation or ground-water fed lakes (called Lagunas in Spanish) are vulnerable to changes in hydrology, climate or anthropogenic modifications. The largest Spanish salt lake, Laguna de Fuente de Piedra (Antequera region, S-Spain), has been investigated and serves as a palaeoenvironmental archive for the Late Pleistocene to Holocene time interval. Several sediment cores taken during drilling campaigns in 2012 and 2013 have revealed sedimentary sequences (up to 14 m length) along the shoreline. A multi-proxy study, including sedimentology, geochemistry and physical properties (magnetic susceptibility) has been performed on the cores. The sedimentary history is highly variable: several decimetre thick silty variegated clay deposits, laminated evaporites, and even few-centimetre thick massive gypsum crystals (i.e., selenites). XRF analysis was focussed on valuable palaeoclimatic proxies (e.g., S, Zr, Ti, and element ratios) to identify the composition and provenance of the sediments and to delineate palaeoenvironmental conditions. First age control has been realized by AMS-radiocarbon dating. The records start with approximately 2-3 m Holocene deposits and reach back to the middle of MIS 3 (GS-3). The sequences contain changes in sedimentation rates as well as colour changes, which can be summarized as brownish-beige deposits at the top and more greenish-grey deposits below as well as highly variegated lamination and selenites below ca. 6 m depth. The Younger Dryas, Bølling/Allerød, and the so-called Mystery Interval/Last Glacial Maximum have presumably been identified in the sediment cores and aligned to other climate records. In general, the cores of the Laguna de Fuente de Piedra show cyclic deposition including evaporitic sequences throughout the Holocene and Late Pleistocene, indicating higher fluxes and reworking of organic/inorganic carbon as well as other indicative proxy elements like Ti, Zr and Ca/Sr ratio during Late Pleistocene times. In order to achieve a better understanding of the palaeoenvironmental history in the study area further studies are planned which encompass biological/palaeontological indicators (e.g., pollen, diatoms) as well as another geochemical isotopic techniques on evaporitic deposits such as fluid inclusion analysis.

Viscoelasticity of multiphase fluids: future directions

NASA Astrophysics Data System (ADS)

Tisato, Nicola; Spikes, Kyle; Javadpour, Farzam

2016-04-01

Recently, it has been demonstrated that rocks saturated with bubbly fluids attenuate seismic waves as the propagating elastic wave causes a thermodynamic disequilibrium between the liquid and the gas phases. The new attenuation mechanism, which is called wave-induced-gas-exsolution-dissolution (WIGED) and previously, was only postulated, opens up new perspectives for exploration geophysics as it could potentially improve the imaging of the subsurface. In particular, accounting for WIGED during seismic inversion could allow to better decipher seismic waves to disclose information about saturating phases. This will improve, for instance, the mapping of subsurface gas-plumes that might form during anthropogenic activities or natural phenomena such as those prior to volcanic eruptions. In the present contribution we will report the theory and the numerical method utilized to calculate the seismic-wave-attenuation related to WIGED and we will underline the assumptions and the limitations related to the theory. Then, we will present the experimental and the numerical strategy that we will employ to improve WIGED theory in order to incorporate additional effects, such as the role of interfacial tensions, or to extend it to fluid-fluid interaction

Dense Nonaqueous Phase Liquids at Former Manufactured Gas Plants: Challenges to Modeling and Remediation

PubMed Central

Birak, P.S.; Miller, C.T.

2008-01-01

The remediation of dense non-aqueous phase liquids (DNAPLs) in porous media continues to be one of the most challenging problems facing environmental scientists and engineers. Of all the environmentally relevant DNAPLs, tars in the subsurface at former manufactured gas plants (FMGP’s) pose one of the biggest challenges due to their complex chemical composition and tendency to alter wettability. To further our understanding of these complex materials, we consulted historic documentation to evaluate the impact of gas manufacturing on the composition and physicochemical nature of the resulting tars. In the recent literature, most work to date has been focused in a relatively narrow portion of the expected range of tar materials, which has yielded a bias toward samples of relatively low viscosity and density. In this work, we consider the dissolution and movement of tars in the subsurface, models used to predict these phenomena, and approaches used for remediation. We also explore the open issues and detail important gaps in our fundamental understanding of these extraordinarily complex systems that must be resolved to reach a mature level of understanding. PMID:19176266

Gypsum crystallization from cadmium-poisoned solutions

NASA Astrophysics Data System (ADS)

Rinaudo, C.; Franchini-Angela, M.; Boistelle, R.

1988-06-01

Gypsum crystals, CaSO4⋯2H2O, are grown from solutions containing large amounts of cadmium chloride as an impurity. The initial supersaturations necessary for the gypsum nucleation increase with increasing cadmium concentration. Accordingly, at constant initial supersaturation, the induction periods also increase with increasing cadmium concentration. Cadmium and chlorine are incorporated into the crystals probably as CdCl+ or CdCl2, which are the most abundant complexes in the solutions. Consequently, the gypsum crystals grow curved, distorted and exhibit fractures along the [100] direction. The amount of incorporated cadmium increases with increasing supersaturation. Cadmium is mainly detected near the {120} faces in the area where the fractures release the internal stresses. Supersaturation and concentration of free ions and complexes are calculated for all solutions. Adsorption on {120} is discussed.

Jefferson Proving Ground, South of the Firing Line, Final Asbestos Survey Summary Report. Volume 3. Buildings 230 through 475

DTIC Science & Technology

1993-09-01

interior is finished with plaster or wallboard (i.e., sheetrock, drywall, gypsum board , etc.) walls and ceilings, "cheese-cloth" wall and ceiling lining...with wallboard (i.e., sheetrock, drywall, gypsum board , etc.) walls and ceilings, acoustical ceiling panels/tiles, and vinyl tile or bare concrete...finished with wallboard (i.e., sheetrock, drywall, gypsum board , etc.) walls and ceilings, and vinyl tile or bare concrete floors. "* No fireproofing or

Origin and chemical composition of evaporite deposits

USGS Publications Warehouse

Moore, George William

1960-01-01

A comparative study of marine evaporite deposits forming at the present time along the pacific coast of central Mexico and evaporite formations of Permian age in West Texas Basin was made in order to determine if the modern sediments provide a basis for understanding environmental conditions that existed during deposition of the older deposits. The field work was supplemented by investigations of artificial evaporite minerals precipitated in the laboratory and by study of the chemical composition of halite rock of different geologic ages. The environment of deposition of contemporaneous marine salt deposits in Mexico is acidic, is strongly reducing a few centimeters below the surface, and teems with microscopic life. Deposition of salt, unlike that of many other sediments, is not wholly a constructional phenomenon. Permanent deposits result only if a favorable balance exists between deposition in the dry season and dissolution in the wet season. Evaporite formations chosen for special study in the West Texas Basin are, in ascending order, the Castile, Salado, and Rustler formations, which have a combined thickness of 1200 meters. The Castile formation is largely composed of gypsum rock, the Salado, halite rock, and the Rustler, quartz and carbonate sandstone. The lower part of the Castile formation is bituminous and contains limestone laminae. The Castile and Rustler formations thicken to the south at the expense of salt of the intervening Salado formation. The clastic rocks of the Rustler formation are interpreted as the deposits of a series of barrier islands north of which halite rock of the Salado was deposited. The salt is believed to have formed in shallow water of uniform density that was mixed by the wind. Where water depth exceeded the depth of the wind mixing, density stratification developed, and gypsum was deposited. Dense water of high salinity below the density discontinuity was overlain by less dense, more normally saline water which was derived from the sea to the south. Mixing of the two water layers at their interface diluted the lower layer so as to prevent halite formation, but at the same time the depressed solubility of calcium sulfate in the mixture at the interface caused precipitation of gypsum. The upper water layer is believed to have supported a flourishing microscopic biota whose remains descended into semisterile brine below where reducing conditions prevailed. This environment generated the bituminous gypsum rock. At times, microcrystalline calcium carbonate of probable biochemical origin formed in the upper layer and settled below to form limestone laminae such as those of the lower part of the Castile formation. Chemical analyses of Permian and present-day salt were compared with analyses of marine salt as old as Cambrian age to determine if evaporite deposits can contribute information on the geologic history of sea water. The results contain uncertainties that cannot be fully resolved, but they suggest that the ratio between ions in sea water has been approximately constant since Precambrian time. In addition, the abrupt initial appearance of rock salt deposits in Cambrian time suggests that the Precambrian ocean may have been rather dilute, but this apparent relationship also could have been caused by other factors.

Performing Mineral Hydration Experiments in the CheMin Diffractometer on Mars

NASA Technical Reports Server (NTRS)

Vaniman, D. T.; Yen, A. S.; Rampe, E. B.; Blake, D. F.; Chipera, S. J.; Morookian, J. M.; Ming, D. W.; Bristow, T. F.; Morris, R. V.; Geller, R.;

River-spring connectivity and hydrogeochemical interactions in a shallow fractured rock formation. The case study of Fuensanta river valley (Southern Spain)

NASA Astrophysics Data System (ADS)

Barberá, J. A.; Andreo, B.

2017-04-01

In upland catchments, the hydrology and hydrochemistry of streams are largely influenced by groundwater inflows, at both regional and local scale. However, reverse conditions (groundwater dynamics conditioned by surface water interferences), although less described, may also occur. In this research, the local river-spring connectivity and induced hydrogeochemical interactions in intensely folded, fractured and layered Cretaceous marls and marly-limestones (Fuensanta river valley, S Spain) are discussed based on field observations, tracer tests and hydrodynamic and hydrochemical data. The differential flow measurements and tracing experiments performed in the Fuensanta river permitted us to quantify the surface water losses and to verify its direct hydraulic connection with the Fuensanta spring. The numerical simulations of tracer breakthrough curves suggest the existence of a groundwater flow system through well-connected master and tributary fractures, with fast and multi-source flow components. Furthermore, the multivariate statistical analysis conducted using chemical data from the sampled waters, the geochemical study of water-rock interactions and the proposed water mixing approach allowed the spatial characterization of the chemistry of the springs and river/stream waters draining low permeable Cretaceous formations. Results corroborated that the mixing of surface waters, as well as calcite dissolution and CO2 dissolution/exsolution, are the main geochemical processes constraining Fuensanta spring hydrochemistry. The estimated contribution of the tributary surface waters to the spring flow during the research period was approximately 26-53% (Fuensanta river) and 47-74% (Convento stream), being predominant the first component during high flow and the second one during the dry season. The identification of secondary geochemical processes (dolomite and gypsum dissolution and dedolomitization) in Fuensanta spring waters evidences the induced hydrogeochemical changes resulting from the allogenic recharge. This research highlights the usefulness of an integrated approach based on river and spring flow examination, dye tracing interpretation and regression and multivariate statistical analysis using hydrochemical data for surface water-groundwater interaction assessment in fractured complex environments worldwide, whose implementation becomes critical for an appropriate groundwater policy.

Permeability Evolution of Fractured Anhydrite Caused by Chemical and Mechanical Alteration

NASA Astrophysics Data System (ADS)

Detwiler, R. L.; Elkhoury, J. E.; Ameli, P.

2011-12-01

Geologic carbon sequestration requires competent structural seals (caprock) to prevent leakage over decadal time scales. Injection of large volumes of CO2 perturbs the target formation from chemical and mechanical equilibrium leading to the possible creation or enhancement of leakage pathways. We investigate the potential for leakage pathways (fractures) to grow over time under reservoir conditions in a series of anhydrite (Ca2SO4) cores. To simulate a potential leakage event in the laboratory, we fractured and jacketed the cores, and placed them in a flow-through reactor vessel. A high-pressure syringe pump applied confining stresses ranging from 7 to 17 MPa and another syringe pump pushed water through the sample at a constant flow rate with pressure control at the outlet. Effluent was sampled periodically and analyzed for Ca2+ and SO42- using an ion chromatograph. Before and after each experiment, we characterized the surfaces of the fractures using a high-resolution optical profilometer and a scanning electron microscope. Careful alignment of the surfaces during optical profiling allowed reproduction of the fracture aperture before and after each experiment. We present results from several experiments each carried out under different conditions in similar fractured anhydrite cores. One involved a well-mated pre-existing fracture and results showed that the permeability of the fractured core was similar to the intact rock matrix (O(10-18 m2); chemical alteration of the core was largely limited to the inflow face of the core and the fracture surfaces remained largely unaltered. To enhance permeability during subsequent experiments, we imposed a small (380 μm) shear displacement between the fracture surfaces resulting in a four-order-of-magnitude increase in initial permeability. The first of these was run at a constant flow rate of 0.6 ml/min for a period of 7 days. The measured pressure gradient within the core increased slowly for a period of 4 days followed by a rapid increase in differential pressure corresponding to a two-order-of-magnitude decrease in permeability. During the experiment, the diameter of the core decreased by ~300 μm at the inlet and a skin of gypsum (Ca2SO42H2O) was created along the length of the fracture. Dissolution of anhydrite and transition to gypsum of additional anhydrite weakened the fracture surfaces leading to closure of the fracture with a corresponding reduction in aperture and permeability. Additional experiments explore the influence of flow at a lower flow rate, which, in the absence of a large confining stress, has been shown to lead to the development of dissolution channels or wormholes.

Major element, trace element, nutrient, and radionuclide mobility in a mining by-product-amended soil.

PubMed

Douglas, G; Adeney, J; Johnston, K; Wendling, L; Coleman, S

2012-01-01

This study investigates the use of a mineral processing by-product, neutralized used acid (NUA), primarily composed of gypsum and Fe-oxyhydroxide, as a soil amendment. A 1489-d turf farm field trial assessed nutrient, trace element, and radionuclide mobility of a soil amended with ∼5% by mass to a depth of 15 cm of NUA. Average PO-P fluxes collected as subsoil leachates were 0.7 and 26.6 kg ha yr for NUA-amended and control sites, respectively, equating to a 97% reduction in PO-P loss after 434 kg P ha was applied. Total nitrogen fluxes in NUA-amended soil leachates were similarly reduced by 82%. Incorporation of NUA conferred major changes in leachate geochemistry with a diverse suite of trace elements depleted within NUA-amended leachates. Gypsum dissolution from NUA resulted in an increase from under- to oversaturation of the soil leachates for a range of Fe- and Ca-minerals including calcite and ferrihydrite, many of which have a well-documented ability to assimilate PO-P and trace elements. Isotopic analysis indicated little Pb addition from NUA. Both Sr and Nd isotope results revealed that NUA and added fertilizer became an important source of Ca to leachate and turf biomass. The NUA-amended soils retained a range of U-Th series radionuclides, with little evidence of transfer to soil leachate or turf biomass. Calculated radioactivity dose rates indicate only a small increment due to NUA amendment. With increased nutrient, trace element, and solute retention, and increased productivity, a range of potential agronomic benefits may be conferred by NUA amendment of soils, in addition to the potential to limit offsite nutrient loss and eutrophication. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Tracing groundwater input into Lake Vanda, Wright Valley, Antarctica using major ions, stable isotopes and noble gas

NASA Astrophysics Data System (ADS)

Dowling, C. B.; Poreda, R. J.; Snyder, G. T.

2008-12-01

The McMurdo Dry Valleys (MDV), Antarctica, is the largest ice-free region on Antarctica. Lake Vanda, located in central Wright Valley, is the deepest lake among the MDV lakes. It has a relatively fresh water layer above 50 m with a hypersaline calcium-chloride brine below (50-72 m). The Onyx River is the only stream input into Lake Vanda. It flows westward from the coastal Lower Wright Glacier and discharges into Lake Vanda. Suggested by the published literature and this study, there has been and may still be groundwater input into Lake Vanda. Stable isotopes, major ions, and noble gas data from this study coupled with previously published data indicate that the bottom waters of Lake Vanda have had significant contributions from a deep groundwater system. The dissolved gas of the bottom waters of Lake Vanda display solubility concentrations rather than the Ar-enriched dissolved gas seen in the Taylor Valley lakes (such as Lake Bonney). The isotopic data indicate that the bottom calcium-chloride-brine of Lake Vanda has undergone very little evaporation. The calcium-chloride chemistry of the groundwater that discharges into Lake Vanda most likely results from the chemical weathering and dissolution of cryogenic evaporites (antarcticite and gypsum) within the glacial sediments of Wright Valley. The high calcium concentrations of the brine have caused gypsum to precipitate on the lake bottom. Our work also supports previous physical and chemical observations suggesting that the upper portion actively circulates and the hypersaline bottom layer does not. The helium and calcium chloride values are concentrated at the bottom, with a very narrow transition layer between it and the above fresh water. If the freshwater layer did not actively circulate, then diffusion over time would have caused the helium and calcium chloride to slowly permeate upwards through the water column.

Superficial alteration mineralogy in active volcanic systems: An example of Poás volcano, Costa Rica

NASA Astrophysics Data System (ADS)

Rodríguez, Alejandro; van Bergen, Manfred J.

2017-10-01

The alteration mineralogy in the crater area of Poás volcano (Costa Rica) has been studied to constrain acid fluid-rock interaction processes and conditions relevant for the formation of sulphate-bearing mineral assemblages found on the surface of Mars. Individual sub-environments, which include the hyperacid lake (Laguna Caliente), ephemeral hot springs, fumarole vents and areas affected by acid rain and/or spray from the lake, are marked by distinct secondary mineral associations, with sulphates commonly as prevailing component. The sulphates occur in a wide mineralogical diversity comprising gypsum/anhydrite, various polyhydrated Al-sulphates, alunite-jarosite group minerals, halotrichite-, voltaite- and copiapite-group minerals, epsomite and römerite. Depending on the sub-environment, they are variably associated with clay minerals (kaolinite-group and smectite-group), zeolites, SiO2-polymorphs, Fe-(hydro)oxides, Ti-oxides, native sulphur, sulphides, chlorides, fluorides, phosphates and carbonates. Geochemical modelling was performed to identify mechanisms responsible for the formation of the secondary minerals found in the field, and to predict their possible stability under conditions not seen at the surface. The results indicate that the appearance of amorphous silica, hematite, anhydrite/gypsum, pyrite, anatase and kaolinite is relatively insensitive to the degree of acidity of the local aqueous system. On the other hand, alunite-jarosite group minerals, elemental sulphur and Al(OH)SO4 only form under acidic conditions (pH < 4). The presence of polyhydrated Mg- and Fe2 +-sulphates is restricted to olivine-bearing rocks exposed to acid rain or brine spray. Modelling suggests that their formation required a repetitive sequence of olivine dissolution and evaporation in an open system involving limited amounts of fluid. The mineral variety in the crater of Poás is remarkably similar to sulphate-bearing assemblages considered to be the product of acid-sulphate alteration on Mars. The analogy suggests that comparable fluid-rock interaction controls operated in Martian volcanic environments.

Microbial exudate promoted dissolution and transformation of chromium containing minerals

NASA Astrophysics Data System (ADS)

Saad, E. M.; Sun, J.; Tang, Y.

2015-12-01

Because of its utility in many industrial processes, chromium has become the second most common metal contaminant in the United States. The two most common oxidation states of chromium in nature are Cr(III), which is highly immobile, and Cr(VI), which is highly mobile and toxic. In both natural and engineered environments, the most common remediation of Cr(VI) is through reduction, which results in chromium sequestration in the low solubility mixed Cr(III)-Fe(III) (oxy)hydroxide phases. Consequently, the stability of these minerals must be examined to assess the fate of chromium in the subsurface. We examined the dissolution of mixed Cr(III)-Fe(III) (oxy)hydroxides in the presence of common microbial exudates, including the siderophore desferrioxamine B (DFOB; a common organic ligand secreted by most microbes with high affinity for ferric iron and other trivalent metal ions) and oxalate (a common organic acid produced by microbes). The solids exhibited incongruent dissolution with preferential leaching of Fe from the solid phase. Over time, this leads to a more Cr rich mineral, which is known to be more soluble than the corresponding mixed mineral phase. We are currently investigating the structure of the reacted mineral phases and soluble Cr(III) species, as well as the potential oxidation and remobilization of the soluble Cr species. Results from this study will provide insights regarding the long term transport and fate of chromium in the natural environment in the presence of microbial activities.

Rapid subsidence in damaging sinkholes: Measurement by high-precision leveling and the role of salt dissolution

NASA Astrophysics Data System (ADS)

Desir, G.; Gutiérrez, F.; Merino, J.; Carbonel, D.; Benito-Calvo, A.; Guerrero, J.; Fabregat, I.

2018-02-01

Investigations dealing with subsidence monitoring in active sinkholes are very scarce, especially when compared with other ground instability phenomena like landslides. This is largely related to the catastrophic behaviour that typifies most sinkholes in carbonate karst areas. Active subsidence in five sinkholes up to ca. 500 m across has been quantitatively characterised by means of high-precision differential leveling. The sinkholes occur on poorly indurated alluvium underlain by salt-bearing evaporites and cause severe damage on various human structures. The leveling data have provided accurate information on multiple features of the subsidence phenomena with practical implications: (1) precise location of the vaguely-defined edges of the subsidence zones and their spatial relationships with surveyed surface deformation features; (2) spatial deformation patterns and relative contribution of subsidence mechanisms (sagging versus collapse); (3) accurate subsidence rates and their spatial variability with maximum and mean vertical displacement rates ranging from 1.0 to 11.8 cm/yr and 1.9 to 26.1 cm/yr, respectively; (4) identification of sinkholes that experience continuous subsidence at constant rates or with significant temporal changes; and (5) rates of volumetric surface changes as an approximation to rates of dissolution-induced volumetric depletion in the subsurface, reaching as much as 10,900 m3/yr in the largest sinkhole. The high subsidence rates as well as the annual volumetric changes are attributed to rapid dissolution of high-solubility salts.

Microbial diversity and impact on carbonate geochemistry across a changing geochemical gradient in a karst aquifer

PubMed Central

Gray, Cassie J; Engel, Annette S

2013-01-01

Although microbes are known to influence karst (carbonate) aquifer ecosystem-level processes, comparatively little information is available regarding the diversity of microbial activities that could influence water quality and geological modification. To assess microbial diversity in the context of aquifer geochemistry, we coupled 16S rRNA Sanger sequencing and 454 tag pyrosequencing to in situ microcosm experiments from wells that cross the transition from fresh to saline and sulfidic water in the Edwards Aquifer of central Texas, one of the largest karst aquifers in the United States. The distribution of microbial groups across the transition zone correlated with dissolved oxygen and sulfide concentration, and significant variations in community composition were explained by local carbonate geochemistry, specifically calcium concentration and alkalinity. The waters were supersaturated with respect to prevalent aquifer minerals, calcite and dolomite, but in situ microcosm experiments containing these minerals revealed significant mass loss from dissolution when colonized by microbes. Despite differences in cell density on the experimental surfaces, carbonate loss was greater from freshwater wells than saline, sulfidic wells. However, as cell density increased, which was correlated to and controlled by local geochemistry, dissolution rates decreased. Surface colonization by metabolically active cells promotes dissolution by creating local disequilibria between bulk aquifer fluids and mineral surfaces, but this also controls rates of karst aquifer modification. These results expand our understanding of microbial diversity in karst aquifers and emphasize the importance of evaluating active microbial processes that could affect carbonate weathering in the subsurface. PMID:23151637

Microbial diversity and impact on carbonate geochemistry across a changing geochemical gradient in a karst aquifer.

PubMed

Gray, Cassie J; Engel, Annette S

2013-02-01

Although microbes are known to influence karst (carbonate) aquifer ecosystem-level processes, comparatively little information is available regarding the diversity of microbial activities that could influence water quality and geological modification. To assess microbial diversity in the context of aquifer geochemistry, we coupled 16S rRNA Sanger sequencing and 454 tag pyrosequencing to in situ microcosm experiments from wells that cross the transition from fresh to saline and sulfidic water in the Edwards Aquifer of central Texas, one of the largest karst aquifers in the United States. The distribution of microbial groups across the transition zone correlated with dissolved oxygen and sulfide concentration, and significant variations in community composition were explained by local carbonate geochemistry, specifically calcium concentration and alkalinity. The waters were supersaturated with respect to prevalent aquifer minerals, calcite and dolomite, but in situ microcosm experiments containing these minerals revealed significant mass loss from dissolution when colonized by microbes. Despite differences in cell density on the experimental surfaces, carbonate loss was greater from freshwater wells than saline, sulfidic wells. However, as cell density increased, which was correlated to and controlled by local geochemistry, dissolution rates decreased. Surface colonization by metabolically active cells promotes dissolution by creating local disequilibria between bulk aquifer fluids and mineral surfaces, but this also controls rates of karst aquifer modification. These results expand our understanding of microbial diversity in karst aquifers and emphasize the importance of evaluating active microbial processes that could affect carbonate weathering in the subsurface.

Dimensional accuracy and surface property of titanium casting using gypsum-bonded alumina investment.

PubMed

Yan, Min; Takahashi, Hidekazu; Nishimura, Fumio

2004-12-01

The aim of the present study was to evaluate the dimensional accuracy and surface property of titanium casting obtained using a gypsum-bonded alumina investment. The experimental gypsum-bonded alumina investment with 20 mass% gypsum content mixed with 2 mass% potassium sulfate was used for five cp titanium castings and three Cu-Zn alloy castings. The accuracy, surface roughness (Ra), and reaction layer thickness of these castings were investigated. The accuracy of the castings obtained from the experimental investment ranged from -0.04 to 0.23%, while surface roughness (Ra) ranged from 7.6 to 10.3microm. A reaction layer of about 150 microm thickness under the titanium casting surface was observed. These results suggested that the titanium casting obtained using the experimental investment was acceptable. Although the reaction layer was thin, surface roughness should be improved.

Consolidation of archaeological gypsum plaster by bacterial biomineralization of calcium carbonate.

PubMed

Jroundi, Fadwa; Gonzalez-Muñoz, Maria Teresa; Garcia-Bueno, Ana; Rodriguez-Navarro, Carlos

2014-09-01

Gypsum plasterworks and decorative surfaces are easily degraded, especially when exposed to humidity, and thus they require protection and/or consolidation. However, the conservation of historical gypsum-based structural and decorative materials by conventional organic and inorganic consolidants shows limited efficacy. Here, a new method based on the bioconsolidation capacity of carbonatogenic bacteria inhabiting the material was assayed on historical gypsum plasters and compared with conventional consolidation treatments (ethyl silicate; methylacrylate-ethylmethacrylate copolymer and polyvinyl butyral). Conventional products do not reach in-depth consolidation, typically forming a thin impervious surface layer which blocks pores. In contrast, the bacterial treatment produces vaterite (CaCO3) biocement, which does not block pores and produces a good level of consolidation, both at the surface and in-depth, as shown by drilling resistance measurement system analyses. Transmission electron microscopy analyses show that bacterial vaterite cement formed via oriented aggregation of CaCO3 nanoparticles (∼20nm in size), resulting in mesocrystals which incorporate bacterial biopolymers. Such a biocomposite has superior mechanical properties, thus explaining the fact that drilling resistance of bioconsolidated gypsum plasters is within the range of inorganic calcite materials of equivalent porosity, despite the fact that the bacterial vaterite cement accounts for only a 0.02 solid volume fraction. Bacterial bioconsolidation is proposed for the effective consolidation of this type of material. The potential applications of bacterial calcium carbonate consolidation of gypsum biomaterials used as bone graft substitutes are discussed. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Thermal analysis of calcium sulfate dihydrate sources used to manufacture gypsum wallboard

DOE PAGES

Engbrecht, Dick C.; Hirschfeld, Deidre A.

2016-07-27

Gypsum wallboard has been used for over 100 years as a barrier to the spread of fire in residential and commercial structures. The gypsum molecule, CaSO 4·2H 2O, provides two crystalline waters that are released upon heating providing an endothermic effect. Manufacturers have recognized that the source of the gypsum ore is a factor that affects all aspects of its performance; thus, it is hypothesized that the impurities present in the gypsum ore are the causes of the performance differences. Differential Thermal Analysis/Thermogravimetric Analysis (DTA/TGA) and X-ray Diffraction (XRD) were used in this paper to compare and characterize samples ofmore » gypsum ore representing sources of natural, synthetic from a Flue Gas Desulfurization process (FGD) and blends thereof. The hemihydrate phase of representative natural, FGD, and reagent grade calcium sulfate were rehydrated with distilled water and evaluated by DTA/TGA. Analysis of the data shows distinct areas of similarity separated by the conversion to anhydrite ~250 °C. Compositional reconstructions based on DTA/TGA and XRD data were compared and although, the results were comparable, the DTA/TGA suggests thermally active compounds that were not detected by XRD. Anhydrite, silica and halite were reported by XRD but were not thermally reactive in the temperature range evaluated by DTA/TGA (ambient to 1050 °C). Finally, the presence of carbonate compounds (e.g., calcite and dolomite) were indicated by XRD and estimated from the thermal decomposition reaction ~700 °C.« less

Geologic and well-construction data for the H-8 borehole complex near the proposed Waste Isolation Pilot Plant site, southeastern New Mexico

USGS Publications Warehouse

Wells, J.G.; Drellack, S.L.

1982-01-01

The H-8 complex, a group of three closely-spaced boreholes, is located 9 miles south of the proposed Waste Isolation Pilot Plant site in southeastern Eddy County, New Mexico. The holes were drilled during July, August, and September of 1979 to obtain geologic and hydrologic data to better define the regional ground-water-flow system. The geologic data presented in this report are part of a site-characterization study for the possible disposal of defense-associated radioactive wastes within salt beds of the Salado Formation of Permian age. The geologic data include detailed descriptions of cores, cuttings, and geophysical logs. Each borehole was designed to penetrate a distinct water-bearing zone: H-8a (total depth 505 feet) was completed just below the Magenta Dolomite Member of the Rustler Formation of Permian Age; H-8b (total depth 624 feet) was completed just belows the Culebra Dolomite Member of the Rustler Formation; and H-8c (total depth 808 feet) was completed just below the Rustler Formation-Salado Formation contact. The geologic units penetrated in borehole H-8c are surficial alluvium and eolian sand of Holocene age (0-4 feet); the Mescalero caliche (4-10 feet) and Gatuna Formation (10-153 feet) , both of Pleistocene age; and the Dewey Lake Red Beds (153-399 feet), the Rustler Formation (399-733 feet), and part of the Salado Formation penetrated by borehole H-8c is composed of residue from dissolution of halite and associated rocks, and the hydration of anhydrite to gypsum, indicating that the eastward-moving dissolution front on top of the Salado, found just to the west of the WIPP site, has reached the H-8 site. (USGS)

Simulating Salt Movement and Transformation using a Coupled Reactive Transport Model in Variably-Saturated Groundwater Systems

NASA Astrophysics Data System (ADS)

Tavakoli Kivi, S.; Bailey, R. T.; Gates, T.

2016-12-01

Salinization is one of the major concerns in irrigated agricultural landscapes. Increasing salinity concentrations are due principally to evaporative concentration; dissolution of salts from weathered minerals and bedrock; and a high water table that results from excessive irrigation, canal seepage, and a lack of efficient drainage systems; leading to decreasing crop yield. High groundwater salinity loading to nearby river systems also impacts downstream areas, with saline river water diverted for application on irrigated fields. In this study, a solute transport model coupled with equilibrium chemistry reactions has been developed to simulate transport of individual salt ions in regional-scale aquifer systems and thereby investigate strategies for salinity remediation. The physically-based numerical model is based on the UZF-RT3D variably-saturated, multi-species groundwater reactive transport modeling code, and accounts for advection, dispersion, carbon and nitrogen cycling, oxidation-reduction reactions, and salt ion equilibrium chemistry reactions such as complexation, ion exchange, and precipitation/dissolution. Each major salt ion (sulfate, chloride, bicarbonate, calcium, sodium, magnesium, potassium) is included. The model has been tested against measured soil salinity at a small scale (soil profile) and against soil salinity, groundwater salinity, and groundwater salinity loading to surface water at the regional scale (500 km2) in the Lower Arkansas River Valley (LARV) in southeastern Colorado, an area acutely affected by salinization for many decades and greatly influenced by gypsum deposits. Preliminary results of using the model in scenario analysis suggest that increasing irrigation efficiency, sealing earthen canals, and rotational fallowing of land can decrease the groundwater salt load to the Arkansas River by 50 to 70% and substantially lower soil salinity in the root zone.

Gypsum addition to soils contaminated by red mud: implications for aluminium, arsenic, molybdenum and vanadium solubility.

PubMed

Lehoux, Alizée P; Lockwood, Cindy L; Mayes, William M; Stewart, Douglas I; Mortimer, Robert J G; Gruiz, Katalin; Burke, Ian T

2013-10-01

Red mud is highly alkaline (pH 13), saline and can contain elevated concentrations of several potentially toxic elements (e.g. Al, As, Mo and V). Release of up to 1 million m(3) of bauxite residue (red mud) suspension from the Ajka repository, western Hungary, caused large-scale contamination of downstream rivers and floodplains. There is now concern about the potential leaching of toxic metal(loid)s from the red mud as some have enhanced solubility at high pH. This study investigated the impact of red mud addition to three different Hungarian soils with respect to trace element solubility and soil geochemistry. The effectiveness of gypsum amendment for the rehabilitation of red mud-contaminated soils was also examined. Red mud addition to soils caused a pH increase, proportional to red mud addition, of up to 4 pH units (e.g. pH 7 → 11). Increasing red mud addition also led to significant increases in salinity, dissolved organic carbon and aqueous trace element concentrations. However, the response was highly soil specific and one of the soils tested buffered pH to around pH 8.5 even with the highest red mud loading tested (33 % w/w); experiments using this soil also had much lower aqueous Al, As and V concentrations. Gypsum addition to soil/red mud mixtures, even at relatively low concentrations (1 % w/w), was sufficient to buffer experimental pH to 7.5-8.5. This effect was attributed to the reaction of Ca(2+) supplied by the gypsum with OH(-) and carbonate from the red mud to precipitate calcite. The lowered pH enhanced trace element sorption and largely inhibited the release of Al, As and V. Mo concentrations, however, were largely unaffected by gypsum induced pH buffering due to the greater solubility of Mo (as molybdate) at circumneutral pH. Gypsum addition also leads to significantly higher porewater salinities, and column experiments demonstrated that this increase in total dissolved solids persisted even after 25 pore volume replacements. Gypsum addition could therefore provide a cheaper alternative to recovery (dig and dump) for the treatment of red mud-affected soils. The observed inhibition of trace metal release within red mud-affected soils was relatively insensitive to either the percentage of red mud or gypsum present, making the treatment easy to apply. However, there is risk that over-application of gypsum could lead to detrimental long-term increases in soil salinity.

The Aspects About of Objectively Appraisals of Modeling Gypsum Quality and Composites of Phonic-Absorbent and Orthopedic on Base of Gypsum

NASA Astrophysics Data System (ADS)

Pop, P. A.; Ungur, P. A.; Lazar, L.; Marcu, F.

2009-11-01

The EU Norms about of protection environment, outside and inside ambient, and human health demands has lead at obtain of new materials on the base of airborne material, with high thermo and phonic-absorbent properties, porous and lightweight. The α and β-modeling gypsum plaster quality and lightweight depend on many factors as: fabrication process, granulation, roast temperature, work temperature, environment, additives used, breakage, etc. Also, the objectively appraisal of modeling gypsum quality depends of proper tests methods selection, which are legislated in norms, standards and recommendations. In Romanian Standards SR EN 13279-1/2005 and SR EN 13279-2/2005, adaptable from EU Norms EN 13279-1/2004 and EN 13279-2/2004, the characteristics gypsum family tests are well specification, as: granule-metric analysis, determination of water/plaster ratio, setting time, mechanical characteristics, adhesions and water restrain. For plaster with special use (phonic-absorbent and orthopedic materials, etc.) these determinations are not concluding, being necessary more parameters finding, as: elastic constant, phonic-absorbent coefficient, porosity, working, etc., which is imposed the completion of norms and standards with new determinations.

Mixture of natural fiber with gypsum to improve the fire resistance rating of a fire door: The effect of kapok fiber

NASA Astrophysics Data System (ADS)

Azieyanti, N. A.; Hakim, Alif; Hasini, Hasril

2017-10-01

A composite mixture of gypsum and natural fibers has been considered in this study to enhance the fire resistance rating of a fire door. Previously the materials used to make a fire door are gypsum and fiber wool where it acts as a protective coating. Normally this fire door must be compact and able to close on its own. Natural fibers have the ability to replace glass fiber cotton because of its features that are available in fiber glass wool. When using fiberglass, it can cause health problem once it is swallowed and inhaled, and may remain in the lungs indefinitely. It also can contribute to lungs cancer. Kapok fiber has been used in this experiment as natural fibers. The objective of the experiment is to analyze the fire resistant rating of the composite mixture of gypsum with kapok fiber. The scopes of the experiment consist of a preparation of composite mixture samples of gypsum with kapok fiber with different composition and thickness, and the fabrication of a fire resistant testing furnace. A testing of samples which were conducted in accordance with the standard MS 1073: PART 2:1996.

Coal Combustion Residual Beneficial Use Evaluation: Fly Ash Concrete and FGD Gypsum Wallboard

EPA Pesticide Factsheets

This page contains documents related to the evaluation of coal combustion residual beneficial use of fly ash concrete and FGD gypsum wallboard including the evaluation itself and the accompanying appendices

Effect of some amendments on leachate properties of a calcareous saline- sodic soil: A laboratory experiment

NASA Astrophysics Data System (ADS)

Yazdanpanah, Najme; Mahmoodabadi, Majid

2010-05-01

Soil salinity and sodicity are escalating problems worldwide, especially in Iran since 90 percent of the country is located in arid and semi-arid. Reclamation of sodic soils involves replacement of exchangeable Na by Ca. While some researches have been undertaken in the controllable laboratory conditions using soil column with emphasis on soil properties, the properties of effluent as a measure of soil reclamation remain unstudied. In addition, little attention has been paid to the temporal variability of effluent quality. The objective of this study was to investigate the effect of different amendments consist of gypsum, manure, pistachio residue, and their combination for ameliorating a calcareous saline sodic soil. Temporal variability of effluent properties during reclamation period was studied, as well. A laboratory experiment was conducted to evaluate the effect of different amendments using soil columns. The amendment treatments were: control, manure, pistachio residue, gypsum powder (equivalent of gypsum requirement), manure+gypsum and pistachio residue+gypsum, which were applied once in the beginning of the experiment. The study was performed in 120 days period and totally four irrigation treatments were supplied to each column. After irrigations, the effluent samples were collected every day at the bottom of the soil columns and were analyzed. The results show that for all treatments, cations (e.g. Ca, Mg, Na and K) in the outflow decreased with time, exponentially. Manure treatment resulted in highest rate of Ca, Mg, Na leaching from soil solution, in spite of the control which had the lowest rate. In addition, pistachio residue had the most effect on K leaching. Manure treatment showed the most EC and SAR in the leachate, while gypsum application leads to the least rate of them. The findings of this research reveal different rates of cations leaching from soil profile, which is important in environmental issues. Keywords: Saline sodic soil, Reclamation, Organic Matter, Gypsum, Leachate.

An in vitro investigation into the physical properties of irreversible hydrocolloid alternatives.

PubMed

Patel, Rishi D; Kattadiyil, Mathew T; Goodacre, Charles J; Winer, Myron S

2010-11-01

A number of manufacturers have introduced new products that are marketed as alternatives to irreversible hydrocolloid impression materials. However, there is a paucity of laboratory and clinical research on these products compared to traditional irreversible hydrocolloid. The purpose of this study was to evaluate the detail reproduction, gypsum compatibility, and linear dimensional change of 3 recently introduced impression materials designed as alternatives to irreversible hydrocolloid. The tested materials were Position Penta Quick, Silgimix, and AlgiNot. An irreversible hydrocolloid impression material, Jeltrate Plus Antimicrobial, served as the control. The parameters of detail reproduction, gypsum compatibility, and linear dimensional change were tested in accordance with ANSI/ADA Specifications No. 18 and 19. The gypsum compatibility was tested using a type III stone (Microstone Golden) and a type IV stone (Die-Keen Green). The data were analyzed using the Kruskal-Wallis rank test and the Mann-Whitney U test (α=.05). The test materials demonstrated significantly (P<.001) better detail reproduction than the control material. Silgimix exhibited the best compatibility with Microstone, whereas AlgiNot and Position Penta Quick exhibited the best gypsum compatibility with Die-Keen. An incompatibility was observed over time between the Jeltrate control material and the Microstone gypsum material. For linear dimensional change, the mean dimension of the control material most closely approximated the distance between the lines on the test die, but it exhibited the greatest variability in measurements. All of the test materials exhibited linear dimensional change within the ADA's accepted limit of 1.0%. The 3 new impression materials exhibited better detail reproduction and less variability in linear dimensional change than the irreversible hydrocolloid control. Gypsum compatibility varied with the brand of gypsum used, with an incompatibility identified between the control material (Jeltrate Plus Antimicrobial) and Microstone related to surface changes observed over time. Copyright © 2010 The Editorial Council of the Journal of Prosthetic Dentistry. Published by Mosby, Inc. All rights reserved.

Analysis of long-term bacterial vs. chemical Fe(III) oxide reduction kinetics

NASA Astrophysics Data System (ADS)

Roden, Eric E.

2004-08-01

Data from studies of dissimilatory bacterial (10 8 cells mL -1 of Shewanella putrefaciens strain CN32, pH 6.8) and ascorbate (10 mM, pH 3.0) reduction of two synthetic Fe(III) oxide coated sands and three natural Fe(III) oxide-bearing subsurface materials (all at ca. 10 mmol Fe(III) L -1) were analyzed in relation to a generalized rate law for mineral dissolution (J t/m 0 = k'(m/m 0) γ, where J t is the rate of dissolution and/or reduction at time t, m 0 is the initial mass of oxide, and m/m 0 is the unreduced or undissolved mineral fraction) in order to evaluate changes in the apparent reactivity of Fe(III) oxides during long-term biological vs. chemical reduction. The natural Fe(III) oxide assemblages demonstrated larger changes in reactivity (higher γ values in the generalized rate law) compared to the synthetic oxides during long-term abiotic reductive dissolution. No such relationship was evident in the bacterial reduction experiments, in which temporal changes in the apparent reactivity of the natural and synthetic oxides were far greater (5-10 fold higher γ values) than in the abiotic reduction experiments. Kinetic and thermodynamic considerations indicated that neither the abundance of electron donor (lactate) nor the accumulation of aqueous end-products of oxide reduction (Fe(II), acetate, dissolved inorganic carbon) are likely to have posed significant limitations on the long-term kinetics of oxide reduction. Rather, accumulation of biogenic Fe(II) on residual oxide surfaces appeared to play a dominant role in governing the long-term kinetics of bacterial crystalline Fe(III) oxide reduction. The experimental findings together with numerical simulations support a conceptual model of bacterial Fe(III) oxide reduction kinetics that differs fundamentally from established models of abiotic Fe(III) oxide reductive dissolution, and indicate that information on Fe(III) oxide reactivity gained through abiotic reductive dissolution techniques cannot be used to predict long-term patterns of reactivity toward enzymatic reduction at circumneutral pH.

Gas hydrate decomposition recorded by authigenic barite at pockmark sites of the northern Congo Fan

NASA Astrophysics Data System (ADS)

Kasten, Sabine; Nöthen, Kerstin; Hensen, Christian; Spieß, Volkhard; Blumenberg, Martin; Schneider, Ralph R.

2012-12-01

The geochemical cycling of barium was investigated in sediments of pockmarks of the northern Congo Fan, characterized by surface and subsurface gas hydrates, chemosynthetic fauna, and authigenic carbonates. Two gravity cores retrieved from the so-called Hydrate Hole and Worm Hole pockmarks were examined using high-resolution pore-water and solid-phase analyses. The results indicate that, although gas hydrates in the study area are stable with respect to pressure and temperature, they are and have been subject to dissolution due to methane-undersaturated pore waters. The process significantly driving dissolution is the anaerobic oxidation of methane (AOM) above the shallowest hydrate-bearing sediment layer. It is suggested that episodic seep events temporarily increase the upward flux of methane, and induce hydrate formation close to the sediment surface. AOM establishes at a sediment depth where the upward flux of methane from the uppermost hydrate layer counterbalances the downward flux of seawater sulfate. After seepage ceases, AOM continues to consume methane at the sulfate/methane transition (SMT) above the hydrates, thereby driving the progressive dissolution of the hydrates "from above". As a result the SMT migrates downward, leaving behind enrichments of authigenic barite and carbonates that typically precipitate at this biogeochemical reaction front. Calculation of the time needed to produce the observed solid-phase barium enrichments above the present-day depths of the SMT served to track the net downward migration of the SMT and to estimate the total time of hydrate dissolution in the recovered sediments. Methane fluxes were higher, and the SMT was located closer to the sediment surface in the past at both sites. Active seepage and hydrate formation are inferred to have occurred only a few thousands of years ago at the Hydrate Hole site. By contrast, AOM-driven hydrate dissolution as a consequence of an overall net decrease in upward methane flux seems to have persisted for a considerably longer time at the Worm Hole site, amounting to a few tens of thousands of years.

Understanding the roles of ligand promoted dissolution, water column saturation and hydrological properties on intense basalt weathering using reactive transport and watershed-scale hydrologic modeling

NASA Astrophysics Data System (ADS)

Perez Fodich, A.; Walter, M. T.; Derry, L. A.

2016-12-01

The interaction of rocks with rainwater generates physical and chemical changes, which ultimately culminates in soil development. The addition of catalyzers such as plants, atmospheric gases and hydrological properties will result in more intense and/or faster weathering transformations. The intensity of weathering across the Island of Hawaii is strongly correlated with exposure age and time-integrated precipitation. Intense weathering has resulted from interaction between a thermodynamically unstable lithology, high water/rock ratios, atmospheric gases (O2, CO2) and biota as an organic acid and CO2 producer. To further investigate the role of different weathering agents we have developed 1-D reactive transport models (RTM) to understand mineralogical and fluid chemistry changes in the initially basaltic porous media. The initial meso-scale heterogeneity of porosity makes it difficult for RTMs to capture changes in runoff/groundwater partitioning. Therefore, hydraulic properties (hydraulic conductivity and aquifer depth) are modeled as a watershed parameter appropriate for this system where sub-surface hydraulic data is scarce(1). Initial results agree with field data in a broad sense: different rainfall regimes and timescales show depletion of mobile cations, increasingly low pH, congruent dissolution of olivine and pyroxene, incongruent dissolution of plagioclase and basaltic glass, precipitation of non-crystalline allophane and ferrihydrite, and porosity changes due to dissolution and precipitation of minerals; ultimately Al and Fe are also exported from the system. RTM is used to examine the roles of unsaturation in the soil profile, ligand promoted dissolution of Al- and Fe-bearing phases, and Fe-oxide precipitation at the outcrop scale. Also, we aim to test the use of recession flow analysis to model watershed-scale hydrological properties to extrapolate changes in the runoff/groundwater partitioning. The coupling between weathering processes and hydrologic properties is a fundamental driver of the evolution of volcanic landscapes and weathering fluxes. 1. G. F. Mendoza, T. S. Steenhuis, M. T. Walter, J. Y. Parlange, Estimating basin-wide hydraulic parameters of a semi-arid mountainous watershed by recession-flow analysis. Journal of Hydrology 279, 57-69 (2003).

Oriented attachment by enantioselective facet recognition in millimeter-sized gypsum crystals.

PubMed

Viedma, Cristóbal; Cuccia, Louis A; McTaggart, Alicia; Kahr, Bart; Martin, Alexander T; McBride, J Michael; Cintas, Pedro

2016-09-22

Crystal growth by oriented attachment involves the spontaneous self-assembly of adjoining crystals with common crystallographic orientations. Herein, we report the oriented attachment of gypsum crystals on agitation to form stereoselective mesoscale aggregates.

Unravelling aquifer-wetland interaction using CSAMT and gravity methods: the Mollina-Camorra aquifer and the Fuente de Piedra playa-lake, southern Spain

NASA Astrophysics Data System (ADS)

Pedrera, A.; Martos-Rosillo, S.; Galindo-Zaldívar, J.; Rodríguez-Rodríguez, M.; Benavente, J.; Martín-Rodríguez, J. F.; Zúñiga-López, M. I.

2016-06-01

The hydrological regime of Fuente de Piedra playa-lake (Málaga, southern Spain) has been significantly affected by the intensive exploitation of groundwater in the area. The playa-lake is situated above clays, marls, and gypsum, and under unaltered conditions received surface-subsurface runoff within the watershed as well as groundwater discharge from two carbonate aquifers. We have analyzed the structure of the main one, the Mollina-Camorra carbonate aquifer, by combining controlled source audio magnetotellurics (CSAMT), gravity prospecting, and time-domain electromagnetic (TDEM) soundings. This geophysical information, together with new structural and hydrogeological data, was gathered to develop a new conceptual hydrogeological model. This model allows the hydrological linkage of the carbonate aquifer with the playa-lake system to be established. Moreover, the intensive exploitation in the carbonate aquifer, even outside the watershed of the playa-lake, has affected the hydrological regime of the system. This multidisciplinary work demonstrates the potential of geophysical methods for understanding wetland-aquifer interaction, having important groundwater management implications.

Compartmentalization of gypsum and halite associated with cyanobacteria in saline soil crusts.

PubMed

Canfora, Loredana; Vendramin, Elisa; Vittori Antisari, Livia; Lo Papa, Giuseppe; Dazzi, Carmelo; Benedetti, Anna; Iavazzo, Pietro; Adamo, Paola; Jungblut, Anne D; Pinzari, Flavia

2016-06-01

The interface between biological and geochemical components in the surface crust of a saline soil was investigated using X-ray diffraction, and variable pressure scanning electron microscopy in combination with energy dispersive X-ray spectrometry. Mineral compounds such as halite and gypsum were identified crystallized around filaments of cyanobacteria. A total of 92 genera were identified from the bacterial community based on 16S gene pyrosequencing analysis. The occurrence of the gypsum crystals, their shapes and compartmentalization suggested that they separated NaCl from the immediate microenvironment of the cyanobacteria, and that some cyanobacteria and communities of sulfur bacteria may had a physical control over the distinctive halite and gypsum structures produced. This suggests that cyanobacteria might directly or indirectly promote the formation of a protective envelope made of calcium and sulfur-based compounds. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Petroleum Sludge as gypsum replacement in cement plants: Its Impact on Cement Strength

NASA Astrophysics Data System (ADS)

Benlamoudi, Ali; Kadir, Aeslina Abdul; Khodja, Mohamed

2017-08-01

Due to high cost of cement manufacturing and the huge amount of resources exhaustion, companies are trying to incorporate alternative raw materials or by-products into cement production so as to produce alternative sustainable cement. Petroleum sludge is a dangerous waste that poses serious imparts on soil and groundwater. Given that this sludge contains a high percentage of anhydrite (CaSO4), which is the main component of gypsum (CaSO4.2H2O), it may play the same gypsum role in strength development. In this research, a total replacement of gypsum (100%) has been substituted by petroleum sludge in cement production and has led to an increase of 28.8% in UCS values after 28 curing days. Nevertheless, the burning of this waste has emitted a considerable amount of carbon monoxide (CO) gas that needs to be carefully considered prior to use petroleum sludge within cement plants.

Environmental chamber measurements of mercury flux from coal utilization by-products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pekney, Natalie J.; Martello, Donald; Schroeder, Karl

2009-05-01

An environmental chamber was constructed to measure the mercury flux from coal utilization by-product (CUB) samples. Samples of fly ash, FGD gypsum, and wallboard made from FGD gypsum were tested under both dark and illuminated conditions with or without the addition of water to the sample. Mercury releases varied widely, with 7- day experiment averages ranging from -6.8 to 73 ng/m(2) h for the fly ash samples and -5.2 to 335 ng/m(2) h for the FGD/wallboard samples. Initial mercury content, fly ash type, and light exposure had no observable consistent effects on the mercury flux. For the fly ash samples,more » the effect of a mercury control technology was to decrease the emission. For three of the four pairs of FGD gypsum and wallboard samples, the wallboard sample released less (or absorbed more) mercury than the gypsum.« less

Environmental chamber measurements of mercury flux from coal utilization by-products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pekney, N.J.; Martello, D.V.; Schroeder, K.T.

2009-05-01

An environmental chamber was constructed to measure the mercury flux from coal utilization by-product (CUB) samples. Samples of fly ash, FGD gypsum, and wallboard made from FGD gypsum were tested under both dark and illuminated conditions with or without the addition of water to the sample. Mercury releases varied widely, with 7-day experiment averages ranging from -6.8 to 73 ng/m2 h for the fly ash samples and -5.2 to 335 ng/m2 h for the FGD/wallboard samples. Initial mercury content, fly ash type, and light exposure had no observable consistent effects on the mercury flux. For the fly ash samples, themore » effect of a mercury control technology was to decrease the emission. For three of the four pairs of FGD gypsum and wallboard samples, the wallboard sample released less (or absorbed more) mercury than the gypsum.« less

Use of flue gas desulfurization gypsum for leaching Cd and Pb in reclaimed tidal flat soil.

PubMed

Yang, Ping; Li, Xian; Tong, Ze-Jun; Li, Qu-Sheng; He, Bao-Yan; Wang, Li-Li; Guo, Shi-Hong; Xu, Zhi-Min

2016-04-01

A soil column leaching experiment was conducted to eliminate heavy metals from reclaimed tidal flat soil. Flue gas desulfurization (FGD) gypsum was used for leaching. The highest removal rates of Cd and Pb in the upper soil layers (0-30 cm) were 52.7 and 30.5 %, respectively. Most of the exchangeable and carbonate-bound Cd and Pb were removed. The optimum FGD gypsum application rate was 7.05 kg·m(-2), and the optimum leaching water amount for the application was 217.74 L·m(-2). The application of FGD gypsum (two times) and the extension of the leaching interval time to 20 days increased the heavy metal removal rate in the upper soil layers. The heavy metals desorbed from the upper soil layers were re-adsorbed and fixed in the 30-70 cm soil layers.

Geologic hazards in the region of the Hurricane fault

USGS Publications Warehouse

Lund, W.R.

1997-01-01

Complex geology and variable topography along the 250-kilometer-long Hurricane fault in northwestern Arizona and southwestern Utah combine to create natural conditions that can present a potential danger to life and property. Geologic hazards are of particular concern in southwestern Utah, where the St. George Basin and Interstate-15 corridor north to Cedar City are one of Utah's fastest growing areas. Lying directly west of the Hurricane fault and within the Basin and Range - Colorado Plateau transition zone, this region exhibits geologic characteristics of both physiographic provinces. Long, potentially active, normal-slip faults displace a generally continuous stratigraphic section of mostly east-dipping late Paleozoic to Cretaceous sedimentary rocks unconformably overlain by Tertiary to Holocene sedimentary and igneous rocks and unconsolidated basin-fill deposits. Geologic hazards (exclusive of earthquake hazards) of principal concern in the region include problem soil and rock, landslides, shallow ground water, and flooding. Geologic materials susceptible to volumetric change, collapse, and subsidence in southwestern Utah include; expansive soil and rock, collapse-prone soil, gypsum and gypsiferous soil, soluble carbonate rocks, and soil and rock subject to piping and other ground collapse. Expansive soil and rock are widespread throughout the region. The Petrified Forest Member of the Chinle Formation is especially prone to large volume changes with variations in moisture content. Collapse-prone soils are common in areas of Cedar City underlain by alluvial-fan material derived from the Moenkopi and Chinle Formations in the nearby Hurricane Cliffs. Gypsiferous soil and rock are subject to dissolution which can damage foundations and create sinkholes. The principal formations in the region affected by dissolution of carbonate are the Kaibab and Toroweap Formations; both formations have developed sinkholes where crossed by perennial streams. Soil piping is common in southwestern Utah where it has damaged roads, canal embankments, and water-retention structures. Several unexplained sinkholes near the town of Hurricane possibly are the result of collapse of subsurface volcanic features. Geologic formations associated with slope failures along or near the Hurricane fault include rocks of both Mesozoic and Tertiary age. Numerous landslides are present in these materials along the Hurricane Cliffs, and the Petrified Forest Member of the Chinle Formation is commonly associated with slope failures where it crops out in the St. George Basin. Steep slopes and numerous areas of exposed bedrock make rock fall a hazard in the St. George Basin. Debris flows and debris floods in narrow canyons and on alluvial fans often accompany intense summer cloudburst thunderstorms. Flooded basements and foundation problems associated with shallow ground water are common on benches north of the Santa Clara River in the city of Santa Clara. Stream flooding is the most frequently occurring and destructive geologic hazard in southwestern Utah. Since the 1850s, there have been three major riverine (regional) floods and more than 300 damaging flash floods. Although a variety of flood control measures have been implemented, continued rapid growth in the region is again increasing vulnerability to flood hazards. Site-specific studies to evaluate geologic hazards and identify hazard-reduction measures are recommended prior to construction to reduce the need for costly repair, maintenance, or replacement of improperly placed or protected facilities.

Investigation on the Permeability Evolution of Gypsum Interlayer Under High Temperature and Triaxial Pressure

NASA Astrophysics Data System (ADS)

Tao, Meng; Yechao, You; Jie, Chen; Yaoqing, Hu

2017-08-01

The permeability of the surrounding rock is a critical parameter for the designing and assessment of radioactive waste disposal repositories in the rock salt. Generally, in the locations that are chosen for radioactive waste storage, the bedded rock salt is a sedimentary rock that contains NaCl and Na2SO4. Most likely, there are also layers of gypsum ( {CaSO}_{ 4} \\cdot 2 {H}_{ 2} {O)} present in the salt deposit. Radioactive wastes emit a large amount of heat and hydrogen during the process of disposal, which may result in thermal damage of the surrounding rocks and cause a great change in their permeability and tightness. Therefore, it is necessary to investigate the permeability evolution of the gypsum interlayer under high temperature and high pressure in order to evaluate the tightness and security of the nuclear waste repositories in bedded rock salt. In this study, a self-designed rock triaxial testing system by which high temperature and pressure can be applied is used; the μCT225kVFCB micro-CT system is also employed to investigate the permeability and microstructure of gypsum specimens under a constant hydrostatic pressure of 25 MPa, an increasing temperature (ranging from 20 to 650 °C), and a variable inlet gas pressure (1, 2, 4, 6 MPa). The experimental results show: (a) the maximum permeability measured during the whole experiment is less than 10-17 m2, which indicates that the gypsum interlayer has low permeability under high temperature and pressure that meet the requirements for radioactive waste repository. (b) Under the same temperature, the permeability of the gypsum specimen decreases at the beginning and then increases as the pore pressure elevates. When the inlet gas pressure is between 0 and 2 MPa, the Klinkenberg effect is very pronounced. Then, as the pore pressure increases, the movement behavior of gas molecules gradually changes from free motion to forced directional motion. So the role of free movement of gas molecules gradually reduced, which eventually leads to a decrease in permeability. When the inlet gas pressure is between 2 and 6 MPa, the Klinkenberg effect dribbles away, and the gas flow gradually obeys to the Darcy's law. Hence, the permeability increased with the increase in inlet gas pressure. (c) The curve of permeability versus temperature is divided into five stages based on its gradient. In the temperature range of 20-100 °C, the permeability of gypsum decreased slowly when the temperature decreased. From 100 to 200 °C, the permeability of gypsum increased dramatically when the temperature increased. However, a dramatic increase in permeability was observed from 200 to 450 °C. Subsequently, in the temperature range of 450-550 °C, due to closure of pores and fractures, the permeability of the specimens slowly lessened when the temperature increased. From 550 to 650 °C, the permeability of gypsum slightly increased when the temperature increased; (d) the micro-cracks and porosity obtained from the CT images show a high degree of consistency to the permeability evolution; (e) when compared to the permeability evolutions of sandstone, granite, and lignite, gypsum exhibits a stable evolution trend of permeability and has a much greater threshold temperature when its permeability increases sharply. The results of the paper may provide essential and valuable references for the design and construction of high-level radioactive wastes repository in bedded salt rock containing gypsum interlayers.

Effect Of Coir Fibres On The Compaction And Unconfined Compressive Strength Of Bentonite-Lime-Gypsum Mixture

NASA Astrophysics Data System (ADS)

Tilak B., Vidya; Dutta, Rakesh Kumar; Mohanty, Bijayananda

2015-06-01

This paper presents the effect of coir fibres on the compaction and unconfined compressive strength of a bentonite-lime-gypsum mixture. The coir fiber content varied from 0.5 to 2 %. The results indicated that the dry unit weight and the optimum moisture content of a bentonite - lime mix increased with the addition of gypsum. The unconfined compressive strength of the bentonite increased with the increase in the lime content up to 8 %. Beyond 8 %, the unconfined compressive strength decreased. The dry unit weight of the reference mix decreased, and the optimum moisture content increased with the addition of coir fibre. The unconfined compressive strength of the bentonite + 8 % lime mix increased up to 4 % with the gypsum. Beyond 4 %, the unconfined compressive strength decreased. The unconfined compressive strength of the reference mix increased with the addition of coir fibre up to a fibre content of 1.5 %. The unconfined compressive strength of the reference mix-coir fibre composite was less in comparison to the reference mix. The unconfined compressive strength of the bentonite increased with the addition of lime and gypsum and with the increase in the curing period. The improvement in the post-peak region was better for the reference mix with reinforced coir fibres as compared to the unreinforced reference mix. The improved post-peak behaviour of the bentonite-lime-gypsum-coir fibre mixture could boost the construction of temporary roads on such problematic soils. Further, its use will also provide an environmental motivation for providing a means of consuming large quantities of coir fibres.

Study of mixed mode fracture toughness and fracture trajectories in gypsum interlayers in corrosive environment

PubMed Central

Xiankai, Bao; Jinchang, Zhao

2018-01-01

Based on the engineering background of water dissolving mining for hydrocarbon storage in multi-laminated salt stratum, the mixed mode fracture toughness and fracture trajectory of gypsum interlayers soaked in half-saturated brine at various temperatures (20°C, 50°C and 80°C) were studied by using CSNBD (centrally straight-notched Brazilian disc) specimens with required inclination angles (0°, 7°, 15°, 22°, 30°, 45°, 60°, 75°, 90°) and SEM (scanning electron microscopy). The results showed: (i) The fracture load of gypsum specimens first decreased then increased with increasing inclination angle, due to the effect of friction coefficient. When soaked in brine, the fracture toughness of gypsum specimens gradually decreased with increasing brine temperature. (ii) When soaked in brine, the crystal boundaries of gypsum separated and became clearer, and the boundaries became more open between the crystals with increasing brine temperature. Besides, tensile micro-cracks appeared on the gypsum crystals when soaked in 50°C brine, and the intensity of tensile cracks became more severe when soaking in 80°C brine. (iii) The experimental fracture envelopes derived from the conventional fracture criteria and lay outside these conventional criteria. The experimental fracture envelopes were dependent on the brine temperature and gradually expanded outward as brine temperature increases. (iv) The size of FPZ (fracture process zone) was greatly dependent on the damage degree of materials and gradually increased with increase of brine temperature. The study has important implication for the control of shape and size of salt cavern. PMID:29410841

MOISTURE MOVEMENT (WICKING) WITHIN GYPSUM WALLBOARD

EPA Science Inventory

Gypsum wallboard with repeated or prolonged exposure to water or excess moisture can lose its structural integrity and provide a growth medium for biological contaminants. Poorly sealed buildings, leaking or failed plumbing systems, or improperly constructed HVAC systems can all ...

Modeling grain size variations of aeolian gypsum deposits at White Sands, New Mexico, using AVIRIS imagery

USGS Publications Warehouse

Ghrefat, H.A.; Goodell, P.C.; Hubbard, B.E.; Langford, R.P.; Aldouri, R.E.

2007-01-01

Visible and Near-Infrared (VNIR) through Short Wavelength Infrared (SWIR) (0.4-2.5????m) AVIRIS data, along with laboratory spectral measurements and analyses of field samples, were used to characterize grain size variations in aeolian gypsum deposits across barchan-transverse, parabolic, and barchan dunes at White Sands, New Mexico, USA. All field samples contained a mineralogy of ?????100% gypsum. In order to document grain size variations at White Sands, surficial gypsum samples were collected along three Transects parallel to the prevailing downwind direction. Grain size analyses were carried out on the samples by sieving them into seven size fractions ranging from 45 to 621????m, which were subjected to spectral measurements. Absorption band depths of the size fractions were determined after applying an automated continuum-removal procedure to each spectrum. Then, the relationship between absorption band depth and gypsum size fraction was established using a linear regression. Three software processing steps were carried out to measure the grain size variations of gypsum in the Dune Area using AVIRIS data. AVIRIS mapping results, field work and laboratory analysis all show that the interdune areas have lower absorption band depth values and consist of finer grained gypsum deposits. In contrast, the dune crest areas have higher absorption band depth values and consist of coarser grained gypsum deposits. Based on laboratory estimates, a representative barchan-transverse dune (Transect 1) has a mean grain size of 1.16 ??{symbol} (449????m). The error bar results show that the error ranges from - 50 to + 50????m. Mean grain size for a representative parabolic dune (Transect 2) is 1.51 ??{symbol} (352????m), and 1.52 ??{symbol} (347????m) for a representative barchan dune (Transect 3). T-test results confirm that there are differences in the grain size distributions between barchan and parabolic dunes and between interdune and dune crest areas. The t-test results also show that there are no significant differences between modeled and laboratory-measured grain size values. Hyperspectral grain size modeling can help to determine dynamic processes shaping the formation of the dunes such as wind directions, and the relative strengths of winds through time. This has implications for studying such processes on other planetary landforms that have mineralogy with unique absorption bands in VNIR-SWIR hyperspectral data. ?? 2006 Elsevier B.V. All rights reserved.

Spectral properties of Ca-sulfates: Gypsum, bassanite, and anhydrite

USGS Publications Warehouse

Bishop, Janice L.; Lane, Melissa D.; Dyar, M. Darby; King, Sara J.; Brown, Adrian J.; Swayze, Gregg A.

2014-01-01

This study of the spectral properties of Ca-sulfates was initiated to support remote detection of these minerals on Mars. Gypsum, bassanite, and anhydrite are the currently known forms of Ca-sulfates. They are typically found in sedimentary evaporites on Earth, but can also form via reaction of acidic fluids associated with volcanic activity. Reflectance, emission, transmittance, and Raman spectra are discussed here for various sample forms. Gypsum and bassanite spectra exhibit characteristic and distinct triplet bands near 1.4–1.5 μm, a strong band near 1.93–1.94 μm, and multiple features near 2.1–2.3 μm attributed to H2O. Anhydrite, bassanite, and gypsum all have SO4 combination and overtone features from 4.2–5 μm that are present in reflectance spectra. The mid-IR region spectra exhibit strong SO4 ν3 and ν4 vibrational bands near 1150–1200 and 600–680 cm−1 (~8.5 and 16 μm), respectively. Additional weaker features are observed near 1005–1015 cm−1 (~10 μm) for ν1 and near 470–510 cm−1 (~20 μm) for ν2. The mid-IR H2O bending vibration occurs near 1623–1630 cm−1 (~6.2 μm). The visible/near-infrared region spectra are brighter for the finer-grained samples. In reflectance and emission spectra of the mid-IR region the ν4 bands begin to invert for the finer-grained samples, and the ν1 vibration occurs as a band instead of a peak and has the strongest intensity for the finer-grained samples. The ν2 vibration is a sharp band for anhydrite and a broad peak for gypsum. The band center of the ν1 vibration follows a trend of decreasing frequency (increasing wavelength) with increasing hydration of the sample in the transmittance, Raman, and reflectance spectra. Anhydrite forms at elevated temperatures compared to gypsum, and at lower temperature, salt concentration, and pH than bassanite. The relative humidity controls whether bassanite or gypsum is stable. Thus, distinguishing among gypsum, bassanite, and anhydrite via remote sensing can provide constraints on the geochemical environment.

Numerical analysis of seawater circulation in carbonate platforms: II. The dynamic interaction between geothermal and brine reflux circulation

USGS Publications Warehouse

Jones, G.D.; Whitaker, F.F.; Smart, P.L.; Sanford, W.E.

2004-01-01

Density-driven seawater circulation may occur in carbonate platforms due to geothermal heating and / or reflux of water of elevated salinity. In geothermal circulation lateral contrasts in temperature between seawater and platform groundwaters warmed by the geothermal heat flux result in upward convective flow, with colder seawater drawn into the platform at depth. With reflux circulation, platform-top waters concentrated by evaporation flow downward, displacing less dense underlying groundwaters. We have used a variable density groundwater flow model to examine the pattern, magnitude and interaction of these two different circulation mechanisms, for mesosaline platform-top waters (50???) and brines concentrated up to saturation with respect to gypsum (150???) and halite (246???). Geothermal circulation, most active around the platform margin, becomes restricted and eventually shut-off by reflux of brines from the platform interior towards the margin. The persistence of geothermal circulation is dependent on the rate of brine reflux, which is proportional to the concentration of platform-top brines and also critically dependent on the magnitude and distribution of permeability. Low permeability evaporites can severely restrict reflux whereas high permeability units in hydraulic continuity enhance brine transport. Reduction in permeability with depth and anisotropy of permeability (kv < < kh) focuses flow laterally in the shallow subsurface (<1 km), resulting in a horizontally elongated brine plume. Aquifer porosity and dispersivity are relatively minor controls on reflux. Platform brines can entrain surficial seawater when brine generating conditions cease but the platform-top remains submerged, a variant of reflux we term "latent reflux". Brines concentrated up to gypsum saturation have relatively long residence times of at least 100 times the duration of the reflux event. They thus represent a long-term control on post-reflux groundwater circulation, and consequently on the rates and spatial patterns of shallow burial diagenesis, such as dolomitization.

Quantifying Rock Weakening Due to Decreasing Calcite Mineral Content by Numerical Simulations

PubMed Central

2018-01-01

The quantification of changes in geomechanical properties due to chemical reactions is of paramount importance for geological subsurface utilisation, since mineral dissolution generally reduces rock stiffness. In the present study, the effective elastic moduli of two digital rock samples, the Fontainebleau and Bentheim sandstones, are numerically determined based on micro-CT images. Reduction in rock stiffness due to the dissolution of 10% calcite cement by volume out of the pore network is quantified for three synthetic spatial calcite distributions (coating, partial filling and random) using representative sub-cubes derived from the digital rock samples. Due to the reduced calcite content, bulk and shear moduli decrease by 34% and 38% in maximum, respectively. Total porosity is clearly the dominant parameter, while spatial calcite distribution has a minor impact, except for a randomly chosen cement distribution within the pore network. Moreover, applying an initial stiffness reduced by 47% for the calcite cement results only in a slightly weaker mechanical behaviour. Using the quantitative approach introduced here substantially improves the accuracy of predictions in elastic rock properties compared to general analytical methods, and further enables quantification of uncertainties related to spatial variations in porosity and mineral distribution. PMID:29614776

Quantifying Rock Weakening Due to Decreasing Calcite Mineral Content by Numerical Simulations.

PubMed

Wetzel, Maria; Kempka, Thomas; Kühn, Michael

2018-04-01

The quantification of changes in geomechanical properties due to chemical reactions is of paramount importance for geological subsurface utilisation, since mineral dissolution generally reduces rock stiffness. In the present study, the effective elastic moduli of two digital rock samples, the Fontainebleau and Bentheim sandstones, are numerically determined based on micro-CT images. Reduction in rock stiffness due to the dissolution of 10% calcite cement by volume out of the pore network is quantified for three synthetic spatial calcite distributions (coating, partial filling and random) using representative sub-cubes derived from the digital rock samples. Due to the reduced calcite content, bulk and shear moduli decrease by 34% and 38% in maximum, respectively. Total porosity is clearly the dominant parameter, while spatial calcite distribution has a minor impact, except for a randomly chosen cement distribution within the pore network. Moreover, applying an initial stiffness reduced by 47% for the calcite cement results only in a slightly weaker mechanical behaviour. Using the quantitative approach introduced here substantially improves the accuracy of predictions in elastic rock properties compared to general analytical methods, and further enables quantification of uncertainties related to spatial variations in porosity and mineral distribution.

ASSESSMENT OF STACHYBOTRYS REGROWTH ON CONTAMINATED WALLBOARD AFTER TREATMENT WITH COMMON SURFACE CLEANERS/DISINFECTANTS

EPA Science Inventory

The paper describes results of experiments assessing the efficacy of treating mold-contaminated gypsum wallboard with cleaners and/or disinfectants. Although the accepted recommendations for handling Stachybotrys chartarum contaminated gypsum wallboard are removal and replacement...

Study of Fresh and Hardening Process Properties of Gypsum with Three Different PCM Inclusion Methods

PubMed Central

Serrano, Susana; Barreneche, Camila; Navarro, Antonia; Haurie, Laia; Fernandez, A. Inés; Cabeza, Luisa F.

2015-01-01

Gypsum has two important states (fresh and hardened states), and the addition of phase change materials (PCM) can vary the properties of the material. Many authors have extensively studied properties in the hardened state; however, the variation of fresh state properties due to the addition of Micronal® DS 5001 X PCM into gypsum has been the object of few investigations. Properties in fresh state define the workability, setting time, adherence and shrinkage, and, therefore the possibility of implementing the material in building walls. The aim of the study is to analyze, compare and evaluate the variability of fresh state properties after the inclusion of 10% PCM. PCM are added into a common gypsum matrix by three different methods: adding microencapsulated PCM, making a suspension of PCM/water, and incorporating PCM through a vacuum impregnation method. Results demonstrate that the inclusion of PCM change completely the water required by the gypsum to achieve good workability, especially the formulation containing Micronal® DS 5001 X: the water required is higher, the retraction is lower (50% less) due to the organic nature of the PCM with high elasticity and, the adherence is reduced (up to 45%) due to the difference between the porosity of the different surfaces as well as the surface tension difference. PMID:28793584

A low-temperature ductile shear zone: The gypsum-dominated western extension of the brittle Fella-Sava Fault, Southern Alps.

PubMed

Bartel, Esther Maria; Neubauer, Franz; Heberer, Bianca; Genser, Johann

2014-12-01

Based on structural and fabric analyses at variable scales we investigate the evaporitic gypsum-dominated Comeglians-Paularo shear zone in the Southern Alps (Friuli). It represents the lateral western termination of the brittle Fella-Sava Fault. Missing dehydration products of gypsum and the lack of annealing indicate temperatures below 100 °C during development of the shear zone. Despite of such low temperatures the shear zone clearly exhibits mylonitic flow, thus evidencing laterally coeval activity of brittle and viscous deformation. The dominant structures within the gypsum rocks of the Lower Bellerophon Formation are a steeply to gently S-dipping foliation, a subhorizontal stretching lineation and pure shear-dominated porphyroclast systems. A subordinate simple shear component with dextral displacement is indicated by scattered σ-clasts. Both meso- and microscale structures are characteristic of a subsimple shear type of deformation with components of both coaxial and non-coaxial strain. Shortening in a transpressive regime was accommodated by right-lateral displacement and internal pure shear deformation within the Comeglians-Paularo shear zone. The shear zone shows evidence for a combination of two stretching faults, where stretching occurred in the rheologically weaker gypsum member and brittle behavior in enveloping lithologies.

Mechanisms of sulfate removal from subsurface calcium chloride brines: Heletz-Kokhav oilfields, Israel

NASA Astrophysics Data System (ADS)

Gavrieli, Ittai; Starinsky, Avraham; Spiro, Baruch; Aizenshtat, Zeev; Nielsen, Heimo

1995-09-01

The evolution of the Ca-chloride brines in the Heletz Formation, Lower Cretaceous, in the southern coastal plain of Israel was reconstructed through the study of its sulfate concentration and isotopic composition. Particular emphasis was given to the brine-oil interaction in the oilfields and to the sulfate depletion and lower SO 4/Cl ratio in brines in contact with hydrocarbons (oil brines) relative to "oil-free" from dry wells in the same oilfields. A method is presented for a calculation of the amount of sulfate removed from the original seawater in the various stages of its evolution to Ca-chloride brine. These stages include evaporation, dolomitization, and sulfate reduction in different stages of its evolution, from early diagenetic processes to the contact with crude oil. In the present study, based on the δ34S SO 4 and SO 4/Cl ratio, it was found that in the Heletz brines most of the sulfate (80-94%) was removed from the original seawater prior to their interaction with the hydrocarbons and only a negligible fraction of few percent of the sulfate was removed during the crude oil-water contact. The Ca-chloride brines evolved from Messinian (Upper Miocene) seawater that underwent evaporation during the desiccation of the Mediterranean. Sulfate was removed from Messinian lagoon (s) during gypsum precipitation due to evaporation and dolomitization. Bacterial sulfate reduction further depleted the brine in sulfate and changed its isotopic composition, from its original Miocene seawater composition of δ34S SO 4 ˜ 20%o, 26%o. Overall, some 50% of the original sulfate, as normalized to chloride, was removed from the original lagoon through the above processes, mostly by gypsum precipitation. Eastward migration of the Messinian Ca-Chloride brine into the Heletz Formation was accompanied by dolomitization of the country rock. Final depletion of sulfate from the brines took place, and possibly still occurs, in the presence of crude oil in the oilfields. The two oil-producing fields, Heletz and Kokhav, occupy different areas on a Rayleigh distillation diagram. Sulfate depletion in both fields is accompanied by an increase in δ34S SO 4, which reaches a maximum value of 59%o. The above correlation is explained by bacterial sulfate reduction facilitated by the contact with the crude. Samples collected from the same boreholes at time intervals of several months show two opposing trends: sulfate concentration decrease accompanied by increase in δ34S SO 4, and vice versa. While the first can be explained as in situ bacterial sulfate reduction, the latter attest to subsurface brine migration, as would be expected in oil-producing fields.

Quantification of a maximum injection volume of CO2 to avert geomechanical perturbations using a compositional fluid flow reservoir simulator

NASA Astrophysics Data System (ADS)

Jung, Hojung; Singh, Gurpreet; Espinoza, D. Nicolas; Wheeler, Mary F.

2018-02-01

Subsurface CO2 injection and storage alters formation pressure. Changes of pore pressure may result in fault reactivation and hydraulic fracturing if the pressure exceeds the corresponding thresholds. Most simulation models predict such thresholds utilizing relatively homogeneous reservoir rock models and do not account for CO2 dissolution in the brine phase to calculate pore pressure evolution. This study presents an estimation of reservoir capacity in terms of allowable injection volume and rate utilizing the Frio CO2 injection site in the coast of the Gulf of Mexico as a case study. The work includes laboratory core testing, well-logging data analyses, and reservoir numerical simulation. We built a fine-scale reservoir model of the Frio pilot test in our in-house reservoir simulator IPARS (Integrated Parallel Accurate Reservoir Simulator). We first performed history matching of the pressure transient data of the Frio pilot test, and then used this history-matched reservoir model to investigate the effect of the CO2 dissolution into brine and predict the implications of larger CO2 injection volumes. Our simulation results -including CO2 dissolution- exhibited 33% lower pressure build-up relative to the simulation excluding dissolution. Capillary heterogeneity helps spread the CO2 plume and facilitate early breakthrough. Formation expansivity helps alleviate pore pressure build-up. Simulation results suggest that the injection schedule adopted during the actual pilot test very likely did not affect the mechanical integrity of the storage complex. Fault reactivation requires injection volumes of at least about sixty times larger than the actual injected volume at the same injection rate. Hydraulic fracturing necessitates much larger injection rates than the ones used in the Frio pilot test. Tested rock samples exhibit ductile deformation at in-situ effective stresses. Hence, we do not expect an increase of fault permeability in the Frio sand even in the presence of fault reactivation.

Effect of amino acids on the precipitation kinetics and Ca isotopic composition of gypsum

NASA Astrophysics Data System (ADS)

Harouaka, Khadouja; Kubicki, James D.; Fantle, Matthew S.

2017-12-01

Stirred gypsum (CaSO4 · 2H2O) precipitation experiments (initial Ωgypsum = 2.4 ± 0.14, duration ≈ 1.0-1.5 h) were conducted in the presence of the amino acids glycine (190 μM), L-alanine (190 μM), D- and L-arginine (45 μM), and L-tyrosine (200 μM) to investigate the effect of simple organic compounds on both the precipitation kinetics and Ca isotopic composition of gypsum. Relative to abiotic controls, glycine, tyrosine, and alanine inhibited precipitation rates by ∼22%, 27%, and 29%, respectively, while L- and D-arginine accelerated crystal growth by ∼8% and 48%, respectively. With the exception of tyrosine, amino acid induced inhibition resulted in fractionation factors (αs-f) associated with precipitation that were no more than 0.3‰ lower than amino acid-free controls. In contrast, the tyrosine and D- and L-arginine experiments had αs-f values associated with precipitation that were similar to the controls. Our experimental results indicate that Ca isotopic fractionation associated with gypsum precipitation is impacted by growth inhibition in the presence of amino acids. Specifically, we propose that the surface-specific binding of amino acids to gypsum can change the equilibrium fractionation factor of the bulk mineral. We investigate the hypothesis that amino acids can influence the growth of gypsum at specific crystal faces via adsorption and that different faces have distinct fractionation factors (αface-fluid). Accordingly, preferential sorption of amino acids at particular faces changes the relative, face-specific mass fluxes of Ca during growth, which influences the bulk isotopic composition of the mineral. Density functional theory (DFT) calculations suggest that the energetic favorability of glycine sorption onto gypsum crystal faces occurs in the order: (1 1 0) > (0 1 0) > (1 2 0) > (0 1 1), while glycine sorption onto the (-1 1 1) face was found to be energetically unfavorable. Face-specific fractionation factors constrained by frequency calculations of clusters derived from DFT structures vary by as much as 1.4‰. This suggests that the equilibrium fractionation factor for the bulk crystal can vary substantially, and that surface sorption can induce changes in αeq associated with gypsum precipitation. While we do not rule out the influence of kinetic isotope effects, our results clearly demonstrate that the mode of crystal growth can have a sizeable effect on the bulk fractionation factor (αs-f). Ultimately, our results suggest that the same mechanism by which organic molecules affect the morphology of a mineral can also impact the isotopic composition of the mineral. The results of our study provide valuable insight into the mechanism of Ca isotopic fractionation during gypsum precipitation. Our results are also important for establishing a framework for accurate interpretations of mineral-hosted Ca isotope records of the past, as we demonstrate a mechanistic pathway by which the biological and chemical environment can impact Ca isotopic fractionation during mineral precipitation.

Geology and evolution of lakes in north-central Florida

USGS Publications Warehouse

Kindinger, J.L.; Davis, J.B.; Flocks, J.G.

1999-01-01

Fluid exchange between surficial waters and groundwater in karst environments, and the processes that control exchange, are of critical concern to water management districts and planners. High-resolution seismic data were collected from 30 lakes of north-central Florida. In each case study, lake structure and geomorphology were controlled by solution and/or mechanical processes. Processes that control lake development are twofold: (1) karstification or dissolution of the underlying limestone, and (2) the collapse, subsidence, or slumping of overburden to form sinkholes. Initial lake formation is directly related to the karst topography of the underlying host limestone. Case studies have shown that lakes can be divided by geomorphic types into progressive developmental phases: (1) active subsidence or collapse phase (young); (2) transitional phase (middle age); (3) baselevel phase (mature); and (4) polje (drowned prairie) - broad flat-bottom that have one or all phases of sinkhole. Using these criteria, Florida lakes can be classified by size, fill, subsurface features, and geomorphology.Fluid exchange between surficial waters and groundwater in karst environments, and the processes that control exchange, are of critical concern to water management districts and planners. High-resolution seismic data were collected from 30 lakes of north-central Florida. In each case study, lake structure and geomorphology were controlled by solution and/or mechanical processes. Processes that control lake development are twofold: (1) karstification or dissolution of the underlying limestone, and (2) the collapse, subsidence, or slumping of overburden to form sinkholes. Initial lake formation is directly related to the karst topography of the underlying host limestone. Case studies have shown that lakes can be divided by geomorphic types into progressive developmental phased: (1) active subsidence or collapse phase (young); (2) transitional phase (middle age); (3) baselevel phase (mature); and (4) polje (drowned prairie) - broad flat-bottom that have one or all phases of sinkhole. Using these criteria, Florida lakes can be classified by size, fill, subsurface features, and geomorphology.

Combined Experimental and Computational Approach to Predict the Glass-Water Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pierce, Eric M.; Bacon, Diana H.

2011-10-01

The use of mineral and glass dissolution rates measured in laboratory experiments to predict the weathering of primary minerals and volcanic and nuclear waste glasses in field studies requires the construction of rate models that accurately describe the weathering process over geologic timescales. Additionally, the need to model the long-term behavior of nuclear waste glass for the purpose of estimating radionuclide release rates requires that rate models be validated with long-term experiments. Several long-term test methods have been developed to accelerate the glass-water reaction [drip test, vapor hydration test, product consistency test B, and pressurized unsaturated flow (PUF)], thereby reducingmore » the duration required to evaluate long-term performance. Currently, the PUF test is the only method that mimics the unsaturated hydraulic properties expected in a subsurface disposal facility and simultaneously monitors the glass-water reaction. PUF tests are being conducted to accelerate the weathering of glass and validate the model parameters being used to predict long-term glass behavior. A one-dimensional reactive chemical transport simulation of glass dissolution and secondary phase formation during a 1.5-year-long PUF experiment was conducted with the Subsurface Transport Over Reactive Multiphases (STORM) code. Results show that parameterization of the computer model by combining direct bench scale laboratory measurements and thermodynamic data provides an integrated approach to predicting glass behavior over the length of the experiment. Over the 1.5-year-long test duration, the rate decreased from 0.2 to 0.01 g/(m2 day) based on B release for low-activity waste glass LAWA44. The observed decrease is approximately two orders of magnitude higher than the decrease observed under static conditions with the SON68 glass (estimated to be a decrease by four orders of magnitude) and suggests that the gel-layer properties are less protective under these dynamic conditions.« less

Combined Experimental and Computational Approach to Predict the Glass-Water Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pierce, Eric M; Bacon, Diana

2011-01-01

The use of mineral and glass dissolution rates measured in laboratory experiments to predict the weathering of primary minerals and volcanic and nuclear waste glasses in field studies requires the construction of rate models that accurately describe the weathering process over geologic time-scales. Additionally, the need to model the long-term behavior of nuclear waste glass for the purpose of estimating radionuclide release rates requires that rate models are validated with long-term experiments. Several long-term test methods have been developed to accelerate the glass-water reaction [drip test, vapor hydration test, product consistency test-B, and pressurized unsaturated flow (PUF)], thereby reducing themore » duration required to evaluate long-term performance. Currently, the PUF test is the only method that mimics the unsaturated hydraulic properties expected in a subsurface disposal facility and simultaneously monitors the glass-water reaction. PUF tests are being conducted to accelerate the weathering of glass and validate the model parameters being used to predict long-term glass behavior. A one-dimensional reactive chemical transport simulation of glass dissolution and secondary phase formation during a 1.5-year long PUF experiment was conducted with the subsurface transport over reactive multi-phases code. Results show that parameterization of the computer model by combining direct bench-scale laboratory measurements and thermodynamic data provides an integrated approach to predicting glass behavior over the length of the experiment. Over the 1.5-year long test duration, the rate decreased from 0.2 to 0.01 g/(m2 d) base on B release. The observed decrease is approximately two orders of magnitude higher than the decrease observed under static conditions with the SON68 glass (estimated to be a decrease by 4 orders of magnitude) and suggest the gel-layer properties are less protective under these dynamic conditions.« less

Method Analysis of Microbial-Resistant Gypsum Products

EPA Science Inventory

Method Analysis of Microbial-Resistant Gypsum ProductsD.A. Betancourt1, T.R.Dean1, A. Evans2, and G.Byfield2 1. US Environmental Protection Agency, Office of Research and Development, National Risk Management Research Laboratory; RTP, NC 277112. RTI International, RTP, NCSeveral...

Gypsum Wallboard as a sink for formaldehyde

EPA Science Inventory

Formaldehyde (HCHO) has been of special concern as an indoor air pollutant because of its presence in a wide range of consumer products and its adverse health effects. Materials acting as HCHO sinks, such as painted gypsum wallboard, can become emission sources. However, adsorpti...

On the Role of Dissolved Gases in the Atmosphere Retention of Low-mass Low-density Planets

NASA Astrophysics Data System (ADS)

Chachan, Yayaati; Stevenson, David J.

2018-02-01

Low-mass low-density planets discovered by Kepler in the super-Earth mass regime typically have large radii for their inferred masses, implying the presence of H2–He atmospheres. These planets are vulnerable to atmospheric mass loss due to heating by the parent star’s XUV flux. Models coupling atmospheric mass loss with thermal evolution predicted a bimodal distribution of planetary radii, which has gained observational support. However, a key component that has been ignored in previous studies is the dissolution of these gases into the molten core of rock and iron that constitute most of their mass. Such planets have high temperatures (>2000 K) and pressures (∼kbars) at the core-envelope boundary, ensuring a molten surface and a subsurface reservoir of hydrogen that can be 5–10 times larger than the atmosphere. This study bridges this gap by coupling the thermal evolution of the planet and the mass loss of the atmosphere with the thermodynamic equilibrium between the dissolved H2 and the atmospheric H2 (Henry’s law). Dissolution in the interior allows a planet to build a larger hydrogen repository during the planet formation stage. We show that the dissolved hydrogen outgasses to buffer atmospheric mass loss. The slow cooling of the planet also leads to outgassing because solubility decreases with decreasing temperature. Dissolution of hydrogen in the interior therefore increases the atmosphere retention ability of super-Earths. The study highlights the importance of including the temperature- and pressure-dependent solubility of gases in magma oceans and coupling outgassing to planetary evolution models.

Structural analysis of S-wave seismics around an urban sinkhole: evidence of enhanced dissolution in a strike-slip fault zone

NASA Astrophysics Data System (ADS)

Wadas, Sonja H.; Tanner, David C.; Polom, Ulrich; Krawczyk, Charlotte M.

2017-12-01

In November 2010, a large sinkhole opened up in the urban area of Schmalkalden, Germany. To determine the key factors which benefited the development of this collapse structure and therefore the dissolution, we carried out several shear-wave reflection-seismic profiles around the sinkhole. In the seismic sections we see evidence of the Mesozoic tectonic movement in the form of a NW-SE striking, dextral strike-slip fault, known as the Heßleser Fault, which faulted and fractured the subsurface below the town. The strike-slip faulting created a zone of small blocks ( < 100 m in size), around which steep-dipping normal faults, reverse faults and a dense fracture network serve as fluid pathways for the artesian-confined groundwater. The faults also acted as barriers for horizontal groundwater flow perpendicular to the fault planes. Instead groundwater flows along the faults which serve as conduits and forms cavities in the Permian deposits below ca. 60 m depth. Mass movements and the resulting cavities lead to the formation of sinkholes and dissolution-induced depressions. Since the processes are still ongoing, the occurrence of a new sinkhole cannot be ruled out. This case study demonstrates how S-wave seismics can characterize a sinkhole and, together with geological information, can be used to study the processes that result in sinkhole formation, such as a near-surface fault zone located in soluble rocks. The more complex the fault geometry and interaction between faults, the more prone an area is to sinkhole occurrence.

Can isotopic variations in structural water of gypsum reveal paleoclimatic changes?

NASA Astrophysics Data System (ADS)

Gatti, E.; Bustos, D.; Coleman, M. L.

2015-12-01

Water of crystallization in gypsum can be used as paleo-environmental proxy to study large scale climatic variability in arid areas. This is because changes in the isotopic composition of water of crystallization are due to isotopic variations in the mother brine from which the mineral precipitated, and the brine isotopic composition is linked to evaporation processes and humidity. This is particularly important when the salts are the only traces left of the original water, i.e. in modern arid areas. This study aims to prove that the 2-D/18-O compositions of the water of crystallization extracted from successive precipitates or even different growth zones of natural gypsum (CaSO4·H2O) can reconstruct the evaporation history and paleo-humidity of the source water basin. The method was tested in a laboratory experiment that evaporated CaSO4 brines under controlled temperature and humidity conditions. The brine was left to evaporate for five days at two different humidities (45 and 75 RH%); subsequently, brines and precipitated gypsum were sampled at 24 hour intervals. In this way we simulated zoned growth of gypsum. The samples were then analyzed for oxygen and hydrogen isotopic composition using a Thermo Scientific TC/EA with modified column, coupled to a MAT 253 Thermo Finnigan mass spectrometer at JPL. If preliminary results validate the novel hypothesis that changes in mineral composition can reveal details of paleo-environmental conditions the theory will be tested on natural gypsum collected from selected areas in White Sands National Monument, New Mexico. The study is currently ongoing but the full dataset will be presented at the conference.

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

The project objective is to demonstrate removal of 90--95% or more of the SO{sub 2} at approximately one-half the cost of conventional scrubbing technology; and to demonstrate significant reduction of space requirements. In this project, Pure Air has built a single SO{sub 2} absorber for a 528-MWe power plant. The absorber performs three functions in a single vessel: prequencher, absorber, and oxidation of sludge to gypsum. Additionally, the absorber is of a co- current design, in which the flue gas and scrubbing slurry move in the same direction and at a relatively high velocity compared to conventional scrubbers. These featuresmore » all combine to yield a state- of-the-art SO{sub 2} absorber that is more compact and less expensive than conventional scrubbers. The project incorporated a number of technical features including the injection of pulverized limestone directly into the absorber, a device called an air rotary sparger located within the base of the absorber, and a novel wastewater evaporation system. The air rotary sparger combines the functions of agitation and air distribution into one piece of equipment to facilitate the oxidation of calcium sulfite to gypsum. Additionally, wastewater treatment is being demonstrated to minimize water disposal problems inherent in many high-chloride coals. Bituminous coals primarily from the Indiana, Illinois coal basin containing 2--4.5% sulfur were tested during the demonstration. The Advanced Flue Gas Desulfurization (AFGD) process has demonstrated removal of 95% or more of the SO{sub 2} while providing a commercial gypsum by-product in lieu of solid waste. A portion of the commercial gypsum is being agglomerated into a product known as PowerChip{reg_sign} gypsum which exhibits improved physical properties, easier flowability and more user friendly handling characteristics to enhance its transportation and marketability to gypsum end-users.« less

Sedimentological and diagenetic patterns of anhydrite deposits in the Badenian evaporite basin of the Carpathian Foredeep, southern Poland

NASA Astrophysics Data System (ADS)

Kasprzyk, Alicja

2003-05-01

Anhydrite deposits are widely distributed in the Middle Miocene Badenian evaporite basin of Poland, including the marginal sulphate platform and adjacent salt depocenter. Particular sedimentological, petrographic and geochemical characteristics of these anhydrite deposits and especially common pseudomorphic features, inherited from the precursor gypsum deposits, allow the interpretation of the original sedimentary facies. The observed facies distribution and succession (lower and upper members) reveal three distinct facies associations that record a range of depositional environments from nearshore to deeper basinal settings. Platform sulphates were deposited in subaerial and shallow-marine environments (shoreline and inner platform-lagoon system) mainly as autochthonous selenitic gypsum. This was reworked and redistributed into deeper waters (outer platform-lagoon, slope and the proximal basin floor system) to form resedimented facies composed mostly of allochthonous clastic gypsum and minor anhydrite. The general variation in petrographic and geochemical compositions of anhydrite lithofacies of the lower and upper members reflects the brine evolution, as the result of interactions between seawater, meteoric runoff and highly saline, residual pore fluids. The results indicate the importance of synsedimentary and diagenetic anhydritisation processes in formation of the Badenian anhydrite lithofacies, all of which preserve the original depositional features of the former gypsum. This also applies to the basinal anhydrite previously interpreted to have a depositional genesis. Two different genetic patterns of anhydrite have been reinforced by this study: (1) synsedimentary anhydritisation of gypsum deposits by highly concentrated brines or elevated temperatures in surficial to shallow-burial environments (lower member), and (2) successive phases (syndepositional de novo growth, early diagenetic to late diagenetic replacement of former gypsum) of anhydrite formation during progressive burial (upper member).

Gypsum treated fly ash as a liner for waste disposal facilities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sivapullaiah, Puvvadi V., E-mail: siva@civil.iisc.ernet.in; Baig, M. Arif Ali, E-mail: reach2arif@gmail.com

2011-02-15

Fly ash has potential application in the construction of base liners for waste containment facilities. While most of the fly ashes improve in the strength with curing, the ranges of permeabilities they attain may often not meet the basic requirement of a liner material. An attempt has been made in the present context to reduce the hydraulic conductivity by adding lime content up to 10% to two selected samples of class F fly ashes. The use of gypsum, which is known to accelerate the unconfined compressive strength by increasing the lime reactivity, has been investigated in further improving the hydraulicmore » conductivity. Hydraulic conductivities of the compacted specimens have been determined in the laboratory using the falling head method. It has been observed that the addition of gypsum reduces the hydraulic conductivity of the lime treated fly ashes. The reduction in the hydraulic conductivity of the samples containing gypsum is significantly more for samples with high amounts of lime contents (as high as 1000 times) than those fly ashes with lower amounts of lime. However there is a relatively more increase in the strengths of the samples with the inclusion of gypsum to the fly ashes at lower lime contents. This is due to the fact that excess lime added to fly ash is not effectively converted into pozzolanic compounds. Even the presence of gypsum is observed not to activate these reactions with excess lime. On the other hand the higher amount of lime in the presence of sulphate is observed to produce more cementitious compounds which block the pores in the fly ash. The consequent reduction in the hydraulic conductivity of fly ash would be beneficial in reducing the leachability of trace elements present in the fly ash when used as a base liner.« less

Accelerated Weathering of Waste Glass at 90°C with the Pressurized Unsaturated Flow (PUF) Apparatus: Implications for Predicting Glass Corrosion with a Reactive Transport Model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pierce, Eric M.; Bacon, Diana H.

2009-09-21

The interest in the long-term durability of waste glass stems from the need to predict radionuclide release rates from the corroding glass over geologic time-scales. Several long-term test methods have been developed to accelerate the glass-water reaction [drip test, vapor hydration test, product consistency test-B, and pressurized unsaturated flow (PUF)]. Currently, the PUF test is the only method that can mimic the unsaturated hydraulic properties expected in a subsurface disposal facility and simultaneously monitor the glass-water reaction. PUF tests are being conducted to accelerate the weathering of glass and validate the model parameters being used to predict long-term glass behavior.more » One dimensional reactive chemical transport simulations of glass dissolution and secondary phase formation during a 1.5-year long PUF experiment was conducted with the subsurface transport over reactive multi-phases (STORM) code. Results show that parameterization of the computer model by combining direct laboratory measurements and thermodynamic data provides an integrated approach to predicting glass behavior over geologic-time scales.« less

Geohydrologic Framework of the Edwards and Trinity Aquifers, South-Central Texas

USGS Publications Warehouse

Blome, Charles D.; Faith, Jason R.; Ozuna, George B.

2007-01-01

This five-year USGS project, funded by the National Cooperative Geologic Mapping Program, is using multidisciplinary approaches to reveal the surface and subsurface geologic architecture of two important Texas aquifers: (1) the Edwards aquifer that extends from south of Austin to west of San Antonio and (2) the southern part of the Trinity aquifer in the Texas Hill Country west and south of Austin. The project's principal areas of research include: Geologic Mapping, Geophysical Surveys, Geochronology, Three-dimensional Modeling, and Noble Gas Geochemistry. The Edwards aquifer is one of the most productive carbonate aquifers in the United States. It also has been designated a sole source aquifer by the U.S. Environmental Protection Agency and is the primary source of water for San Antonio, America's eighth largest city. The Trinity aquifer forms the catchment area for the Edwards aquifer and it intercepts some surface flow above the Edwards recharge zone. The Trinity may also contribute to the Edwards water budget by subsurface flow across formation boundaries at considerable depths. Dissolution, karst development, and faulting and fracturing in both aquifers directly control aquifer geometry by compartmentalizing the aquifer and creating unique ground-water flow paths.

Microbial diversity in Cenozoic sediments recovered from the Lomonosov Ridge in the Central Arctic basin.

PubMed

Forschner, Stephanie R; Sheffer, Roberta; Rowley, David C; Smith, David C

2009-03-01

The current understanding of microbes inhabiting deeply buried marine sediments is based largely on samples collected from continental shelves in tropical and temperate latitudes. The geographical range of marine subsurface coring was expanded during the Integrated Ocean Drilling Program Arctic Coring Expedition (IODP ACEX). This expedition to the ice-covered central Arctic Ocean successfully cored the entire 428 m sediment stack on the Lomonosov Ridge during August and September 2004. The recovered cores vary from siliciclastic sediment low in organic carbon (< 0.2%) to organic rich ( approximately 3%) black sediments that rapidly accumulated in the early middle Eocene. Three geochemical environments were characterized based on chemical analyses of porewater: an upper ammonium oxidation zone, a carbonate dissolution zone and a deep (> 200 m below sea floor) sulfate reduction zone. The diversity of microbes within each zone was assessed using 16S rRNA phylogenetic markers. Bacterial 16S rRNA genes were successfully amplified from each of the biogeochemical zones, while archaea was only amplified from the deep sulfate reduction zone. The microbial communities at each zone are phylogenetically different and are most closely related to those from other deep subsurface environments.

Groundwater flow and potential effects on evaporite dissolution in the Paradox Basin, SE Utah

NASA Astrophysics Data System (ADS)

Reitman, N.; Ge, S.; Mueller, K. J.

2012-12-01

A hydrogeologic study was conducted in the portion of the Paradox Basin south of the Needles District of Canyonlands National Park, Utah. Geology of the study area comprises fractured and faulted Paleozoic sandstone, limestone, and shale, which are underlain by evaporite cycles of the Paradox Formation. The evaporite deposits deform and dissolve when they come in contact with groundwater, generating land subsidence, saline groundwater, and salt input to the Colorado River. Active faults in the region slip at a rate of approximately 2 mm/year, likely due to evaporite dissolution. The objective of this study is to better understand groundwater flow and solute transport dynamics and to help determine the rate and timing of subsurface salt dissolution, which is an important control on the salt tectonics in the region. Study methods include hydrologic fieldwork, laboratory tests, and numerical modeling. No groundwater wells exist in the study area. Water samples from springs and seeps were collected throughout the study area. Analysis of total dissolved solids (TDS), stable oxygen (δ18O) and deuterium (δD) isotopes, spring and seep locations, and prior data are used to gain a preliminary understanding of the shallow groundwater flow in the region. Stable isotope ratios of oxygen (18O/16O) and deuterium (D/H) are used to constrain the source of spring water. Measured δ values are compared to predicted δ values for precipitation from WaterIsotopes.org for each sample site. Measured isotopic values range from -14.9 ‰ to -10.7 ‰ for δ18O and -108 ‰ to -78 ‰ for δD. The majority of samples from above 2000 m match predicted isotopic values for precipitation. Most samples taken below 2000 m are lighter than predicted isotopic values for precipitation. The TDS of spring samples measured in the lab show they range from 184 mg/L to 1552 mg/L with the majority of samples between 220 - 430 mg/L. TDS shows a weak correlation (R2 = 0.54) with altitude, where lower TDS is measured in higher altitude samples. These measurements are consistent with high altitude samples representing precipitation and low altitude samples representing shallow groundwater. Location and altitude of springs sampled in this study, as well as those recorded by earlier studies, were used to create a potentiometric surface map in GIS. From the map, water flow direction is inferred to flow mostly from the Abajo Mountains in the southeast towards the Colorado River in the northwest. A transient groundwater flow and solute transport model is developed for a 2-D cross section from the Abajo Mountains in the SE to the Colorado River in the NW. Recharge is applied in the southeast, driving water flow towards the northwest. Most discharge flows into the Colorado River, primarily via seepage through cliff faces. Surface discharge occurs in topographic lows. The flow and solute concentration patterns from the model are generally consistent with field data. Evaporite dissolution varies laterally depending on groundwater flow pattern. Deep groundwater flow patterns and pore pressure data from the model will contribute to an understanding of subsurface salt dissolution and active salt tectonics in the study region. Additionally, the results of this study will help land and water managers protect scarce freshwater resources in this arid desert region.

MOLD GROWTH ON GYPSUM WALLBOARD--A RESEARCH SUMMARY

EPA Science Inventory

Reducing occupant exposure to mold growing on damp gypsum wallboard is a research objective of the U.S. Environmental Protection Agency. Often mold contaminated building materials are not properly removed but instead surface cleaners are used and then paint is applied in an attem...

Evaluation of gypsum rates on greenhouse crop production

USDA-ARS?s Scientific Manuscript database

This study was to determine the potential of an added value distribution channel for gypsum waste by evaluating various greenhouse crops with captious pH and calcium needs. Three studies consisting of: Zonal geranium (Pelargonium x hortorum) and petunia (Petunia x hybrida); tomato (Solanum lycoper...

Impact of FGD gypsum application on trace elements

USDA-ARS?s Scientific Manuscript database

There are concerns regarding the fate of nutrients from surface application of animal waste. One approach to reduce losses of P is to treat manure with the industrial byproducts flue gas desulfurization gypsum (FGDG). However, concerns regarding heavy metal contributions to the environment have ar...

Effect of Time on Gypsum-Impression Material Compatibility

NASA Astrophysics Data System (ADS)

Won, John Boram

The purpose of this study was to evaluate the compatibility of dental gypsum with three recently introduced irreversible hydrocolloid (alginate) alternatives. The test materials were Alginot® (Kerr™), Position Penta Quick® (3M ESPE™) and Silgimix ® (Sultan Dental™). The irreversible hydrocolloid impression material, Jeltrate Plus antimicrobial® (Dentsply Caulk™) served as the control. Materials and Methods: Testing of materials was conducted in accordance with ANSI/ADA Specification No. 18 for Alginate Impression Materials. Statistical Analysis: The 3-Way ANOVA test was used to analyze measurements between different time points at a significance level of (p < 0.05). Outcome: It was found that there was greater compatibility between gypsum and the alternative materials over time than the traditional irreversible hydrocolloid material that was tested. A statistically significant amount of surface change/incompatibility was found over time with the combination of the dental gypsum products and the control impression material (Jeltrate Plus antimicrobial®).

Tunisian gypsums: Characteristics and use in cement

NASA Astrophysics Data System (ADS)

Mahmoudi, Salah; Bennour, Ali; Chalwati, Youssef; Souidi, Khouloud; Thabet, Manel; Srasra, Ezzedine; Zargouni, Fouad

2016-09-01

Gypsum materials of hundred meters thickness and interbedded with marine claystones and limestones from different paleogeographic sectors in the Tunisian territory are studied to assess their suitability for cement production. For this reason, thirty representative samples are analysed by chemical, physical and geotechnical tests. The obtained results for the studied gypsum materials are compared to Tunisian and European norms and with the local cements, currently marketed and which obey international norms. Indeed, for all samples hydraulic modulus HM, silica modulus SM and alumina modulus AM vary from (2.37-2.44), (2.48-2.68) and (1.45-2.5), respectively; whereas the required values for these modulus are (1.5-2.5), (2-3) and (1.5-2.5). The same behavior is observed for mineralogical analyses of C3S, C2S, C3A and C4AF and compressive strength at different ages. Briefly, Tunisia contains important reserves of gypsum scattered and spread over the Tunisian territory and can be used for cement production.

Friction evaluation of unpaved, gypsum-surface runways at Northrup Strip, White Sands Missile Range, in support of Space Shuttle Orbiter landing and retrieval operations

NASA Technical Reports Server (NTRS)

Yager, T. J.; Horne, W. B.

1980-01-01

Friction measurement results obtained on the gypsum surface runways at Northrup Strip, White Sands Missile Range, N. M., using an instrumented tire test vehicle and a diagonal braked vehicle, are presented. These runways were prepared to serve as backup landing and retrieval sites to the primary sites located at Dryden Flight Research Center for shuttle orbiter during initial test flights. Similar friction data obtained on paved and other unpaved surfaces was shown for comparison and to indicate that the friction capability measured on the dry gypsum surface runways is sufficient for operations with the shuttle orbiter and the Boeing 747 aircraft. Based on these ground vehicle friction measurements, estimates of shuttle orbiter and aircraft tire friction performance are presented and discussed. General observations concerning the gypsum surface characteristics are also included and several recommendations are made for improving and maintaining adequate surface friction capabilities prior to the first shuttle orbiter landing.

Nanostructured calcium silicate hydrate seeds accelerate concrete hardening: a combined assessment of benefits and risks.

PubMed

Bräu, Michael; Ma-Hock, Lan; Hesse, Christoph; Nicoleau, Luc; Strauss, Volker; Treumann, Silke; Wiench, Karin; Landsiedel, Robert; Wohlleben, Wendel

2012-07-01

Nanotechnology creates new possibilities to control and improve material properties for civil infrastructure. Special focus in this area is put on Portland cement and gypsum. Together their annual production is by far larger than for any other material worldwide. Nanomodification of these materials can be done during the few hours between dissolution and hardening, especially by nucleation of the re-crystallization with suitable colloids. Here we report first results in homogeneous seeding of the precipitation of calcium silicate hydrates within a real Portland cement composition. The occupational safety during the production phase and during mixing of concrete paste is addressed in detail by in vivo testing. We perform 5-day inhalation with 21-day recovery in rats and analyze organ-specific toxicity and 71 endpoints from bronchoalveolar lavage (BALF) and blood. In BALF parameters, no test-related changes were observed, indicating the generally low toxicity of the test material. Some mild lesions were observed in larynx level. In the lungs, all animals of the 50 mg/m³ concentration group revealed a minimal to mild increase in alveolar macrophages, which recovered back to control level.

Influence of ammonia and carbon dioxide on the sorption of a basic organic pollutant to carpet and latex-painted gypsum board.

PubMed

Ongwandee, Maneerat; Morrison, Glenn C

2008-08-01

Sorptive interactions with indoor surfaces strongly influence indoor exposure to organic pollutants. Adsorption itself may be influenced by indoor levels of common indoor gases such as CO2, NH3, and H2O. We quantified sorption characteristics of trimethylamine (TMA) on carpet and painted wallboard, while challenging the surface with gas-phase CO2, NH3 and H2O. We show that the capacity of the carpet to sorb TMA, doubles when the CO2 mixing ratio is increased from 0 to 1000 ppm CO2 at 90% relative humidity. In contrast, NH3 decreases the surface capacity of both carpet and latex paint. Sorption of TMA to these indoor materials is primarily caused by interactions at one or more interfaces. Dissolution of TMA and aqueous acid-base chemistry appear to also contribute to the overall sorptive capacity of carpet at high relative humidity. The reduction in the distribution coefficient, k(e), in the presence of NH3 is explained by competition between TMA and NH3 molecules for sites on the substrates at low-to-medium relative humidity conditions.

Rates and cycles of microbial sulfate reduction in the hyper-saline Dead Sea over the last 200 kyrs from sedimentary d34S and d18O(SO4)

NASA Astrophysics Data System (ADS)

Torfstein, Adi; Turchyn, Alexandra V.

2017-08-01

We report the d34S and d18O(SO4) values measured in gypsum, pyrite, and elemental sulfur through a 456-m thick sediment core from the center of the Dead Sea, representing the last 200 kyrs, as well as from the exposed glacial outcrops of the Masada M1 section located on the margins of the modern Dead Sea. The results are used to explore and quantify the evolution of sulfur microbial metabolism in the Dead Sea and to reconstruct the lake’s water column configuration during the late Quaternary. Layers and laminae of primary gypsum, the main sulfur-bearing mineral in the sedimentary column, display the highest d34S and d18O(SO4) in the range of 13-28‰ and 13-30‰, respectively. Within this group, gypsum layers deposited during interglacials have lower d34S and d18O(SO4) relative to those associated with glacial or deglacial stages. The reduced sulfur phases, including chromium reducible sulfur, and secondary gypsum crystals are characterized by extremely low d34S in the range of -27 to +7‰. The d18O(SO4) of the secondary gypsum in the M1 outcrop ranges from 8 to 14‰. The relationship between d34S and d18O(SO4) of primary gypsum suggests that the rate of microbial sulfate reduction was lower during glacial relative to interglacial times. This suggests that the freshening of the lake during glacial wet intervals, and the subsequent rise in sulfate concentrations, slowed the rate of microbial metabolism. Alternatively, this could imply that sulfate-driven anaerobic methane oxidation, the dominant sulfur microbial metabolism today, is a feature of the hypersalinity in the modern Dead Sea. Sedimentary sulfides are quantitatively oxidized during epigenetic exposure, retaining the lower d34S signature; the d18O(SO4) of this secondary gypsum is controlled by oxygen atoms derived equally from atmospheric oxygen and from water, which is likely a unique feature in this hyperarid environment.

Depositional setting and extension of the evaporitic units in the Neogene Santa Rosalía basin, Baja California Sur, México

NASA Astrophysics Data System (ADS)

Munoz, V. O. S.; Maher, A.; Jaime-Geraldo, A. J.; Niemi, T.

2017-12-01

Most geologic studies of the Santa Rosalía basin (SRB) have focused on the mineralization of the ore deposits, depositional environment of the sedimentary formations, and volcanism associated with the opening of the Gulf of California. Studies on the depositional setting, features, and patterns of the thick evaporite sequences in the SRB have been neglected even though one of the largest gypsum mines in the world is located in these deposits. Previous reports on the thick gypsum deposits suggested that the deposits were precipitated from hydrothermal submarine springs or from evaporation from bodies of water partly enclosed and cut off from the sea (Wilson and Rocha, 1955; Ochoa-Landin et al., 2000). Contemporary studies on the geochemistry of the gypsum supports an interpretation of marine deposition based on the isotopic values of δ34S and δ18O congruent with the precipitation of Miocene water (Conly et al., 2006). Nonetheless, our sedimentologic and stratigraphic descriptions suggest a more dynamic terrestrial to nearshore setting with graded fluvial beds, debris flow, and a clastic dike within a clastic unit of the gypsum along the Arroyo Boleo. This is compatible with the description of the San Marco Formation reported by Anderson (1940) composed of clastic sediments with no marine fossils, carbonized wood and leaf fragments as well as gypsum along the southeastern shore of the San Marcos Island asserting there is sufficient lithologic resemblance and proximity to indicate that they are the same formation. Furthermore, a multichannel seismic transect study of the Guaymas Basin by Miller and Lizarralde (2013) revealed an approximately 2-km-thick, 50 × 100 km evaporite body under the shelf on the eastern margin of the Guaymas Basin and suggest that this thick evaporitic unit correlates with the gypsum beds of the SRB on the Baja California peninsula. Additional research on the source of water and depositional evolution based on sedimentological characteristics and geochemistry of the gypsum unit is ongoing. Wilson & Rocha, USGS PP273; Ochoa-Landin et al., RMCG 17(2); Conly et al., Miner Deposita (41); Miller & Lizarralde, Geology, 41(2).

Uranium minerals in Oligocene gypsum near Chadron, Dawes County, Nebraska

USGS Publications Warehouse

Dunham, R.J.

1955-01-01

Carnotite, sabugalite [HAI(UO2)4(PO4)4 • 16H2O] and autunite occur in the basal 25 feet of a 270-foot sequence of nonmarine bedded gypsum and gypsiferous clay in the Brule formation of Oligocene age about 12 miles northeast of Chadron in northeastern Dawes County, Nebraska. Uranium minerals are visible at only two localities and are associated with carbonaceous matter. Elsewhere the basal 25 feet of the gypsum sequence is interbedded with carbonate rocks and is weakly but persistently uraniferous. Uranium probably was emplaced from above by uranyl solutions rich in sulfate.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Detwiler, Russell

Fractures provide flow paths that can potentially lead to fast migration of fluids or contaminants. A number of energy-­related applications involve fluid injections that significantly perturb both the pressures and chemical composition of subsurface fluids. These perturbations can cause both mechanical deformation and chemical alteration of host rocks with potential for significant changes in permeability. In fractured rock subjected to coupled chemical and mechanical stresses, it can be difficult to predict the sign of permeability changes, let alone the magnitude. This project integrated experimental and computational studies to improve mechanistic understanding of these coupled processes and develop and test predictivemore » models and monitoring techniques. The project involved three major components: (1) study of two-­phase flow processes involving mass transfer between phases and dissolution of minerals along fracture surfaces (Detwiler et al., 2009; Detwiler, 2010); (2) study of fracture dissolution in fractures subjected to normal stresses using experimental techniques (Ameli, et al., 2013; Elkhoury et al., 2013; Elkhoury et al., 2014) and newly developed computational models (Ameli, et al., 2014); (3) evaluation of electrical resistivity tomography (ERT) as a method to detect and quantify gas leakage through a fractured caprock (Breen et al., 2012; Lochbuhler et al., 2014). The project provided support for one PhD student (Dr. Pasha Ameli; 2009-­2013) and partially supported a post-­doctoral scholar (Dr. Jean Elkhoury; 2010-­2013). In addition, the project provided supplemental funding to support collaboration with Dr. Charles Carrigan at Lawrence Livermore National Laboratory in connection with (3) and supported one MS student (Stephen Breen; 2011-­2013). Major results from each component of the project include the following: (1) Mineral dissolution in fractures occupied by two fluid phases (e.g., oil-­water or water-­CO{sub 2}) causes changes in local capillary forces and redistribution of fluids. These coupled processes enhance channel formation and the potential for development of fast flow paths through fractures. (2) Dissolution in fractures subjected to normal stress can result in behaviors ranging from development of dissolution channels and rapid permeability increases to fracture healing and significant permeability decreases. The timescales associated with advective transport of dissolved ions in the fracture, mineral dissolution rates, and diffusion within the adjacent porous matrix dictate the sign and magnitude of the resulting permeability changes. Furthermore, a high--resolution mechanistic model that couples elastic deformation of contacts and aperture-­dependent dissolution rates predicts the range of observed behaviors reasonably well. (3) ERT has potential as a tool for monitoring gas leakage in deep formations. Using probabilistic inversion methods further enhances the results by providing uncertainty estimates of inverted parameters.« less

COMPARING MOISTURE METER READINGS WITH MEASURED EQUILIBRIUM MOISTURE CONTENT OF GYPSUM BOARD

EPA Science Inventory

Moisture meters routinely used in the field to determine the moisture content in gypsum wallboard are primarily designed and manufactured to measure the moisture content of wood. Often they are used to decide whether to replace wallboard by determining if moisture is qualitativel...

Hyperspectral mapping of alteration assemblages within a hydrothermal vug at the Haughton impact structure, Canada

NASA Astrophysics Data System (ADS)

Greenberger, Rebecca N.; Mustard, John F.; Osinski, Gordon R.; Tornabene, Livio L.; Pontefract, Alexandra J.; Marion, Cassandra L.; Flemming, Roberta L.; Wilson, Janette H.; Cloutis, Edward A.

2016-12-01

Meteorite impacts on Earth and Mars can generate hydrothermal systems that alter the primary mineralogies of rocks and provide suitable environments for microbial colonization. We investigate a calcite-marcasite-bearing vug at the 23 km diameter Haughton impact structure, Devon Island, Nunavut, Canada, using imaging spectroscopy of the outcrop in the field (0.65-1.1 μm) and samples in the laboratory (0.4-2.5 μm), point spectroscopy (0.35-2.5 μm), major element chemistry, and X-ray diffraction analyses. The mineral assemblages mapped at the outcrop include marcasite; marcasite with minor gypsum and jarosite; fibroferrite and copiapite with minor gypsum and melanterite; gypsum, Fe3+ oxides, and jarosite; and calcite, gypsum, clay, microcline, and quartz. Hyperspectral mapping of alteration phases shows spatial patterns that illuminate changes in alteration conditions and formation of specific mineral phases. Marcasite formed from the postimpact hydrothermal system under reducing conditions, while subsequent weathering oxidized the marcasite at low temperatures and water/rock ratios. The acidic fluids resulting from the oxidation collected on flat-lying portions of the outcrop, precipitating fibroferrite + copiapite. That assemblage then likely dissolved, and the changing chemistry and pH resulting from interaction with the calcite-rich host rock formed gypsum-bearing red coatings. These results have implications for understanding water-rock interactions and habitabilities at this site and on Mars.

Towards establishing a combined rate law of nucleation and crystal growth - The case study of gypsum precipitation

NASA Astrophysics Data System (ADS)

Rendel, Pedro M.; Gavrieli, Ittai; Wolff-Boenisch, Domenik; Ganor, Jiwchar

2018-03-01

The main obstacle in the formulation of a quantitative rate-model for mineral precipitation is the absence of a rigorous method for coupling nucleation and growth processes. In order to link both processes, we conducted a series of batch experiments in which gypsum nucleation was followed by crystal growth. Experiments were carried out using various stirring methods in several batch vessels made of different materials. In the experiments, the initial degree of supersaturation of the solution with respect to gypsum (Ωgyp) was set between 1.58 and 1.82. Under these conditions, heterogeneous nucleation is the dominant nucleation mode. Based on changes in SO42- concentration with time, the induction time of gypsum nucleation and the following rate of crystal growth were calculated for each experiment. The induction time (6-104 h) was found to be a function of the vessel material, while the rates of crystal growth, which varied over three orders of magnitude, were strongly affected by the stirring speed and its mode (i.e. rocking, shaking, magnetic stirrer, and magnetic impeller). The SO42- concentration data were then used to formulate a forward model that couples the simple rate laws for nucleation and crystal growth of gypsum into a single kinetic model. Accordingly, the obtained rate law is based on classical nucleation theory and heterogeneous crystal growth.

Assessment of contamination by percolation of septic tank effluent through natural and amended soils.

PubMed

Cheung, K C; Venkitachalam, T H

2004-01-01

Fly ash has been found to be a potential material for the treatment of municipal and industrial wastewater, and may be useful in the treatment of septic tank effluent. Laboratory columns (30 cm) were used to determine the sorption capacity and hydraulic properties of lagoon fly ash, loamy sand, sand, and sand amended by lagoon fly ash (30 and 60%) and red mud gypsum (20%). The removal of chemical oxygen demand (COD) was high in all column effluents (71-93%). Extent of nitrification was high in Spearwood sand, Merribrook loamy sand and 20% red mud gypsum amended Spearwood sand. However, actual removal of nitrogen (N) was high in columns containing lagoon fly ash. Unamended Spearwood sand possessed only minimal capacity for P sorption. Merribrook loamy sand and red mud gypsum amended sand affected complete P removal throughout the study period of 12 weeks. Significant P leakage occurred from lagoon fly ash amended sand columns following 6-10 weeks of operation. Neither lagoon fly ash nor red mud gypsum caused any studied heavy metal contamination including manganese (Mn), lead (Pb), zinc (Zn), cadmium (Cd) and chromium (Cr) of effluent. It can be concluded that Merribrook loamy sand is better natural soil than Spearwood sand as a filter medium. The addition of lagoon fly ash enhanced the removal of P in Spearwood sand but the efficiency was lower than with red mud gypsum amendment.

AquaDiva: Understanding the Link between the Surface and Subsurface Biogeosphere

NASA Astrophysics Data System (ADS)

Trumbore, S.; Küsel, K.; Totsche, K. U.; Schwab, V.; Herrmann, M.; Nowak, M. E.; Gleixner, G.

2017-12-01

In the collaborative research project AquaDiva, we combine hydrogeochemical, metagemonic and biogeochemical tools to understand how the complex interactions between geologic setting and surface land use influence the function and biodiversity of the subsurface, especially ground water ecosystems. At the Hainich Critical Zone Exploratory in central Germany, we investigate soil and seepage waters in recharge areas and aquifers in a fractured limestone setting characterized by a dynamic water infiltration regime. Within the Exploratory, we have so far identified three distinct biogeochemical zones in which land use and lithologic differences combine to give rise to surprisingly different biotic communities and hydrogeochemical properties with different degrees of connection to the surface. Here we will focus on how we have combined carbon isotopic, organic biomarkers such as phospholipid fatty acids, and `omics' approaches to determine (i) how deep soil-borne microorganisms can be traced into the subsurface, and (ii) which energy sources sustain microbial life in oligotrophic limestone aquifers. With increasing travel distance to the surface, there is a decline in the abundance of microbes, with less than 5% of the taxa identified overlapping with those identified in the soils. Dissolved organic matter also is altered as it passes through soils, demonstrating an overall increase in molecular weight and a change in molecular makeup as well as radiocarbon content. Using the radiocarbon signature (corrected for the influence of carbonate dissolution), as a way to identify if organic C is being supplied recently by plants, atmosphere sources of energy for communities within the aquifer differ for the identified biogeochemical zones and include (i) dominance of inputs of fresh organic carbon from the surface feeding heterotrophy in oxygenic environments; (ii) CO2 fixation linked to nitrogen and sulfur cycling in anoxic environments and (iii) rock-derived organic matter that enters the food web and supplies up to a quarter of the carbon recycled by heterotrophic groundwater microbial communities. The degree of importance of these metabolisms, and therefore their connection to the surface is different in the three zones, with the importance of internal cycling and rock-derived organic matter as a C source surprisingly higher in anoxic aquifers. The second major goal of AquaDiva is to determine the impact of individual precipitation events on the groundwater. Initial results show dramatic effects of singular precipitation events, particularly of events during snowmelt season when the major recharge takes place. Observed large fluctuations in the water table have been linked to changes in the vertical distribution of oxygen and events of carbonate dissolution/precipitation can be identified based on variations of CO2 and O2. Ongoing research in AquaDiva seeks to better quantify the rates of groundwater movement and mixing as a way of further understanding how the emergent subsurface properties can be better linked to processes of transport and transformation within the Critical Zone.

Modeling Subsurface Behavior at the System Level: Considerations and a Path Forward

NASA Astrophysics Data System (ADS)

Geesey, G.

2005-12-01

The subsurface is an obscure but essential resource to life on Earth. It is an important region for carbon production and sequestration, a source and reservoir for energy, minerals and metals and potable water. There is a growing need to better understand subsurface possesses that control the exploitation and security of these resources. Our best models often fail to predict these processes at the field scale because of limited understanding of 1) the processes and the controlling parameters, 2) how processes are coupled at the field scale 3) geological heterogeneities that control hydrological, geochemical and microbiological processes at the field scale and 4) lack of data sets to calibrate and validate numerical models. There is a need for experimental data obtained at scales larger than those obtained at the laboratory bench that take into account the influence of hydrodynamics, geochemical reactions including complexation and chelation/adsorption/precipitation/ion exchange/oxidation-reduction/colloid formation and dissolution, and reactions of microbial origin. Furthermore, the coupling of each of these processes and reactions needs to be evaluated experimentally at a scale that produces data that can be used to calibrate numerical models so that they accurately describe field scale system behavior. Establishing the relevant experimental scale for collection of data from coupled processes remains a challenge and will likely be process-dependent and involve iterations of experimentation and data collection at different intermediate scales until the models calibrated with the appropriate date sets achieve an acceptable level of performance. Assuming that the geophysicists will soon develop technologies to define geological heterogeneities over a wide range of scales in the subsurface, geochemists need to continue to develop techniques to remotely measure abiotic reactions, while geomicrobiologists need to continue their development of complementary technologies to remotely measure microbial community parameters that define their key functions at a scale that accurately reflects their role in large scale subsurface system behavior. The practical questions that geomicrobiologist must answer in the short term are: 1) What is known about the activities of the dominant microbial populations or those of their closest relatives? 2) Which of these activities is likely to dominate under in situ conditions? In the process of answering these questions, researchers will obtain answers to questions of a more fundamental nature such as 1) How deep does "active" life extend below the surface of the seafloor and terrestrial subsurface? 2) How are electrons exchanged between microbial cells and solid phase minerals? 3) What is the metabolic state and mechanism of survival of "inactive" life forms in the subsurface? 4) What can genomes of life forms trapped in geological material tell us about evolution of life that current methods cannot? The subsurface environment represents a challenging environment to understand and model. As the need to understand subsurface processes increases and the technologies to characterize them become available, modeling subsurface behavior will approach the level of sophistication of models used today to predict behavior of other large scale systems such as the oceans.

Assessment of Mercury in Soils, Crops, Earthworms, and Water when Soil is Treated with Gypsum

USDA-ARS?s Scientific Manuscript database

Flue gas desulfurization (FGD) gypsum from fossil fuel combustion has many potential uses in agriculture, but there is concern about the potential environmental effects of its elevated mercury (Hg) concentration. The wet limestone scrubbing process that removes sulfur from flue gas (and produces gyp...

Composting and gypsum amendment of broiler litter to reduce nutrient leaching loss

USDA-ARS?s Scientific Manuscript database

Relative to fresh broiler litter, little is known about the dynamics of composted litter derived-nutrient in the ecosystem. In this study, the potential leaching losses of nutrients from compost relative to fresh broiler litter along with flue gas desulfurization (FGD gypsum), as a nutrient immobil...

Impact of Leaching Conditions on Constituents Release from Flue Gas Desulfurization Gypsum (FGDG) and FGDG-Soil Mixture

EPA Science Inventory

The interest in using Flue Gas Desulfurization Gypsum(FGDG) has increased recently. This study evaluates the leaching characteristics of trace elements in "modern" FGDG (produced after fly ash removal) and FGDG-mixed soil (SF) under different environmental conditions using rece...

Results using flue gas desulfurization gypsum in soilless substrates for greenhouse crops

USDA-ARS?s Scientific Manuscript database

Recent availability of Flue Gas Desulfurization gypsum (FGDG) has led to interested in its possible use in horticulture greenhouse production. Three studies were conducted to determine the effects of increasing rates of FGDG on six greenhouse crops. In the first study, substrates (6:1 pine bark:san...

Determination of partition and diffusion coefficient of formaldehyde in selected building materials and impact of relative humidity

EPA Science Inventory

The partition and effective diffusion coefficients of formaldehyde were measured for three materials (conventional gypsum wallboard, "green" gypsum wallboard, and "green" carpet) under three relative humidity (RH) conditions (20%, 50% and 70% RH). A dynamic dual-chamber test meth...

Determination of partition and diffusion coefficients of formaldehyde in selected building materials and impact of relative humidity (journal)

EPA Science Inventory

The partition and effective diffusion coefficients of formaldehyde were measured for three materials (conventional gypsum wallboard, "green" gypsum wallboard, and "green" carpet) under three relative humidity (RH) conditions (20%, 50% and 70% RH). A dynamic dual-chamber test meth...

Composite Gypsum Binders with Silica-containing Additives

NASA Astrophysics Data System (ADS)

Chernysheva, N. V.; Lesovik, V. S.; Drebezgova, M. Yu; Shatalova, S. V.; Alaskhanov, A. H.

2018-03-01

New types of fine mineral additives are proposed for designing water-resistant Composite Gypsum Binders (CGB); these additives significantly differ from traditional quartz feed: wastes from wet magnetic separation of Banded Iron Formation (BIF WMS waste), nanodispersed silica powder (NSP), chalk. Possibility of their combined use has been studied as well.

Microbial Volatile Organic Compound Emissions from Stachybotrys chartarum growing on Gypsum Wallboard and Ceiling tile

EPA Science Inventory

This study compared seven toxigenic strains of S. chartarum found in water-damaged buildings to characterize the microbial volatile organic compound (MVOC) emissions profile while growing on gypsum wallboard (W) and ceiling tile (C) coupons. The inoculated coupons with their sub...

Hydrologic transport of fecal bacteria attenuated by flu gas desulfurized (FGD) gypsum

USDA-ARS?s Scientific Manuscript database

Background Flue gas desulfurized (FGD) gypsum is a byproduct of coal-fired power plants. As a soil amendment for crop production it has the potential of improving soil water infiltration, soil conservation, and decreasing nutrient losses from broiler litter applications. Because broiler litter is a ...

Hydrologic transport of fecal bacteria attenuated by flue gas desulfurization gypsum

USDA-ARS?s Scientific Manuscript database

Flue gas desulfurization (FGD) gypsum is a byproduct of coal-fired power plants. As a soil amendment for crop and pasture production it may increase water infiltration, reduce soil erosion, and decrease nutrient losses from applications of animal manures. Broiler litter is used as a source of plan...

Use of Flue Gas Desulfurization (FGD) Gypsum as a Heavy Metal Stabilizer in Contaminated Soils

EPA Science Inventory

Flue Gas Desulfurization (FGD) gypsum is a synthetic by-product generated from the flue gas desulfurization process in coal power plants. It has several beneficial applications such as an ingredient in cement production, wallboard production and in agricultural practice as a soil...

Flue gas desulfurization gypsum: Its effectiveness as an alternative bedding material for broiler production

USDA-ARS?s Scientific Manuscript database

Flue gas desulfurization gypsum (FGDG) may be a viable low-cost alternative bedding material for broiler production. In order to evaluate FGD gypsum’s viability, three consecutive trials were conducted to determine its influence on live performance (body weight, feed consumption, feed efficiency, an...

Decreasing phosphorus loss in tile-drained landscapes using flue gas desulfurization gypsum

USDA-ARS?s Scientific Manuscript database

Elevated phosphorus (P) loading from agricultural non-point source pollution continues to impair inland waterbodies throughout the world. The application of flue gas desulfurization (FGD) gypsum to agricultural fields has been suggested to decrease P loading because of its high calcium content and P...

Gypsum at Olympia Undae

NASA Technical Reports Server (NTRS)

2006-01-01

This Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) 'targeted image' shows a region of sand dunes surrounding the Martian north polar cap. CRISM, an instrument on NASA's Mars Reconnaissance Orbiter, acquired the image at 1811 UTC (2:11 p.m. EDT) on Oct. 1, 2006. The imaged site is near 80.0 degrees north latitude, 240.7 degrees east longitude. It covers an area about 12 kilometers (7.5 miles) square. At the center of the image, the spatial resolution is as good as 20 meters (65 feet) per pixel. The image was taken in 544 colors covering 0.36 to 3.92 micrometers.

CRISM's sister instrument on the Mars Express spacecraft, OMEGA, has spectrally mapped Mars at lower spatial resolution and discovered that several regions of the planet are rich in sulfate minerals formed by liquid water. Surprisingly, one of the sulfate-rich deposits is a part of the giant field of sand dunes surrounding the north polar cap. CRISM is remapping the dune field at about five times higher resolution than OMEGA, and imaging selected regions at 50 times higher resolution. This image is the first of the high-resolution images of the dune field.

This visualization includes two renderings of the data, both map-projected. The left images are false-color representations showing brightness of the surface at selected infrared wavelengths. The right images show strength of an absorption band at 1900 nanometers wavelength, which indicates the relative abundance of the sulfate mineral gypsum. Brighter areas have more gypsum, and darker areas have less gypsum. The bottom views are enlargements of the central part of the two versions of the image shown at top.

Gypsum is a light-colored, whitish mineral, so it was anticipated that gypsum-rich parts of the sand dunes would be light in color. In fact, there are light-colored areas in the left images, but the images of the gypsum absorption at right show that the light areas have only low gypsum abundance. The dark sand dunes contain most of the gypsum, which is particularly concentrated at the dune crests. CRISM's scientists are taking more high-resolution images of the dune fields to see if this pattern is prevalent, and to attempt to track down the source of the gypsum that makes an arid dune field so rich in minerals formed long ago in liquid water.

The Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) is one of six science instruments on NASA's Mars Reconnaissance Orbiter. Led by The Johns Hopkins University Applied Physics Laboratory, the CRISM team includes expertise from universities, government agencies and small businesses in the United States and abroad.

CRISM's mission: Find the spectral fingerprints of aqueous and hydrothermal deposits and map the geology, composition and stratigraphy of surface features. The instrument will also watch the seasonal variations in Martian dust and ice aerosols, and water content in surface materials -- leading to new understanding of the climate.

NASA's Jet Propulsion Laboratory, a division of the Califonia Institute of Technology, Pasadena, manages the Mars Reconnaissance Orbiter for the NASA Science Mission Directorate, Washington. Lockheed Martin Space Systems, Denver, is the prime contractor and built the spacecraft.

BLT-EC (Breach, Leach and Transport-Equilibrium Chemistry) data input guide. A computer model for simulating release and coupled geochemical transport of contaminants from a subsurface disposal facility

DOE Office of Scientific and Technical Information (OSTI.GOV)

MacKinnon, R.J.; Sullivan, T.M.; Kinsey, R.R.

1997-05-01

The BLT-EC computer code has been developed, implemented, and tested. BLT-EC is a two-dimensional finite element computer code capable of simulating the time-dependent release and reactive transport of aqueous phase species in a subsurface soil system. BLT-EC contains models to simulate the processes (container degradation, waste-form performance, transport, chemical reactions, and radioactive production and decay) most relevant to estimating the release and transport of contaminants from a subsurface disposal system. Water flow is provided through tabular input or auxiliary files. Container degradation considers localized failure due to pitting corrosion and general failure due to uniform surface degradation processes. Waste-form performancemore » considers release to be limited by one of four mechanisms: rinse with partitioning, diffusion, uniform surface degradation, and solubility. Transport considers the processes of advection, dispersion, diffusion, chemical reaction, radioactive production and decay, and sources (waste form releases). Chemical reactions accounted for include complexation, sorption, dissolution-precipitation, oxidation-reduction, and ion exchange. Radioactive production and decay in the waste form is simulated. To improve the usefulness of BLT-EC, a pre-processor, ECIN, which assists in the creation of chemistry input files, and a post-processor, BLTPLOT, which provides a visual display of the data have been developed. BLT-EC also includes an extensive database of thermodynamic data that is also accessible to ECIN. This document reviews the models implemented in BLT-EC and serves as a guide to creating input files and applying BLT-EC.« less

Mapping Site Remediation with Electrical Resistivity Tomography Explored via Coupled-Model Simulations

NASA Astrophysics Data System (ADS)

Power, C.; Gerhard, J. I.; Tsourlos, P.; Giannopoulos, A.

2011-12-01

Remediation programs for sites contaminated with dense non-aqueous phase liquids (DNAPLs) would benefit from an ability to non-intrusively map the evolving volume and extent of the DNAPL source zone. Electrical resistivity tomography (ERT) is a well-established geophysical tool, widely used outside the remediation industry, that has significant potential for mapping DNAPL source zones. However, that potential has not been realized due to challenges in data interpretation from contaminated sites - in either a qualitative or quantitative way. The objective of this study is to evaluate the potential of ERT to map realistic, evolving DNAPL source zones within complex subsurface environments during remedial efforts. For this purpose, a novel coupled model was developed that integrates a multiphase flow model (DNAPL3D-MT), which generates realistic DNAPL release scenarios, with 3DINV, an ERT model which calculates the corresponding resistivity response. This presentation will describe the developed model coupling methodology, which integrates published petrophysical relationships to generate an electrical resistivity field that accounts for both the spatial heterogeneity of subsurface soils and the evolving spatial distribution of fluids (including permeability, porosity, clay content and air/water/DNAPL saturation). It will also present an example in which the coupled model was employed to explore the ability of ERT to track the remediation of a DNAPL source zone. A field-scale, three-dimensional release of chlorinated solvent DNAPL into heterogeneous clayey sand was simulated, including the subsurface migration and subsequent removal of the DNAPL source zone via dissolution in groundwater. Periodic surveys of this site via ERT applied at the surface were then simulated and inversion programs were used to calculate the subsurface distribution of electrical properties. This presentation will summarize this approach and its potential as a research tool exploring the range of site conditions under which ERT may prove useful in aiding DNAPL site remediation. Moreover, it is expected to provide a cost-effective avenue to test optimum ERT data acquisition, inversion and interpretative tools at contaminated sites.

Conceptual Model of Iodine Behavior in the Subsurface at the Hanford Site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Truex, Michael J.; Lee, Brady D.; Johnson, Christian D.

Isotopes of iodine were generated during plutonium production within the nine production reactors at the U.S. Department of Energy Hanford Site. The short half-life 131I that was released from the fuel into the atmosphere during the dissolution process (when the fuel was dissolved) in the Hanford Site 200 Area is no longer present at concentrations of concern in the environment. The long half-life 129I generated at the Hanford Site during reactor operations was (1) stored in single-shell and double-shell tanks, (2) discharged to liquid disposal sites (e.g., cribs and trenches), (3) released to the atmosphere during fuel reprocessing operations, ormore » (4) captured by off-gas absorbent devices (silver reactors) at chemical separations plants (PUREX, B-Plant, T-Plant, and REDOX). Releases of 129I to the subsurface have resulted in several large, though dilute, plumes in the groundwater. There is also 129I remaining in the vadose zone beneath disposal or leak locations. The fate and transport of 129I in the environment and potential remediation technologies are currently being studied as part of environmental remediation activities at the Hanford Site. A conceptual model describing the nature and extent of subsurface contamination, factors that control plume behavior, and factors relevant to potential remediation processes is needed to support environmental remedy decisions. Because 129I is an uncommon contaminant, relevant remediation experience and scientific literature are limited. In addition, its behavior in subsurface is different from that of other more common and important contaminants (e.g., U, Cr and Tc) in terms of sorption (adsorption and precipitation), and aqueous phase species transformation via redox reactions. Thus, the conceptual model also needs to both describe known contaminant and biogeochemical process information and identify aspects about which additional information is needed to effectively support remedy decisions.« less

Impact experiments onto heterogeneous targets and their interpretation in relation with formation of the asteroid families

NASA Astrophysics Data System (ADS)

Leliwa-Kopystynski, J.; Arakawa, M.

2014-07-01

Results of laboratory impact experiments, when extrapolated to the planetary scale of events, are aimed for better understanding of cratering and/or disruption of asteroids, satellites, and cometary nuclei. There is absolutely no reason to assume that these bodies are uniform rocky or icy monoliths. So, we studied reactions of the heterogeneous targets on the impacts. A series of impact experiments onto solid decimeter-sized cylinders made of porous gypsum mixed with approximately one-centimeter-sized pebbles have been performed. The mean density of the material of the targets was 1867 kg m^{-3}, the mean mass ratio (pebbles / gypsum) = 0.856 / 0.144, and the mean volume ratio (pebbles / gypsum / pores) = 0.585 / 0.116 / 0.299. The target densities and their heterogeneous structures could be representative of those of the asteroids Ida, Eros, and many others, because asteroid sub-surface volumes could be composed of consolidated boulders formed by self-compaction and/or by impact compaction. Impact velocities in the experiments ranged from 2.0 km/s to 6.7 km/s (collision velocity in the asteroid main belt is approximately 5 km/s). By means of weighting and counting the post-impact fragments, their distribution function was found. Let Q [J/kg] be the specific energy of impact per unit of the target mass. Of particular interest is the value of impact strength, that is, the specific energy of disruption Q^*, corresponding to the ratio (mass of the largest fragment) / (mass of the target) = m_l/M = 0.5, which is, by convention, the value separating the cratering events from the catastrophic disruption impacts. Mass or size distribution of the post-impact fragments is expressed by the power law N ∝ m^{-p} ∝ r^{-3p}, p=p(Q/Q^{*}) A parameter that can be measured in the laboratory is the exponent p. For the case of a swarm of asteroids forming an asteroid family, the observationally estimated value is not the exponent p but rather the exponent q = 3p, since the sizes r of the family members are better known than their masses m (because then the asteroids' densities should be known). We have found that, for the gypsum/pebbles targets, there is Q^* ≈ 270 J/kg and the exponent q varies linearly with rather high slope: q = (0.705 ± 0.093)(Q/Q^{*}) + (2.7 ± 1.2) for 1 < Q/Q^* < 40, approximately. For comparison, this result differs considerably from that for porous water ice targets with porosity equal to 0.37 and specific energy of disruption Q^* ≈ 39 J/kg (based on the data presented in Fig. 9 of Arakawa et al., 2002). In that case, q has only a slight slope: q = (0.092 ± 0.020)(Q/Q^*) + (1.30 ± 0.22) for 1 < Q/Q^* < 20, approximately. The presence of pebbles strongly influences the impact strength of the target as well as the size distribution of the post-impact fragments. Formulae (2) and (3) indicate that the increase of specific impact energy delivered to the target leads to more efficient comminuting. Comparison with the experimental size distribution within families of asteroids is in progress.

Comparison of lead attenuation and lead hardening equivalence of materials used in respect of diagnostic X-ray shielding.

PubMed

Okunade, Akintunde Akangbe

2002-12-01

Present interest is in the shielding of diagnostic X-ray units. Numerical comparison has been made of the attenuation and hardening properties of lead and some particular alternative materials: steel, plate glass and gypsum wallboard. Results show, for particular choices of thickness, that lead and steel can be made to provide closely similar attenuation and spectral hardening, values of lead attenuation equivalent (LAE) and lead hardening equivalent (LHE) thicknesses being nearly the same. Significant differences in the attenuation and hardening properties of lead are found in comparison with plate glass and gypsum wallboard. LAE produces better matching of exposure for lead-plate glass and lead-gypsum wallboard than LHE.

Fractography of cast gypsum.

PubMed

Mori, T; Yamane, M

1982-02-01

A fractographical study of dental cast gypsum was made in order to correlate the mechanical properties with the microstructure. Wet specimens fractured under tensile stress showed intercrystalline fracture and the tensile strength depended on the porosity present. Thus, it was assumed that tensile strength was dependent on the contact area between individual gypsum crystals and changes in porosity approximated to changes in contact area. Strength differences among specimens of a given W/P ratio, therefore, can be related to differences in intercrystalline contact areas. These theoretical considerations suggest that the classification of dental die stone and dental stone into high and low strength types based on strength properties only would be more practical and less confusing than at present.

Animal waste and FGD gypsum effects on bermudagrass and soil leachate nutrient contents

USDA-ARS?s Scientific Manuscript database

In previous experiments on newly relcaimed coal mine soils in northeastern Mississippi, applying poultry litter at 22.4 Mg ha-1 yr-1 enhanced bermudagrass (Cynodon dactylon L.) biomass and selected soil quality parameters. Additionally, co-application of 11.2 Mg ha-1 FGD gypsum and litter reduced so...

FGD gypsum filters remove soluble phosphorus from agricultural drainage waters

USDA-ARS?s Scientific Manuscript database

Decades of chicken litter applications has led to phosphorus (P) levels up to ten times the agronomic optimum in soils of the Delmarva Peninsula. This legacy P is a major source of P entering drainage ditches that eventually empty into the Chesapeake Bay. A Flue Gas Desulfurization (FGD) gypsum ditc...

Gypsum as a best management practice for reducing P loss from agricultural fields

USDA-ARS?s Scientific Manuscript database

Phosphorus loss from agricultural fields fertilized with poultry litter (PL) may contribute to eutrophication of nearby rivers, lakes, and streams. It has been suggested that gypsum can be used as a soil amendment to reduce P loss from these fields. Also, a new USDA-NRCS National Conservation Practi...

Framework of risk assessment in relation to FGD-gypsum use as agricultural amendment

USDA-ARS?s Scientific Manuscript database

Due to the concerns by EPA of air pollution from coal fired power plants, the industry are building and retrofitting existing facilities to remove more impurities from the environment. Industry has introduced removal of fly ash contaminates before SO2 removal, allowing generation of FGD-gypsum with...

Transport of Water, Dissolved Substances, Heat and Electric Current through Shales and Clay-Rich Sediments.

DTIC Science & Technology

1984-03-20

E. Anderson reviewed what was known about the dehydrations of gypsum, smectite, halloysite , vermiculite, and the zeolite minerals. Simple...dehydrations such as those of gypsum and halloysite occur at sharply-defined temperatures and thus contribute a time-limited fluid pulse at a given point. The

Salt composition of groundwater and reclaimed solonetzes in the Baraba Lowland

NASA Astrophysics Data System (ADS)

Semendyaeva, N. V.; Elizarov, N. V.

2017-10-01

Solonetzes of experimental trials established in 1981 and 1986 in the Baraba Lowland were examined. It was found that gypsum-based ameliorants improve the soil and lead to a decrease in the content of soluble salts in the soil profile. Exchange processes between cations of the soil adsorption complex and calcium of gypsum were particularly intensive in the first years after gypsum application. This resulted in a sharp rise in the content of soluble salts that migrated down the soil profile to the groundwater. In the following years, the reclaimed solonetzes were desalinized under the conditions of relatively stable groundwater level. On the 30th year after single gypsum application, the groundwater level sharply rose (to 50 cm), and the soil was subjected to the secondary salinization; the contents of bicarbonates, carbonates, and sodium in the soils increased. Spring leaching caused some desalinization, but the content of soluble salts in the upper soil meter increased again in the fall. A close correlation between the salt compositions of the groundwater and the reclaimed solonetzes was revealed.

Testing antimicrobial paint efficacy on gypsum wallboard contaminated with Stachybotrys chartarum.

PubMed

Menetrez, M Y; Foarde, K K; Webber, T D; Dean, T R; Betancourt, D A

2008-02-01

The goal of this research was to reduce occupant exposure to indoor mold through the efficacy testing of antimicrobial paints. An accepted method for handling Stachybotrys chartarum-contaminated gypsum wallboard (GWB) is removal and replacement. This practice is also recommended for water-damaged or mold-contaminated GWB but is not always followed completely. The efficacy of antimicrobial paints to eliminate or control mold regrowth on surfaces can be tested easily on nonporous surfaces. The testing of antimicrobial efficacy on porous surfaces found in the indoor environment, such as gypsum wallboard, can be more complicated and prone to incorrect conclusions regarding residual organisms. The mold S. chartarum has been studied for toxin production and its occurrence in water-damaged buildings. Research to control its growth using seven different antimicrobial paints and two commonly used paints on contaminated, common gypsum wallboard was performed in laboratory testing at high relative humidity. The results indicate differences in antimicrobial efficacy for the period of testing, and that proper cleaning and resurfacing of GWB with an antimicrobial paint can be an option in those unique circumstances when removal may not be possible.

Fabrication of hydroxyapatite block from gypsum block based on (NH4)2HPO4 treatment.

PubMed

Suzuki, Yumiko; Matsuya, Shigeki; Udoh, Koh-ichi; Nakagawa, Masaharu; Tsukiyama, Yoshihiro; Koyano, Kiyoshi; Ishikawa, Kunio

2005-12-01

The aim of this study was to evaluate the feasibility of fabricating low-crystalline, porous apatite block using set gypsum as a precursor based on the fact that apatite is thermodynamically more stable than gypsum. When the set gypsum was immersed in 1 mol/L diammonium hydrogen phosphate aqueous solution at 100 degrees C, it transformed to low-crystalline porous apatite retaining its original shape. The transformation reaction caused a release of sulfate ions due to an ion exchange with phosphate ions, thus leading to a decrease in the pH of the solution. Then, due to decreased pH, dicalcium phosphate anhydrous--which has similar thermodynamic stability at lower pH--was also produced as a by-product. Apatite formed in the present method was low-crystalline, porous B-type carbonate apatite that contained approximately 0.5 wt% CO3, even though no carbonate sources--except carbon dioxide from air--were added to the reaction system. We concluded therefore that this is a useful bone filler fabrication method since B-type carbonate apatite is the biological apatite contained in bone.

Pore-scale simulation of calcium carbonate precipitation and dissolution under highly supersaturated conditions in a microfludic pore network

NASA Astrophysics Data System (ADS)

Yoon, H.; Dewers, T. A.; Valocchi, A. J.; Werth, C. J.

2011-12-01

Dissolved CO2 during geological CO2 storage may react with minerals in fractured rocks or confined aquifers and cause mineral precipitation. The overall rate of reaction can be affected by coupled processes among hydrodynamics, transport, and reactions at pore-scale. Pore-scale models of coupled fluid flow, reactive transport, and CaCO3 precipitation and dissolution are applied to account for transient experimental results of CaCO3 precipitation and dissolution under highly supersaturated conditions in a microfluidic pore network (i.e., micromodel). Pore-scale experiments in the micromodel are used as a basis for understanding coupled physics of systems perturbed by geological CO2 injection. In the micromodel, precipitation is induced by transverse mixing along the centerline in pore bodies. Overall, the pore-scale model qualitatively captured the governing physics of reactions such as precipitate morphology, precipitation rate, and maximum precipitation area in first few pore spaces. In particular, we found that proper estimation of the effective diffusion coefficient and the reactive surface area is necessary to adequately simulate precipitation and dissolution rates. As the model domain increases, the effect of flow patterns affected by precipitation on the overall reaction rate also increases. The model is also applied to account for the effect of different reaction rate laws on mineral precipitation and dissolution at pore-scale. Reaction rate laws tested include the linear rate law, nonlinear power law, and newly-developed rate law based on in-situ measurements at nano scale in the literature. Progress on novel methods for upscaling pore-scale models for reactive transport are discussed, and are being applied to mineral precipitation patterns observed in natural analogues. H.Y. and T. D. were supported as part of the Center for Frontiers of Subsurface Energy Security, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001114. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Gypsum (CaSO4·2H2O) Scaling on Polybenzimidazole and Cellulose Acetate Hollow Fiber Membranes under Forward Osmosis

PubMed Central

Chen, Si Cong; Su, Jincai; Fu, Feng-Jiang; Mi, Baoxia; Chung, Tai-Shung

2013-01-01

We have examined the gypsum (CaSO4·2H2O) scaling phenomena on membranes with different physicochemical properties in forward osmosis (FO) processes. Three hollow fiber membranes made of (1) cellulose acetate (CA), (2) polybenzimidazole (PBI)/polyethersulfone (PES) and (3) PBI-polyhedral oligomeric silsesquioxane (POSS)/polyacrylonitrile (PAN) were studied. For the first time in FO processes, we have found that surface ionic interactions dominate gypsum scaling on the membrane surface. A 70% flux reduction was observed on negatively charged CA and PBI membrane surfaces, due to strong attractive forces. The PBI membrane surface also showed a slightly positive charge at a low pH value of 3 and exhibited a 30% flux reduction. The atomic force microscopy (AFM) force measurements confirmed a strong repulsive force between gypsum and PBI at a pH value of 3. The newly developed PBI-POSS/PAN membrane had ridge morphology and a contact angle of 51.42° ± 14.85° after the addition of hydrophilic POSS nanoparticles and 3 min thermal treatment at 95 °C. Minimal scaling and an only 1.3% flux reduction were observed at a pH value of 3. Such a ridge structure may reduce scaling by not providing a locally flat surface to the crystallite at a pH value of 3; thus, gypsum would be easily washed away from the surface. PMID:24957062

Evolution of limited seed dispersal ability on gypsum islands.

PubMed

Schenk, John J

2013-09-01

Dispersal is a major feature of plant evolution that has many advantages but is not always favored. Wide dispersal, for example, leads to greater seed loss in oceanic-island endemics, and evolution has favored morphologies that limit dispersal. I tested the hypothesis that selection favored limited dispersal on gypsum islands in western North America, where edaphic communities are sparsely vegetated except for a specialized flora that competes poorly with the surrounding flora. • I applied a series of comparative phylogenetic approaches to gypsophilic species of Mentzelia section Bartonia (Loasaceae) to investigate the evolution of limited dispersal function in seed wings, which increase primary dispersal by wind. Through these tests, I determined whether narrowed wings were selected for in gypsophilic species. • Gypsophily was derived four to seven times. Seed area was not significantly correlated with gypsophily or wing area. Wing area was significantly smaller in the derived gypsum endemics, supporting the hypothesis in favor of limited dispersal function. A model-fitting approach identified two trait optima in wing area, with gypsum endemics having a lower optimum. • Evolution into novel ecologies influences morphological evolution. Morphological characters have been selected for limited dispersal following evolution onto gypsum islands. Selection for limited dispersal ability has occurred across animals and plants, both in oceanic and terrestrial systems, which suggests that reduced dispersal ability may be a general process: selection favors limited dispersal if the difference in survival between the habitat of the parent and the surrounding area is great enough.

High-yield synthesis of vaterite microparticles in gypsum suspension system via ultrasonic probe vibration/magnetic stirring

NASA Astrophysics Data System (ADS)

Wang, Bo; Pan, Zihe; Cheng, Huaigang; Chen, Zuliang; Cheng, Fangqin

2018-06-01

Vaterite-type calcium carbonate particles have some unique properties such as high hydrophilicity, large surface areas, and hierarchical structures consisting of primary vaterite particles in comparison with calcite or aragonite-type polymorphs. In this paper, gypsum (CaSO4·2H2O) suspension is used to synthesize micro-sized vaterite CaCO3 through magnetic stirring (MS) and ultrasonic probe vibration (UPV) methods. The effects of ammonia concentration, CO2 flow rate, solid-liquid ratio on the gypsum carbonation process, mineral phase composition, morphology and particle size distribution of CaCO3 are investigated. The results show that the carbonation process is significantly influenced by ammonia concentration, CO2 flow rate and ultrasound. Comparing with magnetic stirring, ultrasonic probe vibration take less time to reach the complete carbonate reaction. Gypsum is transformed to vaterite with the conversion rate about ∼95% when the mole ratio of NH4+/Ca2+ is 2.4 otherwise the carbonation reaction was uncompleted with gypsum residues left. Comparing with MS method, the UPV method resulted in smaller size and narrower size distribution of as-prepared microparticles and approximately 80% reduction of the particle size was achieved. It is established that increasing the solid-liquid ratio resulted in larger particle size in MS system and smaller particle size in UPV system. Increasing CO2 flow rate caused the particle size decreased in MS system and increased in UPV system.

Geology of the north end of the Salt Valley Anticline, Grand County, Utah

USGS Publications Warehouse

Gard, Leonard Meade

1976-01-01

This report describes the geology and hydrology of a portion of the Salt Valley anticline lying north of Moab, Utah, that is being studied as a potential site for underground storage of nuclear waste in salt. Selection of this area was based on recommendations made in an earlier appraisal of the potential of Paradox basin salt deposits for such use. Part of sec. 5, T. 23 S., R. 20 E. has been selected as a site for subsurface investigation as a potential repository for radioactive waste. This site has easy access to transportation, is on public land, is isolated from human habitation, is not visible from Arches National Park, and the salt body lies within about 800 feet (244 m) of the surface. Further exploration should include investigation of possible ground water in the caprock and physical exploration of the salt body to identify a thick bed of salt for use as a storage zone that can be isolated from the shaly interbeds that possibly contain quantities of hydrocarbons. Salt Valley anticline, a northwest-trending diapiric structure, consists of Mesozoic sedimentary rocks arched over a thick core of salt of the Paradox Member of the Middle Pennsylvanian Hermosa Formation. Salt began to migrate to form and/or develop this structure shortly after it was deposited, probably in response to faulting. This migration caused upwelling of the salt creating a linear positive area. This positive area, in turn, caused increased deposition of sediments in adjacent areas which further enhanced salt migration. Not until late Jurassic time had flowage of the salt slowed sufficiently to allow sediments of the Morrison and younger formations to be deposited across the salt welt. A thick cap of insoluble residue was formed on top of the salt diapir as a result of salt dissolution through time. The crest of the anticline is breached; it collapsed in two stages during the Tertiary Period. The first stage was graben collapse during the early Tertiary; the second stage occurred after Miocene regional uplift had caused downcutting streams to breach the salt core resulting in further collapse. The axis of the anticline is a narrow generally flat-floored valley containing a few hills composed of downdropped Mesozoic rocks foundered, in the caprock. The caprock, which underlies thin alluvium in the valley, is composed of contorted gypsum, shale, sandstone, and limestone--the insoluble residue of the Paradox salt.

H2S in Shallow Groundwater: Hydrogeochemical Processes, Degassing Experiments and Health Impacts

NASA Astrophysics Data System (ADS)

Broers, H. P.; Weert, J. D.; Bouma, R.

2016-12-01

Hydrogen sulfide is known to be a hazardous gas even at rather low concentrations and may pose a serious health risk. Occurrences of H2S in groundwater and degassing into the atmosphere are known for volcanic or tectonic active regions, coal mining or gypsum dissolution regions. We studied the occurrence and origin of H2S in shallow groundwater and its degassing into air after pumping in a setting of shallow unconsolidated deposits in the south of the Netherlands, where the sulfate source is antropogenic. We measured H2S concentrations in water using a field photo spectrometer and the degassing into air with a Jerome 631. We analyzed for macro-ions and determined the apparent 3H/3He age to assess the origin of the sulfide in the groundwater. H2S was formed in-situ within organic-rich and carbonate free sediments and peat layers of a fluvio-glacial sediment series in groundwater that infiltrated approximately 15 years ago. Sulfate is omnipresent in Dutch shallow groundwater due to historical atmospheric inputs of SOx, sulfur inputs from intensive livestock farming and subsurface production of sulfate from pyrite oxidation following nitrate leaching from agricultural fields (Zhang et al. 2009 GCA, 2012 AppGeochem). The co-existence of H2S and sulfate in our groundwater appears to be determined by the low pH of the water (4.8-5.5) which limits the precipitation of mackinawite or amorphous FeS. Mapping the combination of observations wells with pH < 5.5, sulfate > 75 mg/L and Fe > 10 mg/l delineated large areas where H2S appeared to be present in concentration between 0.1 and 1.0 mg/L S2- in water. Degassing of groundwater with 0.7 mg S2-/L into a contained volume of air yielded concentrations > 50 ppmv within 15 minutes. Using the degassing rates observed in the experiments and assuming equilibrium degassing, we calibrated a simple model which describes the inflow of water, the degassing and the export of gas in relation to wind velocity. We used the model to evaluate scenario's of human exposure for typical private and commercial uses. The private uses are at largest risk for exposure to harmful concentrations of H2S in air, due to closer exposure distances towards the degassing water, especially under conditions of low wind speeds. Indeed, a health incident was reported at a site where groundwater was pumped into a children's water play.

Chemical and Mineralogical Characterization of Arsenic, Lead, Chromium, and Cadmium in a Metal-contaminated Histosol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, X.; Schulze, D

2010-01-01

The chemical and mineralogical forms of As, Pb, Cr, and Cd were studied in a metal-contaminated organic soil (Histosol) that received runoff and seepage water from a site that was once occupied by a lead smelter. Soil samples were collected from different depth intervals during both wet and dry seasons and analyzed using bulk powder X-ray diffraction (XRD), synchrotron-based micro X-ray diffraction ({mu}-XRD), and micro X-ray fluorescence ({mu}-SXRF) spectroscopy. There was a clear pattern of mineral distribution with depth that indicated the presence of an intense redox gradient. The oxidized reddish brown surface layer (0-10 cm) was dominated by goethitemore » ({alpha}-FeOOH) and poorly crystalline akaganeite ({beta}-FeOOH). Lead and arsenic were highly associated with these Fe oxides, possibly by forming inner-sphere surface complexes. Gypsum (CaSO{sub 4} {center_dot} 2H{sub 2}O) was abundant in the layer as well, particularly for samples collected during dry periods. Fe(II)-containing minerals, such as magnetite (Fe{sub 3}O{sub 4}) and siderite (FeCO{sub 3}), were identified in the intermediate layers (10-30 cm) where the reductive dissolution of Fe(III) oxides occurred. A number of high-temperature minerals, such as mullite (3Al{sub 2}O{sub 3} {center_dot} 2Si{sub 2}O), corundum ({alpha}-Al{sub 2}O{sub 3}), hematite ({alpha}-Fe{sub 2}O{sub 3}), and wustite (FeO) were identified in the subsurface and they probably formed as a result of a burning event. Several sulfide minerals were identified in the most reduced layers at depths > 30 cm. They included realgar (AsS), alacranite (As{sub 4}S{sub 4}), galena (PbS), and sphalerite (Zn, Fe{sup 2+})S, and a series of Fe sulfides, including greigite (Fe{sup 2+}Fe{sub 2}{sup 3+} S{sub 4}), pyrrhotite (Fe{sub 1-x}S), mackinawite (FeS), marcasite (FeS{sub 2}), and pyrite (FeS{sub 2}). Most of these minerals occurred as almost pure phases in sub-millimeter aggregates and appeared to be secondary phases that had precipitated from solution. Despite the elevated levels of Cd in the soil, no specific Cd phases were identified. The complex mineralogy has important implications for risk assessment and the design of in-situ remediation strategies for this and similar metal-contaminated sites.« less

A thermodynamic model for the prediction of phase equilibria and speciation in the H 2O-CO 2-NaCl-CaCO 3-CaSO 4 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to halite saturation

NASA Astrophysics Data System (ADS)

Li, Jun; Duan, Zhenhao

2011-08-01

A thermodynamic model is developed for the calculation of both phase and speciation equilibrium in the H 2O-CO 2-NaCl-CaCO 3-CaSO 4 system from 0 to 250 °C, and from 1 to 1000 bar with NaCl concentrations up to the saturation of halite. The vapor-liquid-solid (calcite, gypsum, anhydrite and halite) equilibrium together with the chemical equilibrium of H+,Na+,Ca, CaHCO3+,Ca(OH)+,OH-,Cl-, HCO3-,HSO4-,SO42-, CO32-,CO,CaCO and CaSO 4(aq) in the aqueous liquid phase as a function of temperature, pressure and salt concentrations can be calculated with accuracy close to the experimental results. Based on this model validated from experimental data, it can be seen that temperature, pressure and salinity all have significant effects on pH, alkalinity and speciations of aqueous solutions and on the solubility of calcite, halite, anhydrite and gypsum. The solubility of anhydrite and gypsum will decrease as temperature increases (e.g. the solubility will decrease by 90% from 360 K to 460 K). The increase of pressure may increase the solubility of sulphate minerals (e.g. gypsum solubility increases by about 20-40% from vapor pressure to 600 bar). Addition of NaCl to the solution may increase mineral solubility up to about 3 molality of NaCl, adding more NaCl beyond that may slightly decrease its solubility. Dissolved CO 2 in solution may decrease the solubility of minerals. The influence of dissolved calcite on the solubility of gypsum and anhydrite can be ignored, but dissolved gypsum or anhydrite has a big influence on the calcite solubility. Online calculation is made available on www.geochem-model.org/model.

A 2.5D Reactive Transport Model for Fracture Alteration Simulation

DOE PAGES

Deng, Hang; Molins, Sergi; Steefel, Carl; ...

2016-06-30

Understanding fracture alteration resulting from geochemical reactions is critical in predicting fluid migration in the subsurface and is relevant to multiple environmental challenges. Here in this paper, we present a novel 2.5D continuum reactive transport model that captures and predicts the spatial pattern of fracture aperture change and the development of an altered layer in the near-fracture region. The model considers permeability heterogeneity in the fracture plane and updates fracture apertures and flow fields based on local reactions. It tracks the reaction front of each mineral phase and calculates the thickness of the altered layer. Given this treatment, the modelmore » is able to account for the diffusion limitation on reaction rates associated with the altered layer. The model results are in good agreement with an experimental study in which a CO 2-acidified brine was injected into a fracture in the Duperow Dolomite, causing dissolution of calcite and dolomite that result in the formation of a preferential flow channel and an altered layer. Finally, with an effective diffusion coefficient consistent with the experimentally observed porosity of the altered layer, the model captures the progressive decrease in the dissolution rate of the fast-reacting mineral in the altered layer.« less

Evaluation of CO 2 -Fluid-Rock Interaction in Enhanced Geothermal Systems: Field-Scale Geochemical Simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Feng; McPherson, Brian J.; Kaszuba, John

Recent studies suggest that using supercritical CO 2 (scCO 2 ) instead of water as a heat transmission fluid in Enhanced Geothermal Systems (EGS) may improve energy extraction. While CO 2 -fluid-rock interactions at “typical” temperatures and pressures of subsurface reservoirs are fairly well known, such understanding for the elevated conditions of EGS is relatively unresolved. Geochemical impacts of CO 2 as a working fluid (“CO 2 -EGS”) compared to those for water as a working fluid (H 2 O-EGS) are needed. The primary objectives of this study are (1) constraining geochemical processes associated with CO 2 -fluid-rock interactions undermore » the high pressures and temperatures of a typical CO 2 -EGS site and (2) comparing geochemical impacts of CO 2 -EGS to geochemical impacts of H 2 O-EGS. The St. John’s Dome CO 2 -EGS research site in Arizona was adopted as a case study. A 3D model of the site was developed. Net heat extraction and mass flow production rates for CO 2 -EGS were larger compared to H 2 O-EGS, suggesting that using scCO 2 as a working fluid may enhance EGS heat extraction. More aqueous CO 2 accumulates within upper- and lower-lying layers than in the injection/production layers, reducing pH values and leading to increased dissolution and precipitation of minerals in those upper and lower layers. Dissolution of oligoclase for water as a working fluid shows smaller magnitude in rates and different distributions in profile than those for scCO 2 as a working fluid. It indicates that geochemical processes of scCO 2 -rock interaction have significant effects on mineral dissolution and precipitation in magnitudes and distributions.« less

The effect of bicarbonate on the microbial dissolution of autunite mineral in the presence of gram-positive bacteria.

PubMed

Sepulveda-Medina, Paola M; Katsenovich, Yelena P; Wellman, Dawn M; Lagos, Leonel E

2015-06-01

Bacteria are key players in the processes that govern fate and transport of contaminants. The uranium release from Na and Ca-autunite by Arthrobacter oxydans strain G968 was evaluated in the presence of bicarbonate ions. This bacterium was previously isolated from Hanford Site soil and in earlier prescreening tests demonstrated low tolerance to U(VI) toxicity compared to other A. oxydans isolates. Experiments were conducted using glass serum bottles as mixed bioreactors and sterile 6-well cell culture plates with inserts separating bacteria cells from mineral solids. Reactors containing phosphorus-limiting media were amended with bicarbonate ranging between 0 and 10 mM and meta-autunite solids to provide a U(VI) concentration of 4.4 mmol/L. Results showed that in the presence of bicarbonate, A. oxydans G968 was able to enhance the release of U(VI) from Na and Ca autunite at the same capacity as other A. oxydans isolates with relatively high tolerance to U(VI). The effect of bacterial strains on autunite dissolution decreases as the concentration of bicarbonate increases. The results illustrate that direct interaction between the bacteria and the mineral is not necessary to result in U(VI) biorelease from autunite. The formation of secondary calcium-phosphate mineral phases on the surface of the mineral during the dissolution can ultimately reduce the natural autunite mineral contact area, which bacterial cells can access. This thereby reduces the concentration of uranium released into the solution. This study provides a better understanding of the interactions between meta-autunite and microbes in conditions mimicking arid and semiarid subsurface environments of western U.S. Copyright © 2015 Elsevier Ltd. All rights reserved.

Sherwood correlation for dissolution of pooled NAPL in porous media

NASA Astrophysics Data System (ADS)

Aydin Sarikurt, Derya; Gokdemir, Cagri; Copty, Nadim K.

2017-11-01

The rate of interphase mass transfer from non-aqueous phase liquids (NAPLs) entrapped in the subsurface into the surrounding mobile aqueous phase is commonly expressed in terms of Sherwood (Sh) correlations that are expressed as a function of flow and porous media properties. Because of the lack of precise methods for the estimation of the interfacial area separating the NAPL and aqueous phases, most studies have opted to use modified Sherwood expressions that lump the interfacial area into the interphase mass transfer coefficient. To date, there are only two studies in the literature that have developed non-lumped Sherwood correlations; however, these correlations have undergone limited validation. In this paper controlled dissolution experiments from pooled NAPL were conducted. The immobile NAPL mass is placed at the bottom of a flow cell filled with porous media with water flowing horizontally on top. Effluent aqueous phase concentrations were measured for a wide range of aqueous phase velocities and for two different porous media. To interpret the experimental results, a two-dimensional pore network model of the NAPL dissolution kinetics and aqueous phase transport was developed. The observed effluent concentrations were then used to compute best-fit mass transfer coefficients. Comparison of the effluent concentrations computed with the two-dimensional pore network model to those estimated with one-dimensional analytical solutions indicates that the analytical model which ignores the transport in the lateral direction can lead to under-estimation of the mass transfer coefficient. Based on system parameters and the estimated mass transfer coefficients, non-lumped Sherwood correlations were developed and compared to previously published data. The developed correlations, which are a significant improvement over currently available correlations that are associated with large uncertainties, can be incorporated into future modeling studies requiring non-lumped Sh expressions.

Micromechanical Tests and Geochemical Modeling to Evaluate Evolution of Rock Alteration by CO2-Water Mixtures

NASA Astrophysics Data System (ADS)

Aman, M.; Sun, Y.; Ilgen, A.; Espinoza, N.

2015-12-01

Injection of large volumes of CO2 into geologic formations can help reduce the atmospheric CO2 concentration and lower the impact of burning fossil fuels. However, the injection of CO2 into the subsurface shifts the chemical equilibrium between the mineral assemblage and the pore fluid. This shift will situationally facilitate dissolution and reprecipitation of mineral phases, in particular intergranular cements, and can potentially affect the long term mechanical stability of the host formation. The study of these coupled chemical-mechanical reservoir rock responses can help identify and control unexpected emergent behavior associated with geological CO2 storage.Experiments show that micro-mechanical methods are useful in capturing a variety of mechanical parameters, including Young's modulus, hardness and fracture toughness. In particular, micro-mechanical measurements are well-suited for examining thin altered layers on the surfaces of rock specimens, as well as capturing variability on the scale of lithofacies. We performed indentation and scratching tests on sandstone and siltstone rocks altered in natural CO2-brine environments, as well as on analogous samples altered under high pressure, temperature, and dissolved CO2 conditions in a controlled laboratory experiment. We performed geochemical modeling to support the experimental observations, in particular to gain the insight into mineral dissolution/precipitation as a result of the rock-water-CO2reactions. The comparison of scratch measurements performed on specimens both unaltered and altered by CO2 over geologic time scales results in statistically different values for fracture toughness and scratch hardness, indicating that long term exposure to CO2 caused mechanical degradation of the reservoir rock. Geochemical modeling indicates that major geochemical change caused by CO2 invasion of Entrada sandstone is dissolution of hematite cement, and its replacement with siderite and dolomite during the alteration process.

Evaluation of CO 2 -Fluid-Rock Interaction in Enhanced Geothermal Systems: Field-Scale Geochemical Simulations

DOE PAGES

Pan, Feng; McPherson, Brian J.; Kaszuba, John

2017-01-01

Recent studies suggest that using supercritical CO 2 (scCO 2 ) instead of water as a heat transmission fluid in Enhanced Geothermal Systems (EGS) may improve energy extraction. While CO 2 -fluid-rock interactions at “typical” temperatures and pressures of subsurface reservoirs are fairly well known, such understanding for the elevated conditions of EGS is relatively unresolved. Geochemical impacts of CO 2 as a working fluid (“CO 2 -EGS”) compared to those for water as a working fluid (H 2 O-EGS) are needed. The primary objectives of this study are (1) constraining geochemical processes associated with CO 2 -fluid-rock interactions undermore » the high pressures and temperatures of a typical CO 2 -EGS site and (2) comparing geochemical impacts of CO 2 -EGS to geochemical impacts of H 2 O-EGS. The St. John’s Dome CO 2 -EGS research site in Arizona was adopted as a case study. A 3D model of the site was developed. Net heat extraction and mass flow production rates for CO 2 -EGS were larger compared to H 2 O-EGS, suggesting that using scCO 2 as a working fluid may enhance EGS heat extraction. More aqueous CO 2 accumulates within upper- and lower-lying layers than in the injection/production layers, reducing pH values and leading to increased dissolution and precipitation of minerals in those upper and lower layers. Dissolution of oligoclase for water as a working fluid shows smaller magnitude in rates and different distributions in profile than those for scCO 2 as a working fluid. It indicates that geochemical processes of scCO 2 -rock interaction have significant effects on mineral dissolution and precipitation in magnitudes and distributions.« less

The Effect of Bicarbonate on the Microbial Dissolution of Autunite Mineral in the Presence of Gram-Positive Bacteria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sepulveda-Medina, Paola; Katsenovich, Yelena; Wellman, Dawn M.

Bacteria are key players in the processes that govern fate and transport of contaminants. The uranium release from Na and Ca-autunite by Arthrobacter oxydans strain G968 was evaluated in the presence of bicarbonate ions. This bacterium was previously isolated from Hanford Site soil and in earlier prescreening tests demonstrated low tolerance to U(VI) toxicity compared to other A.oxydans isolates. Experiments were conducted using glass serum bottles as mixed bioreactors and sterile 6-well cell culture plates with inserts separating bacteria cells from mineral solids. Reactors containing phosphorus-limiting media were amended with bicarbonate ranging between 0-10 mM and metaautunite solids to providemore » a U(VI) concentration of 4.4 mmol/L. Results showed that in the presence of bicarbonate, A.oxydans G968 was able to enhance the release of U(VI) from Na and Ca autunite at the same capacity as other A.oxydans isolates with relatively high tolerance to U(VI). The effect of bacterial strains on autunite dissolution decreases as the concentration of bicarbonate increases. The results illustrate that direct interaction between the bacteria and the mineral is not necessary to result in U (VI) biorelease from autunite. The formation of secondary calcium-phosphate mineral phases on the surface of the mineral during the dissolution can ultimately reduce the natural autunite mineral contact area, which bacterial cells can access. This thereby reduces the concentration of uranium released into the solution. This study provides a better understanding of the interactions between meta-autunite and microbes in conditions mimicking arid and semiarid subsurface environments of western U.S.« less