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USGS2012

Effect of organic-matter type and thermal maturity on methane adsorption in shale-gas systems

A series of methane (CH 4 ) adsorption experiments on bulk organic rich shales and their isolated kerogens were conducted at 35 °C, 50 °C and 65 °C and CH 4 pressure of up to 15 MPa under dry conditions. Samples from the Eocene Green River Formation, Devonian–Mississippian Woodford Shale and Upper Cretaceous Cameo coal were studied to examine how differences in organic matter type affect natural gas adsorption. Vitrinite reflectance values of these samples ranged from 0.56–0.58 %R o . In addition, thermal maturity effects were determined on three Mississippian Barnett Shale samples with measured vitrinite reflectance values of 0.58, 0.81 and 2.01 %R o . For all bulk and isolated kerogen samples, the total amount of methane adsorbed was directly proportional to the total organic carbon (TOC) content of the sample and the average maximum amount of gas sorption was 1.36 mmol of methane per gram of TOC. These results indicate that sorption on organic matter plays a critical role in shale-gas storage. Under the experimental conditions, differences in thermal maturity showed no significant effect on the total amount of gas sorbed. Experimental sorption isotherms could be fitted with good accuracy by the Langmuir function by adjusting the Langmuir pressure (P L ) and maximum sorption capacity (Γ max ). The lowest maturity sample (%R o = 0.56) displayed a Langmuir pressure (P L ) of 5.15 MPa, significantly larger than the 2.33 MPa observed for the highest maturity (%R o > 2.01) sample at 50 °C. The value of the Langmuir pressure (P L ) changes with kerogen type in the following sequence: type I > type II > type III. The thermodynamic parameters of CH 4 adsorption on organic rich shales were determined based on the experimental CH 4 isotherms. For the adsorption of CH4 on organic rich shales and their isolated kerogen, the heat of adsorption (q) and the standard entropy (Δs 0 ) range from 7.3–28.0 kJ/mol and from −36.2 to −92.2 J/mol/K, respectively.

Organic Geochemistry↗

USGS1998

Oxalate adsorption at a plagioclase (An47) surface and models for ligand-promoted dissolution

Previous work on adsorption of oxalate at aluminosilicate surfaces suggests that maximum adsorption occurs through a bidentate attachment of the organic ligand, at near-neutral pH. Rates of ligand-promoted dissolution are expected to be greatest at this pH as well. We tested this model by measuring oxalate adsorption on the surface of andesine (An47), in solutions of pH 3- 5 and total oxalate concentrations of 0-8 mM. Contrary to expectation, the greatest adsorption density of 24 ??mol m-2 total oxalate was observed at pH 3 and 8 mM total oxalate. Adsorption is dependent upon the activities of both oxalate (C2O42-) and bioxalate (HC2O4-) in solution and can be modeled with either a two-term Langmuir or a two-term Freundlich isotherm. A Freundlich adsorption model provided the best fit to rate data because it was not constrained to a finite number of adsorption sites, as was the Langmuir model. The two-term ligand adsorption model was incorporated into a rate model: R(tot) = k(H-)[H(ads)/+](L) + k(HOx-)[HOx(ads)/-] + k(Ox2- )[Ox2(ads)/-] where R(tot) is the net dissolution rate of the feldspar, [i(ads)] is the concentration of species i adsorbed to the surface, and k(i) is the rate constant for release of the surface complex. The model was fit to data for oxalate-promoted dissolution of andesine, resulting in estimates for the rate constants of k(HOx-) = 1.16 x 10-12, k(Ox2-) = 1.05 x 10-12, and k(H-) = 9.61 x 10-13 mol of feldspar (??mol of i) (??mol of i)-1 s-1.Previous work on adsorption of oxalate at aluminosilicate surfaces suggests that maximum adsorption occurs through a bidentate attachment of the organic ligand, at near-neutral pH. Rates of ligand-promoted dissolution are expected to be greatest at this pH as well. We tested this model by measuring oxalate adsorption on the surface of andesine (An47), in solutions of pH 3-5 and total oxalate concentrations of 0-8 mM. Contrary to expectation, the greatest adsorption density of 24 ??mol m-2 total oxalate was observed at pH 3 and 8 mM total oxalate. Adsorption is dependent upon the activities of both oxalate (C2O42-) and bioxalate (HC2O4-) in solution and can be modeled with either a two-term Langmuir or a two-term Freundlich isotherm. A Freundlich adsorption model provided the best fit to rate data because it was not constrained to a finite number of adsorption sites, as was the Langmuir model. The two-term ligand adsorption model was incorporated into a rate model: Rtot = kH(+)[Hads+]L +kHOx(-) [HOxads-]+kOx(2-) [Oxads 2-] where Rtot is the net dissolution rate of the feldspar, [iads] is the concentration of species i adsorbed to the surface, and ki is the rate constant for release of the surface complex. The model was fit to data for oxalate-promoted dissolution of andesine, resulting in estimates for the rate constants of kHOx(-) = 1.16??10-12, kOx(2-) = 1.05??10-12, and kH(+) = 9.61??10-13 mol of feldspar (??mol of i)-1 s-1.

Environmental Science & Technology↗

USGS2003

Modeling Np and Pu transport with a surface complexation model and spatially variant sorption capacities: Implications for reactive transport modeling and performance assessments of nuclear waste disposal sites

One-dimensional (1D) geochemical transport modeling is used to demonstrate the effects of speciation and sorption reactions on the ground-water transport of Np and Pu, two redox-sensitive elements. Earlier 1D simulations (Reardon, 1981) considered the kinetically limited dissolution of calcite and its effect on ion-exchange reactions (involving 90 Sr, Ca, Na, Mg and K), and documented the spatial variation of a 90 Sr partition coefficient under both transient and steady-state chemical conditions. In contrast, the simulations presented here assume local equilibrium for all reactions, and consider sorption on constant potential, rather than constant charge, surfaces. Reardon's (1981) seminal findings on the spatial and temporal variability of partitioning (of 90 Sr) are reexamined and found partially caused by his assumption of a kinetically limited reaction. In the present work, sorption is assumed the predominant retardation process controlling Pu and Np transport, and is simulated using a diffuse-double-layer-surface-complexation (DDLSC) model. Transport simulations consider the infiltration of Np- and Pu-contaminated waters into an initially uncontaminated environment, followed by the cleanup of the resultant contamination with uncontaminated water. Simulations are conducted using different spatial distributions of sorption capacities (with the same total potential sorption capacity, but with different variances and spatial correlation structures). Results obtained differ markedly from those that would be obtained in transport simulations using constant K d , Langmuir or Freundlich sorption models. When possible, simulation results (breakthrough curves) are fitted to a constant K d advection–dispersion transport model and compared. Functional differences often are great enough that they prevent a meaningful fit of the simulation results with a constant K d (or even a Langmuir or Freundlich) model, even in the case of Np, a weakly sorbed radionuclide under the simulation conditions. Functional behaviors that cannot be fit include concentration trend reversals and radionuclide desorption spikes. Other simulation results are fit successfully but the fitted parameters ( K d and dispersivity) vary significantly depending on simulation conditions (e.g. “infiltration” vs. “cleanup” conditions). Notably, an increase in the variance of the specified sorption capacities results in a marked increase in the dispersion of the radionuclides. The results presented have implications for the simulation of radionuclide migration in performance assessments of nuclear waste-disposal sites, for the future monitoring of those sites, and more generally for modeling contaminant transport in ground-water environments.

Computers & Geosciences↗

USGS2013

Sorption of pure N 2 O to biochars and other organic and inorganic materials under anhydrous conditions

Suppression of nitrous oxide (N 2 O) emissions from soil is commonly observed after amendment with biochar. The mechanisms accounting for this suppression are not yet understood. One possible contributing mechanism is N 2 O sorption to biochar. The sorption of N 2 O and carbon dioxide (CO 2 ) to four biochars was measured in an anhydrous system with pure N 2 O. The biochar data were compared to those for two activated carbons and other components potentially present in soils—uncharred pine wood and peat—and five inorganic metal oxides with variable surface areas. Langmuir maximum sorption capacities ( Q max ) for N 2 O on the pine wood biochars (generated between 250 and 500 °C) and activated carbons were 17–73 cm 3 g –1 at 20 °C (median 51 cm 3 g –1 ), with Langmuir affinities ( b ) of 2–5 atm –1 (median 3.4 atm –1 ). Both Q max and b of the charred materials were substantially higher than those for peat, uncharred wood, and metal oxides [ Q max 1–34 cm 3 g –1 (median 7 cm 3 g –1 ); b 0.4–1.7 atm –1 (median 0.7 atm –1 )]. This indicates that biochar can bind N 2 O more strongly than both mineral and organic soil materials. Q max and b for CO 2 were comparable to those for N 2 O. Modeled sorption coefficients obtained with an independent polyparameter—linear free-energy relationship matched measured data within a factor 2 for mineral surfaces but underestimated by a factor of 5–24 for biochar and carbonaceous surfaces. Isosteric enthalpies of sorption of N 2 O were mostly between −20 and −30 kJ mol –1 , slightly more exothermic than enthalpies of condensation (−16.1 kJ mol –1 ). Q max of N 2 O on biochar (50000–130000 μg g –1 biochar at 20 °C) exceeded the N 2 O emission suppressions observed in the literature (range 0.5–960 μg g –1 biochar; median 16 μg g –1 ) by several orders of magnitude. Thus, the hypothesis could not be falsified that sorption of N 2 O to biochar is a mechanism of N 2 O emission suppression.

Environmental Science & Technology↗

USGS1973

The sorption of silver by poorly crystallized manganese oxides

The sorption of silver by poorly crystallized manganese oxides was studied using synthesized samples of three members of the manganous manganite (birnessite) group, of different chemical composition and crystallinity, and a poorly organized γ-MnO 2 . All four oxides sorbed significant quantities of silver. The manganous manganites showed the greatest sorption (up to 0.5 moles silver/mole MnO x at pH 7) while the γ-MnO 2 showed the least (0.3 moles silver/ mole MnO x at pH 7). Sorption of silver was adequately described by the Langmuir equation over a considerable concentration range. The relationship failed at low pH values and high equilibrium silver concentrations. The sorption capacity showed a direct relationship with pH. However, the rate of increase of sorption capacity decreased at the higher pH values. Silver sorption maxima. were not directly related to surface area but appeared to vary with the amount of occluded sodium and potassium present in the manganese oxide. The important processes involved in the uptake of silver by the four poorly crystallized manganese oxides ara considered to be surface exchange for manganese, potassium and sodium as well as exchange for structural manganese, potassium and sodium.

Geochimica et Cosmochimica Acta↗

USGS1980

Speculations on processes responsible for mesoscale current lineations on the continental shelf, southern California

A side-scan sonar survey of San Pedro shelf, California, reveals areas of mesoscale current lineations oriented approximately north-northeast in water depths of 20-25 m. Widths of sand ribbons range from 40 to 120 m and intervening erosional furrows, from 15 to 50 m. A conceptual model shows that the scale and orientation of current lineations agree with the dimensions and axial directions of Langmuir circulations theoretically generated by a combination either of southerly and southwesterly winds with regular trains of swell from the southern hemisphere or of two sets of wave trains crossing from the south and west. These longitudinal bedforms indicate shore-normal sediment transport at the times and on the areas of the shelf when and where they have been observed.

California↗

USGS2006

Sorption processes affecting arsenic solubility in oxidized surface sediments from Tulare Lake Bed, California

Elevated concentrations of arsenic (As) in shallow groundwater in Tulare Basin pose an environmental risk because of the carcinogenic properties of As and the potential for its migration to deep aquifers that could serve as a future drinking water source. Adsorption and desorption are hypothesized to be the major processes controlling As solubility in oxidized surface sediments where arsenate [As(V)] is dominant. This study examined the relationship between sorption processes and arsenic solubility in shallow sediments from the dry Tulare Lake bed by determining sorption isotherms, pH effect on solubility, and desorption-readsorption behavior (hysteresis), and by using a surface complexation model to describe sorption. The sediments showed a high capacity to adsorb As(V). Estimates of the maximum adsorption capacity were 92 mg As kg- 1 at pH 7.5 and 70 mg As kg- 1 at pH 8.5 obtained using the Langmuir adsorption isotherm. Soluble arsenic [> 97% As(V)] did not increase dramatically until above pH 10. In the native pH range (7.5-8.5), soluble As concentrations were close to the lowest, indicating that As was strongly retained on the sediment. A surface complexation model, the constant capacitance model, was able to provide a simultaneous fit to both adsorption isotherms (pH 7.5 and 8.5) and the adsorption envelope (pH effect on soluble As), although the data ranges are one order of magnitude different. A hysteresis phenomenon between As adsorbed on the sediment and As in solution phase was observed in the desorption-readsorption processes and differs from conventional hysteresis observed in adsorption-desorption processes. The cause is most likely due to modification of adsorbent surfaces in sediment samples upon extensive extractions (or desorption). The significance of the hysteresis phenomenon in affecting As solubility and mobility may be better understood by further microscopic studies of As interaction mechanisms with sediments subjected to extensive leaching in natural environments. ?? 2006 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2019

Aluminum- and iron-based coagulation for in-situ removal of dissolved organic carbon, disinfection byproducts, mercury and other constituents from agricultural drain water

Agricultural production on wetland soils can be significant sources of dissolved organic carbon (DOC), disinfection byproduct precursors, mercury and nutrients to downstream water bodies and accelerate land subsidence. Presented as a potential solution for in-situ water quality improvement and land subsidence mitigation, chemically enhanced treatment wetlands (CETWs) were used to leverage both coagulation and wetland processes. In this study, we evaluated the performance of coagulants ferric sulfate (Fe dosing) and polyaluminum chloride (Al dosing) to remove pollutants from agricultural drain water using the coagulation system designed for CETWs. Both coagulation treatments removed over 70% DOC from source waters, resulting in removal efficiencies (mg-DOC removed per mg-metal dosed) of 1 under Al dosing and 0.5 under Fe dosing. Coagulation by both treatments preferentially removed UV254 active compounds compared to the bulk DOC concentration, suggesting coagulation targeted aromatics more effectively. Phosphates and haloacetic acids were also removed more readily, whereas trihalomethanes, dissolved organic nitrogen and filtered mercury species were removed at similar or lower rates than DOC. Dissolved inorganic nitrogen was not amenable to coagulation and removal was not observed. Freundlich, Langmuir and Monod models explained 33% of the variance for Al dosing and 78 – 89% of the variance for Fe dosing. All three models indicated Al dosing had higher removal efficiency and affinity for DOC than Fe dosing under study conditions, but when used to predict maximum removal efficiency there was no cohesiveness between the three models due to different model assumptions. Consideration of fluorescence dissolved organic matter and UV254 as surrogates for DOC concentration showed both were equally suitable before coagulant application, but as surrogates after coagulant application, neither could be deemed more fit as a surrogate since both were shown suitable for different treatment scenarios.

Ecological Engineering↗

USGS2014

Experimental investigation of changes in methane adsorption of bitumen-free Woodford Shale with thermal maturation induced by hydrous pyrolysis

This study quantifies the effects of organic-matter (OM) thermal maturity on methane (CH 4 ) sorption, on the basis of five samples that were artificially matured through hydrous pyrolysis achieved by heating samples of immature Woodford Shale under five different time–temperature conditions. CH 4 -sorption isotherms at 35 °C, 50 °C, and 65 °C, and pressures up to 14 MPa on dry, solvent-extracted samples of the artificially matured Woodford Shale were measured. The results showed that CH 4 -sorption capacity, normalized to TOC, varied with thermal maturity, following the trend: maximum oil (367 °C) > oil cracking (400 °C) > maximum bitumen/early oil (333 °C) > early bitumen (300 °C) > immature stage (130 °C). The Langmuir constants for the samples at maximum-oil and oil-cracking stages are larger than the values for the bitumen-forming stages. The total pore volume, determined by N 2 physisorption at 77 K, increases with increased maturation: mesopores, 2–50 nm in width, were created during the thermal conversion of organic-matter and a dramatic increase in porosity appeared when maximum-bitumen and maximum-oil generation stages were reached. A linear relationship between thermal maturity and Brunauer–Emmett–Teller (BET) surface area suggests that the observed increase in CH 4 -sorption capacity may be the result of mesopores produced during OM conversion. No obvious difference is observed in pore-size distribution and pore volume for samples with pores <2.0 nm with the increase of thermal maturity based on CO 2 physisorption at 273 K. The isosteric heat of adsorption and the standard entropy for artificially matured samples ranged from 17.9 kJ mol −1 to 21.9 kJ mol −1 and from −85.4 J mol −1 K −1 to −101.8 J mol −1 K −1 , respectively. These values are similar to the values of immature Woodford kerogen concentrate previously observed, but are larger than naturally matured organic-rich shales. High-temperature hydrous pyrolysis might have induced Lewis acid sites on both organic and mineral surfaces, resulting to some extent, in chemical interactions between the adsorption site and the methane C–H bonds. The formation of abundant mesopores (2–50 nm) within organic matter during organic-matter thermal maturation makes a great contribution to the increase in both BET surface area and pore volume, and a significant increase in 2–6 nm pores occurs at maximum-oil-generation and oil-cracking to gas, ultimately controlling the methane-adsorption capacity. Therefore, consideration of pore-size effects and thermal maturity is very important for gas in place (GIP) prediction in organic-rich shales.

Marine and Petroleum Geology↗

USGS2021

Organo-facies and mineral effects on sorption capacity of low-maturity Permian Barakar shales from the Auranga Basin, Jharkhand, India

Shales associated with the Lower Permian (Barakar Formation) sediments of the Auranga Coalfield, India, occur in the immature–early mature stage. The sorption capacity of Barakar shale samples has been studied through high-pressure methane (CH 4 ) adsorption and low-pressure N 2 gas adsorption (LPN 2 GA) methods, supported with proximate analyses, programmed pyrolysis, optical petrography, and with energy-dispersive spectroscopy, X-ray diffraction, and inductively coupled plasma mass spectrometry. The sorption capacity is a function of the organic and inorganic constituents present in the shale samples. The methane sorption capacity (MSC) and Langmuir volume of the shale samples vary from 0.217 to 0.314 and 0.315 to 0.429 mmol/g rock, respectively. The BET-calculated surface area of the studied shales varies from 8.12 to 30.36 m 2 /g. The sorption capacities show the importance of the total organic content (TOC) through weak but positive correlations with MSC ( r 2 = 0.45) and S 1 values (mg hydrocarbons/g rock from programmed pyrolysis; r 2 = 0.40). Moreover, apparent inverse relationships were observed between MSC and clay mineral abundances, suggesting that individual clay mineral types may influence MSC, although more work is needed. The TOC-normalized MSC (MSC*) of shale samples shows a positive trend with quartz plus clay mineral content and ash yield of r 2 = 0.64 for both. In addition, MSC* shows a negative logarithmic relationship with S 1 + S 2 ( r 2 = 0.63) and a positive linear relationship with TOC-normalized total organic matter (TOM*) ( r 2 = 0.88, when 5 low TOM* samples are excluded) indicating complex relationships possibly including bitumen retention in the sample pore spaces. The micropore study of the samples through LPN 2 GA, applying Dubinin–Radushkevich, Dubinin–Astakhov, and density functional theory models, shows the dominance of micro-mesopore concentrations in the shale matrix of ∼2 nm pore diameter. However, these pores might be present as blind or closed pores. The presence of thorium and zirconium is reflective of terrigenous detrital matter, i.e., moderately to strongly recycled sediments. The fluviatile facies of deposited shales in the Auranga Coalfield are noted by the significant presence of kaolinite (32.5–78.3%), which suggests the importance of its effect on the sorption capacity of proximal terrigenous shales.

Jharkhand↗

USGS2005

Arsenate adsorption mechanisms at the allophane: Water interface

We investigated arsenate (As(V)) reactivity and surface speciation on amorphous aluminosilicate mineral (synthetic allophane) surfaces using batch adsorption experiments, powder X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The adsorption isotherm experiments indicated that As(V) uptake increased with increasing [As(V)] o from 50 to 1000 μM (i.e., Langmuir type adsorption isotherm) and that the total As adsorption slightly decreased with increasing NaCl concentrations from 0.01 to 0.1 M. Arsenate adsorption was initially (0−10 h) rapid followed by a slow continuum uptake, and the adsorption processes reached the steady state after 720 h. X-ray absorption spectroscopic analyses suggest that As(V) predominantly forms bidentate binuclear surface species on aluminum octahedral structures, and these species are stable up to 11 months. Solubility calculations and powder XRD analyses indicate no evidence of crystalline Al−As(V) precipitates in the experimental systems. Overall, macroscopic and spectroscopic evidence suggest that the As(V) adsorption mechanisms at the allophane−water interface are attributable to ligand exchange reactions between As(V) and surface-coordinated water molecules and hydroxyl and silicate ions. The research findings imply that dissolved tetrahedral oxyanions (e.g., H 2 PO 4 2 - and H 2 AsO 4 2 - ) are readily retained on amorphous aluminosilicate minerals in aquifer and soils at near neutral pH. The inner-sphere adsorption mechanisms might be important in controlling dissolved arsenate and phosphate in amorphous aluminosilicate-rich low-temperature geochemical environments.

Environmental Science & Technology↗

USGS2005

Inhibition of calcite precipitation by natural organic material: Kinetics, mechanism, and thermodynamics

The inhibition of calcite precipitation by natural organic material (NOM) in solutions seeded with calcite was investigated using a pH-stat system. Experiments were carried out using three NOMs with different physical/chemical properties. For each of the materials, inhibition was found to be more effective at lower carbonate/calcium ratios and lower pH values. The reduction in the precipitation rate could be explained by a Langmuir adsorption model using a conditional equilibrium constant. By identification of the type of site on the NOM molecules that is involved in the adsorption reaction, the "conditional" equilibrium constants obtained at different solution compositions converged to a single "nonconditional" value. The thermodynamic data determined at 25??C and 1 atm suggest that the interaction between NOM molecules and the calcite surface is chemisorptive in nature and that adsorption is an endothermic reaction driven by the entropy change. The greatest degree of inhibition was observed for the NOM with the highest molecular weight and aromatic carbon content. For a given type of NOM, the degree of inhibition of calcite precipitation was dictated by the balance between the enthalpy change and the entropy change of the adsorption reaction. ?? 2005 American Chemical Society.

Environmental Science & Technology↗

USGS2010

Direct comparison of kinetic and local equilibrium formulations for solute transport affected by surface reactions

Modeling transport of reacting solutes in porous media often requires a choice between models based on the local equilibrium assumption (LEA) and models involving reaction kinetics. Direct comparison of the mathematical formulations for these two types of transport models can aid in this choice. For cases of transport affected by surface reaction, such a comparison is made possible by a new derivation procedure. This procedure yields a kinetics-based formulation that is the sum of the LEA formulation and one or more kinetically influenced terms. The dimensionless form of the new kinetics-based formulation facilitates identification of critical parameter groupings which control the approach to transport behavior consistent with LEA model predictions. Results of numerical experiments demonstrate that criteria for LEA applicability can be expressed conveniently in terms of these parameter groupings. The derivation procedure is demonstrated for examples of surface reactions including first-order reversible sorption, Langmuir-type kinetics and binary, homovalent ion exchange.

Water Resources Research↗

USGS2013

Petrogenesis of Mount Rainier andesite: Magma flux and geologic controls on the contrasting differentiation styles at stratovolcanoes of the southern Washington Cascades

Quaternary Mount Rainier (Washington, USA) of the Cascades magmatic arc consists of porphyritic calc-alkaline andesites and subordinate dacites, with common evidence for mingling and mixing with less evolved magmas encompassing andesites, basaltic andesites, and rarely, basalts. Basaltic andesites and amphibole andesites (spessartites) that erupted from vents at the north foot of the volcano represent some of Mount Rainier’s immediate parents and overlap in composition with regional basalts and basaltic andesites. Geochemical (major and trace elements) and isotopic (Sr, Nd, Pb, O) compositions of Mount Rainier andesites and dacites are consistent with modest assimilation (typically ≤20 wt%) of evolved sediment or sediment partial melt. Sandstones and shales of the Eocene Puget Group, derived from the continental interior, are exposed in regional anticlines flanking the volcano, and probably underlie it in the middle to lower crust, accounting for their assimilation. Mesozoic and Cenozoic igneous basement rocks are unsuitable as assimilants due to their high 143 Nd/ 144 Nd, diverse 206 Pb/ 204 Pb, and generally high δ 18 O. The dominant cause of magmatic evolution at Mount Rainier, however, is inferred to be a version of in situ crystallization-differentiation and mixing ( Langmuir, 1989 ) wherein small magma batches stall as crustal intrusions and solidify extensively, yielding silicic residual liquids with trace element concentrations influenced by accessory mineral saturation. Subsequent magmas ascending through the intrusive plexus entrain and mix with the residual liquids and low-degree re-melts of those antecedent intrusions, producing hybrid andesites and dacites. Mount St. Helens volcanic rocks have geochemical similarities to those at Mount Rainier, and may also result from in situ differentiation and mixing due to low and intermittent long-term magma supply, accompanied by modest crustal assimilation. Andesites and dacites of Mount Adams isotopically overlap the least contaminated Mount Rainier magmas and derive from similar parental magma types, but have trace element variations more consistent with progressive crystallization-differentiation, probably due to higher magma fluxes leading to slower crystallization of large magma batches, allowing time for progressive separation of minerals from melt. Mount Adams also sits atop the southern projection of a regional anticlinorium, so Eocene sediments are absent, or are at shallow crustal levels, and so are cold and difficult to assimilate. Differences between southwest Washington stratovolcanoes highlight some ways that crustal geology and magma flux are primary factors in andesite generation.

Washington↗

USGS2013

Effect of organic matter properties, clay mineral type and thermal maturity on gas adsorption in organic-rich shale systems

A series of CH 4 adsorption experiments on natural organic-rich shales, isolated kerogen, clay-rich rocks, and artificially matured Woodford Shale samples were conducted under dry conditions. Our results indicate that physisorption is a dominant process for CH 4 sorption, both on organic-rich shales and clay minerals. The Brunauer–Emmett–Teller (BET) surface area of the investigated samples is linearly correlated with the CH 4 sorption capacity in both organic-rich shales and clay-rich rocks. The presence of organic matter is a primary control on gas adsorption in shale-gas systems, and the gas-sorption capacity is determined by total organic carbon (TOC) content, organic-matter type, and thermal maturity. A large number of nanopores, in the 2–50 nm size range, were created during organic-matter thermal decomposition, and they significantly contributed to the surface area. Consequently, methane-sorption capacity increases with increasing thermal maturity due to the presence of nanopores produced during organic-matter decomposition. Furthermore, CH 4 sorption on clay minerals is mainly controlled by the type of clay mineral present. In terms of relative CH 4 sorption capacity: montmorillonite ≫ illite – smectite mixed layer > kaolinite > chlorite > illite. The effect of rock properties (organic matter content, type, maturity, and clay minerals) on CH 4 adsorption can be quantified with the heat of adsorption and the standard entropy, which are determined from adsorption isotherms at different temperatures. For clay-mineral rich rocks, the heat of adsorption (q) ranges from 9.4 to 16.6 kJ/mol. These values are considerably smaller than those for CH 4 adsorption on kerogen (21.9–28 kJ/mol) and organic-rich shales (15.1–18.4 kJ/mol). The standard entropy (Δs°) ranges from -64.8 to -79.5 J/mol/K for clay minerals, -68.1 to -111.3 J/mol/K for kerogen, and -76.0 to -84.6 J/mol/K for organic-rich shales. The affinity of CH 4 molecules for sorption on organic matter is stronger than for most common clay minerals. Thus, it is expected that CH 4 molecules may preferentially occupy surface sites on organic matter. However, active sites on clay mineral surfaces are easily blocked by water. As a consequence, organic-rich shales possess a larger CH 4 -sorption capacity than clay-rich rocks lacking organic matter. The thermodynamic parameters obtained in this study can be incorporated into model predictions of the maximum Langmuir pressure and CH 4 - sorption capacity of shales under reservoir temperature and pressure conditions.

Conference Paper↗

USGS1984

Computer model of one-dimensional equilibrium controlled sorption processes

A numerical solution to the one-dimensional solute-transport equation with equilibrium-controlled sorption and a first-order irreversible-rate reaction is presented. The computer code is written in FORTRAN language, with a variety of options for input and output for user ease. Sorption reactions include Langmuir, Freundlich, and ion-exchange, with or without equal valance. General equations describing transport and reaction processes are solved by finite-difference methods, with nonlinearities accounted for by iteration. Complete documentation of the code, with examples, is included. (USGS)

Water-Resources Investigations Report↗

USGS1988

Nitrogen transport in a shallow outwash aquifer at Olean, Cattaraugus County, New York

Groundwater beneath an industrial park at Olean, New York, contained nitrogen compounds in concentrations that in 1983 ranged from 10 to 1,280 mg/L as nitrogen, mainly in the form of ammonium. Continuous pumping from an industrial well field creates a cone of depression that prevents the nitrogen compounds from migrating to municipal-supply wells, 7,000 ft away. A two-dimensional solute transport model was used to simulate changes in nitrogen concentrations that would result from a permanent shutdown of the well field. The model assumed the nitrogen source decayed at an exponential rate with a decay constant of 0.3/year to account for nitrogen removed from the aquifer by pumping during 1978-84. The source of contamination was found to be sensitive to the volume of pumpage at the industrial well field, which altered the rate of groundwater flow through the contaminated area. Simulations of a permanent shutdown of the well field, assuming nitrogen migrates as a conservative solute, indicated that nitrogen-bearing groundwater would reach the municipal well field within 5 years and the peak concentrations at the municipal well field would range from 2 to 5 mg/L. Simulations of Langmuir adsorption of the dissolved ammonium with a one-dimensional model indicated that the arrival of the solute front at the municipal well field would be retarded by a factor of three.

New York↗

USGS1989

Modification of a method-of-characteristics solute-transport model to incorporate decay and equilibrium-controlled sorption or ion exchange

The U.S. Geological Survey computer model of two-dimensional solute transport and dispersion in ground water (Konikow and Bredehoeft, 1978) has been modified to incorporate the following types of chemical reactions: (1) first-order irreversible rate-reaction, such as radioactive decay; (2) reversible equilibrium-controlled sorption with linear, Freundlich, or Langmuir isotherms; and (3) reversible equilibrium-controlled ion exchange for monovalent or divalent ions. Numerical procedures are developed to incorporate these processes in the general solution scheme that uses method-of- characteristics with particle tracking for advection and finite-difference methods for dispersion. The first type of reaction is accounted for by an exponential decay term applied directly to the particle concentration. The second and third types of reactions are incorporated through a retardation factor, which is a function of concentration for nonlinear cases. The model is evaluated and verified by comparison with analytical solutions for linear sorption and decay, and by comparison with other numerical solutions for nonlinear sorption and ion exchange.

Water-Resources Investigations Report↗