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At least 109 records · Page 6Linked to original sources
USGS1964

Geology and ground water of the Luke area, Maricopa County, Arizona

Luke Air Force Base, in the Salt River Valley in central Arizona. is within an intermontane basin--the Phoenix basin--in the Basin and Range lowlands province. The Luke area, the subject of this study, extends beyond the limits of the base. Ground-water resources of the Luke area were studied to determine the possibility of developing a water supply of optimum quantity and quality to supplement the base supply. Several wells drilled for this purpose, prior to the study, either produced an inadequate supply of water or produced ware-that had a high dissolved-solids content. The Phoenix basin is filled with unconsolidated to semiconsolidated Tertiary and Quaternary sedimentary rocks that are referred to as valley fill. Although its total thickness is unknown, 2,784 feet of valley fill--primarily consisting of clay, silt, sand, and gravel--has been penetrated. Percentage-distribution maps of fine-grained materials indicate a gross-facies pattern and a selective depositional area of the valley-fill materials. The maps also indicate that the areal distribution of fine-grained materials increases with depth. In general, the better producing wells, regardless of depth, are in areas where tee valley fill is composed of less than 60 percent fine-grained materials. The water table in the area is declining because large quantities of water are withdrawn and recharge is negligible. The decline near Luke Air Force Base during the period 1941-61 was about 150 feet. Ground water was moving generally southwest in the spring of 1961. Locally, changes in the direction of movement indicate diversion toward two major depressions. The dissolved-solids content of the ground water ranged from about 190 to 6,300 ppm. The highest concentration of dissolved solids is in water from the southern part of the area and seems to come from relatively shallow depths; wells in the northern part generally yield water of good quality. After a reconnaissance of the area, the U.S. Geological Survey located and supervised the drilling of two test wells--wells (B-2-1) 9bcb and (B-2-1) 5abc?on Luke Air Force Base. The quantity of water produced by the wells was adequate. The dissolved-solids content of water from the wells was low, and the overall quality of water from well (B-2-1) 5abc was good. When well (B-2-1) 9bcb was perforated between 907 and 977 feet, the water had a fluoride concentration of 4.4 ppm; however, the fluoride concentration decreased to 2.8 ppm when new perforations were cut at a shallower depth, and it was decided that dilution with other base water supplies probably would alleviate any possible fluoride problem.

Water Supply Paper↗
USGS1972

Chemical quality of the water in the Tucson basin, Arizona

The Tucson basin is a broad mountain-rimmed area of about 1,000 square miles in the Basin and Range physiographic province in southeastern Arizona. The altitude ranges from 2,000 feet in the basin to as much as 8,000 feat in the mountains. The major streams in the area are the Santa Cruz River and its principal tributaries--Cafiada del Oro, Rillito Creek, and Pantano Wash. The climate is semiarid, and the distribution and amount of precipitation vary greatly. The potential evapotranspiration is about four times the average annual precipitation. The streamflow is of excellent chemical quality, although most of the flow occurs during floods and generally has large concentrations of suspended sediment. Because of the erratic occurrence and quantity of streamflow and because of the lack of surface-water storage reservoirs, all the water for municipal, industrial, and agricultural uses is obtained from the many wells that tap the permeable sedimentary deposits, which constitute the principal aquifer in the Tucson basin. The aquifer consists of three sedimentary formations that range in age from middle Tertiary to Quaternary. The aquifer is as much as 2,000 feet thick and is composed mainly of sand, gravel, sandstone, and conglomerate. The upper part of the aquifer is more permeable than the lower part, and most wells obtain water at depths of less than 700 feet below the land surface. Most ground water contains less than 500 mg/l (milligrams per liter) of dissolved solids and is of suitable chemical quality for most uses. The water to depths of as much as 700 feet is a calcium sodium bicarbonate type, is hard to moderately hard, and contains less than 1.0 mg/l fluoride. Water at greater depth is a sodium bicarbonate type, is soft, and is of excellent chemical quality; however, water below about 1,0.00 feet may contain fluoride in excess of the maximum allowable limit of 1.4 mg/l for public supply. The ground water of poorest quality for public supply is at shallow depths along the major streams, in the Pantano Formation along the northeast margin of the basin, at depth in gypsiferous mudstone, and along a narrow zone that trends northwestward across the basin. Water from these hydrologic environ- may contain as much as 500 mg/1 dissolved solids an4 in places may contain more than 1,000 mg/1 dissolved solids. The anomalously large concentrations of calcium, bicarbonate, nitrate and sulfate in the ground water along the major streams, where the water table is from 25 to 150 feet below the land surface, are the result of near-surface phenomena. The large concentrations of these ions are derived from solution of relict salts, which were deposited in marshes along the streams prior to about 1900 by infiltrating surface water. In the narrow zone the trends northwestward across the basin, the large concentrations of calcium and sulfate are the result of the solution of limestone and gypsiferous mudstone in the sedimentary rocks in the headwaters area of Pantano Wash. The largest nitrate concentrations occur in the ground water along the Santa Cruz River; the nitrate probably is derived from irrigation return water, decayed vegetation from the marshes that occupied parts of the channel prior to 1900, and sewage effluent. Anomalously large concentrations of sodium, sulfate, chloride, and fluoride occur in ground water along the Santa Cruz River near the major faults that displace the older formations. These anomalously large concentrations probably are derived from the upward leakage of deep water that has reacted with the gypsiferous mudstone in the center of the basin and moved along the faults into the near-surface deposits. In the Tucson basin the water is divided into seven chemical types based on the relative amount of four major ions--calcium, sodium, bicarbonate, and sulfate---and the absolute amount of chloride. Most of the water is either a calcium sodium bicarbonate or a sodium bicarbonate type. Gr

Water Supply Paper↗
USGS1977

Solubility of natural fluorite at 25°C

The solubility products of two samples of natural fluorite from Rosiclare, Ill., and from Madoc, Ontario, were determined at 25°C by analyses of calcium and fluoride in sodium perchlorate solutions of varying ionic strength over a period of 3 years. Calcium concentrations were analyzed by atomic absorption spectrophotometry, fluoride concentrations were measured colorimetrically, and fluoride activities were measured using a specific ion electrode. The solubility products at the end of 3 years were determined by extrapolation to zero ionic strength. The final solubility product was found to be 10 -10.58±0.17 .

Journal of Research of the U.S. Geological Survey↗
USGS2002

A Geochemical Trophic Cascade in Yellowstone's Geothermal Environments

We contrast the geochemistry of the Madison drainage, which has high concentrations of geothermal features, with the Lamar drainage of Yellowstone National Park, USA, and trace the consequences of geochemical differences through abiotic and biotic linkages in the ecosystem. Waters in the geothermal-dominated drainage contained anomalously high levels of fluoride (F) and silica (SiO 2 ). Soils, stream sediments, and surface waters that interact or mix with geothermal waters, in turn, had elevated F and SiO 2 concentrations compared to similar samples from the Lamar drainage. The geochemical differences were reflected in the chemistry of forage plants, with some plants from geothermally influenced areas containing four- to eightfold higher concentrations of F and SiO 2 than similar plants in the Lamar drainage. Geothermal heat reduced snowpack, and we found that elk (Cervus elaphus) concentrated in these refugia as snowpack increased each winter. The consequent high dietary intake of F in animals associated with the geothermal areas was confirmed by the finding that bone samples from elk living in the Madison drainage contained sixfold higher concentrations of F than samples collected from animals wintering in the Lamar drainage. High F exposure resulted in compromised dentition due to fluoride toxicosis, which was undoubtedly exacerbated by the abrasive action of silica. The consequent accelerated and aberrant tooth wear resulted in early onset of senescence, reduced life span, and an abbreviated age structure. We speculate that these altered demographics, combined with spatial heterogeneity of snowpack, will result in increased vulnerability of this large herbivore population to wolf predation and less resiliency to compensate demographically for predation.

Wyoming↗
USGS1977

Fluorite solubility equilibria in selected geothermal waters

Calculation of chemical equilibria in 351 hot springs and surface waters from selected geothermal areas in the western United States indicate that the solubility of the mineral fluorite, CaF 2 , provides an equilibrium control on dissolved fluoride activity. Waters that are undersaturated have undergone dilution by non-thermal waters as shown by decreased conductivity and temperature values, and only 2% of the samples are supersaturated by more than the expected error. Calculations also demonstrate that simultaneous chemical equilibria between the thermal waters and calcite as well as fluorite minerals exist under a variety of conditions. Testing for fluorite solubility required a critical review of the thermodynamic data for fluorite. By applying multiple regression of a mathematical model to selected published data we have obtained revised estimates of the p K (10,96), ΔG o f (−280.08 kcal/mole), ΔH o f (−292.59 kcal/mole), S° (16.39 cal/deg/mole) and C o P (16.16 cal/deg/mole) for CaF 2 at 25°C and 1 atm. Association constants and reaction enthalpies for fluoride complexes with boron, calcium and iron are included in this review. The excellent agreement between the computer-based activity products and the revised p K suggests that the chemistry of geothermal waters may also be a guide to evaluating mineral solubility data where major discrepancies are evident.

Geochimica et Cosmochimica Acta↗
USGS1990

Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide

This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites is reflected in decreasing equilibrium constants for selenite with increasing adsorption density and both experimental observations and modeling results suggest that manganese dioxide has fewer sites of higher energy for selenite adsorption than amorphous iron oxyhydroxide. Modeling and interpreting the adsorption of phosphate, molybdate, and silicate on the oxides are made difficult by the lack of constraint in choosing surface species and the fact that equally good fits can be obtained with different surface species. Finally, predictions of anion competition using the model results from single adsorbate systems are not very successful because the model does not account for surface site heterogeneity. Selenite adsorption data from a multi-adsorbate system could be fit if the equilibrium constant for selenite is decreased with increasing anion adsorption density.

Geochimica et Cosmochimica Acta↗
USGS1995

A comparison of two nitrification inhibitors used to measure nitrification rates in estuarine sediments

Nitrification rates were measured using intact sediment cores from South San Francisco Bay and two different nitrification inhibitors: acetylene and methyl fluoride. Sediment oxygen consumption and ammonium and nitrate fluxes were also measured in these cores. Four experiments were conducted in the spring, and one in the fall of 1993. There was no significant difference in nitrification rates measured using the two inhibitors, which suggests that methyl fluoride can be used as an effective inhibitor of nitrification. Nitrification was positively correlated with sediment oxygen consumption and numbers of macrofauna. This suggests that bioturbation by macrofauna is an important control of nitrification rates. Irrigation by the tube-dwelling polychaete, Asychis elongata, which dominates the benthic biomass at this location, appears particularly important. Ammonium fluxes out of the sediment were greatest about one week after the spring bloom, while nitrification peaked about one month later.

FEMS Microbiology Ecology↗
USGS1996

Mount St. Augustine volcano fumarole wall rock alteration: Mineralogy, zoning, composition and numerical models of its formation process

Intensely altered wall rock was collected from high-temperature (640 °C) and low-temperature (375 °C) vents at Augustine volcano in July 1989. The high-temperature altered rock exhibits distinct mineral zoning differentiated by color bands. In order of decreasing temperature, the color bands and their mineral assemblages are: (a) white to grey (tridymite-anhydrite); (b) pink to red (tridymite-hematite-Fe hydroxide-molysite (FeCl 3 ) with minor amounts of anhydrite and halite); and (c) dark green to green (anhydrite-halite-sylvite-tridymite with minor amounts of molysite, soda and potash alum, and other sodium and potassium sulfates). The alteration products around the low-temperature vents are dominantly cristobalite and amorphous silica with minor potash and soda alum, aphthitalite, alunogen and anhydrite. Compared to fresh 1986 Augustine lava, the altered rocks exhibit enrichments in silica, base metals, halogens and sulfur and show very strong depletions in Al in all alteration zones and in iron, alkali and alkaline earth elements in some of the alteration zones. To help understand the origins of the mineral assemblages in altered Augustine rocks, we applied the thermochemical modeling program, GASWORKS, in calculations of: (a) reaction of the 1987 and 1989 gases with wall rock at 640 and 375 °C; (b) cooling of the 1987 gas from 870 to 100 °C with and without mineral fractionation; (c) cooling of the 1989 gas from 757 to 100 °C with and without mineral fractionation; and (d) mixing of the 1987 and 1989 gases with air. The 640 °C gas-rock reaction produces an assemblage consisting of silicates (tridymite, albite, diopside, sanidine and andalusite), oxides (magnetite and hercynite) and sulfides (bornite, chalcocite, molybdenite and sphalerite). The 375 °C gas-rock reaction produces dominantly silicates (quartz, albite, andalusite, microcline, cordierite, anorthite and tremolite) and subordinate amounts of sulfides (pyrite, chalcocite and wurtzite), oxides (magnetite), sulfates (anhydrite) and halides (halite). The cooling calculations produce: (a) anhydrite, halite, sylvite; (b) Cu, Mo, Fe and Zn sulfides; (c) Mg fluoride at high temperature (> 370 °C); (d) chlorides, fluorides and sulfates of Mn, Fe, Zn, Cu and Al at intermediate temperature (170–370 °C); and (e) hydrated sulfates, liquid sulfur, crystalline sulfur, hydrated sulfuric acid and water at low temperature (< 170°C). The volcanic gas-air mixing calculation produces major amounts of Na and K sulfates, minor amounts of hematite and trace amounts (< 1%) of anhydrite at log gas/air (Ig/a) ratios > 0.41 (> 628°C). This is followed by precipitation of sulfates of Fe, Cu. Pb. Zn and Al at Ig/a ratios between 0.31 and -0.4 (>628-178°C). At a lg/r ratio of ≤ -0.4 (178°C). anhydrous sulfates are replaced by their hydrated forms and hygroscopic sulfuric acid forms. At these low g/a ratios. hydrated sulfuric acid becomes the dominant phase in the system. Comparison of the thermochemical modeling results with the natural samples suggests that the alteration assemblages include: (1) minerals that precipitate from direct cooling of the volcanic gas; (2) phases that form by volcanic gases mixing with air: and (3) phases that form by volcanic gas-air-rock reaction. A complex interplay of the three processes produces the observed mineral zoning. Another implication of the numerical simulation results is that most of the observed incrustation and sublimate minerals apparently formed below 700°C.

Journal of Volcanology and Geothermal Research↗
USGS2025

Statewide cumulative human health risk assessment of inorganics-contaminated groundwater wells, Montana, USA

Across the United States, rural residents rely on unregulated and generally unmonitored private wells for drinking water, which may pose serious health risks due to unrecognized contaminants. We assessed the nature, degree, and spatial distribution of cumulative health risks from inorganic contaminants in groundwater. Our analysis included nearly 84,000 data points from 6500+ wells, across 51 of Montana's 98 watersheds, using a public groundwater database. We compared a drinking water screening level cumulative risk assessment (CRA) for inorganics based on the U.S. Environmental Protection Agency (EPA) protective health thresholds (Maximum Contaminant Level Goals, Health Advisories [MCLG-HAs]) to a CRA based on EPA public supply enforceable Maximum Contaminant Levels (MCLs). Based on median concentrations of 19 inorganics (antimony, arsenic, barium, beryllium, boron, cadmium, chromium, copper, fluoride, manganese, molybdenum, nickel, nitrate, lead, selenium, strontium, thallium, uranium, zinc), 75% of watersheds had MCLG-HA-based cumulative risk values > 1.0; arsenic and uranium contributed the most risk, followed by strontium, fluoride, manganese and boron. Hence, this screening level (Tier I) CRA indicated widespread potential for unrecognized human health risk to private well users from inorganic contaminants considering both carcinogenic and non-carcinogenic risks. Sensitivity analysis showed that benchmarks applied (MCLG-HAs versus MCLs) exerted the largest control on results. Our findings identify priority regions for Tier 2 risk assessments to elucidate local sources and distributions of geogenic versus anthropomorphic contaminants. Our study is the first statewide assessment of cumulative health risk from groundwater that we are aware of, and results support increased statewide drinking water education and testing to reduce human health risks from contaminated private well water.

Montana↗
USGS2020

Sources, fate, and flux of riverine solutes in the Southwest Yellowstone Plateau Volcanic Field, USA

Since the 1970s, temporal variations of hydrothermal discharge and thermal output from the numerous hydrothermal features in the Yellowstone Plateau Volcanic Field (YPVF) have been studied by measuring the chloride flux in the major rivers. In this study, the sources, fate, and flux of solutes in the Fall River and its major tributaries, in southwest Yellowstone National Park, were determined. The considerable precipitation in southwest YPVF and high groundwater flow through Quaternary rhyolites results in river solute fluxes that originate from shallow non-thermal groundwater and deep-thermal water. Specific conductance serves as a surrogate measure for thirteen riverine solute concentrations. Combining continuous 15-minute specific conductance and discharge data, the annual chloride, arsenic, fluoride, and silica fluxes from the Fall River were determined to be 11%, 5%, 25%, and 19% of the total flux exiting YPVF. Approximately 11% of the Fall River chloride flux is from non-thermal waters, which is larger than the previous estimate of 4 to 6%. Furthermore, a large proportion of fluoride and silica in the Fall River are derived from water-rock interaction in the shallow non-thermal groundwater system and the non-thermal weathering rate (30 ± 2 t/yr·km 2 ) is higher than other rivers draining the Yellowstone caldera. Consequently, 73 ± 3% of the annual total dissolved solid flux in the Fall River is from thermal sources. Synoptic sampling of river water and discharge measurements was performed during low-flow conditions that allowed for the determination of solute sources and their downstream fate. It was determined that chloride, sodium, arsenic, rubidium, lithium, and boron are primarily (>89%) associated with thermal waters and the Bechler River is the primary source of most hydrothermal solutes in the Fall River, but the major source of arsenic is Boundary Creek. Using the chloride inventory method, the thermal water discharge from several thermal areas was also determined.

Wyoming↗
USGS1965

Solution of rocks and refractory minerals by acids at high temperatures and pressures. Determination of silica after decomposition with hydrofluoric acid

A modified Morey bomb was designed which contains a removable nichromecased 3.5-ml platinium crucible. This bomb is particularly useful for decompositions of refractory samples for micro- and semimicro-analysis. Temperatures of 400–450° and pressures estimated as great as 6000 p.s.i. were maintained in the bomb for periods as long as 24 h. Complete decompositions of rocks, garnet, beryl, chrysoberyl, phenacite, sapphirine, and kyanite were obtained with hydrofluoric acid or a mixture of hydrofluoric and sulfuric acids; the decomposition of chrome refractory was made with hydrochloric acid. Aluminum-rich samples formed difficultly soluble aluminum fluoride precipitates. Because no volatilization losses occur, silica can be determined on sample solutions by a molybdenum-blue procedure using aluminum(III) to complex interfering fluoride.

Analytica Chimica Acta↗
USGS2002

Aromatic fluorine compounds. XI. Replacement of chlorine by fluorine in halopyridines

The α -halogenated pyridines react with potassium fluoride in various solvents to give replacement of the α -halogen by fluorine. A 50% yield of 2-fluoropyridine was obtained from 2-chloropyridine by heating with potassium fluoride in dimethyl sulfone or tetramethylene sulfone for twenty-one days; 2-bromopyridine gave a similar yield with a heating period of only seven days. The α -halogens of the polyhalopyridines undergo the exchange reaction more readily than do the halogens of the α -monohalopyridines. The proposed structures of the fluoropyridines are supported by alternate syntheses and by n.m.r. studies.

Journal of Organic Chemistry↗
USGS1997

Inhibition of methane oxidation by Methylococcus capsulatus with hydrochlorofluorocarbons and fluorinated methanes

The inhibition of methane oxidation by cell suspensions of Methylococcus capsulatus (Bath) exposed to hydrochlorofluorocarbon 21 (HCFC-21; difluorochloromethane [CHF 2 Cl]), HCFC-22 (fluorodichloromethane [CHFCl 2 ]), and various fluorinated methanes was investigated. HCFC-21 inhibited methane oxidation to a greater extent than HCFC-22, for both the particulate and soluble methane monooxygenases. Among the fluorinated methanes, both methyl fluoride (CH 3 F) and difluoromethane (CH 2 F 2 ) were inhibitory while fluoroform (CHF 3 ) and carbon tetrafluoride (CF 4 ) were not. The inhibition of methane oxidation by HCFC-21 and HCFC-22 was irreversible, while that by methyl fluoride was reversible. The HCFCs also proved inhibitory to methanol dehydrogenase, which suggests that they disrupt other aspects of C1 catabolism in addition to methane monooxygenase activity.

Applied and Environmental Microbiology↗
USGS1998

Difluoromethane, a new and improved inhibitor of methanotrophy

Difluoromethane (HFC-32; DFM) is compared to acetylene and methyl fluoride as an inhibitor of methanotrophy in cultures and soils. DFM was found to be a reversible inhibitor of CH 4 oxidation by Methylococcus capsulatus (Bath). Consumption of CH 4 in soil was blocked by additions of low levels of DFM (0.03 kPa), and this inhibition was reversed by DFM removal. Although a small quantity of DFM was consumed during these incubations, its remaining concentration was sufficiently elevated to sustain inhibition. Methanogenesis in anaerobic soil slurries, including acetoclastic methanogenesis, was unaffected by levels of DFM which inhibit methanotrophy. Low levels of DFM (0.03 kPa) also inhibited nitrification and N 2 O production by soils. DFM is proposed as an improved inhibitor of CH 4 oxidation over acetylene and/or methyl fluoride on the basis of its reversibility, its efficacy at low concentrations, its lack of inhibition of methanogenesis, and its low cost.

Applied and Environmental Microbiology↗
USGS1999

Oxidation of methyl halides by the facultative methylotroph strain IMB-1

Washed cell suspensions of the facultative methylotroph strain IMB-1 grown on methyl bromide (MeBr) were able to consume methyl chloride (MeCl) and methyl iodide (MeI) as well as MeBr. Consumption of >100 μM MeBr by cells grown on glucose, acetate, or monomethylamine required induction. Induction was inhibited by chloramphenicol. However, cells had a constitutive ability to consume low concentrations (<20 nM) of MeBr. Glucose-grown cells were able to readily oxidize [ 14 C]formaldehyde to 14 CO 2 but had only a small capacity for oxidation of [ 14 C]methanol. Preincubation of cells with MeBr did not affect either activity, but MeBr-induced cells had a greater capacity for [ 14 C]MeBr oxidation than did cells without preincubation. Consumption of MeBr was inhibited by MeI, and MeCl consumption was inhibited by MeBr. No inhibition of MeBr consumption occurred with methyl fluoride, propyl iodide, dibromomethane, dichloromethane, or difluoromethane, and in addition cells did not oxidize any of these compounds. Cells displayed Michaelis-Menten kinetics for the various methyl halides, with apparent K s values of 190, 280, and 6,100 nM for MeBr, MeI, and MeCl, respectively. These results suggest the presence of a single oxidation enzyme system specific for methyl halides (other than methyl fluoride) which runs through formaldehyde to CO 2 . The ease of induction of methyl halide oxidation in strain IMB-1 should facilitate its mass culture for the purpose of reducing MeBr emissions to the atmosphere from fumigated soils.

Applied and Environmental Microbiology↗
USGS1996

Deicing chemicals as source of constituents of highway runoff

The dissolved major and trace constituents of deicing chemicals as a source of constituents in highway runoff must be quantified for interpretive studies of highway runoff and its effects on surface water and groundwater. Dissolved constituents of the deicing chemicals—sodium chloride, calcium chloride, and premix (a mixture of sodium and calcium chloride)—were determined by analysis of salt solutions created in the laboratory and are presented as mass ratios to chloride. Deicing chemical samples studied are about 98 and 97 percent pure sodium chloride and calcium chloride, respectively; however, each has a distinct major and trace ion constituent signature. The greatest impurity in sodium chloride road salt samples was sulfate, followed by calcium, potassium, bromide, vanadium, magnesium, fluoride, and other constituents with a ratio to chloride of less than 0.0001 by mass. The greatest impurity in the calcium chloride road salt samples was sodium, followed by potassium, sulfate, bromide, silica, fluoride, strontium, magnesium, and other constituents with a ratio to chloride of less than 0.0001 by mass. Major constituents of deicing chemicals in highway runoff may account for a substantial source of annual chemical loads. Comparison of estimated annual loads and first flush concentrations of deicing chemical constituents in highway runoff with those reported in the literature indicate that although deicing chemicals are not a primary source of trace constituents, they are not a trivial source, either. Therefore, deicing chemicals should be considered as a source of many major and trace constituents in highway and urban runoff.

Transportation Research Record↗
USGS2022

Evaluation for internal consistency in the thermodynamic network involving fluorite, cryolite and villiaumite solubilities and aqueous species at 25°C and 1 bar

Thermodynamic data are constrained by the interrelated thermodynamic equations in addition to the observational measurements and their uncertainties. The consequence is a network of thermodynamic properties that can be evaluated for their internal consistency. In this study, three fluoride minerals that can cause high fluoride concentrations in groundwaters are evaluated for their solubilities and their internal thermodynamic consistency with calorimetric, isopiestic and electrochemical measurements: fluorite, CaF 2 , cryolite, Na 3 AlF 6 , and villiaumite, NaF. This evaluation involves the three solids and 13 aqueous species, the free ions of Ca 2+ , Na + , Al 3+ and F – , and the hydroxido and fluorido complexes of Al 3+ , and the CaF + ion pair. For the fluorite–cryolite–villiaumite–aqueous species network, the number of components is minimal, and the solubility studies are mostly of high quality. Re-evaluations of original data using PHREEQC helps to broaden the quantitative evaluation of thermodynamic properties and to resolve apparent discrepancies. A check on this thermodynamic network shows that through a careful appraisal of the literature, a highly consistent set of values can be derived. The resultant infinite-dilution solubility-product constants at 25°C and 1 bar are: for fluorite solubility, log K sp = –10.57 ± 0.08; for cryolite solubility, log K sp = –33.9 ± 0.2; and for villiaumite solubility, log K sp = –0.4981 ± 0.003.

Mineralogical Magazine↗
USGS1961

Sulfide ores formed from sulfide-deficient solutions 1

Assuming that many hydrothermal ore deposits are formed from emanations given off from a magma at depth while it cools through the interval in which latent heat of crystallization is generated, it is shown that this cooling interval for magmatic bodies of moderate size must be measured in tens or hundreds of thousands of years. Emanations from such a magma should change at the source with time: relatively insoluble volatiles should depart early and the more soluble ones late; the general order is probably sulfur gases and oxides of carbon, water, chlorides, and fluorides. Experimental and field evidence indicates that this order approximates the increasing solubility of these gases in natural magmas. Theoretical considerations show that within a hydrothermal conduit a relatively small gradient would soon be established between the magma and the surface. A small gradient suggests that temperature drop is a minor factor in precipitating substances in solution , whereas a drop in pressure and reaction with wall rocks or with material precipitated from earlier emanations would be of major importance. The sulfur-rich early emanations tend to react with indigenous iron of the country rock, or with iron carried by carbon dioxide-rich solutions to where a marked pressure drop occurs; either of these reactions will form abundant early iron sulfide . Later sulfur-deficient emanations, which then carry soluble halides of ore metals, react with this early iron sulfide to precipitate the ore mineral sulfides by replacement and deposition with loss of iron to the solution . Precipitation of much sulfide ore is thus commonly accomplished by sulfur that was fixed near the site of the ore body by earlier emanations from the magmatic source; a large amount of ore , however, may be precipitated from late-stage magmatic solutions where they mingle with early-stage sulfur-bearing solutions from a different magmatic source.

Economic Geology↗