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USGS1986

Application of the Flory-Huggins theory to the solubility of solids in glyceryl trioleate

The conventional thermodynamic deviation for ideal solid–liquid solubilities is modified by substituting the Flory–Huggins model for Raoult's law. A comparison of published data for eleven solides in glyceryl trioleate with the predictions of the conventional and modified equations shows that the significantly higher athermal solubilities from the modified equation are in much better agreement with the experimental data. This suggests that discrepancies between the data and the predictions of the conventional model for ideal systems result from the inappropriate use of Raoult's law for systems with significant solute–solvent size disparity rather than from specific interactions.

Journal of the Chemical Society, Faraday Transacti↗

USGS1995

Entropy of adsorption of mixed surfactants from solutions onto the air/water interface

The partial molar entropy change for mixed surfactant molecules adsorbed from solution at the air/water interface has been investigated by surface thermodynamics based upon the experimental surface tension isotherms at various temperatures. Results for different surfactant mixtures of sodium dodecyl sulfate and sodium tetradecyl sulfate, decylpyridinium chloride and sodium alkylsulfonates have shown that the partial molar entropy changes for adsorption of the mixed surfactants were generally negative and decreased with increasing adsorption to a minimum near the maximum adsorption and then increased abruptly. The entropy decrease can be explained by the adsorption-orientation of surfactant molecules in the adsorbed monolayer and the abrupt entropy increase at the maximum adsorption is possible due to the strong repulsion between the adsorbed molecules.

Journal of the Chemical Society, Faraday Transacti↗

USGS1999

Formation of natural gas hydrates in marine sediments 1. Conceptual model of gas hydrate growth conditioned by host sediment properties

The stability of submarine gas hydrates is largely dictated by pressure and temperature, gas composition, and pore water salinity. However, the physical properties and surface chemistry of deep marine sediments may also affect the thermodynamic state, growth kinetics, spatial distributions, and growth forms of clathrates. Our conceptual model presumes that gas hydrate behaves in a way analogous to ice in a freezing soil. Hydrate growth is inhibited within fine-grained sediments by a combination of reduced pore water activity in the vicinity of hydrophilic mineral surfaces, and the excess internal energy of small crystals confined in pores. The excess energy can be thought of as a "capillary pressure" in the hydrate crystal, related to the pore size distribution and the state of stress in the sediment framework. The base of gas hydrate stability in a sequence of fine sediments is predicted by our model to occur at a lower temperature (nearer to the seabed) than would be calculated from bulk thermodynamic equilibrium. Capillary effects or a build up of salt in the system can expand the phase boundary between hydrate and free gas into a divariant field extending over a finite depth range dictated by total methane content and pore-size distribution. Hysteresis between the temperatures of crystallization and dissociation of the clathrate is also predicted. Growth forms commonly observed in hydrate samples recovered from marine sediments (nodules, and lenses in muds; cements in sands) can largely be explained by capillary effects, but kinetics of nucleation and growth are also important. The formation of concentrated gas hydrates in a partially closed system with respect to material transport, or where gas can flush through the system, may lead to water depletion in the host sediment. This "freeze-drying" may be detectable through physical changes to the sediment (low water content and overconsolidation) and/or chemical anomalies in the pore waters and metastable presence of free gas within the normal zone of hydrate stability.

Journal of Geophysical Research B: Solid Earth↗

USGS1991

Chemical equilibrium and mass balance relationships associated with the Long Valley hydrothermal system, California, U.S.A.

Recent drilling and sampling of hydrothermal fluids from Long Valley permit an accurate characterization of chemical concentrations and equilibrium conditions in the hydrothermal reservoir. Hydrothermal fluids are thermodynamically saturated with secondary quartz, calcite, and pyrite but are in disequilibrium with respect to aqueous sulfide-sulfate speciation. Hydrothermal fluids are enriched in 18O by approximately 1??? relative to recharge waters. 18O and Cl concentrations in well cuttings and core from high-temperature zones of the reservoir are extensively depleted relative to fresh rhyolitic tuff compositions. Approximately 80% of the Li and 50% of the B are retained in the altered reservoir rock. Cl mass balance and open-system 18O fractionation models produce similar water-rock ratios of between 1.0 and 2.5 kg kg-1. These water-rock ratios coupled with estimates of reservoir porosity and density produce a minimum fluid residence time of 1.3 ka. The low fluid Cl concentrations in Long Valley correlate with corresponding low rock concentrations. Mass balance calculations indicate that leaching of these reservoir rocks accounts for Cl losses during hydrothermal activity over the last 40 ka. ?? 1991.

Journal of Volcanology and Geothermal Research↗

USGS1981

Thermodynamic tabulations for selected phases in the system CaO-Al 2 O 3 -SiO 2 -H 2 at 101.325 kPa (1 atm) between 273.15 and 1800 K

The standard thermodynamic properties of phases in the lime‐alumina‐silica‐ water system between 273.15 and 1800 K at 101.325 kPa (1 atm) were evalated from published experimental data. Phases included in the compilation are boehmite, diaspore, gibbsite, kaolinite, dickite, halloysite, andalusite, kyanite, sillimanite, Ca‐Al cliniopyroxene, anorthite, gehlenite, grossular, prehnite, zoisite, margarite, wollastonite, cyclowollastonite ( = pseudowollastonite), larnite, Ca olivine, hatrurite, and rankinite. The properties include heat capacity, entropy, relative enthalpy, and the Gibbs energy function of the phases and the enthalpies, Gibbs energies, and equilibrium constants for formation both from the elements and the oxides. Tabulated values are given at 50 K intervals with the 2‐sigma confidence limit at 250 K intervals. Summaries for each phase give the temperature‐ dependent functions for heat capacity, entropy, and relative enthalpy and the experimental data used in the final evaluation.

Journal of Physical and Chemical Reference Data↗

USGS2021

Regional occurrence of aqueous tungsten and relations with antimony, arsenic and molybdenum concentrations (Sardinia, Italy)

T ungsten (W) is rarely found in natural waters, yet it can be introduced into the food chain and cause potentially toxic effects. Uptake of W by plants and vegetables, or trace presence of W in drinking water are possible vectors for ingestion of W by humans. The latter is recognized as a possible cause of lymphatic leukemia. Increased uses of W might result in a degradation of water resources, with attendant adverse effects on biota and human health. Therefore, this study was aimed at investigating regional occurrence and speciation of W in aquatic systems in Sardinia, Italy, factors affecting W mobility and possible relations with other oxyanion-forming trace elements such as Sb, As and Mo. Although our results are specifically from Sardinia, the implications are broader and should prompt future studies in other areas with known high W concentrations. A total of 350 sample sites are reported here, including surface waters, groundwaters, mine drainages, thermal waters and local seawater. The waters were analyzed for major and trace components, including W, Sb, As and Mo. The waters showed a variety of major chemical compositions and W concentrations. High concentrations of W were found in some mine waters and drainages from slag heaps, with W, Sb and As up to 140, 5000 and 800 μg L −1 , respectively. The highest concentrations of W occurred under slightly alkaline pH and oxygenated conditions, and were likely due to the dissolution of scheelite [CaWO 4 ] hosted in materials with which the water came into contact. High W concentrations also were observed in thermal waters, under alkaline pH and reducing conditions, and sometimes coincided with relatively high concentrations either of As or Mo. Previous studies of W geochemistry have focused on WO 4 2− as the major dissolved form of W. For this study, we have augmented the thermodynamic database in PHREEQC to include possible formation of many other W-bearing complexes gleaned from the literature. The results of the speciation calculations with the newly added complexation reactions shows that the neutral species CaWO 4 ° and MgWO 4 ° are particularly dominant in most W-bearing waters and lead to undersaturation with respect to scheelite and other W-bearing minerals. Assessing W contamination in water systems and establishing W limits in drinking water may prevent potential adverse effects of W on human and ecosystem health.

Sardinia↗

USGS2006

Thermodynamic properties and crystal structure refinement of ferricopiapite, coquimbite, rhomboclase, and Fe2(SO4)3(H2O)5

Enthalpies of formation of ferricopiapite [nominally Fe4.67(SO4)6(OH)2 (H2O)20]. coquimbite [Fe2(SO4)3(H2O)9], rhomboclase [(H3O)Fe(SO4)2 (H2O)3], and Fe2(SO4)3(H2O)5 were measured by acid (5 N HCl) solution calorimetry. The samples were characterized by wet chemical analyses and synchrotron powder X-ray diffraction (XRD). The refinement of XRD patterns gave lattice parameters, atomic positions, thermal factors, and occupancies of the sites. The calculated formulae differ slightly from the nominal compositions: Fe4.78(SO4)6 (OH)2.34(H2O)20.71 (ferricopiapite), (Fe1.47Al0.53)(SO4)3 (H2O)9.65 (coquimbite), (H3O)1.34Fe(SO4)2.17 (H2O)3.06 (rhomboclase), and Fe2(SO4)3 (H2O)5.03. All thermodynamic data are given per mole of these formulae. The measured standard enthalpies (in kJ/mol) of formation from the elements (crystalline Fe, Al, S, and ideal gases O2 and H2) at T = 298.15 K are -4115.8??4.1 [Fe2(SO4)3 (H2O)5.03], -12045.1??9.2 (ferricopiapite), -5738.4??3.3 (coquimbite), and -3201.1??2.6 (rhomboclase). Standard entropy (S??) was estimated as a sum of entropies of oxide, hydroxide, and sulfate components. The estimated S?? (in J/mol.K) values for the iron sulfates are 488.2 [Fe2(SO4)3 (H2O)5.03], 1449.2 (ferricopiapite), 638.3 (coquimbite), and 380.1 (rhomboclase). The calculated Gibbs free energies of formation (in kJ/mol) are -3499.7??4.2 [Fe2(SO4)3 (H2O)5.03], -10089.8??9.3 (ferricopiapite), -4845.6??3.3 (coquimbite), and -2688.0??2.7 (rhomboclase). These results combined with other available thermodynamic data allow construction of mineral stability diagrams in the FeIII2(SO4)3-FeII SO4-H2O system. One such diagram is provided, indicating that the order of stability of ferric sulfate minerals with decreasing pH in the range of 1.5 to -0.5 is: hydronium jarosite, ferricopiapite, and rhomboclase. ?? 2006 E. Schweizerbart'sche Verlagsbuchhandlung.

European Journal of Mineralogy↗

USGS1984

Volcanic glasses, their origins and alteration processes

Natural glass can be formed by volcanic processes, lightning (fulgarites) burning coal, and by meteorite impact. By far the most common process is volcanic - basically the glass is rapidly chilled molten rock. All natural glasses are thermodynamically unstable and tend to alter chemically or to crystallize. The rate of these processes is determined by the chemical composition of the magma. The hot and fluid basaltic melts have a structure that allows for rapid crystal growth, and seldom forms glass selvages greater than a few centimeters thick, even when the melt is rapidly cooled by extrusion in the deep sea. In contrast the cooler and very viscous rhyolitic magmas can yield bodies of glass that are tens of meters thick. These highly polymerized magmas have a high silica content - often 71-77% SiO2. Their high viscosity inhibits diffusive crystal growth. Basalt glass in sea water forms an alteration zone called palagonite whose thickness increases linearly with time. The rate of diffusion of water into rhyolitic glass, which follows the relationship - thickness = k (time) 1 2, has been determined as a function of the glass composition and temperature. Increased SiO2 increases the rate, whereas increased CaO, MgO and H2O decrease the rate. The activation energy of water diffusion varies from about 19 to 22 kcal/mol. for the glasses studied. The diffusion of alkali out of rhyolite glass occurs simultaneously with water diffusion into the glass. The rate of devitrification of rhyolitic glass is a function of the glass viscosity, which in turn is a function of water content and temperature. Although all of the aforementioned processes tend to destroy natural glasses, the slow rates of these processes, particularly for rhyolitic glass, has allowed samples of glass to persist for 60 million years. ?? 1984.

Journal of Non-Crystalline Solids↗

USGS2014

Methane hydrates in nature - Current knowledge and challenges

Recognizing the importance of methane hydrate research and the need for a coordinated effort, the United States Congress enacted the Methane Hydrate Research and Development Act of 2000. At the same time, the Ministry of International Trade and Industry in Japan launched a research program to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough. India, China, the Republic of Korea, and other nations also have established large methane hydrate research and development programs. Government-funded scientific research drilling expeditions and production test studies have provided a wealth of information on the occurrence of methane hydrates in nature. Numerous studies have shown that the amount of gas stored as methane hydrates in the world may exceed the volume of known organic carbon sources. However, methane hydrates represent both a scientific and technical challenge, and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of methane hydrates in nature, (2) assessing the volume of natural gas stored within various methane hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural methane hydrates, (5) analyzing the methane hydrate role as a geohazard, (6) establishing the means to detect and characterize methane hydrate accumulations using geologic and geophysical data, and (7) establishing the thermodynamic phase equilibrium properties of methane hydrates as a function of temperature, pressure, and gas composition. The U.S. Department of Energy (DOE) and the Consortium for Ocean Leadership (COL) combined their efforts in 2012 to assess the contributions that scientific drilling has made and could continue to make to advance our understanding of methane hydrates in nature. COL assembled a Methane Hydrate Project Science Team with members from academia, industry, and government. This Science Team worked with COL and DOE to develop and host the Methane Hydrate Community Workshop, which surveyed a substantial cross section of the methane hydrate research community for input on the most important research developments in our understanding of methane hydrates in nature and their potential role as an energy resource, a geohazard, and/or as an agent of global climate change. Our understanding of how methane hydrates occur in nature is still growing and evolving, and it is known with certainty that field, laboratory, and modeling studies have contributed greatly to our understanding of hydrates in nature and will continue to be a critical source of the information needed to advance our understanding of methane hydrates.

Journal of Chemical and Engineering Data↗

USGS1986

Fumarole emissions at Mount St. Helens volcano, June 1980 to October 1981: Degassing of a magma-hydrothermal system

This study is an investigation of the chemical changes in the Mount St. Helens fumarole gases up to October 1981, the sources of the fumarole gases, and the stability of gas species in the shallow magma system. These problems are investigated by calculations of element compositions, thermodynamic equilibria, and magmatic volatile-hydrothermal steam mixing models. The fumarole gases are treated as mixtures of magmatic volatiles and hydrothermal steam formed by magma degassing and boiling of local waters in a dryout zone near conduit and dome magma. The magmatic volatile fraction is significant in fumaroles with temperatures in excess of the magma cracking-temperature (??? 700??C) - i.e., the temperature below which cracking is induced by thermal stresses during cooling and solidification. Linear composition changes of the fumarole gases over time appear to be the result of a steady decline in the magmatic volatile mixing fraction, which may be due to the tapping of progressively volatile-depleted magma. The maximum proportion of hydrothermal steam in the fumaroles rose from about 25-35% in September 1980 to around 50-70% by October 1981. Fractional degassing of magmatic CO2 and sulfur also contributed to the chemical changes in the fumarole gases. The steady chemical changes indicate that replenishment of the magma system with undegassed magma was not significant between September 1980 and September 1981. Extrapolations of chemical trends suggest that fumarole gases emitted at the time of formation of the first dome in mid-June 1980 were more enriched in a magmatic volatile fraction and contained a minimum of 9% CO2. Calculations show H2S is the predominant sulfur species in Mount St. Helens magma below depths of 200 m. Rapid release of gases from magma below this depth is a plausible mechanism for producing the high H2S/SO2 observed in Mount St. Helens plumes during explosive eruptions. This study suggests that dacite-andesite volcanos may emit gases richer in CO2 during the earlier episodes of an eruptive cycle and burden the atmosphere with much more H2S than SO2 during explosive eruptions. ?? 1986.

Journal of Volcanology and Geothermal Research↗

USGS2005

Mineralogy and arsenic mobility in arsenic-rich Brazilian soils and sediments

Background. Soils and sediments in certain mining regions of Brazil contain an unusually large amount of arsenic (As), which raises concerns that mining could promote increased As mobility, and thereby increase the risks of contaminating water supplies. Objectives. The purpose of t his study was to identify the most important factors governing As mobility in sediments and soils near three gold-mining sites in the State of Minas Gerais, Brazil. Methods. Surface and sub-surface soil samples were collected at those sites and characterized by chemical and mineralogical analyses. Oxalate (Feo) and citrate-bicarbonate-dithionite (Fed) iron contents were determined by atomic absorption spectroscopy (AAS). Arsenic mobilization was measured after incubating the samples in a 2.5 mM CaCl2 solution under anaerobic conditions for 1, 28, 56, 84, or 112 days. The solution concentrations of As, Fe, and Mn were then measured by inductively coupled plasma-mass spectrometry (ICP-MS) and AAS, respectively. Results and Discussion. Results indicated that As mobilization is largely independent of both the total As and the Feo/Fed ratio of the solid phase. Soluble As is roughly controlled by the Fe (hydr)oxide content of the soil, but a closer examination of the data revealed the importance of other highly weathered clay minerals and organic matter. Large amounts of organic matter and a low iron oxide content should favor As leaching from soils and sediments. Under reducing conditions, As is mobilized by the reductive dissolution of Fe and/or Mn oxides. However, released As may be readsorbed depending on the sorptive properties of the soil. Gibbsite is particularly effective in adsorbing or readsorbing As, as is the remaining unreduced fraction of the iron (hydr)oxides. Conclusion and Outlook. In general, low soluble As is rel ated to the presence of gibbsite, a large amount of iron oxides, and a lack of organic matter in the solid phase. This has environmental significance because gibbsite is thermodynamically more stable than Fe oxides under anaerobic conditions, such as those found in waterlogged soils and lake sediments. ?? 2006 ecomed publishers (Verlagsgruppe Hu??thig Jehle Rehm GmbH), D-86899 Landsberg and Tokyo.

Journal of Soils and Sediments↗

USGS2012

Geochemical modeling of changes in shallow groundwater chemistry observed during the MSU-ZERT CO2 injection experiment

A field experiment involving the release of carbon dioxide (CO 2 ) into a shallow aquifer was conducted near Bozeman, Montana, during the summer of 2008, to investigate the potential groundwater quality impacts in the case of leakage of CO 2 from deep geological storage. As an essential part of the Montana State University Zero Emission Research and Technology (MSU-ZERT) field program, food-grade CO 2 was injected over a 30 day period into a horizontal perforated pipe a few feet below the water table of a shallow aquifer. The impact of elevated CO 2 concentrations on groundwater quality was investigated by analyzing water samples taken before, during, and following CO 2 injection, from observation wells located in the vicinity of the injection pipe, and from two distant monitoring wells. Field measurements and laboratory analyses showed rapid and systematic changes in pH, alkalinity, and conductance, as well as increases in the aqueous concentrations of naturally occurring major and trace element species. The geochemical data were evaluated using principal component analysis (PCA) to (1) understand potential correlations between aqueous species, and (2) to identify minerals controlling the chemical composition of the groundwater prior to CO 2 injection. These evaluations were used to assess possible geochemical processes responsible for the observed increases in the concentrations of dissolved constituents, and to simulate these processes using a multicomponent reaction path model. Reasonable agreement between observed and modeled data suggests that (1) calcite dissolution was the primary pH buffer, yielding increased Ca +2 concentrations in the groundwater, (2) increases in the concentrations of most major and trace metal cations except Fe could be a result of Ca +2 -driven exchange reactions, (3) the release of anions from adsorption sites due to competitive adsorption of carbonate could explain the observed trends of most anions, and (4) the dissolution of reactive Fe minerals (presumed ferrihydrite and fougerite, from thermodynamic analyses) could explain increases in total Fe concentration. Highlights ► Because the possibility of CO 2 leakage cannot be completely ruled out, the potential impact of CO 2 intrusion on the quality of fresh water aquifers overlying CO 2 storage sites needs to be investigated. ► Geochemical data from a field experiment involving the release of carbon dioxide (CO 2 ) into a shallow aquifer were evaluated. ► Geochemical model used to assess possible geochemical processes responsible for the observed increases in the concentrations of dissolved constituents. ► Reasonable agreement between observed and modeled data suggests that increases in the concentrations of most major and trace metal cations except Fe could be a result of Ca +2 -driven exchange reactions and the release of anions from adsorption sites due to competitive adsorption of carbonate could explain the observed trends of most anions.

Montana↗

USGS2026

Petrological, textural, and volatile constraints on the architecture of Mauna Loa’s magmatic system over 170 years (1852–2022)

Mauna Loa’s reawakening in 2022 highlighted the limited availability of petrological constraints characterizing the geometry and dynamics of pre-eruptive storage at this volcano. In particular, there has been relatively little prior work constraining pre-eruptive volatile budgets, mineral zoning and textures. To address this, we examine olivine- and orthopyroxene-hosted melt inclusions (MIs), their mineral hosts, and matrix glasses from seven Mauna Loa eruptions spanning 170 years (1852–2022). We present the first extensive MI dataset from Mauna Loa with direct Raman measurements of vapor bubble CO 2 . Olivine- and orthopyroxene-hosted MIs contain 0.3–0.5 wt % H 2 O and 100–600 μg/g CO 2 . MI saturation pressures reveal that the dominant reservoir is located at ~2–5 km depth, consistent with fluid inclusion barometry and geophysical constraints. This depth has remained consistent over the past 170 years, although some eruptions appear to have tapped a narrower range of depths than others. Even the high-Mg# orthopyroxene phenocryst-hosted MIs record saturation pressures of <150 MPa (<6 km depth), which is inconsistent with a deep sub-Moho origin proposed by previous studies that rely on thermodynamic modeling. Our Raman measurements also provide an opportunity to assess the accuracy of different methods to reconstruct the amount of CO 2 in vapor bubbles, with applications to MI datasets published without direct Raman measurements. In general, models that partition CO 2 between the melt and bubble using the bubble volume prior to pre-eruptive quenching (e.g. Melt Inclusion Modification Corrections, MIMiC) systematically underestimate CO 2 contents by a median of ~100–200 μg/g (depending on the model and K D choice) and thus underestimate storage depths by ~0.5–1.5 km. While these methods are useful for first-order estimates of bubble CO 2 in published datasets, new studies should measure bubble CO 2 by Raman spectroscopy or perform MI rehomogenization. The zoning and textures of the crystals that host the MIs provide additional constraints on the plumbing system to supplement MI barometry. Orthopyroxene crystals exhibit varied zoning patterns, including oscillatory zoning that records repeated fluctuations in magmatic conditions, and sector zoning indicating rapid, kinetically controlled crystal growth. While faster Fe-Mg diffusion in olivine results in a simpler zoning record, complexly zoned olivines with higher-Fo ‘shoulders’ from 1852, 1868, and 1950 also record the injection of more primitive melts at shallow levels. Electron backscatter diffraction reveals that touching crystals in orthopyroxene glomerocrysts exhibit only very weakly systematic crystallographic orientation relationships, perhaps due to rapid aggregation in a dynamic system. Overall, our data are consistent with a large, shallow (~2–5 km) pre-eruptive reservoir repeatedly recharged by primitive magma injections that homogenized prior to eruption due to their small volume relative to the overall size of this reservoir. This chemical complexity is effectively recorded in mineral and MI compositions (orthopyroxene zoning in particular) but is obscured in glass and whole-rock analyses.

Hawaii↗