Evaluating the use of 3'-(p-Aminophenyl) fluorescein for determining the formation of highly reactive oxygen species in particle suspensions

Background  

Given the importance of highly reactive oxygen species (hROS) as reactants in a wide range of biological, photochemical, and environmental systems there is an interest in detection and quantification of these species. The extreme reactivity of the hROS, which includes hydroxyl radicals, presents an analytical challenge. 3'-(p-Aminophenyl) fluorescein (APF) is a relatively new probe used for measuring hROS. Here, we further evaluate the use of APF as a method for the detection of hydroxyl radicals in particle suspensions.     

Crystal field and covalency of octahedral chromium in natural [8](Mg1?xCax) 3[6] (Al0.67Cr0.33)2Si3O12 garnets from upper mantle rocks

In the course of a thorough study of the influences of the second coordination sphere on the crystal field parameters of the 3d ^N -ions and the character of 3d ^N –O bonds in oxygen based minerals, 19 natural Cr³⁺-bearing (Mg,Ca)-garnets from upper mantle rocks were analysed and studied by electronic absorption spectroscopy, EAS. The garnets had compositions with populations of the ^[8] X-sites by 0.881 ± 0.053 (Ca + Mg) and changing Ca-fractions in the range 0.020 ≤ w _Ca[8] ≤ 0.745, while the ^[6] Y-site fraction was constant with x _Cr³⁺ _[6] = 0.335 ± 0.023. The garnets had colours from deeply violet-red for low Ca-contents (up to x _Ca = 0.28), grey with 0.28 ≤ x _Ca ≤ 0.4 and green with 0.4 ≤ x _Ca. The crystal field parameter of octahedral Cr³⁺ 10Dq decreases strongly on increasing Ca-fraction from 17,850 cm⁻¹ at x _Ca[8] = 0.020 to 16,580 cm⁻¹ at x _Ca[8] = 0.745. The data could be fit with two model which do statistically not differ: (1) two linear functions with a discontinuity close to x _Ca[8] ≈ 0.3,

Periodic density functional theory calculations of bulk and the (010) surface of goethite

Background  

Goethite is a common and reactive mineral in the environment. The transport of contaminants and anaerobic respiration of microbes are significantly affected by adsorption and reduction reactions involving goethite. An understanding of the mineral-water interface of goethite is critical for determining the molecular-scale mechanisms of adsorption and reduction reactions. In this study, periodic density functional theory (DFT) calculations were performed on the mineral goethite and its (010) surface, using the Vienna Ab Initio Simulation Package (VASP).     

Methane and carbon at equilibrium in source rocks

Background

Previously described methods to separate dissolved U(IV) from dissolved U(VI) under acidic anoxic conditions prior to laboratory analysis were ineffective with materials currently available commercially. Three strong anion exchange resins were examined for their efficiency in separating, recovering, and preserving both redox states during separation.

Results

Under oxic conditions, recovery of U(VI) from three exchange resins (Bio-Rad AG® 1x8 Poly-Prep® prefilled columns, Bio-Rad AG® 1x8 powder, and Dowex® 1x8 powder) ranged from 72% to 100% depending on the dosed mass, eluent volume, and resin selected. Dowex® 1x8 resin was the only resin found to provide 100% recovery of U(VI) with fewer than 5 bed volumes of eluent. Under anoxic conditions, all three resins oxidized U(IV) in aqueous solutions with relatively low U(IV) concentrations (<3x10^-6 M). Resin-induced oxidation was observed visually using a leuco dye, safranin-o. Oxidants associated with the resin were irreversibly reduced by the addition of Ti(III). After anoxic resin pre-treatment, a series of U(IV)/U(VI) mixtures at micro-molar levels were prepared and separated using the Dowex® 1x8 resin with 100% recovery of both U(IV) and U(VI) with no resin-induced changes in oxidation state.

Conclusions

Currently available anion exchange resins with apparently identical physical properties were found to have significantly different recoveries for hexavalent uranium at micro-molar concentrations. A novel qualitative technique was developed to visually assess oxidative capacities of anion exchange resins under acidic anoxic conditions. A protocol was developed for pre-treatment and use of currently available anion exchange resins to achieve quantitative separation of U(IV) and U(VI) in aqueous solutions with low U(IV) concentrations. This method can be applied to future work to quantitatively assess dissolved U(IV) and U(VI) concentrations in both laboratory and field samples.     

Ab initio study of the high-pressure behavior of CaSiO3 perovskite

Using density functional simulations, within the generalized gradient approximation and projector-augmented wave method, we study structures and energetics of CaSiO₃ perovskite in the pressure range of the Earths lower mantle (0–150 GPa). At zero Kelvin temperature the cubic CaSiO₃ perovskite structure is unstable in the whole pressure range, at low pressures the orthorhombic (Pnam) structure is preferred. At 14.2 GPa there is a phase transition to the tetragonal (I4/mcm) phase. The CaIrO₃-type structure is not stable for CaSiO₃. Our results also rule out the possibility of decomposition into oxides.

Measurement of the Isotopic Composition of Molybdenum in Geological Samples by MC‐ICP‐MS using a Novel Chromatographic Extraction Technique

A novel preconcentration method is presented for the determination of Mo isotope ratios by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS) in geological samples. The method is based on the separation of Mo by extraction chromatography using N‐benzoyl‐N‐phenylhydroxylamine (BPHA) supported on a microporous acrylic ester polymeric resin (Amberlite CG‐71). By optimising the procedure, Mo could be simply and effectively separated from virtually all matrix elements with a single pass through a small volume of BPHA resin (0.5 ml). This technique for separation and enrichment of Mo is characterised by high selectivity, column efficiency and recovery (~ 100%), and low total procedural blank (~ 0.18 ng). A ¹⁰⁰Mo‐⁹⁷Mo double spike was mixed with samples before digestion and column separation, which enabled natural mass‐dependent isotopic fractionation to be determined with a measurement reproducibility of  < 0.09‰ (δ^98/95Mo, 2s) by MC‐ICP‐MS. The mean δ^98/95Mo_{SRM 3134} (NIST SRM 3134 Mo reference material; Lot No. 891307) composition of the IAPSO seawater reference material measured in this study was 2.00 ± 0.03‰ (2s, n = 3), which is consistent with previously published values. The described procedure facilitated efficient and rapid Mo isotopic determination in various types of geological samples.     

利用套柱法快速分离提纯Sr和Nd元素

样品放射性成因Sr-Nd同位素比值受控于源区初始同位素组成、放射性元素母体与子体相对丰度,以及衰变时间等因素。它们具有极强的示踪能力,因而在地质学领域有广泛的应用。传统的Sr-Nd同位素分析使用的是阳离子树脂,提纯Nd元素时往往涉及有机试剂以及调节pH值等操作,其分析效率较低。近年来特效树脂的出现使得分离这些元素变得简单,但是受硫酸根等因素影响,特效树脂使用次数有限。为了提高分析效率,缩短分析时间,本文开发了一种套柱法,该方法结合阳离子树脂和特效树脂,实现了Sr-Nd元素的快速分离,并且能延长特效树脂的使用寿命。实验采用阳离子树脂、Sr特效树脂和LN稀土特效树脂对玄武岩BCR-2标样进行了分析。Sr-Nd回收率均90%,BCR-2玄武岩~(87)Sr/~(86)Sr比值为0.705016±0.000016(n=36,1SD),~(143)Nd/~(144)Nd比值为0.512624±0.000012(n=39,1SD),与前人TIMS法获得的结果吻合(~(87)Sr/~(86)Sr:0.705000～0.705023;~(143)Nd/~(144)Nd:0.512630～0.512650)。最终分离提纯的溶液中~(85)Rb/~(86)Sr值小于0.01,~(147)Sm/~(144)Nd值小于0.001,表明该方法可以高效分离Rb-Sr和Sm-Nd,实现Sr、Nd同位素的准确分析。     

Oxygen isotopic fractionation during inorganic calcite precipitation ― Effects of temperature, precipitation rate and pH

Stable oxygen isotopic fractionation during inorganic calcite precipitation was experimentally studied by spontaneous precipitation at various pH (8.3 < pH < 10.5), precipitation rates (1.8 < log R < 4.4 μmol m^− 2 h^− 1) and temperatures (5, 25, and 40 °C) using the CO₂ diffusion technique.The results show that the apparent stable oxygen isotopic fractionation factor between calcite and water (α_{calcite–water}) is affected by temperature, the pH of the solution, and the precipitation rate of calcite. Isotopic equilibrium is not maintained during spontaneous precipitation from the solution. Under isotopic non-equilibrium conditions, at a constant temperature and precipitation rate, apparent 1000lnα_{calcite–water} decreases with increasing pH of the solution. If the temperature and pH are held constant, apparent 1000lnα_{calcite–water} values decrease with elevated precipitation rates of calcite. At pH = 8.3, oxygen isotopic fractionation between inorganically precipitated calcite and water as a function of the precipitation rate (R) can be described by the expressions

at 5, 25, and 40 °C, respectively.The impact of precipitation rate on 1000lnα_{calcite–water} value in our experiments clearly indicates a kinetic effect on oxygen isotopic fractionation during calcite precipitation from aqueous solution, even if calcite precipitated slowly from aqueous solution at the given temperature range. Our results support Coplen's work [Coplen T. B. (2007) Calibration of the calcite–water oxygen isotope geothermometer at Devils Hole, Nevada, a natural laboratory. Geochim. Cosmochim. Acta 71, 3948–3957], which indicates that the equilibrium oxygen isotopic fractionation factor might be greater than the commonly accepted value.     

Identification of non-indigenous phytoplankton species dominated bloom off Goa using inverted microscopy and pigment (HPLC) analysis

An unusual phytoplankton bloom dominated by unidentified green coloured spherical algal cells (∼5μm diameter) and dinoflagellates (Heterocapsa, Scripsiella and Gymnodinium) was encountered along the coast of Goa, India during 27 and 29 January, 2005. Pigment analysis was carried out using both fluorometric and HPLC methods. Seawater samples collected from various depths within the intense bloom area showed high concentrations of Chl a (up to 106 mg m^− 3) associated with low bacterial production (0.31 to 0.52 mg C m^− 3 h^− 1) and mesozooplankton biomass (0.03 ml m^− 3). Pigment analyses of the seawater samples were done using HPLC detected marker pigments corresponding to prasinophytes, dinoflagellates and diatoms. Chlorophyll b (36–56%) followed by peridinin (15–30%), prasinoxanthin (11–17%) and fucoxanthin (7–15%) were the major diagnostic pigments while pigments of cryptophytes and cyanobacteria including alloxanthin and zeaxanthin formed <10%. Although microscopic analysis indicated a decline in the bloom, pheaophytin concentrations in the water column measured by both techniques were very low, presumably due to fast recycling and/or settling rate. The unique composition of the bloom and its probable causes are discussed in this paper.     

Heat capacity, entropy, and magnetic properties of jarosite-group compounds

Jarosite phases are common minerals in acidic, sulfate-rich environments. Here, we report heat capacities (C _p) and standard entropies (S°) for a number of jarosite samples. Most samples are close to the nominal composition AFe₃(SO₄)₂(OH)₆, where A = K, Na, Rb, and NH₄. One of the samples has a significant number of defects on the Fe sites and is called the defect jarosite; others are referred to as A-jarosite. The samples, their compositions, and the entropies at T = 298.15 K are:

Sensitivity of high-resolution tropical cyclone intensity forecasts to surface flux parameterization

Surface flux parameterization schemes used in current dynamic models are primarily based upon measurements at low and moderate wind speeds. Recent studies show that these parameterization schemes may be incorrect at high wind speeds (e.g., tropical cyclone forecasts). Five high-resolution numerical model experiments are designed to assess the sensitivity of tropical cyclone intensity forecasts to changes in the surface flux parameterization. The sensitivity experiments are conducted by running 48 h forecasts of the Coupled Ocean/Atmosphere Mesoscale Prediction System (COAMPS) for six selected tropical cyclones with individual modifications to surface flux calculation that include: (1) limiting the surface stress for wind speeds greater than 33 m s⁻¹, or 64 knots (kt); (2) computing the stress at the top of the model bottom grid layer (MBGL) by averaging results from surface layer similarity and turbulence mixing parameterization for wind speeds greater than 33 m s⁻¹; (3) increasing the roughness lengths for heat and moisture transfer by a factor of ten; (4) setting the roughness lengths for heat and moisture transfer to 1/10 of the momentum roughness length; and (5) cooling the sea surface temperature (SST) by a prescribed rate at high winds. Averaged responses for the six storms to these sensitivity tests show that: (i) the limit on surface stress at high winds significantly increases the cyclone intensity in 48 h forecasts; (ii) the averaged surface layer stress at high winds increases the cyclone intensity but to a much lesser degree than limiting the surface stress; (iii) large increases in the roughness lengths for heat and moisture transfer are needed to significantly impact the intensity forecast; (iv) the different roughness length formula for surface transfer coefficients notably increases C _h/C _d ratio from 0.59 to 0.79 for 25 m s⁻¹ and 0.41 to 0.75 for 50 m s⁻¹ that significantly increases the predicted cyclone intensity; and (v) cooling of the SST by −5.8°C in 48 h reduces the maximum surface wind speed by −32 kt, or 16.5 m s⁻¹, at 48 h forecast. These results suggest that a surface flux parameterization scheme suitable for tropical cyclone intensity forecast must correctly model the leveling-off character of surface stress and C _h/C _d ratio at high winds. All modifications to surface flux calculation have little influence on 48 h track forecasts, even though they may significantly impact the intensity forecasts.

An Equation of State for Hypersaline Water in Great Salt Lake,Utah, USA

Great Salt Lake (GSL) is one of the largest and most saline lakes in the world. In order to accurately model limnological processes in GSL, hydrodynamic calculations require the precise estimation of water density (ρ) under a variety of environmental conditions. An equation of state was developed with water samples collected from GSL to estimate density as a function of salinity and water temperature. The ρ of water samples from the south arm of GSL was measured as a function of temperature ranging from 278 to 323 degrees Kelvin (^oK) and conductivity salinities ranging from 23 to 182 g L⁻¹ using an Anton Paar density meter. These results have been used to develop the following equation of state for GSL (σ = ± 0.32 kg m⁻³):

The motion of Adria during the Late Jurassic and Cretaceous: New paleomagnetic results from stable Istria

The motion of Adria, the largest lithospheric fragment in the Central Mediterranean region, has played an important role in the tectonic development of the surrounding mountain chains and even of distant areas, like the Eastern Alps or the Pannonian basin. The available paleomagnetic data were insufficient to constrain this motion, except in a general way. In this paper, new paleomagnetic results are presented from one of the stable parts of Adria which emerge from the Adriatic Sea. The results were obtained on weakly magnetic platform carbonates of the mud-supported type, collected from 21 geographically distributed localities.The results, combined with mean paleomagnetic directions from selected localities from a pioneer study in Istria that were chosen using statistical criteria, were divided into three age groups (Tithonian–Aptian, Albian–Cenomanian, Turonian–Coniacian). The paleomagnetic poles calculated for each of them (Tithonian–Aptian): λ(N) = 47°, (E) = 275°, k = 67, α₉₅ = 9.4°, N = 5; Albian-Cenomanian: λ(N) = 58°, (E) = 253°, k = 145, α₉₅ = 4.3°, N = 9; Turonian–Coniacian: λ(N) = 63°, (E) = 261°, k = 50, α₉₅ = 7.3°, N = 9) reveal a moderate shift during the Cretataceous, which is comparable with that calculated from the African reference poles. However, the Istrian apparent polar wander path is slightly displaced from the African curve, as a consequence of about 10° counterclockwise rotation of Istria, with respect to Africa. This rotation angle is more that 10° smaller than the difference measured for the Mid-Late Eocene between the paleomagnetic direction of platform carbonates from Istria and the African reference direction. This difference may be the consequence of a small clockwise rotation of Istria, with respect to Africa, most probably at the end of Cretaceous.     

Description of an aerodynamic levitation apparatus with applications in Earth sciences

Background  

In aerodynamic levitation, solids and liquids are floated in a vertical gas stream. In combination with CO₂-laser heating, containerless melting at high temperature of oxides and silicates is possible. We apply aerodynamic levitation to bulk rocks in preparation for microchemical analyses, and for evaporation and reduction experiments.     

A comparative study on the dissolution and solubility of hydroxylapatite and fluorapatite at 25 °C and 45 °C

Dissolution of the synthetic hydroxylapatite (HAP) and fluorapatite (FAP) in pure water was studied at 25 °C and 45 °C in a series of batch experiments. The XRD, FT-IR and SEM analyses indicated that the synthetic, microcrystalline HAP and FAP with apatite structure used in the experiments were found to have no obvious variation after dissolution except that the existence of OH groups in FT-IR spectra for FAP after 2880 h dissolution was observed. During the HAP dissolution (0–4320 h), the aqueous calcium and phosphate concentrations reached the maxima after 120 h and then decreased slowly with time. For the FAP dissolution in pure water, after a transient time of 1440 h (< 60 d), element concentrations and pH became constant suggesting attainment of a steady-state between the solution and solid. During early stages of the FAP dissolution reaction (< 72–120 h), mineral components were released in non-stoichiometric ratios with reacted solution ratios of dissolved Ca:P, Ca:F and P:F being lower than mineral stoichiometric ratios of Ca₅(PO₄)₃F, i.e., 1.67, 5.0 and 3.0, respectively. This indicated that F were preferentially released compared to Ca from the mineral structure. The mean K_sp values were calculated by using PHREEQC for HAP of 10^− 53.28 (10^− 53.02–10^− 53.51) and for FAP of 10^− 55.71 (10^− 55.18–10^− 56.13) at 25 °C, the free energies of formation ΔG_f^o[HAP] and ΔG_f^o[FAP] were calculated to be − 6282.82 kJ/mol and − 6415.87 kJ/mol, respectively.     

Geochemistry and geochronology of pre-Brasiliano rocks from the Transversal Zone, Borborema Province, Northeast Brazil

Proterozoic metamorphosed sequences are identified in the Transversal Zone (TZ) domain of the Borborema geological province, Northeast Brazil. This TZ domain is located between the well-known E–W Patos and Pernambuco continental shear zones. In its eastern part, in the Taquaritinga region, a large mass of augen gneisses with a conspicuous horizontal to subhorizontal tectonic foliation forms one of the most important rock types in the region that displays U–Pb zircon ages ca. 1.52 Ga. Paleoproterozoic orthogneisses dated by U–Pb on zircon at ca. 1.97 Ga and older paragneisses and banded gneisses represent basement rocks, which were cross-cut by these Mesoproterozoic augen gneisses, and have been in turn intruded by plutonic rocks in upper Neoproterozoic (U–Pb and Rb–Sr, ca. 0.6 Ga) times.Chemical analyses of major, minor, and trace elements (including REE) for the basement orthogneisses indicate calcalkaline affinities and a signature very similar to volcanic arc granites, representing crustal accretion during the Paleoproterozoic Transamazonian/Eburnean orogenesis in the region. In turn, the chemical data for augen gneisses indicate that they are relatively homogeneous and evolved metaluminous metaplutonic rocks with characteristics very similar to A-type granites generated and emplaced in an extensional anorogenic setting. Relatively high ⁸⁷Sr/⁸⁶Sr initial ratio and negative _Nd(t) are signatures of crustal components in these rocks.Based on geochemical, geochronological, and structural data, the Taquaritinga region is composed of Paleoproterozoic (>1.97 Ga) rocks intruded by Mesoproterozoic (ca. 1.5 Ga) anorogenic granites and Neoproterozoic granites (ca. 0.6 Ga). These data also suggest that the tectonometamorphic structures displayed by Meso and Neoproterozoic suites were developed by the Brasiliano/Pan-African orogeny and that the record of Transamazonian/Eburnean orogeny is restricted to basement rocks. This means that there is no evidence for a compressional event in Mesoproterozoic times (Cariris Velhos=Grenville) as suggested for the central and western part of the TZ. It is important to remark that the Taquaritinga augen gneisses are, up to now, the only unit that represents magmatic pulses associated with extensional episodes with this age (ca. 1.5 Ga) in the TZ and in the whole Borborema Province.

Resumen

A zona Transversal da Província Borborema está geologicamente situada entre os lineamentos Pernambuco e Patos. Na sua parte oriental, na região de Taquaritinga (PE), dominam augen gnaisses com uma penetrativa e proeminente foliação tectônica subhorizontal, com idade de cristalização de 1.52 Ga obtida em zircão. Estas rochas são intrusivas em ortognaisses e paragnaisses do embasamento com idade mínima em torno de 1.97 Ga, e são intrudidas por rochas plutônicas associadas ao Ciclo Brasiliano (ca. 0.6 Ga).Análises de elementos maiores, menores e traços (incluindo terras raras) nos augen gnaisses mostram caráter metaluminoso para esta suíte ígnea e fortes semelhanças com os granitos tipo-A gerados em ambiente anorogênico. Razões iniciais ⁸⁷Sr/⁸⁶Sr relativamente altas e _Nd(t) negativos são assinaturas indicadoras de forte contribuição crustal nestes augen gnaisses.A conjunção dos dados geoquímicos, geocronológicos e de campo indicam que na região de Taquaritinga onde são identificadas rochas de idades paleo (>1.95 Ga), meso (ca. 1.5 Ga) e neoproterozóicas (ca. 0.6 Ga), o ciclo orogênico Transamazônico é restrito às rochas do embasamento, e que todas as estruturas dúcteis identificadas nas rochas meso e neoproterozóicas foram desenvolvidas durante o Ciclo orogênico Brasiliano. Não foram encontradas evidências que atestem a existência do Ciclo Cariris Velhos nesta parte da Província Borborema. Contudo, está bem marcado que nesta Zona Transversal e na Província Borborema, os augen gnaisses de Taquaritinga são, até o momento, os únicos marcadores de pulsos magmáticos associados com eventos extensionais crustais datados do Mesoproterozóico inferior.     

Kinetics of leaching of oxidized and reduced ilmenite in dilute hydrochloric acid solutions

Ilmenite separated from beach sands of Bangladesh was oxidized for 1 h at 950 °C and then reduced in charcoal for 4 h at 1050 °C. This was followed by leaching in 5% to 15% hydrochloric acid solution in temperature range of 30 to 75 °C for periods of up to 2 h. The results were compared with those obtained by leaching of ilmenite reduced without oxidizing. Oxidation prior to reduction of the ilmenite was found to increase both the extent and the rate of leaching. The residual iron contents after leaching were also found to be lower than that obtained for non-oxidized samples. The kinetic data of leaching of ilmenite reduced after oxidation was found to follow first order reaction model, i.e., G(α) = − ln(1 − α) up to an α value of 0.5 (i.e. up to 50% reduction) and then changed to spherical model, i.e., G(α) = [1 − (1 − α)]³. On the other hand, leaching of ilmenite reduced without oxidizing was found to follow the Ginstling-Brounshtein reaction, i.e., G(α) = 1 − (2/3)α − (1 − α)^2/3 throughout the leaching process. Oxidation of ilmenite prior to reduction was also found to have decreased the activation energy of leaching from 43 kJ/mol, found for samples leached after reduction without oxidizing, to 30 kJ/mol.     

H<Subscript>2</Subscript>O diffusion in peralkaline to peraluminous rhyolitic melts

The diffusion of water in a peralkaline and a peraluminous rhyolitic melt was investigated at temperatures of 714–1,493 K and pressures of 100 and 500 MPa. At temperatures below 923 K dehydration experiments were performed on glasses containing about 2 wt% H₂O _t in cold seal pressure vessels. At high temperatures diffusion couples of water-poor (<0.5 wt% H₂O _t ) and water-rich (~2 wt% H₂O _t ) melts were run in an internally heated gas pressure vessel. Argon was the pressure medium in both cases. Concentration profiles of hydrous species (OH groups and H₂O molecules) were measured along the diffusion direction using near-infrared (NIR) microspectroscopy. The bulk water diffusivity () was derived from profiles of total water () using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between and Both methods consistently indicate that is proportional to in this range of water contents for both bulk compositions, in agreement with previous work on metaluminous rhyolite. The water diffusivity in the peraluminous melts agrees very well with data for metaluminous rhyolites implying that an excess of Al₂O₃ with respect to alkalis does not affect water diffusion. On the other hand, water diffusion is faster by roughly a factor of two in the peralkaline melt compared to the metaluminous melt. The following expression for the water diffusivity in the peralkaline rhyolite as a function of temperature and pressure was obtained by least-squares fitting:

The Equation of State for Caspian Sea Waters

The density ρ of Caspian Sea waters was measured as a function of temperature (273.15–343.15) K at conductivity salinities of 7.8 and 11.3 using the Anton-Paar Densitometer. Measurements were also made on one of the samples (S = 11.38) diluted with water as a function of temperature (T = 273.15–338.15 K) and salinity (2.5–11.3). These latter results have been used to develop an equation of state for the Caspian Sea (σ = ±0.007 kg m⁻³)

Solubility and dissolution rate of silica in acid fluoride solutions

We performed 57 batch reactor experiments in acidic fluoride solutions to measure the dissolution rate of quartz. These rate data along with rate data from published studies were fit using multiple linear regression to produce the following non-unique rate law for quartz

where 10^−5.13 < a_HF < 10^1.60, −0.28 < pH < 7.18, and 298 < T < 373 K. Similarly, 97 amorphous silica dissolution rate data from published studies were fit by multiple linear regression to produce the following non-unique rate law for amorphous silica

where 10^−2.37 < a_HF < 10^1.61, −0.32 < pH < 4.76 and 296 < T < 343 K. Regression of the rates versus other combinations of solution species, e.g.  + H⁺, F⁻ + H⁺, HF + , HF + F⁻, or  + F⁻, produced equally good fits. Any of these rate laws can be interpreted to mean that the rate-determining step for silica dissolution in fluoride solutions involves a coordinated attack of a Lewis acid, on the bridging O atom and a Lewis base on the Si atom. This allows a redistribution of electrons from the Si–O bond to form a O–H group and a Si–FH group.