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Results for “Journal of Solution Chemistry”

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USGS1976

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↗

USGS2012

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↗

USGS1993

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↗

USGS2002

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↗

USGS2004

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↗

USGS1977

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↗

USGS1964

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↗

USGS2018

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↗

USGS1999

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↗

USGS1965

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↗

USGS2023

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↗

USGS1982

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↗

USGS1990

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↗

USGS2026

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↗

USGS2012

Rapid runoff via shallow throughflow and deeper preferential flow in a boreal catchment underlain by frozen silt (Alaska, USA)

In high-latitude catchments where permafrost is present, runoff dynamics are complicated by seasonal active-layer thaw, which may cause a change in the dominant flowpaths as water increasingly contacts mineral soils of low hydraulic conductivity. A 2-year study, conducted in an upland catchment in Alaska (USA) underlain by frozen, well-sorted eolian silt, examined changes in infiltration and runoff with thaw. It was hypothesized that rapid runoff would be maintained by flow through shallow soils during the early summer and deeper preferential flow later in the summer. Seasonal changes in soil moisture, infiltration, and runoff magnitude, location, and chemistry suggest that transport is rapid, even when soils are thawed to their maximum extent. Between June and September, a shift occurred in the location of runoff, consistent with subsurface preferential flow in steep and wet areas. Uranium isotopes suggest that late summer runoff erodes permafrost, indicating that substantial rapid flow may occur along the frozen boundary. Together, throughflow and deep preferential flow may limit upland boreal catchment water and solute storage, and subsequently biogeochemical cycling on seasonal to annual timescales. Deep preferential flow may be important for stream incision, network drainage development, and the release of ancient carbon to ecosystems

Alaska↗

USGS2021

Storm-scale and seasonal dynamics of carbon export from a nested subarctic watershed underlain by permafrost

Subarctic catchments underlain by permafrost sequester a major stock of frozen organic carbon (C), which may be mobilized as the Arctic warms. Warming can impact C export from thawing soils by altering the depth and timing of runoff related to changing storm and fire regimes and altered soil thaw depths. We investigated C export in a first order headwater stream (West Twin Creek) and its receiving third order river (Beaver Creek) in interior Alaska using discrete sampling of dissolved organic and inorganic C (DOC and DIC) and 15-min collection of specific conductance (SC), fluorescent dissolved organic matter (fDOM) and water discharge (Q). Storm SC-Q relationships displayed negative slopes, indicating solute limitation and limited influence of seasonal soil thaw on storm runoff chemistry. Concurrently, fDOM-Q displayed positive slopes that decreased over the summer, indicating flushing of a limited fDOM pool. Baseflow DIC increased over the season concurrent with soil thaw, with higher DIC at the larger scale indicating greater influence of deeper, mineral-rich flow paths. Storm and seasonal trends were generally similar at both scales. The biggest difference was in fDOM, which displayed higher concentrations and slower depletion in the first order stream. Improved process understanding from this study can be used to better predict carbon export and cycling by stream networks as northern forests and arctic regions continue to warm.

Alaska↗

USGS2021

Machine learning predictions of mean ages of shallow well samples in the Great Lakes Basin, USA

The travel time or “age” of groundwater affects catchment responses to hydrologic changes , geochemical reactions, and time lags between management actions and responses at down-gradient streams and wells. Use of atmospheric tracers has facilitated the characterization of groundwater ages, but most wells lack such measurements. This study applied machine learning to predict ages in wells across a large region around the Great Lakes Basin using well, chemistry, and landscape characteristics. For a dataset of age tracers in 961 samples, the travel time from the land surface to the sample location was estimated for each sample using parametric functions. The mean travel times were then modeled using a gradient boosting machine (GBM) algorithm with cross validation tuning of model metaparameters. The GBM approach was able to closely match estimated ages for the training data (RMSE = 0.26 natural-log scale years) and provided a reasonable match to testing data (RMSE = 0.84). Of the variables tested, well characteristics (e.g. depth), land use, hydrologic indicators (e.g. topographic wetness index), and water chemistry (e.g. nitrate, fluoride, and pH), substantially affected the predictions of age. GBM prediction was applied to 14,335 groundwater samples with median sample depth of 5.4 m, indicating for the Great Lakes Basin a broad distribution of ages among wells with a median of 32.9 years. Lag times of decades are likely for these wells to respond to changing solute fluxes near land surface. While depth variables most strongly affected predicted mean ages, chemical constituents exhibited smooth trends with age, consistent with prevailing conceptual models of evolving sources and geochemistry flowpaths. The results provide proof of concept for use of readily available variables of well, landscape, and chemical characteristics to improve groundwater age estimates across large regions.

Great Lakes basin↗

USGS2012

Chemistry of hydrothermal solutions from the southern Juan de Fuca Ridge

Fluids from three vent fields on the southern Juan de Fuca Ridge were sampled in September 1984 using the DSRV Alvin. The fluids are uniquely high in both chloride, which ranges up to twice the seawater value, and in metal content. Simple vapor-liquid phase separation could not have produced both the high chlorinity and gas concentrations observed in these fluids. The cause of the elevated chlorinity can not be uniquely identified but may be the result of either or a combination of two processes: (1) subsurface formation of a degassed brine and subsequent mixing of a small amount of this brine with a hydrothermal seawater which has not undergone a phase separation and (2) dissolution of a chloride-rich phase combined with a possible small loss of gas during sampling procedures. Although measured temperatures were all less than 300°C, quartz geothermometry suggests that the fluids have equilibrated at greater than 340°C. Quartz geobarometry is also in agreement with geophysical estimates of depth to the local magma chamber.

Journal of Geophysical Research B: Solid Earth↗