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The solubility of the noble gases He, Ne, Ar, Kr, and Xe in water up to the critical point

The solubility of the noble gases Ar, He, Ne, Kr, and Xe in pure water was measured from 298 to 561??K. These data in turn were extrapolated to the critical point of water, thus providing a complete set of Henry's law constants from 274 to 647??K when combined with the existing literature data. Equations describing the behavior of the Henry's law constants over this temperature range are also given. The data do not confirm extrapolations of empirical correlations based on low-temperature solubility data. ?? 1978 Plenum Publishing Corporation.

Journal of Solution Chemistry↗

An investigation of the critical liquid-vapor properties of dilute KCl solutions

The three parameters that define the critical point, temperature, pressure, and volume have been experimentally determined by means of filling studies in a platinum-lined system for five KCl solutions ranging from 0.006 to 0.568 m . The platinum-lined vessels were used to overcome the problems with corrosion experienced by earlier workers. The critical temperature ( t c ), pressure ( P c ), and volume ( V c ) were found to fit the equations t c = 374.14   +   16.602 m   +   41.740 m  ± 0.5 ∘ C P c = 220.9   +   135.164 m  +   41.173 m 2   ±   0.5 b a r s V c = 3.155   −   1.373 m   +   0.507 m  ±   0.008 c m 3 − g − 1 "> t c = 374.14 + 16.602 m −−√ + 41.740 m ± 0.5 ∘ C P c = 220.9 + 135.164 m + 41.173 m 2 ± 0.5 b a r s V c = 3.155 − 1.373 m −−√ + 0.507 m ± 0.008 c m 3 − g − 1 tc=374.14 + 16.602m + 41.740m ±0.5∘CPc=220.9 + 135.164m + 41.173m2 ± 0.5barsVc=3.155 − 1.373m + 0.507m ± 0.008cm3−g−1 from infinite dilution to 1.0 m .

Journal of Solution Chemistry↗

The structure of Yb 3+ aquo ion and chloro complexes in aqueous solutions at up to 500 °C and 270 MPa

We report here on X-ray absorption fine structure (XAFS) measurements used to determine the structure of the Yb 3+ ion in aqueous solutions over a range of temperatures from 25 to 500 °C and pressures up to 270 MPa. Fluorescence Yb L 3 -edge spectra were collected separately from nitrate (0.006 m Yb/0.16 m HNO 3 ) and chloride (0.006 m YbCl 3 /0.017 m HCl) aqueous solutions within a hydrothermal diamond anvil cell. The Yb−O distance of the Yb 3+ aquo ion in the nitrate solution exhibits a uniform reduction at a rate of 0.02 Å/100 °C, whereas the number of oxygens decreases from 8.3 ± 0.6 to 4.8 ± 0.7, in going from 25 to 500 °C. No evidence for nitrate complexes was found from measurements made on this solution. The Yb 3+ is found to persist as an aquo ion up to 150 °C in the chloride aqueous solution. In the 300−500 °C range, chloro complexes are found to occur in the solution, most likely of the type Yb(H 2 O) δ - n Cl n +3- n (δ ≈ 7). The Yb−Cl distance of the chloro ytterbium(III) complexes is found to decrease uniformly at a rate of about 0.02 Å/100 °C, whereas the number of chlorines increases from 0.5 ± 0.3 to 1.8 ± 0.2 in the 300−500 °C temperature range. Conversely, the Yb−O distance undergoes a lower uniform reduction at a rate of 0.007 Å/100 °C, whereas the number of oxygens decreases from 8.3 ± 0.5 to 5.1 ± 0.3 in going from 25 to 500 °C in the same solution.

Journal of Physical Chemistry A↗

Hydrochemical evolution of sodium-sulfate and sodium-chloride groundwater beneath the Northern Chihuahuan Desert, Trans-Pecos, Texas, USA

Groundwater beneath the northern Chihuahuan Desert, Trans-Pecos, Texas, USA, occurs in both carbonate and siliciclastic aquifers beneath a thick unsaturated zone in shallow Rio Grande alluvium. Groundwater hydrochemical evolution was investigated by analyzing soils, soils leachates, bolson-fill sediments, water from the unsaturated zone, and groundwater from three major aquifers. Ionic relations, mineral saturation states, and geochemical modeling show that groundwater compositions are controlled by reactions in the unsaturated zone, mineralogy of unsaturated sediments and aquifers, position in the groundwater flow system, and extensive irrigation. Recharge to aquifers unaffected by irrigation is initially a Ca-HCO 3 type as a result of dissolving carbonate surficial salts. With continued flow and mineral-water interaction, saturation with calcite and dolomite is maintained, gypsum is dissolved, and aqueous Ca and Mg are exchanged for adsorbed Na to produce a Na-SO 4 water. Groundwater in Rio Grande alluvium is a Na-Cl type, reflecting river-water composition and the effects of irrigation, evapotranspiration, and surficial salt recycling. These results document two hydrochemical evolution paths for groundwater in arid lands. If recharge is dilute precipitation, significant changes in water chemistry can occur in unsaturated media, ion exchange can be as important as dissolution-precipitation reactions in determining groundwater composition, and mineral-water reactions ultimately control groundwater composition. If recharge is return flow of irrigation water that already contains appreciable solutes, mineral-water reactions are less important than irrigation-water composition in determining groundwater chemistry.

Hydrogeology Journal↗

Aquatic photolysis: photolytic redox reactions between goethite and adsorbed organic acids in aqueous solutions

Photolysis of mono and di-carboxylic acids that are adsorbed onto the surface of the iron oxyhydroxide (goethite) results in an oxidation of the organic material and a reduction from Fe(III) to Fe(II) in the iron complex. There is a subsequent release of Fe2+ ions into solution. At constant light flux and constant solution light absorption, the factors responsible for the degree of photolytic reaction include: the number of lattice sites that are bonded by the organic acid; the rate of acid readsorption to the surface during photolysis; the conformation and structure of the organic acid; the degree of oxidation of the organic acid; the presence or absence of an ??-hydroxy group on the acid, the number of carbons in the di-acid chain and the conformation of the di-acid. The ability to liberate Fe(III) at pH 6.5 from the geothite lattice is described by the lyotropic series: tartrate>citrate> oxalate > glycolate > maleate > succinate > formate > fumarate > malonate > glutarate > benzoate = butanoate = control. Although a larger amount of iron is liberated, the series is almost the same at pH 5.5 except that oxalate > citrate and succinate > maleate. A set of rate equations are given that describe the release of iron from the goethite lattice. It was observed that the pH of the solution increases during photolysis if the solutions are not buffered. There is evidence to suggest the primary mechanism for all these reactions is an electron transfer from the organic ligand to the Fe(III) in the complex. Of all the iron-oxyhydroxide materials, crystalline goethite is the least soluble in water; yet, this study indicates that in an aqueous suspension, iron can be liberated from the goethite lattice. Further, it has been shown that photolysis can occur in a multiphase system at the sediment- water interface which results in an oxidation of the organic species and release of Fe2+ to solution where it becomes available for further reaction. ?? 1993.

Journal of Photochemistry and Photobiology A: Chem↗

Employment of Gibbs-Donnan-based concepts for interpretation of the properties of linear polyelectrolyte solutions

Earlier research has shown that the acid dissociation and metal ion complexation equilibria of linear, weak-acid polyelectrolytes and their cross-linked gel analogues are similarly sensitive to the counterion concentration levels of their solutions. Gibbs-Donnan-based concepts, applicable to the gel, are equally applicable to the linear polyelectrolyte for the accommodation of this sensitivity to ionic strength. This result is presumed to indicate that the linear polyelectrolyte in solution develops counterion-concentrating regions that closely resemble the gel phase of their analogues. Advantage has been taken of this description of linear polyelectrolytes to estimate the solvent uptake by these regions. ?? 1991 American Chemical Society.

Journal of Physical Chemistry↗

Aqueous photolysis of niclosamide

The photodegradation of [ 14 C]niclosamide was studied in sterile, pH 5, 7, and 9 buffered aqueous solutions under artificial sunlight at 25.0 ± 1.0 °C. Photolysis in pH 5 buffer is 4.3 times faster than in pH 9 buffer and 1.5 times faster than in pH 7 buffer. In the dark controls, niclosamide degraded only in the pH 5 buffer. After 360 h of continuous irradiation in pH 9 buffer, the chromatographic pattern of the degradates was the same regardless of which ring contained the radiolabel. An HPLC method was developed that confirmed these degradates to be carbon dioxide and two- and four-carbon aliphatic acids formed by cleavage of both aromatic rings. Carbon dioxide was the major degradate, comprising ∼40% of the initial radioactivity in the 360 h samples from both labels. The other degradates formed were oxalic acid, maleic acid, glyoxylic acid, and glyoxal. In addition, in the chloronitroaniline-labeled irradiated test solution, 2-chloro-4-nitroaniline was observed and identified after 48 h of irradiation but was not detected thereafter. No other aromatic compounds were isolated or observed in either labeled test system.

Journal of Agricultural and Food Chemistry↗

Cell dimensions and antiferromagnetism of lunar and terrestrial ilmenite single crystals

X-Ray diffraction and anisotropic magnetic measurements have been made on single crystals of lunar ilmenite and on terrestrial ilmenite from Bancroft, Ontario, Canada and the Ilmen Mountains, U.S.S.R. The elongated c "> c -axis of lunar ilmenite, previously reported, is confirmed by new measurements. The shorter c "> c -axis found in terrestrial specimens is ascribed to Fe 3+ substitution for Ti 4+ in the titanium layer. Magnetic measurements on the same specimens show that, in agreement with the Ishikawa-Shirane et al . model, the initial shortening of the c "> c -axis by the above substitution of small amounts of Fe 3+ (<8%) causes an increase in Fe 2+ −Fe 2+ exchange coupling through Fe 3+ in the titanium layer that lowers the Néel transition temperature. The Weiss temperatures and other magnetic parameters confirm this model proposed by Ishikawa and Shirane et al . Additional transitions found in one of the terrestrial specimens (Bancroft) have been ascribed to a small amount of an exsolved spinel phase, possibly a solid solution phase of magnetite-ülvospinel. The spinel phase is localized in hematite-rich blebs which exsolved from the host ilmenite-rich phase.

Journal of Physics and Chemistry of Solids↗

The system K2Mg2(SO4)3 (langbeinite)-K2Ca2(SO4)3 (calcium-langbeinite)

The join between the compositions K 2 Mg 2 (SO 4 ) 3 and K 2 Ca 2 (SO 4 ) 3 was studied by means of high-temperature equilibrium quenching techniques and by means of a heating stage mounted on an X-ray diffractometer. Complete solid solution exists in the system, but at 25°C members of the solid solution series are isometric only in the composition range 0–73·5 wt. per cent K 2 Ca 2 (SO 4 ) 3 . At compositions richer in K 2 Ca 2 (SO 4 ) 3 than 73·5 wt. per cent, members of the series are optically biaxial. At higher temperatures members of the solid solution series are isometric at successively more calcium-rich compositions and pure K 2 Ca 2 (SO 4 ) 3 is isometric above about 200 ± 2°C. The system is not binary, as mixtures richer in K 2 Ca 2 (SO 4 ) 3 than 42 wt. per cent decompose with the formation of liquid and CaSO 4 .

Journal of Inorganic and Nuclear Chemistry↗

The chemistry of eolian quartz dust and the origin of chert

Among the numerous models that have been suggested for the primary and predominant source of silica for chert, we suggest that eolian dust is worthy of further considerations. Such considerations are supported by the common association of Phanerozoic chert with evaporites, limestones, dolomites, or other strata that were deposited within or near arid paleoclimates. This association suggests a direct or indirect causal link between aridity and chert formation. In addition, eolian processes export large quantities of quartz-rich dust from arid climate ergs or loess lands. The chemistry of abraded quartz particles derived therefrom is consistent with chert formation. Abrasion of quartz particles produces an amorphous surface layer and underlying lattice disorder. An inverse relation between particle size distribution (< 64 μm) and the enthalpy of solution of abraded quartz is indicative of the degree of lattice disorder; as particle size decreases, the enthalpy of solution increases. The amorphous surface layer and underlying lattice disorder enhance both the rate and amount of dissolution of quartz dust particles; the solubilized silica can then be reprecipitated and diagenetically altered to the various silica polymorphs that occur in chert. An eolian supply and the chemistry of eolian abraded quartz particles may account for chert formation in disparate depositional environments that encompass deep-sea chert, chert in epicontinental seas including shallow shelves, and chert that formed in continental eolinites, lakes, and soils (arid climate silcretes).

Journal of Sedimentary Research↗

Nearshore versus offshore copper loading in Lake Superior sediments: Implications for transport and cycling

A thorough understanding of the fate and transport of metals in Lake Superior is necessary in order to predict the ability of Lake Superior to recover from anthropogenic perturbations (copper mining). Sediment cores were collected from nearshore and offshore sites in Lake Superior and used to evaluate spatial and temporal variations in copper loading associated with mining-related activities. Although both settings have been strongly affected by anthropogenic releases of copper, copper concentrations in nearshore cores are significantly greater than those found in offshore cores, implying that nearshore copper loading is dominated by simple deposition and burial of sediment generated from mining activities. Temporal variations in copper profiles in sediments from nearshore environments closelymimic copper production rates. Conversely, copper loading histories derived from offshore sediments are not well correlated to production rates. The offshore sediment cores, when compared with analogous cores from Lakes Ontario and Michigan, show that the average, lake-wide intensity of copper loading in Lake Superior is comparable to the other two lakes, despite the fact that Lake Superior has received the largest total burden of anthropogenic copper. Cu/Zn ratios, used to evaluate the amount of copper loading derived from mining discharges, vary strongly in nearshore environments in response to loading. Cu/Zn ratios in offshore sediments are much less variable, implying that copper loading may be regulated by additional mechanisms (solution chemistry and/or biologic uptake). Study of trace metal partitioning within Lake Superior sediments indicates that the organic fraction of the sediment contains the majority of the copper. Copper concentrations in offshore sediments are significantly correlated to organic carbon content of the sediment whereas copper concentrations in nearshore sediments are not. These findings support the model that transport and deposition of particles released from mining discharges dominate copper loading in nearshore sediments, whereas biologic uptake and settling of particulate organic matter may regulate copper loading in offshore sediments.

Journal of Great Lakes Research↗

The binary system K2SO4CaSO4

The binary system K 2 SO 4 CaSO 4 was studied by means of heating-cooling curves, differential thermal analysis, high-temperature quenching technique and by means of a heating stage mounted on an X-ray diffractometer. Compositions and quench products were identified optically and by X-ray. Limited solid solution of CaSO 4 in K 2 SO 4 was found. There is a eutectic at 875°C and 34 wt. per cent CaSO 4 . Calcium langbeinite melts incongruently at 1011°C. The melting-point of CaSO 4 (1462°C) was determined by the quenching technique using sealed platinum tubes. The only intermediate crystalline phase found in the system is K 2 SO 4 ·2CaSO 4 (calcium langbeinite).

Journal of Inorganic and Nuclear Chemistry↗

Global review reveals how disparate study motivations, analytical designs, and focal ions limit understanding of salinization effects on freshwater animals

Global salinization of freshwaters is adversely affecting biotic communities and ecosystem processes. We reviewed six decades (1960–2020) of literature published on animal responses to increased salinities across different taxonomic and ecological contexts and identified knowledge gaps. From 585 journal articles, we characterized 5924 responses of mollusks, crustaceans, zooplankton, non-arthropod invertebrates (NAI), insects, fishes, and amphibians to salinization. Insects and fishes were the most studied taxa; Na + and Cl − were the most studied ions − . Collectively, concentrations of the ions examined typically spanned five orders of magnitude. Species' invasiveness was a key motivation for studying mollusks, crustaceans, and fishes; threats of urbanization and road salts were key motivations for studying NAI, zooplankton, and amphibians. Laboratory studies were more common than field studies for most taxa. Focal life stages in laboratory studies varied widely but juveniles and adults were represented similarly in field studies. Studies of mollusks, NAI, and crustacean focused on adults; studies of zooplankton, insects, fishes, and amphibians focused on juveniles. Organismal- and population-level responses measuring solute uptake, internal chemistry, body condition, or ion concentrations predominated laboratory studies; population- and assemblage-level responses measuring abundance, spatial distribution, or assemblage composition predominated field studies. Negative responses to salinization predominated but positive and unimodal responses were apparent across all taxa and organizational levels. Key topics for further research include a) salinity responses by more taxa, b) responses to especially toxic ions (i.e., potassium, bicarbonate, sulfate, magnesium), c) mechanisms causing positive and unimodal responses, d) traits underpinning responses, e) effects transcending organizational levels, f) ion-specific response thresholds, and g) interactions between salinity and other stressors. Our review suggests inter-taxa variation in sensitivity to salinization reflects occurrence of certain biological traits, including gill-breathing, semi-permeable skin, multiple life stages, and limited mobility. We propose a traits-based framework to predict salinization sensitivity from shared traits. This evolutionary approach could inform management aimed at preventing or reducing adverse impacts of freshwater salinization.

Science of the Total Environment↗

Anion-exchange separation of Pt and Pd using perchloric and hydrochloric acid solutions

On Biorad Ag-1X8 anion-exchange resin (200-400 mesh), Pd and Pt may be separated from one another by elution with 0.2M HClO4, and 5M HClO4, respectively. If present, Au may be retained by making the elutriants 0.003M in HCl. Alternatively, reduction by H2SO3 enables elution of Pt2+ with 6M HCl before recovery of Pd2+ with 0.2M HClO4??Ir4+ is reduced to Ir3+ by H2SO3 and may be eluted ahead of Pt2+ by 2M HCl. ?? 1982 Akade??miai Kiado??.

Journal of Radioanalytical Chemistry↗

Modelling streamwater chemistry as a mixture of soilwater end-members - An application to the Panola Mountain catchment, Georgia, U.S.A.

Streamwater chemistry at Panola Mountain research catchment, Georgia, U.S.A., is explained as a mixture of representative soilwater solutions that are considered to be temporally invariant to a first approximation. The selection of three end-members from all sampled soil waters is evaluated by comparing the observed and predicted streamwater concentration of six solutes (alkalinity, sulfate, sodium, magnesium, calcium and dissolved silica), which are assumed to mix conservatively, and by assessing the consistency of the implied hydrograph separation with the hydrological mechanisms that are believed to be operating in this catchment. The percentage of variation in the streamwater solute concentrations explained by the end-member mixing analysis (EMMA) ranges from 82 to >97%, and the hydrograph separation is, intuitively, physically reasonable. If the correct end-members have been identified, the streamwater chemical response to different levels of acidic deposition can be predicted by examining the change in each end-member under different loads; no hydrological model is required. If a traditional hydrochemical model, which is driven by rainfall quantity and quality, is desired, this analysis provides an indication of the model structure that would be necessary to reproduce both streamwater and soilwater chemistry.

Georgia↗

Major geochemical processes in the evolution of carbonate-Aquifer systems

As a result of recent advances by carbonate petrologists and geochemists, hydrologists are provided with new insights into the origin and explanation of many aquifer characteristics and hydrologic phenomena. Some major advances include the recognition that: (1) most carbonate sediments are of biological origin; (2) they have a strong bimodal size-distribution; and (3) they originate in warm shallow seas. Although near-surface ocean water is oversaturated with respect to calcite, aragonite, dolomite and magnesite, the magnesium-hydration barrier effectively prevents either the organic or inorganic formation of dolomite and magnesite. Therefore, calcareous plants and animals produce only calcite and aragonite in hard parts of their bodies. Most carbonate aquifers that are composed of sand-size material have a high initial porosity; the sand grains that formed these aquifers originated primarily as small shells, broken shell fragments of larger invertebrates, or as chemically precipitated oolites. Carbonate rocks that originated as fine-grained muds were initially composed primarily of aragonite needles precipitated by algae and have extremely low permeability that requires fracturing and dissolution to develop into aquifers. Upon first emergence, most sand beds and reefs are good aquifers; on the other hand, the clay-sized carbonate material initially has high porosity but low permeability, a poor aquifer property. Without early fracture development in response to influences of tectonic activity these calcilutites would not begin to develop into aquifers. As a result of selective dissolution, inversion of the metastable aragonite to calcite, and recrystallization, the porosity is collected into larger void spaces, which may not change the overall porosity, but greatly increases permeability. Another major process which redistributes porosity and permeability in carbonates is dolomitization, which occurs in a variety of environments. These environments include back-reefs, where reflux dolomites may form, highly alkaline, on-shore and continental lakes, and sabkha flats; these dolomites are typically associated with evaporite minerals. However, these processes cannot account for most of the regionally extensive dolomites in the geologic record. A major environment of regional dolomitization is in the mixing zone (zone of dispersion) where profound changes in mineralogy and redistribution of porosity and permeability occur from the time of early emergence and continuing through the time when the rocks are well-developed aquifers. The reactions and processes, in response to mixing waters of differing chemical composition, include dissolution and precipitation of carbonate minerals in addition to dolomitization. An important control on permeability distribution in a mature aquifer system is the solution of dolomite with concomitant precipitation of calcite in response to gypsum dissolution (dedolomitization). Predictive models developed by mass-transfer calculations demonstrate the controlling reactions in aquifer systems through the constraints of mass balance and chemical equilibrium. An understanding of the origin, chemistry, mineralogy and environments of deposition and accumulation of carbonate minerals together with a comprehension of diagenetic processes that convert the sediments to rocks and geochemical, tectonic and hydrologic phenomena that create voids are important to hydrologists. With this knowledge, hydrologists are better able to predict porosity and permeability distribution in order to manage efficiently a carbonate-aquifer system.

Journal of Hydrology↗

The role of water in gas hydrate dissociation

When raised to temperatures above the ice melting point, gas hydrates release their gas in well-defined, reproducible events that occur within self-maintained temperature ranges slightly below the ice point. This behavior is observed for structure I (carbon dioxide, methane) and structure II gas hydrates (methane-ethane, and propane), including those formed with either H2O- or D2O-host frameworks, and dissociated at either ambient or elevated pressure conditions. We hypothesize that at temperatures above the H2O (or D2O) melting point: (1) hydrate dissociation produces water + gas instead of ice + gas, (2) the endothermic dissociation reaction lowers the temperature of the sample, causing the water product to freeze, (3) this phase transition buffers the sample temperatures within a narrow temperature range just below the ice point until dissociation goes to completion, and (4) the temperature depression below the pure ice melting point correlates with the average rate of dissociation and arises from solution of the hydrate-forming gas, released by dissociation, in the water phase at elevated concentrations. In addition, for hydrate that is partially dissociated to ice + gas at lower temperatures and then heated to temperatures above the ice point, all remaining hydrate dissociates to gas + liquid water as existing barriers to dissociation disappear. The enhanced dissociation rates at warmer temperatures are probably associated with faster gas transport pathways arising from the formation of water product.

Journal of Physical Chemistry B↗

Magmatic source of the opening phase of Kīlauea’s 2018 Lower East Rift Zone eruption

The 2018 eruption of Kīlauea volcano in its Lower East Rift Zone began with the discharge of evolved high-Ti basalt as weak lava fountains and short, slow-moving lava flows. The lavas were quickly geochemically recognized as being derived from magmas stored within the rift zone and remobilized by a new intrusion, a sequence that is common at Kīlauea. This initial phase of the 2018 eruption, referred to as phase 1a, lasted for 6 days and was followed by extrusion of mixed magma after a 3-day pause. Even though remobilization of older rift zone magmas is common within Kīlauea’s rift zones, it is difficult to determine which past intrusion(s) may have initially emplaced those stored magmas. This difficulty stems from the tendency for Kīlauea magmas to follow very similar differentiation paths without significant variations in major, minor, or even trace element chemistry. We investigate possible magma sources for the lavas erupted during phase 1a of the 2018 eruption using whole-rock, mineral, and glass major and trace element compositions from historical East Rift Zone eruptions with adjacent fissures. We consider two primary hypotheses for the phase 1a source: magmas associated with the 1955 Lower East Rift Zone eruption or the nine eruptions in the Middle and Upper East Rift Zone during the 1960s. Our results suggest that magma associated with the earliest phases of Kīlauea’s 1955 eruption was the most likely source of the 2018 phase 1a remobilized magma. We determine volatile saturation pressures from melt inclusion chemistry and find similar storage depths for the 2018 phase 1a and early 1955 magmas. The phase 1a and early 1955 lavas are nearly indistinguishable in all of the compositional criteria considered, implying that the leftover 1955 magma body barely cooled and differentiated in the 63 years between eruptions (cooling rates of ~0.1 °C/year). This study sheds light on the potential for protracted storage of eruptible magmas in rift zones at Kīlauea, and highlights some of the challenges and solutions to identifying genetic relationships between magmas at Kīlauea.

Hawaii↗