Interstitial solutions and diagenesis in deeply buried marine sediments: results from the Deep Sea Drilling Project

Through the Deep Sea Drilling Project samples of interstitial solutions of deeply buried marine sediments throughout the World Ocean have been obtained and analyzed. The studies have shown that in all but the most slowly deposited sediments pore fluids exhibit changes in composition upon burial. These changes can be grouped into a few consistent patterns that facilitate identification of the diagenetic reactions occurring in the sediments.Pelagic clays and slowly deposited (<1 cm/10³yr) biogenic sediments are the only types that exhibit little evidence of reaction in the pore waters.In most biogenic sediments sea water undergoes considerable alteration. In sediments deposited at rates up to a few cm/10³ yr the changes chiefly involve gains of Ca²⁺ and Sr²⁺ and losses of Mg²⁺ which balance the Ca²⁺ enrichment. The Ca-Mg substitution may often reach 30 mM/kg while Sr²⁺ may be enriched 15-fold over sea water. These changes reflect recrystallization of biogenic calcite and the substitution of Mg²⁺ for Ca²⁺ during this reaction. The Ca-Mg-carbonate formed is most likely a dolomitic phase. A related but more complex pattern is found in carbonate sediments deposited at somewhat greater rates. Ca²⁺ and Sr²⁺ enrichment is again characteristic, but Mg²⁺ losses exceed Ca²⁺ gains with the excess being balanced by SO₄^{post staggered2?} losses. The data indicate that the reactions are similar to those noted above, except that the Ca²⁺ released is not kept in solution but is precipitated by the HCO₃^{post staggered?} produced in SO₄^{post staggered2?} reduction. In both these types of pore waters Na⁺ is usually conservative, but K⁺ depletions are frequent.In several partly consolidated sediment sections approaching igneous basement contact, very marked interstitial calcium enrichment has been found (to 5.5 g/kg). These phenomena are marked by pronounced depletion in Na⁺, Si and CO₂, and slight enhancement in Cl^?. The changes are attributed to exchange of Na⁺ for Ca²⁺ in silicate minerals forming from submarine weathering of igneous rocks such as basalts. Water is also consumed in these reactions, accounting for minor increases in total interstitial salinity.Terrigenous, organic-rich sediments deposited rapidly along continental margins also exhibit significant evidences of alteration. Microbial reactions involving organic matter lead to complete removal of SO₄^{post staggered2?}, strong HCO₃^{post staggered?} enrichment, formation of NH₄^{post staggered+}, and methane synthesis from H₂ and CO₂ once SO₄^{post staggered2?} is eliminated. K⁺ and often Na⁺ (slightly) are depleted in the interstitial waters. Ca²⁺ depletion may occur owing to precipitation of CaCO₃. In most cases interstitial Cl^? remains relatively constant, but increases are noted over evaporitic strata, and decreases in interstitial Cl^? are observed in some sediments adjacent to continents.     

Thermochemical Sulfate Reduction in the Tazhong District,Tarim Basin,Northeast China: Evidence from Formation Water and Natural Gas Geochemistry

<正>Systematic analyses of the formation water and natural gas geochemistry in the Central Uplift of the Tarim Basin(CUTB) show that gas invasion at the late stage is accompanied by an increase of the contents of H_2S and CO_2 in natural gas,by the forming of the high total dissolved solids formation water,by an increase of the content of HCO_3~-,relative to Cl~-,by an increase of the 2nd family ions(Ca~(2+),Mg~(2+),Sr~(2+) and Ba~(2+)) and by a decrease of the content of SO_4~(2-),relative to Cl~-.The above phenomena can be explained only by way of thermochemical sulfate reduction(TSR).TSR often occurs in the transition zone of oil and water and is often described in the following reaction formula:ΣCH+CaSO_4+H-_2O→H_2S+CO_2+CaCO_3.(1) Dissolved SO_4~(2-) in the formation water is consumed in the above reaction,when H_2S and CO_2 are generated,resulting in a decrease of SO_4~(2-) in the formation water and an increase of both H_2S and CO_2 in the natural gas.If formation water exists, the generated CO_2 will go on reacting with the carbonate to form bicarbonate,which can be dissolved in the formation water,thus resulting in the enrichment of Ca~(2+) and HCO_3~-.The above reaction can be described by the following equation:CO_2+H_2O+CaCO_3→Ca~(2+)+2HCO_3~-.The stratigraphic temperatures of the Cambrian and lower Ordovician in CUTB exceeded 120℃,which is the minimum for TSR to occur.At the same time,dolomitization,which might be a direct result of TSR,has been found in both the Cambrian and the lower Ordovician.The above evidence indicates that TSR is in an active reaction,providing a novel way to reevaluate the exploration potentials of natural gas in this district.     

The estimation of the pK1HA of acids in seawater using the Pitzer equations

The equations of Pitzer have been used to calculate the stoichiometric ionization constants, pK¹_HA, for acids in NaCl media at 25°C. The calculated results for the ionization of HAc, H₂O, B(OH)₃, H₂CO^?₃, H₃PO₄, H₂PO^?₄, HPO^2?₄, H₃AsO₄, H₂AsO^?₄ and HAsO^2?₄ are in good agreement with the measured values, providing higher order interaction terms (θ and ψ) are used. The pK¹_HA measurements of these acids in NaCl media containing Mg²⁺ and Ca²⁺ were used to determine Pitzer specific interaction parameters at I = 0.7. With these Pitzer coefficients, it was possible to make reliable estimates for the activity coefficients of anions in seawater (S = 35) that form strong interactions with Mg²⁺ and Ca²⁺. The calculated activity coefficients yield reliable estimates for the pK¹_HA of acids in seawater.     

Measurement of the effects of temperature and partial pressure of oxygen on the oxidation states of europium in silicate glasses

The techniques of electron paramagnetic resonance (EPR) were used to measure the concentration ratio of Eu²⁺ to Eu³⁺ in quenched CaMgSi₂O₆, Ca₃Si₃O₁₂, and CaAl₂Si₂O₈ liquids as functions of partial pressure of oxygen and temperature. The redox equilibrium of the Eu ions was described by the reaction 4Eu³⁺ + 20^2? = 4Eu²⁺ + O₂. The reduction of Eu³⁺ to Eu²⁺ was endothermic, and for CaMgSi₂O₆ and Ca₃Al₂Si₃O₁₂ liquids the mean value of ΔH⁰ and the standard deviation from that mean were 25 ± 7 kcal/mole.The magnitude of the Eu anomaly in the distribution coefficients is discussed in terms of the compositions of the solid and liquid phases.     

The solubility of gold and silver in the system AuAgSO2H2O at 25°C and 1 atm.

During supergene alteration of auriferous carbonate ore, the weathering fluids formed are likely to be alkaline and therefore unsuitable as a medium for gold transport as a chloride complex. Secondary gold remobilization in such deposits can often be attributed instead to gold complexing by sulphur-bearing ligands. Gold and silver solubility in the systems AuSO₂H₂O and AgSO₂H₂O respectively, from the thermodynamic data available, is due to complex formation with thiosulphate and bisulphide ligands. The most stable gold complexes, Au(S₂O₃)₂³⁻ (at φO₂ > 10⁻⁶⁰) and Au(HS)⁻₂ (atφO₂ < 10⁻⁶⁰), exist in neutral or alkaline solutions. Like gold, silver forms a stable thiosulphate complex, Ag(S₂O₃)³⁻₂ in moderately oxidizing, and bisulphide complexes, AgHS⁰ and Ag(HS)⁻₂ in reducing, alkaline media. Silver solubility in highly oxidized, neutral or acid solutions is increased by formation of AgS₂O₃⁻, Ag⁺ and AgSO₄⁻ complexes.Colloidal, crystalline and alloyed gold and silver reacted with 0.1 M Na₂S₂O₃ do not, however, demonstrate independent solubility. The rate of gold solubility in 0.1 M Na₂S₂O₃, for example, is increased both by the presence of silver-thiosulphate complexes and alloyed silver. It is possible that such behaviour is due to the formation a mixed metal complex of the type (Au, Ag)(S₂O₃)₂³⁻.The nature and mineral association of secondary gold in the oxidized zone of carbonate ore at Wau. in Papua New Guinea, is consistent with prior remobilization as a thiosulphate complex. Here the secondary gold is coarsely crystalline, alloyed with 50–75 at% Ag and enriched at the watertable and with manganese dioxide in the oxidized zone.     

The distribution of Fe3+ and Ga3+ between two tetrahedral sites in melilites,Ca2(Mg,Fe3+, Ga,Si)3O7

The distribution of Fe³⁺ and Ga³⁺ between the two tetrahedral sites in three synthetic melilites has been studied by using ⁵⁷Fe Mössbauer spectroscopy. In the melilite, (Ca₂Ga₂SiO₇)₅₀ (Ca₂Fe³⁺GaSiO₇)₅₀ (mol %), the distribution of Fe³⁺ and Ga³⁺ in T1 and T2 sites is apparently random, which can be explained in terms of the electrostatic valence rule. However in the melilites, (Ca₂MgSi₂O₇)₅₂ (Ca₂Fe³⁺GaSiO₇)₄₂ (Ca₂Ga₂SiO₇)₆ and (Ca₂MgSi₂O₇)₆₂ (Ca₂Fe³⁺GaSiO₇)₃₆ (Ca₂Ga₂SiO₇)₂ (mol %), Fe³⁺ shows preference for the more ionic T1 site and Ga³⁺ for the more covalent T2 site. If the electronegativity of Ga³⁺ is assumed to be larger than that of Fe³⁺, the mode of distribution of Fe³⁺ and Ga³⁺ can be explained in terms of our previous hypothesis that a large electronegativity induces a stronger preference for the more covalent T2 site.     

Mössbauer effect study of anapaite, Ca2Fe2+(PO4)2 · 4H2O, and of its oxidation products

Mössbauer spectra (MS) of anapaite (Ca₂ Fe²⁺(PO₄)₂?·?4H₂O) and of a sample after being immersed in a 4% H₂O₂ solution at room temperature (RT) over 12 days (hereafter an4ox) were collected at temperatures in the range 4.2 to 420?K and 11 to 300?K respectively. All MS consist of symmetrical doublets, hence magnetic ordering was not observed. The temperature dependencies of the Fe²⁺ centre shifts of anapaite and an4ox were analysed with the Debye model for the lattice vibrations. The characteristic Mössbauer temperatures were found as 370?K?±?25?K and 340?K?±?25?K, and the intrinsic isomer shifts as 1.427?±?0.005?mm/s and 1.418?±?0.005?mm/s respectively. From the external-field (60?kOe) MS recorded at 4.2 and 189?K for the non-treated sample, the principal component V _zz of the electric field gradient (EFG) is determined to be positive and the asymmetry parameter η?≈?0.2 and 0.4 respectively. The temperature variations of the quadrupole splittings, ΔE _Q(T), cannot be interpreted on the basis of the thermal population of the ⁵ D electronic levels resulting from the tetragonal compression of the O₆ co-ordination. The low-temperature linear behaviour of ΔE _Q(T) is attributed to a strong orbit-lattice coupling. A field of 60 kOe applied to anapaite at 4.2?K produces magnetic hyperfine splitting with effective hyperfine fields of ?136, ?254 and ?171?kOe along the principal axes Ox, Oy and Oz of the EFG tensor respectively. Additional oxidation treatments in solutions with various H₂O₂ concentrations up to 20% and subsequent Mössbauer experiments at room temperature, have revealed that the anapaite structure is not sensitive to oxidation since eventually only a small amount of Fe²⁺ (～6.5%) is converted into Fe³⁺.     

Kyzylkumite: a finding in the southern Baikal region, Russia and refinement of its crystal chemical formula

Kyzylkumite has been found in Cr-V-bearing metamorphic rocks of the Sludyanka Complex, Southern Baikal region; it has been identified by X-ray powder diffraction method. This is a late secondary mineral developed after Ti-V-oxides (schreyerite, berdesinskiite) and V-bearing rutile and titanite. Kyzylkumite represents a new structural type with composition Ti₄V ₂ ³⁺ O₁₀(OH)₂ corresponding to octahedral coordination of Ti⁴⁺ and V³⁺. Its unit-cell dimensions are: a = 8.4787(1), b = 4.5624(1), c = 10.0330(1) Å, β = 93.174(1)°. The ideal formula of kyzylkumite Ti₄V ₂ ³⁺ O₁₀(OH)₂ corresponds to composition, wt %: 65.56 TiO₂, 30.75 V₂O₃, 3.69 H₂O. Indeed, the contents (wt %) of these constituents range from 62 to 70 TiO₂ and from 23 to 33 V₂O₃. Variations in contents and the Ti/V value are caused by partial substitution V³⁺ for V⁴⁺, isovalent substitutions Ti⁴⁺ and V³⁺ for V⁴⁺ and Cr³⁺, respectively, and coupled substitution V³⁺ + OH^? ? Ti⁴⁺ + O^2?. Smyslova et al. (1981)—the discovereres of kyzylkumite—assumed its composition to be the same as for schreyerite V ₂ ³⁺ Ti₃O₉ that principally different from kyzylkumite from the Sludyanka Complex. Therefore, re-examination of the kyzylkumite holotype or cotype from its type locality is needed.     

Geochemistry of organic matter in natural apatites of phosphorites according to EPR spectra of free radicals

The following organic radicals were identified by EPR spectroscopy in apatite from marine phosphorites (granular, nodular, shelly, and microcrystalline), supergene phosphorites (from ocean islands only), and modern and fossil biological materials (human dental enamel, fossil shark teeth, and pathogenic cardioliths): ?H₃, ?H₂-R, HO?HR,(CH₃)₂-?R,₃?_org, PO ₃ ^2? , P(OR)₃, and perinaphteenyl. Each textural and petrographic type of apatite corresponds to a specific model of organic radicals, which correlates with the type of organic matter (sapropelic, humic, guano, or collagen). The latter is controlled by the conditions of mineral formation, including climatic ones, and postdiagenetic (catagenetic) processes. A relationship was established between the EPR spectra of observed organic radicals and the valence state and structural position of impurity ions: (1) vanadium: V⁴⁺ (VO²⁺) in the Ca²⁺ II site or V⁵⁺ (VO₄)^3? ?? (PO₄)^3? and (2) uranium: U⁴⁺(UO₂) in the Ca²⁺ II site or U⁶⁺ chemisorbed on the surface as UO ₂ ²⁺      

Major ions chemistry of groundwater in the arid region of Zhangye Basin, northwestern China

As one of the most arid regions in the world, the study area, Zhangye Basin is located in the middle reaches of the Heihe River, northwest China. Besides aridity, rapid social and economic development also stimulates greater demand for water, which is gradually fulfilled by groundwater extraction. In this study, the conventional hydrochemical techniques and statistical analyses were applied to examine the major ions chemistry and hydrochemical processes of groundwater in the Zhangye Basin. The results of chemical analysis indicate that no one pair of cations and anions proportions is more than 50% in the groundwater samples of the study area. High-positive correlations were obtained among the following ions: HCO₃ ^?–Mg²⁺, SO₄ ^2?–Mg²⁺, SO₄ ^2?–Na⁺ and Cl^?–Na⁺. TDS depends mainly on the concentration of major ions such as HCO₃ ^?, SO₄ ^2?, Cl^?, Mg²⁺ and Na⁺. The hydrochemical types in the area can be divided into two major groups: the first group includes Mg²⁺–Na⁺–HCO₃ ^?, Mg²⁺–Na⁺–Ca²⁺–HCO₃ ^?–SO₄ ^2? and Mg²⁺–Ca²⁺–Na⁺–SO₄ ^2?–HCO₃ ^? types. The second group comprises Mg²⁺–Ca²⁺–SO₄ ^2? type, Mg²⁺–Ca²⁺–SO₄ ^2?–Cl^? type and Mg²⁺–Na⁺–SO₄ ^2?–Cl^? type. The ionic ratio plot and saturation index calculation suggests that the silicate weathering, to some extent, and evaporation are dominant factors that determine the major ionic composition in the study area.     

A commensurate-incommensurate phase transition in iron-bearing åkermanites

Synthetic melilites on the join Ca₂MgSi₂O₇ (åkermanite) — Ca₂FeSi₂O₇ (iron åkermanite) with Fe/(Fe+Mg) from 0.0 to 0.7 exhibit, at room temperature, an incommensurate phase with a rectangular modulation of a wavelength of about 19 Å in the [110] direction. Upon increase of temperature, they transform to a commensurate melilite structure at about 80° C for Fe/(Fe+Mg)=0.0 and about 250° C for Fe/(Fe+Mg)=0.6. In addition to the T(2) positions of the melilite structure filled by Si, the incommensurate phase exhibits two distinguishable T(1) sites containing the Mg and Fe²⁺. These two sites merge into one site during the phase transition from the incommensurate to the commensurate phase. A structural model for the incommensurate phase is based on the misfit between the tetrahedral (Mg, Fe²⁺)Si₂O ₇ ^4? sheets and the Ca²⁺ ions.     

Phase transitions in langbeinites I: Crystal chemistry and structures of K-double sulfates of the langbeinite type M 2 + + K2(SO4)3, M + +=Mg,Ni, Co,Zn, Ca

The crystal structures of the langbeinite type M ₂ ^{+ +} K₂(SO₄)₃ with M ^{+ +}=Mg, Ni, Co, Zn, Ca in their cubic phase (P 2 ₁ 3) and Ca₂K₂(SO₄)₃ in its orthorhombic phase (P 2 ₁ 2 ₁ 2 ₁) are determined. Whereas the SO₄-tetrahedra in these compounds are almost undistorted, the two symmetry-independent coordination polyhedra of M ^{+ +} are highly distorted octahedra with trigonal site symmetry in P 2 ₁ 3. The deformation of the oxygen octahedra and the off-centering of M ^{+ +} along the trigonal axis show systematic dependences on the ionic radii and the electronegativities of the M ^{+ +}-ions. The correlations are remarkably different for the two symmetry-independent M ^{+ +}-ions indicating different M ^{+ +} — O bonding. The octahedral deformations show also linear correlations with the phase transition temperatures (P 2 ₁ 3 — P 2 ₁ 2 ₁ 2 ₁) of the different compounds. This observation leads to a new model for the phase transition mechanism which is based on thermal instabilities of the M ^{+ +} — O and K — O polyhedral distortions. The cubic high temperature phase is characterized by high symmetric oxygen coordinations around M ^{+ +} which distort with decreasing temperature. At T _c the trigonal site symmetry is broken in such a way that the K — O coordination becomes denser at the expense of a wider and less symmetric M ^{+ +} — O coordination.     

Study on Composition of Inclusions in Minerals and Simulation Experiment on Hydrothermal Metasomatic Process of the Bayan Obo Iron Deposit

On the basis of the mechanism of formation of mineral inclusions, it may be assumed that a certain relation exists between the compositions of fluid inclusions in various minerals formed at the same stage of hydrothermal activity. In order to study the genetic relationships between different minerals in the Bayan Obo iron deposit, the compositions(K~+, Na~+, Ca~+, Mg~+, F~+, Cl~+, CO_2~(2-), ΣSO_4~(2-) and pH) of inclusions in fluorite(23), hematite(13), magnetite(3), sodium pyroxene(2) and dolomite(5) from the main mine and the eastern mine were determined by using the vacuum decrepitation and leaching methods, and cluster analyses of the data on the compostions were made. The Q-mode cluster analysis indicates that some iron oxide minerals in the deposit are related to dolomite of sedimentary origin, while others are related to fluorite and sodium pyroxene--products of hydrothermal activity. The R-mode cluster analysis shows that the components of the leaching solution may be divided into two groups: one includes CO_2~(2-), Mg~(2+) and H~+(pH), which are obviously associated with dolomite; the other comprises Na~+, K~+, Ca~+, F~+, Cl~+ and SO_4~(2-), which may possibly represent the composition of hydrothermal solutions.The reaction of the Na-F-Cl solution(pH 4.72) with hematite dolomite at 300℃ and 5 × 10~7 Pa and under alternately"static and dynamic" conditions produced large amounts of hematite and fluorite and small amounts of smectite and Na(Fe) silicates, and the hematite-fluorite assemblage accords with the actual geological conditions in the deposit. From a comparison between the compositions of"static" and"dynamic" solution samples, it may be known that the flow reaction facilitates the migration of Fe, F, Ca and other components as well as Na-metasomatism(Na and Si are fixed in a solid phase).The study of the compositions of mineral inclusions and simulation experiments on hydrothermal metasomatism have provided new evidence for the hypothesis of metamorphosed-sedimentary and hydrothermal-remoulding origin of the Bayan Obo deposit, and pointed out emphatically that hydrothermal metasomatism plays an important role in the formation of the mineral deposit, particularly in the main and the east mine.     

Distribution of gold and rhenium between nickel-iron and silicate melts: implications for the abundance of siderophile elements on the Earth and Moon

The distribution equilibrium of Au and Re between nickel-iron and basaltic melts was studied at 1400–1600°C, using radioactive tracers. Metal/silicate distribution coefficients were 1–3 orders of magnitude higher than earlier estimates, as follows. Mauna Loa basalt—Fe₁₀Ni₉₀: D_Au = 3.3 × 10⁴, D_Re = (2.4?89) × 10⁴. Gorda Ridge basalt—Fe₁₀Ni₉₀: D_Au = (18?75) × 10⁴. Synthetic lunar basalt—Fe₇₀ Ni₃₀: D_Au≥ 2 × 10⁴, D_Re ≥ 2 × 10³. The experimental ΔG₁₈₀₀^° for the distribution of Au between nickel-iron and Mauna Loa basalt is ?40 kcal/mole, compared to a calculated value of about ?110 kcal/mole for a reaction involving simple Au³⁺ ions. Presumably the difference represents stabilization of Au(III) by complex formation with ligands such as Cl^?, H₂O, etc.Gold abundances in lunar basalts are roughly consistent with the measured D_Au, but those in terrestrial basalts are two orders of magnitude too high. This discrepancy may reflect complexing by volatiles in the Earth's upper lithosphere, as well as oxidative destruction of metal in the final stages of accretion. In the absence of a metal phase, siderophile trace elements would remain trapped in the upper mantle and crust.     

Dissolution Kinetics of Calcite in NaCl–CaCl2–MgCl2 Brines at 25 °C and 1 bar pCO2

Calcite dissolution rates were measured as a function of saturation state in NaCl–CaCl₂–MgCl₂ solutions at 1 bar (0.1 MPa) pCO₂ and 25 °C. Rates measured in phosphate- and sulfate-free pseudo-seawater (Ca²⁺:Mg²⁺= 0.2, I= 0.7) were compared with those in synthetic brines. The brines were prepared by co-varying calcium and magnesium (Ca²⁺:Mg²⁺= 0.9; 2.0; 2.8; 3.1; 4.8; 5.8) along with ionic strength (I= 0.9; 1.1; 1.6; 2.1; 3.0; 3.7; 4.4 m) to yield solutions approximating those of subsurface formation waters. The rate data were modeled using the equation, R = k(1 ? Omega;) ⁿ , where k is the empirical rate constant, n describes the order of the reaction and ω is saturation state. For rates measured in the pseudo-seawater, n= 1.5 and k= 4.7 × 10^?2 mol m^?2 hr^?1. In general, rates were not significantly faster in the synthetic brines (n= 1.4 ± 0.2 and k= 5.0 ± 7 × 10^?2 mol m^?2 hr^?1). The rate coefficients agree within experimental error indicating that they are independent of ionic strength and Ca²⁺:Mg²⁺ over a broad range of brine compositions. These findings have important application to reaction-transport modeling because carbonate bearing saline reservoirs have been identified as potential repositories for CO₂ sequestration.     

Ionic diffusion in naturally-occurring aqueous solutions: transition-state models that use either empirical expressions or statistically-derived relationships to predict mutual diffusion coefficients in the concentrated-solution regions of 8 binary systems

Mutual diffusion coefficients for the systems NaCl-H₂O, KCl-H₂O, CaCl₂-H₂O, SrCl₂-H₂O, BaCl₂-H₂O, MgCl₂-H₂O, Na₂SO₄-H₂O, and MgSO₄-H₂O are computed using a model that postulates exchanges between ions and water molecules. Limiting ionic equivalent conductances, a solution-density function, and a mean ionic activity-coefficient function are required as input. A region of changing solution structure extends up to concentrations ranging from about 0.01 molar in MgCl₂-H₂O to about 0.2 molar in KCl-H₂O. In the remaining concentration range to saturation, a single expression in each system containing one variable parameter can be fitted empirically to reproduce selected sets of experimentally measured D^v₁₂ with maximum errors for individual compositions ranging from about 0.25% in KCl-H₂O and Na₂SO₄-H₂O to about 4% in MgCl₂-H₂O. The experimentally measured D^v₁₂ can be reproduced with errors comparable to those of the empirical fits by further postulating that individual ion-water molecule exchanges are coupled to yield hydrated neutral exchange complexes (the activated complexes), and defining probability expressions that describe the following exchanges: Ba²⁺ + 2Cl^? for 3H₂O, 2Ca²⁺ + 4Cl^? for 6H₂O, 2Sr²⁺ + 4Cl^? for 6H₂O, Na⁺ + Cl^? for 3H₂O, 2K⁺ + 2Cl^? for 5H₂O, NaSO^?₄ + Na⁺ for 5H₂O, Mg²⁺ + SO^2?₄ (+MgSO⁰₄) for 4H₂O, and MgCl⁺ + Cl^? for 2H₂O. This calculation also contains one variable parameter. Solute transport between exchange sites is by movement of ions, except for the ion-pair contribution indicated in parentheses.     

The formation of lead(II) chloride complexes to 300°C: A spectrophotometric study

The spectra of chlorolead(II) complexes in the ultraviolet region have been measured in acid chloride solutions from 0.0012 to 3.223 m and at temperatures from 25 to 300°C. The thermodynamic cumulative and stepwise formation constants as well as the spectra of the individual chlorolead(II) species have been calculated from the spectrophotometric data. At 25°C, the five species PbCl^2?n_n (0 ≤ n ≤ 4) occur, however, at 300°C the predominant species were PbCl⁺, PbCl⁰₂ and PbCl^?₃. Pb²⁺ occurs as a minor species in dilute solutions where total chloride is <0.003 m at 300°C and the presence of PbCl^2?₄ in concentrated solutions was not detected above 150°C. With increasing temperature, chlorolead(II) complex stability is characterised by large endothermic enthalpies and large positive entropies of formation. Lead(II) chloride complexes are important in the transport and deposition of lead by hydrothermal ore solutions of moderate to high salinity.     

Geoelectric model and hydrochemistry of salinity affected lower Atrai floodplain aquifer,NW Bangladesh: An approach for irrigation management

In the salinity affected lower Atrai floodplain aquifer in the NW Bangladesh, geoelectric resistivity survey and hydrochemical analysis are carried out with an aim to identify fresh and saline groundwater zones; investigate the status of salinity; evaluate hydrochemical processes involved and suggest management approaches for irrigation. Here a two-fold aquifer system, inter-layered by silt, clay and silty-clay aquitard and aquiclude is classified as: upper aquifer — spatially affected by salinity of varying degrees; and lower aquifer — generally characterized by high salinity. The aquifer with resistivity values greater than 69 Ωm is safe for irrigation use. Concentrations of major ions vary as: Ca²⁺>Na⁺>Mg²⁺>K⁺ and HCO₃>Cl>NO₃>SO₄ ^2?. Groundwater is dominated by Na-Ca to Ca-Na, HCO₃-Cl-SO₄, Cl-SO₄-HCO₃ and Cl-SO₄ ^2? facies where Ca²⁺, Mg²⁺, SO₄ ^2?, HCO₃ ^?, Cl^? and NO₃ ^2? ion concentrations are statistically dominant and water is of Ca-Mg, HCO₃-SO₄-Cl and NO₃ types. Geochemically, groundwater is hard and saline to fresh water type. Salinity increases with depth, but spatially towards the southern part. Groundwater quality is a product of water-rock interaction, direct mixing and marine spraying, or fall-out of airborne marine salts, where silicate weathering is the primary source of bivalent cations. Sediment provenance of alkaline earth silicates and higher concentrations of alkalis are derived from sources other than precipitation. In general partially or fully salinity affected upper and lower aquifers in the area except in its eastern part are not suitable for tubewell irrigation. As groundwater demand for irrigation is increasing, the saline water has progressively invaded relatively fresher parts of the aquifer by upconning. So, special salinity control management approaches can be adopted through engineering techniques such as groundwater abstraction optimization, as also through scientific behavioral approaches like groundwater demand management, salt tolerant crops production. In this context, surface water conservation and rain water harvesting for domestic and irrigational uses are recommended in the salinity affected area.     

Crystal chemistry of perovskite-type compounds in the tausonite-loparite series, (Sr1−2 x Na x La x )TiO3

Perovskite-type compounds in the series tausonite-loparite, (Sr_{1?2 x} Na _x La _x )TiO₃, were synthesized by solid-state reaction (final heating at 1200–1300?°C), and studied using “conventional” and synchrotron X-ray powder diffractometry. The structures of intermediate compositions were determined using the Rietveld profile refinement method. In the compositional range 0?≤x?≤ 0.1, the series comprises perovskites characterized by an undistorted cubic structure (space group Pm3¯m, a?≈ 3.905–3.902?Å, Z?=?1). Intermediate compounds in the range 0.15?≤?x?≤?0.35 crystallize with tetragonal symmetry (I4/mcm, a?≈? , c?≈? , Z?=?4) derived from the cubic aristotype by antiphase rotation of the TiO₆ octahedra about a fourfold axis. The angle of rotation estimated from the positional parameters of oxygen atoms ranges from 2.5(7)° to 5.5(4)°. The cubic-to-tetragonal transition arises from substitution of Sr²⁺ by the comparatively smaller Na¹⁺ and La³⁺ cations. A further transition from the tetragonal to rhombohedral symmetry (R3¯c, a?≈? , c?≈?2 , Z?=?6) occurs between x?=?0.35 and 0.40, and apparently does not involve formation of perovskite with an intermediate two-tilt structure (Imma). The rhombohedral structure is characterized by a multicomponent octahedral tilt about a threefold axis ranging in magnitude from 6.5(2)° to 7.7(2)°. In the series (Sr_{1?2 x} Na _x La _x )TiO₃, the unit-cell dimensions decrease, and the degree of structural distortion increases with x.     

A thermochemical study of monohydrocalcite

The thermodynamic properties of monohydrocalcite, CaCO₃ · H₂O, have been obtained using a well-characterized natural specimen. Equilibration of the solid with water at 25°C under 0.97 atm CO₂ led to an activity product [Ca²⁺][CO₃^2?] = 10^?7.60±0.03 and a free energy of formation ΔG_f^o = ?325,430 ± 270 calmol^?. The enthalpy of solution of monohydrocalcite in 0.1 N HCl at 25°C led to a standard enthalpy of formation ΔH_f^o = ?358,100 ± 280 cal mol^?1. Estimates of the variation of ΔG_f with temperature and pressure showed monohydrocalcite to be metastable with respect to calcite and aragonite.