Basal plane reactivity of phyllosilicates studied in situ by hydrothermal atomic force microscopy (HAFM)

The basal plane reactivities of the sheet silicates apophyllite and phlogopite have been studied by hydrothermal atomic force microscopy (HAFM) in situ in aqueous solutions at temperatures from 20 to 140 °C. At pH 4-5.6 (T = 20-100 °C), the apophyllite basal surface undergoes a swelling process which forms square hillocks on the surface. The reaction comprises three sequential morphological transformations that cause swelling to increase from 0.15 to 2.5 nm. In the first two transformations, interlayer cations are replaced by hydronium ions from the solution; the third transformation involves a depolymerization and partial cross-linking of the protonated silicate sheets. The reaction of phlogopite with acidic aqueous solutions (pH 1.5-2) at high temperature (T = 100-140 °C) causes the nucleation of numerous monolayer etch pits on the pristine surface. Where the 2D pits recur at the same lateral position, they can accumulate to a total pit depth of up to 50 nm. The formation of an altered layer has also been detected at these conditions. The alteration affects the uppermost 4-5 layers. The layers are expanded, corrugated, highly unstable, and readily peel off the surface. Etch pit formation has been detected even underneath the altered layer. On the basis of HAFM data, dissolution rates and activation energies were calculated. The presented data show that the basal surface of phlogopite plays an important role in the dissolution process at least at elevated temperatures and that the absolute amount of released material has comparable contributions from both basal surfaces and edge surfaces.     

Evidence for aqueous alteration in a carbonaceous xenolith from the Plainview (H5) chondrite

Within a CM-like clast in the Plainview (H5) chondrite are two inclusions which have the distinctive morphologies of an Allende-like, coarse-grained CAI and an amoeboid olivine inclusion respectively. The compositions of the mineral components within the inclusions were ascertained in this microprobe study. The major constituents of the altered inclusions are calcite, Mg-Fe-rich phyllosilicates, Fe-Ti oxides, and an unusually Al-rich (21–32 wt% A1₂O₃) phyllosilicate. Assuming the starting compositions for these inclusions suggested by their morphologies, namely, Ca-Al refractory-rich oxides and silicates, the alteration process would have required transport of Na, Cl, H₂O, “CO₂” and “FeO”. Because significant quantities of iron are required to produce the mineral assemblages now present from the inferred starting materials, and because of the presence of hydrous phases, it seems that liquid water was probably the medium in which the alteration reactions took place. The two possible sources of liquid water in meteorite parent bodies are primordially formed clay minerals and water ice. As yet neither source can be ruled out.     

Stable Fe isotope fractionations produced by aqueous Fe(II)-hematite surface interactions

Stable Fe isotope fractionations were investigated during exposure of hematite to aqueous Fe(II) under conditions of variable Fe(II)/hematite ratios, the presence/absence of dissolved Si, and neutral versus alkaline pH. When Fe(II) undergoes electron transfer to hematite, Fe(II) is initially oxidized to Fe(III), and structural Fe(III) on the hematite surface is reduced to Fe(II). During this redox reaction, the newly formed reactive Fe(III) layer becomes enriched in heavy Fe isotopes and light Fe isotopes partition into aqueous and sorbed Fe(II). Our results indicate that in most cases the reactive Fe(III) that undergoes isotopic exchange accounts for less than one octahedral layer on the hematite surface. With higher Fe(II)/hematite molar ratios, and the presence of dissolved Si at alkaline pH, stable Fe isotope fractionations move away from those expected for equilibrium between aqueous Fe(II) and hematite, towards those expected for aqueous Fe(II) and goethite. These results point to formation of new phases on the hematite surface as a result of distortion of Fe-O bonds and Si polymerization at high pH. Our findings demonstrate how stable Fe isotope fractionations can be used to investigate changes in surface Fe phases during exposure of Fe(III) oxides to aqueous Fe(II) under different environmental conditions. These results confirm the coupled electron and atom exchange mechanism proposed to explain Fe isotope fractionation during dissimilatory iron reduction (DIR). Although abiologic Fe(II)_aq - oxide interaction will produce low δ⁵⁶Fe values for Fe(II)_aq, similar to that produced by Fe(II) oxidation, only small quantities of low-δ⁵⁶Fe Fe(II)_aq are formed by these processes. In contrast, DIR, which continually exposes new surface Fe(III) atoms during reduction, as well as production of Fe(II), remains the most efficient mechanism for generating large quantities of low-δ⁵⁶Fe aqueous Fe(II) in many natural systems.     

Biosorption of Cu(II) and Pb(II) from aqueous solutions by chemically modified spent coffee grains

In this research, spent coffee grains were modified with citric acid solutions (0.1 and 0.6 M) to increase the quantity of carboxylic groups improving its metal adsorption capacity. Added functional groups on modified and non-modified spent coffee grains were identified and quantified by attenuated total reflection Fourier transform infrared analyses and potentiometric titrations, respectively. These adsorbents were used for the removal of lead (II) and copper (II) from aqueous solutions at 30 °C and different pH in batch systems. In addition, adsorption–desorption experiments were conducted to evaluate the possibility of re-using the modified adsorbent. Potentiometric titrations data reveal that the quantity of carboxylic groups was increased from 0.47 to 2.2 mmol/g when spent coffee grains were modified with 0.1 and 0.6 M citric acid. Spent coffee grains treated with 0.6 M citric acid, achieved a maximum adsorption capacity of 0.77 and 1.53 mmol/g for lead (II) and copper (II), respectively, whereas non-modified spent coffee grains only reached 0.24 and 0.19 mmol/g for lead (II) and copper (II), respectively. Desorption of lead (II) and copper (II) achieved around 70 % using 0.1 N HCl for non-modified and modified spent coffee grains with 0.6 M citric acid. It is suggested that lead (II) and copper (II) species were adsorbed mainly on the carboxylic groups of modified spent coffee grains and these metals may be exchanged for hydrogen and calcium (II) ions during adsorption on non-modified spent coffee grains. Finally, the adsorption equilibrium was reached after 400 min for modified spent coffee grains with 0.6 M citric acid. Modified spent coffee grains are a promising option for removing metal cations from aqueous solutions due to its low cost and high adsorption capacity (about 10 times higher than the activated carbons).     

Two-dimensional reactive transport modeling of the alteration of a fractured limestone by hyperalkaline solutions at Maqarin (Jordan)

Two-dimensional reactive transport modeling of the Maqarin Eastern Springs site, a natural analogue for the alteration of a fractured limestone by high-pH Portland cement waters, has been performed using the CrunchFlow code. These 2D calculations included transport by advection–dispersion–diffusion along a single fracture and diffusion in the wall rock. Solute transport was coupled to mineral dissolution and precipitation. A limited sensitivity analysis evaluated the effect of different values of primary mineral surface areas, flow velocity and sulfate concentration of the inflowing high-pH solution.Major secondary minerals include ettringite–thaumasite, C–S–H/C–A–S–H and calcite. C–S–H/C–A–S–H precipitation is controlled by the dissolution of primary silicates. Ettringite precipitation is controlled by diffusion of sulfate and aluminum from the wall rock to the fracture, with aluminum provided by the dissolution of albite. Calcite precipitation is controlled by diffusion of carbonate from the wall rock. Extents of porosity sealing along the fracture and in the fracture-wall rock interface depend on assumptions regarding flow velocity and composition of the high-pH solution. The multiple episodes of fracture sealing and reactivation evidenced in the fracture infills were not included in the simulations. Results can qualitatively reproduce the reported decrease in porosity in the fractures and in the wall rock next to the fractures. Instances of porosity increase next to fractures caused by carbonate dissolution were not reproduced by the calculations.     

The concentration of Cu(II), Pb(II) and Zn(II) from aqueous solutions by particulate algal matter

Experimental studies of the reactions of Cu(II), Pb(II), and Zn(II) in aqueous solutions with organic matter derived from fresh samples of the green filamentous algae Ulothrix spp. and the green unicellular algae Chlamydomonas spp. and Chlorella vulgaris show that, under suitable conditions, a significant proportion of the metals is removed from solution by sorption onto the particulate organic matter of the algal suspension.The metal sorption is strongly suppressed by H⁺ but is only marginally influenced by the proportion of whole cells in the suspension and by complexing of metals in solution by the soluble organic matter. The presence of relatively small amounts of the cations Na⁺ and Mg²⁺ in solution reduces the sorption of Zn(II) to near zero, but Pb(II) and Cu(II) sorption occurs to an appreciable extent even in strong brines. This may be a means for the selective precipitation of Pb(II) from brines rich in Pb(II) and Zn(II).Metal “saturation” values indicate that particulate algal matter of the type used in these experiments could sorb sufficient quantities of metal to form an ore deposit if a weight of organic matter of similar order of magnitude to that of the inorganic sediments in the deposits was available. However, the metal sorption is an equilibrium reaction, and the experimentally determined “enrichment factors” suggest that the “saturation” values could be approached only in solutions whose metal contents were initially at least two orders of magnitude above those of normal seawater.     

Studies on hydrothermal alteration by acid solutions dominated by SO4 2−: Formation of the alteration products of the Gleichenberg latitic rock (Styria,Austria)—Experimental evidence

Summary The latitic rock mined at the Gossendorf open pit in the Gleichenberg Volcanic Area of Styria, Austria, has in places been completely altered to various associations of the secondary minerals opal-C/-CT, alunite, kaolinite and montmorillonite. These associations occur in a zonal arrangement, in which the innermost part has been totally altered to opal and moreover has retained its original latitic structure. The results of experimental alteration tests on the latitic rock in open hydrological systems suggest that these secondary minerals and some of the associations observed in the field as well as their zonal distribution, may have been formed by an originally strongly acid solution rich in SO₄ ^2– which, undergoing progressive chemical variation by reaction with the rock, exhibits a chemical gradient. Some of the mineral associations, however, may not be explained by a single alteration process, but must be regarded as the result of multi-stage alteration in which alteration products from weak leaching are super-imposed on alteration products from intense leaching.

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Untersuchungen zur hydrothermalen Umwandlung unter dem Einfluß saurer SO₄ ^2–-Lösungen: Diskussion der Bildungsbedingungen der Umwandlungsprodukte der Latite von Gleichenberg, Steiermark, Österreich anhand experimenteller Umwandlungen.

Zusammenfassung Latitische Gesteine sind im Tagbau Gossendorf des Gleichenberger Vulkangebietes, Steiermark, Österreich, z. T. vollständig in verschieden zusammengesetzte Kombinationen der Mineralneubildungen Opal-C/-CT, Alunit, Kaohnit und Montmorillonit umgewandelt. Diese Kombinationen treten in einer zonaren Anordnung auf, wobei der zentrale Bereich vollständig in Opal umgewandelt ist und darüberhinaus noch das ehemalige Latitgefüge aufweist. Experimentelle Umwandlungsversuche mit dem latititschen Gestein im offenen System haben gezeigt, daß diese Neubildungen und einige der beobachteten Kombinationen sowie deren zonare Anordnung durch den Einfluß einer ursprünglich stark sauren SO₄ ^2–-Lösung entstehen können, die sich durch die Reaktion mit dem Gestein chemisch ständig ändert, d. h. einen chemischen Gradienten aufweist. Einige der auftretenden Kombinationen sind jedoch nicht durch ein Umwandlungsgeschehen zu erklären, sondern nur als Ergebnis einer mehraktigen Umwandlung, wodurch sich Umwandlungsprodukte einer starken Auslaugung und die einer schwachen Auslaugung überlagern können.

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With 9 Figures     

Removal of uranium(VI) from aqueous solutions using Eucalyptus citriodora distillation sludge

Adsorption and desorption of uranium(VI) from dilute aqueous solutions by Eucalyptus citriodora distillation sludge was studied in a batch mode. The potential of Eucalyptus citriodora distillation sludge to remove uranium(VI) from aqueous solutions has been investigated at different conditions of solution pH, metal ion concentrations, biosorbent dosage, biosorbent particle size, contact time and temperature. The results indicated that biosorption capacity of Eucalyptus citriodora distillation sludge was strongly affected by the medium pH, the biosorbent dose, metal ion concentrations and medium temperature. Reduction in particle size increased the biosorption capacity. Langmuir and Freundlich isotherm models were applied to biosorption data to determine the biosorption characteristics. An optimum biosorption capacity (57.75 mg/g) was achieved with pH 4.0, particle size 0.255 mm, biosorbent dose 0.5 g/100 mL and initial uranium(VI) concentration of 100 mg/L. Uranium(VI) removal by Eucalyptus citriodora distillation sludge was rapid, the equilibrium was established within 60 min and pseudo-second-order model was found to fit with the experimental data. The biosorption process decreased with an increase in the temperature indicating its exothermic nature. Pretreatments of biomass with different reagents affected its biosorption capacity. A significant increase (34 %) in biosorption capacity (83.25 mg/g) was observed with benzene treatment. Fourier-transform infra-red studies showed the involvement of carbonyl, carboxyl and amide groups in the biosorption process. The results indicated that sulfuric acid had the best effects as an eluent showing 93.24 % desorption capacity.     

Modal mineralogy of CM chondrites by X-ray diffraction (PSD-XRD): Part 2. Degree, nature and settings of aqueous alteration

Within 5 million years after formation of calcium aluminium rich inclusions (CAI), high temperature anhydrous phases were transformed to hydrous phyllosilicates, mostly serpentines, which dominate the matrices of the most primitive carbonaceous chondrites. CMs are the largest group of meteorites to provide samples of this material. To understand the nature of the availability, and role of H₂O in the early solar system - as well as the settings of aqueous alteration - defining CM petrogenesis is critical. By Position Sensitive Detector X-ray Diffraction (PSD-XRD), we determine the modal abundance of crystalline phases present in volumes >1% for a suite of CMs - extending Part 1 of this work that dealt only with CM2 falls (Howard et al., 2009) to now include CM2 and CM1 finds. CM2 samples contain 13-31% Fe,Mg silicates (olivine + pyroxene) and from 67% to 82% total phyllosilicate (mean 75% ± 1.3 2σ). CM1 samples contain 6-10% olivine + pyroxene and 86-88% total phyllosilicate. Magnetite (0.6-5.2%), sulphide (0.6-3.9%), calcite (0-1.9%) and gypsum (0-0.8%) are minor phases across all samples. Since phyllosilicate forms from hydration of anhydrous Fe,Mg silicates (olivine + pyroxene), the ratio of total phyllosilicate to total anhydrous Fe,Mg silicate defines the degree of hydration and the following sequence results (in order of increasing hydration): QUE 97990 < Y 791198 < Murchison < Murray < Mighei < ALHA 81002 < Nogoya ? Cold Bokkeveld ? Essebi < QUE 93005 < ALH 83100 < MET 01070 < SCO 06043. High activities of Al (mostly from reactive mesostasis) and Si help to explain the composition and structure of CM serpentines that are distinct from terrestrial standards. Our data allows inference as to CM mineralogy at the point of accretion and challenges the conceptual validity of progressive alteration sequences. Modal mineralogy also provides new insights into CM petrogenesis and hints at a component of aqueous alteration occurring in the nebula, in addition to on the CM parent body(ies).     

Predicting the surface tension of aqueous 1:1 electrolyte solutions at high salinity

The surface tension of the air/water interface is a phenomenon of particular interest in the water-unsaturated zone of porous media because it influences the contact angle and consequently the capillary water volume. A mechanistic model based on the modified Poisson-Boltzmann equation and the Pitzer theory is described and used to predict, under isothermal and isobaric conditions, the surface tension of 1:1 electrolytes at high salinity. These theories enable the determination of the electrical potential at the air/water interface and the activity coefficient of the ionic species in the bulk pore water, respectively. Hydration free energies of the structure-making and structure-breaking ions that influence the surface tension at high salinity are taken into account. Structure-making ions flee the air/water surface because they can better organize the water dipoles in bulk water than at the interface. Structure-breaking ions are positively adsorbed at the air/water interface because the bulk water can better organize their hydrogen-bonding network without these ions. The resulting surface tension increases and decreases, respectively, compared to the surface tension of pure water. The predictions are in good agreement with the surface tension data of 1:1 electrolytes (NaCl, KCl, HCl, NaNO₃, KNO₃, HNO₃ aqueous solutions) and the optimized parameters depend on the effective electrostatic diameters of cations and on the hydration free energies of the ions at the interface.     

Removal of cadmium and humic acid from aqueous solutions using surface modified nanozeolite A

The sorption of cadmium and humic acids from aqueous solutions using surface-modified nanozeolite A has been investigated under various examination conditions. The morphology of untreated and treated nanozeolite was studied under scanning electron microscope and transmission electron microscope. Isotherms of cadmium adsorption onto surface-modified nanozeolite A were studied at different pH, solid to liquid ratio, adsorbate concentration and interaction time. Kinetic and equilibrium studies were conducted and the equilibrium data have been analyzed using Langmuir and Freundlich isotherm models. The study revealed that experimental results were in agreement with the Freundlich model. The Langmuir monolayer adsorption capacity was found to be 1666.67 g cadmium and 6.75 g humic acid per gram of modified nanozeolite A, which is higher than that of reported value for other zeolites. The sorption ability was enhanced by surface modification and reduction in size and enabled the zeolite to adsorb cadmium. The adsorption of cadmium and humic acid on nanozeolite was found to be the highest at pH 6 and 3, respectively. Results showed that solid to liquid ratio and pH are the most important factors for cadmium and humic acid removal, respectively. Effect of competitive ions was studied and results showed that there is no competition between cadmium and humic acid sorption and presence of these ions.     

Removal of dexamethasone from aqueous solutions using modified clinoptilolite zeolite (equilibrium and kinetic)

The aim of this study was to remove a known pharmaceutics, dexamethasone, from an aqueous solution using clinoptilolite zeolite (CP). CP is a natural, versatile and inexpensive mineral, which has been investigated and applied in the last few decades. Herein, the experiments were carried out in the common conditions of a batch system in room temperature, and the effects of some parameters such as pH of the solution, initial concentration of dexamethasone, adsorbent dose and contact time were studied. Kinetic and isotherm of adsorption processes of dexamethasone on CP were surveyed in the current study. Results revealed that the maximum efficiency (78 %) occurred in pH = 4. The adsorption process followed a pseudo-second-order kinetic model as well as Freundlich and Sips isotherm models fitted with the experimental data well.     

Adsorption kinetics of chromium(III) removal from aqueous solutions using natural red earth

Laboratory-scale-simulated experiments were carried out using Cr(III) solutions to identify the Cr(III) retention behavior of natural red earth (NRE), a natural soil available in the northwestern coastal belt of Sri Lanka. The effects of solution pH, initial Cr(III) concentration and the contact time were examined. The NRE showed almost 100 % Cr(III) adsorption within the first 90 min. [initial [Cr(III)] = 0.0092–0.192 mM; initial pH 4.0–9.0]. At pH 2 (298 K), when particle size ranged from 125 to 180 μm the Cr(III) adsorption data were modeled according to Langmuir convention assuming site homogeneity. The pH-dependent Cr(III) adsorption data were quantified by diffused layer model assuming following reaction stoichiometries: $$ \begin{aligned} 2\, {>}{\text{AlOH}}_{{({\text{s}})}} + {\text{ Cr }}\left( {\text{OH}} \right)_{{ 2\,({\text{aq}})}}^{ + } \, \to \, \left( { {>}{\text{AlO}}} \right)_{ 2} {\text{Cr}}_{{({\text{s}})}}^{ + } + {\text{ 2H}}_{ 2} {\text{O}} \quad {\text{log K 15}}. 5 6\\ 2\, {>}{\text{FeOH}}_{{({\text{s}})}} + {\text{ Cr}}\left( {\text{OH}} \right)_{{ 2\,({\text{aq}})}}^{ + } \, \to \, \left( { {>}{\text{FeO}}} \right)_{ 2} {\text{Cr}}_{{({\text{s}})}}^{ + } + {\text{ 2H}}_{ 2} {\text{O}}\quad {\text{log K 5}}.0 8.\\ \end{aligned} $$ The present data showed that NRE can effectively be used to mitigate Cr(III) from aqueous solutions and this method is found to be simple, effective, economical and environmentally benign.     

Gold(I) complexing in aqueous sulphide solutions to 500°C at 500 bar

The solubility of gold has been measured in aqueous sulphide solutions from 100 to 500°C at 500 bar in order to determine the stability and stoichiometry of sulphide complexes of gold(I) in hydrothermal solutions. The experiments were carried out in a flow-through system. The solubilities, measured as total dissolved gold, were in the range 3.6 × 10⁻⁸ to 6.65 × 10⁻⁴ mol kg⁻¹ (0.007-131 mg kg⁻¹), in solutions of total reduced sulphur between 0.0164 and 0.133 mol kg⁻¹, total chloride between 0.000 and 0.240 mol kg⁻¹, total sodium between 0.000 and 0.200 mol kg⁻¹, total dissolved hydrogen between 1.63 × 10⁻⁵ and 5.43 × 10⁻⁴ mol kg⁻¹ and a corresponding pH_{T, p} of 1.5 to 9.8. A non-linear least squares treatment of the data demonstrates that the solubility of gold in aqueous sulphide solutions is accurately described by the reactions

Au(s)+H₂S(aq)=AuHS(aq)+0.5H₂(g) K_s,100     

Surface alteration of arsenopyrite (FeAsS) by Thiobacillus ferrooxidans

The surface of arsenopyrite was characterized after acidic, oxidative leaching in the presence of the bacterial species Thiobacillus ferrooxidans. Polished single-crystal grains of arsenopyrite were reacted for 1, 2, and 3 weeks with T. ferrooxidans suspended in a solution (pH 2.3) of essential salts (MgSO₄·7H₂O, [NH₄]₂SO₄, KH₂PO₄, and KCl). Abiotic control experiments were conducted in identical solutions. Reaction between arsenopyrite and T. ferrooxidans in the essential salts solution produced a uniform solid FePO₄ overlayer (∼0.2 μm thick) on the arsenopyrite surface within 1 week. The overlayer was detected visually by scanning electron microscopy (SEM) and chemically by X-ray photoelectron spectroscopy (XPS). It could not be distinguished by energy-dispersive X-ray analyses. No overlayer formed in the abiotic control. The uniform thickness and lateral continuity of the overlayer suggest an inorganic origin promoted by bacterial production of Fe³⁺. Iron released from arsenopyrite was oxidized by bacteria and subsequently precipitated with PO₄³⁻ (from the essential salts), forming ferric phosphate. After 2 and 3 weeks, SEM images revealed a roughened arsenopyrite surface, and XPS depth profiles indicated a progressively thicker phosphate overlayer and continued oxidation, diffusion, and dissolution of arsenopyrite beneath the overlayer. After only 1 week, the cells were isolated from the arsenopyrite surface by the uniform overlayer. Therefore, bacteria need not be attached to arsenopyrite to promote rapid reaction, and the mechanism of alteration at the arsenopyrite surface must have been inorganic. Because the delicate overlayer did not prevent continued alteration of arsenopyrite, FePO₄ may not be an effective barrier to oxidation in the tailings environment. The FePO₄ coating has likely formed in other experiments using these bacteria but was not detected because analytical techniques were not sufficiently surface sensitive to identify a separate, compositionally distinct overlayer. Some previous experimental results thus may be misleading or inapplicable to the tailings environment.     

Structure of the orthoclase (001)- and (010)-water interfaces by high-resolution X-ray reflectivity

High-resolution in situ X-ray specular reflectivity was used to measure the structures of orthoclase (001) and (010) cleavage surfaces in contact with deionized water at 25°C. X-ray reflectivity data demonstrate a high degree of structural similarity between these two orthoclase-water interfaces. Both interfacial structures include cleavage along the plane of minimal bond breakage resulting in surfaces terminated by non-bridging oxygens; structured water within 5 Å of the orthoclase surface (consisting of adsorbed species at the surface and layered water above the surface), with a featureless water profile beyond 5 Å; substitution of outermost K⁺ ions by an oxygen containing species (presumably H₃O⁺); and small structural displacements of the near surface atoms. The interfacial water structure, in comparison with recent results for other mineral-water interfaces, is intermediate between the minimal structure found at calcite-, barite-, and quartz-water interfaces and the more extensive structure found at the muscovite-water interface.     

Planetesimal sulfate and aqueous alteration in CM and CI carbonaceous chondrites

Water-soluble sulfate salts extracted from six CM chondrites have oxygen isotope compositions that are consistent with an extraterrestrial origin. The Δ¹⁷O of sulfate are correlated with previously reported whole rock δ¹⁸O and with an index of meteorite alteration, and may display a correlation with the date of the fall. The enrichments and depletions for Δ¹⁷O of water-soluble sulfate from the CM chondrites relative to the terrestrial mass dependent fractionation line are consistent with sulfate formation in a rock dominated asteroidal environment, and from aqueous fluids that had undergone relatively low amounts of oxygen isotope exchange and little reaction with anhydrous components of the meteorites. It is unresolved how the oxidation of sulfide to sulfate can be reconciled with the inferred low oxidation state during the extraterrestrial alteration process. Oxygen isotope data for two CI chondrites, Orgueil and Ivuna, as well as the ungrouped C2 chondrite Essebi are indistinguishable from sulfate of terrestrial origin and may be terrestrial weathering products, consistent with previous assertions. Our oxygen isotope data, however, can not rule out a preterrestrial origin either.     

Decomposition of alkyl dixanthogens in aqueous solutions

Alkyl dixanthogens, (ROCSS)₂, decompose in aqueous solution in the presence of nucleophiles in many ways.It is proposed here that in alkaline solution the principal methods of decomposition of ethyl dixanthogen are by simultaneous attack of OH^? ions on the sulphur-sulphur bond to give products which include xanthate ion (ROCSS^?) and peroxide (H₂O₂) and on the carbon-sulphur bond to give products which include monothiocarbonate ion (ROSCO^?), sulphide ion (S^2?), and sulphur (S⁰). Above pH 12 reaction is complete in a few minutes, and more monothiocarbonate than xanthate is formed. At pH 9 the reaction takes over 20 h and more xanthate than monothiocarbonate is formed.The primary products react further to give various ions which depend in part on the pH of the system. In alkaline solution some of the xanthate and peroxide react to give perxanthate (ROCSSO^?). In acid solution both xanthate and monothiocarbonate decompose rapidly; CS₂ is formed from xanthate and OCS from monothiocarbonate.In the presence of other nucleophiles at pH 9.2, dissolved dixanthogen decomposes much more quickly than with OH^? alone, and other reactions occur. With thiosulphate a higher proportion of xanthate is formed together with some xanthyl thiosulphate and monothiocarbonate but no perxanthate. With sulphite (in the absence of oxygen) or cyanide the products include xanthate and monothiocarbonate but no perxanthate. With sulphite in the presence of oxygen, perxanthate is also formed.Suspensions of dixanthogens react slowly but in a similar fashion to dissolved dixanthogens.Longer-chain dixanthogens are much less soluble than ethyl dixanthogen but, in general, react in a similar way. Higher temperatures increase the rate of decomposition by OH^?.This work has various implications in operating plants.