Interactions of uranium with bacteria and kaolinite clay

We assessed the accumulation of uranium (VI) by a bacterium, Bacillus subtilis, suspended in a slurry of kaolinite clay, to elucidate the role of microbes on the mobility of U(VI). Various mixtures of bacteria and the koalinite were exposed to solutions of 8 × 10^− 6 M- and 4 × 10^− 4 M-U(VI) in 0.01 M NaCl at pH 4.7. After 48 h, the mixtures were separated from the solutions by centrifugation, and treated with a 1 M CH₃COOK for 24 h to determine the associations of U within the mixture. The mixture exposed to 4 × 10^− 4 M U was analyzed by transmission electron microscope (TEM) equipped with EDS. The accumulation of U by the mixture increased with an increase in the amount of B. subtilis cells present at both U concentrations. Treatment of kaolinite with CH₃COOK, removed approximately 80% of the associated uranium. However, in the presence of B. subtilis the amount of U removed was much less. TEM–EDS analysis confirmed that most of the U removed from solution was associated with B. subtilis. XANES analysis of the oxidation state of uranium associated with B. subtilis, kaolinite, and with the mixture containing both revealed that it was present as U(VI). These results suggest that the bacteria have a higher affinity for U than the kaolinite clay mineral under the experimental conditions tested, and that they can immobilize significant amount of uranium.     

Adsorption of zinc on colloidal (hydr)oxides of Si,Al and Fe in the presence of a fulvic acid

The adsorption of Zn (total concentration 10⁻⁶ M) to colloidal quartz, hydrargillite and goethite (50, 300 and 70 mg/l, respectively) was studied by a batch technique at a constant ionic strength (0.01 M) but with variation of pH (3–10) and fulvic acid (FA) concentration (0, 2 or 20 mg/l). The adsorption had similar pH-dependence in all systems in the absence of FA giving a pH₅₀ (pH of 50% adsorption) of 7.6 under these conditions. The presence of the FA reduced the overall adsorption to quartz (pH₅₀ of 7.9 at 2 mg FA/I and 9.3 at 20 mg/1) and shifted the adsorption curves downwards (pH₅₀ of 6.8) in the hydrargillite and goethite systems at 2 mg FA/l. At 20 mg FA/l, the adsorption in the two latter systems was increased at pH <6.5 and reduced at pH >6.5. The results reflect the affinity of the surfaces for FA as well as the formation of Zn–FA complexes (in solution and on solid surfaces).     

Ternary interactions in a humic acid–Cd–bacteria system

Humic acid adsorption onto the bacterial surface of Bacillus subtilis was measured with and without Cd, as a function of pH and humic–bacteria–Cd ratios. These experiments tested for the existence of ternary interactions in a bacteria–humic–metal system. We determine both the effects of humic acid on the bacterial adsorption of Cd, as well as the effects of the aqueous metal cation on the bacterial adsorption of humic acid. The presence of Cd does not affect the extent of humic acid adsorption onto the bacterial surface, indicating that there is no competition for sorption sites between humic acid and Cd under the experimental conditions, and that changes in the charging properties of the bacterial surface, as a result of the Cd adsorption, are not significant enough to affect humic acid adsorption.

The presence of humic acid does diminish Cd adsorption onto the bacterial surface, suggesting the presence of an aqueous Cd–humate complex under mid to high pH conditions. However, we also observe that the solubility of humic acid is unaffected by the presence of aqueous Cd. This apparently inconsistent behavior of an aqueous Cd–humate complex affecting Cd adsorption but not affecting humic acid solubility is not observed with simpler ionizable organic molecules. We propose that the solubility of humic acid is controlled by the solubility of a less soluble fraction of the acid. Cd forms an aqueous complex with the more soluble fraction of humic acid and there is no interdependence between the aqueous activities of the more and less soluble fractions. That is, the solubility of one humic acid fraction is unaffected by the presence of an aqueous Cd–humate complex involving another humic acid fraction. These experimental results constrain the relative importance of surface ternary and aqueous metal–humate complexes on the bacterial adsorption of both humic acid and metal cations.     

Thermodynamic and kinetic aspects of formation of bauxites

Experiments in which cleavage nepheline samples were reacted with aqueous solutions at fixed pH's and temperature were carried out in the laboratory. The chemistry of the solution as a function of time was monitored, as well as the chemistry of the nepheline surfaces.

At 25°C, Al derived from the nepheline stays in solution due to slow precipitation kinetics of Al(OH)₃. At 60° and 80°C, precipitation of Al(OH)₃ is so rapid that Al concentration in solution is below 0.05 ppm. This indicates that precipitation kinetics favour the formation of bauxite deposits in tropical regions (i.e. T25°C), but not in temperate regions.

Precipitation products on the surface of the nepheline fragments at 60° and 80°C depend on the pH. At pH 3.0, an amorphous aluminium silicate (proto-kaolinite?) is formed. At pH>7.0, the precipitated phase contains, in addition to Al and Si, high amounts of Na and K (proto-muscovite?). The optimum pH for the formation of bauxite is in the range 5–7. These results are in agreement with thermodynamic calculations.     

Multisite surface reaction versus transport control during the hydrolysis of a complex oxide

Dissolution experiments of a tholeiite basalt glass carried out at different pH and T (up to 300°C) using a rotatingdisc apparatus show that, depending on pH and T, dissolution can be controlled by one of the following steps: (1) surface reaction; (2) transport of reactants in solution; and (3) mixed reaction. The activation energies of these different processes were found to be 60, 9 and 15–50 kJ mol⁻¹, respectively. Taking account of these results, it appears likely that surface reactions are not rate limiting for the hydrolysis of most crystalline silicate minerals in hydrothermal and metamorphic processes, and that caution should be exercised when predicting rate of reactions at high temperatures solely on the basis of activation energies measured at low temperatures.

Comparison of experimental and theoretical potentiometric titrations of the basalt glass and its constituent oxides indicates that the adsorption of H⁺ and OH⁻ ions at the basalt surface is metal cation specific and that the net adsorption can be predicted from the sole knowledge of the acidity constants of the network-forming constituent oxides. We found that in the acidic pH region dissolution is promoted by the adsorption of H⁺ on al and Fe surface sites while in the basic region, dissolution is promoted by the adsorption of OH⁻ on Si sites. The combination of the two distinct types of surface sites, Al and Fe on the one hand, and Si on the other hand, results in a dissolution rate minimum at a pH-value between the pH_zpc of the two groups of oxide components. Linear regressions with a slope n=3.8 are observed both in acid and alkaline solutions in logarithmic plots of the rate of dissolution vs. the surface charge. The value of n, which represents the number of protonation or hydroxylation steps prior to metal detachment, has been found equal to the mean valence of the network-forming metals.

Combining concepts of surface coordination chemistry with transition state theory afforded characterisation of the activated complexes involved in basalt dissolution processes. From the values obtained for the thermodynamic properties of activation for basalt dissolution it is assumed that the activated complexes formed during the H₂O-promoted dissolution of the basalt glass are more tightly bonded than those formed during H⁺- or OH⁻-promoted dissolution.     

Effects of pH and Ca competition on complexation of cadmium by fulvic acids and by natural organic ligands from a river and a lake

The technique of competitive ligand-exchange/anodic stripping voltammetry (CLE-SV) was used to investigate effects of pH and Ca concentration on cadmium complexation by fulvic acid (FA), as well as Cd speciation in two different freshwaters, a hardwater Lake Greifen and a softwater River Wyre. Binding of Cd to Suwannee river FA (10 mg/l) was determined at different pH (7–8.5) and in the presence of various concentration of Ca²⁺ (0–2 mmol/l). The results from one-ligand discrete models were compared to simulations by the WHAM VI model. In Lake Greifen, the determined dissolved [Cd²⁺] ranged from 10⁻¹³ to 10⁻¹² mol/l, and the conditional stability constant with natural ligands was log K _CdL about 9.5–10.5 (pH 8.6–8.8) with ligand concentrations of 1.2–7.8 × 10⁻⁶ mol/g C. In the softwater River Wyre, dissolved [Cd²⁺] ranged from 4 × 10⁻¹² to 1 × 10⁻¹¹ mol/l, and the ligands were weaker (log K _CdL 8.9–9.8, pH 8.0) with lower ligand concentrations (0.9–2.3 × 10⁻⁶ mol/g C). The titration curves of FA samples were close to the simulated curves by the WHAM VI model at pH 8.0–8.5, but deviated more from the model at lower pH, indicating that the results determined with CLE-SV for Cd-FA complexation are relevant to the data base in the model. Calculation of the Ca competition for Cd binding by FA showed a competition effect of similar strength as the measured one, but indicated a systematic difference between measured and modeled data at pH 7.5. Using the WHAM model for comparison with FA, the complexation of Cd by the River Wyre ligands was close to that of FA, whereas stronger complexation was observed in the Lake Greifen water. These differences may originate from different ligand composition in the lake and the river.     

Oxidative dissolution of pyritic sludge from the Aznalcóllar mine (SW Spain)

As a result of the collapse of a mine tailing dam, a large extension of the Guadiamar valley was covered with a layer of pyritic sludge. Despite the removal of most of the sludge, a small amount remained in the soil, constituting a potential risk of water contamination. The kinetics of the sludge oxidation was studied by means of laboratory flow-through experiments at different pH and oxygen pressures. The sludge is composed mainly of pyrite (76%), together with quartz, gypsum, clays, and sulphides of zinc, copper, and lead. Trace elements, such as arsenic and cadmium, also constitute a potential source of pollution. The sludge is fine grained (median of 12 μm) and exhibits a large surface (BET area of 1.4±0.2 m² g⁻¹).

The dissolution rate law of sludge obtained is r=10^{−6.1(±0.3)} [O₂(aq)]^0.41(±0.04) a_H+^0.09(±0.06) g_sludge m⁻² s⁻¹ (22 °C, pH=2.5–4.7). The dissolution rate law of pyrite obtained is r=10^{−7.8(±0.3)} [O₂(aq)]^0.50(±0.04) a_H+^0.10(±0.08) mol m⁻² s⁻¹ (22 °C, pH=2.5–4.7). Under the same experimental conditions, sphalerite dissolved faster than pyrite but chalcopyrite dissolves at a rate similar to that of pyrite. No clear dependence on pH or oxygen pressure was observed. Only galena dissolution seemed to be promoted by proton activity. Arsenic and antimony were released consistently with sulphate, except at low pH conditions under which they were released faster, suggesting that additional sources other than pyrite such as arsenopyrite could be present in the sludge. Cobalt dissolved congruently with pyrite, but Tl and Cd seemed to be related to galena and sphalerite, respectively.

A mechanism for pyrite dissolution where the rate-limiting step is the surface oxidation of sulphide to sulphate after the adsorption of O₂ onto pyrite surface is proposed.     

高岭石对重金属离子的吸附机理及其溶液的pH条件

高岭石对Cu^2+,Pb^2+离子的吸附实验及高岭石的溶解实验表明,高岭石对重金属离子的吸附有别于石英单一表面配位模式,离子交换和表面配位模式并存,并随溶液pH由酸性往碱性的变化发生规律性的演替：pH<6.5时主要表现为外圈层配位的离子交换吸附,且在pH<4时由于受到高岭石表层中铝的高溶出及溶液中较高离子强度的影响,高岭石对Cu^2+,Pb^2+离子的吸附率较低,pH为5～6时由于高岭石端面的荷电性为近中性,吸附率则有明显的提升并且表现为一个吸附平台;pH>6.5时离子交换和表面配位均为重要吸附机制,pH再升高时沉淀机制则起着重要作用。研究表明,pH调控高岭石-水界面溶解与质子化-去质子化反应过程,并影响着Cu^2+,Pb^2+离子的吸附行为。最后采用Sverjensky(1993)表面配位的物理模型对吸附结果作了描述。     

Behavior of metals (Cu,Zn and Cd) in the initial stage of water system contamination: Effect of pH and suspended particles

The fate of potentially harmful metals (PHM) after their entry into an unpolluted fresh water body depends on the physicochemical and biological parameters of the aquatic ecosystem. This paper considers the effect of pH and suspended particles (SP) on the behavior of Cu, Zn and Cd when they enter a fresh water reservoir. In a field experiment, four mesocosms were constructed in the Novosibirskoye Reservoir to allow systematic variation of SP concentration (15 or 250 mg/L) and pH (8.5 or 6.5). The initial concentrations of Cu, Zn and Cd in the mesocosms were 1000, 1000 and 200 μg/L, respectively. Natural bottom sediments were used to provide additional mineral SP, and water hyacinth was used as a floating plant species. Over 11 days, measurements were made of several indicators: residual metal concentration in solution ([PHM]_w); metal concentration in SP ([PHM]_s); primary productivity of the phytoplankton community; mass of settled SP; PHM concentration in settled SP; and PHM bioaccumulation by water hyacinth. The ratio [PHM]_w/[PHM]_s in the water varied in the order Cu < Zn < Cd and was higher at pH 6.5 than at pH 8.5. This observation reflects different PHM sorption (Cu > Zn > Cd) onto mineral SP and PHM biosorption by planktonic organisms. Phytoplankton acts as a renewable source of organic SP and plays an important role in metal removal from the water in the mesocosms. After 11 days the residual concentrations of Cu, Zn and Cd in the mesocosm without SP addition (initial SP concentration was 15 mg/L) were 272, 355 and 84 μg/L, respectively. The residual concentrations of Cu, Zn and Cd in mesocosms with SP addition were 57, 100 and 14 μg/L at pH 8.5 and 80, 172 and 20 μg/L at pH 6.5, respectively. Therefore, addition of SP resulted in faster and more complete removal of metals into the bottom sediments. Floating plants (water hyacinth) accumulated PHM (Cu > Zn > Cd) more effectively at pH 8.5 than at pH 6.5, and PHM concentrations in the roots were higher than in settling SP. The general trends of PHM removal from contaminated water via sedimentation and bioaccumulation are compared with changes of metal speciation in solution.     

Thermodynamics of U(VI) sorption onto Shewanella putrefaciens

We have conducted acid–base potentiometric titrations and U(VI) sorption experiments using the Gram negative, facultatively anaerobic bacterium Shewanella putrefaciens. Results of reversed titration studies on live, inactive bacteria indicate that their pH-buffering properties result from the equilibrium ionization of three discrete populations of functional groups. Carboxyl (pK_a=5.16±0.04), phosphoryl (pK_a=7.22±0.15) and amine (pK_a=10.04±0.67) groups most likely represent these three resolvable functionalities, based on their pK_a values. Site densities for carboxyl, phosphoryl and amine groups on the bacterial surface were approximately 31.7 μmol sites/g bacteria (0.35±0.02 sites/nm²), 8.95 μmol/g (0.11±0.007 sites/nm²) and 38.0 μmol/g (0.42±0.008 sites/nm²), respectively, based on an estimated bacterial specific surface area of 55 m²/g. Sorption experiments showed that U(VI) can reversibly complex with the bacterial surface in the pH 2–8 interval, with maximum adsorption occurring at a pH of 5. Sorption is not strongly sensitive to ionic strength (NaCl) in the range 0.02–0.10 M. The pH and ionic strength dependence of U(VI) sorption onto S. putrefaciens is similar to that measured for metal-oxide surfaces and Gram positive bacteria, and appears to be similarly governed by competitive speciation constraints. Measured U(VI) sorption is accounted for by using two separate adsorption reactions forming the surface complexes >COO–UO₂⁺ and >PO₄H–UO₂(OH)₂. Using S. putrefaciens as a model organism for dissimilatory metal-reducing Gram negative anaerobes, our results extend the applicability of geochemical speciation models to include bacteria that are capable of reductively solubilizing or precipitating a wide variety of environmentally and geologically important metals and metallic species.     

Studies of Cd(II)-sulfate interactions at the goethite-water interface by ATR-FTIR spectroscopy

A combination of macroscopic experiments and in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy was used to study Cd(II)-sulfate interactions on the goethite-water interface. The presence of SO₄ dramatically promoted Cd adsorption at lower pH (pH 5.5-6.5) and had a smaller effect at higher pH. ATR-FTIR studies indicated sulfate adsorption on goethite occurred via both outer- and inner-sphere complexation. The relative importance of both complexes was a function of pH and sulfate concentration. ATR-FTIR spectra provided direct evidence of the formation of Cd-SO₄ ternary surface complexes on goethite. In addition to ternary complexes, Cd specifically sorbed on goethite promoted SO₄ adsorption via changing the surface charge, and caused additional SO₄ adsorption as both inner- and outer-sphere complexes. The relative importance of ternary complexes versus electrostatic effects depended upon pH values and Cd concentration. Ternary complex formation was promoted by low pH and high Cd levels, whereas electrostatic effects were more pronounced at high pH and low Cd levels. A portion of SO₄ initially sorbed in inner-sphere complexes in the absence of Cd was transformed into Cd-SO₄ ternary complexes with increased Cd concentration.     

Coesite inclusions and prograde compositional zonation of garnet in whiteschist of the HP-UHPM Kokchetav massif, Kazakhstan: a record of progressive UHP metamorphism

Coarse-grained whiteschist, containing the assemblage: garnet+kyanite+phengite+talc+quartz/coesite, is an abundant constituent of the ultrahigh-pressure metamorphic (UHPM) belt in the Kulet region of the Kokchetav massif of Kazakhstan.

Garnet displays prograde compositional zonation, with decreasing spessartine and increasing pyrope components, from core to rim. Cores were recrystallized at T=380°C (inner) to 580°C (outer) at P<10 kbar (garnet–ilmenite geothermometry, margarite+quartz stability), and mantles at T=720–760°C and P_H20=34–36 kbar (coesite+graphite stability, phengite geobarometer, KFMASH system reaction equilibria). Textural evidence indicates that rims grew during decompression and cooling, within the Qtz-stability field.

Silica inclusions (quartz and/or coesite) of various textural types within garnets display a systematic zonal distribution. Cores contain abundant inclusions of euhedral quartz (type 1 inclusions). Inner mantle regions contain inclusions of polycrystalline quartz pseudomorphs after coesite (type 2), with minute dusty micro-inclusions of chlorite, and more rarely, talc and kyanite in their cores; intense radial and concentric fractures are well developed in the garnet. Intermediate mantle regions contain bimineralic inclusions with coesite cores and palisade quartz rims (type 3), which are also surrounded by radial fractures. Subhedral inclusions of pure coesite without quartz overgrowths or radial fractures (type 4) occur in the outer part of the mantle. Garnet rims are silica-inclusion-free.

Type 1 inclusions in garnet cores represent the low-P, low-T precursor stage to UHPM recrystallization, and attest to the persistence of low-P assemblages in the coesite-stability field. Coesites in inclusion types 2, 3, and 4 are interpreted to have sequentially crystallized by net transfer reaction (kyanite+talc=garnet+coesite+H₂O), and were sequestered within the garnet with progressively decreasing amounts of intragranular aqueous fluid.

During the retrograde evolution of the rock, all three inclusion types diverged from the host garnet P–T path at the coesite–quartz equilibrium, and followed a trajectory parallel to the equilibrium boundary resulting in inclusion overpressure. Coesite in type 2 inclusions suffered rapid intragranular H₂O-catalysed transformation to quartz, and ruptured the host garnet at about 600°C (when inclusion P27 kbar, garnet host P9 kbar). Instantaneous decompression to the host garnet P–T path, passed through the kyanite+talc=chlorite+quartz reaction equilibrium, resulting in the dusty micro-assemblage in inclusion cores. Type 3 inclusions suffered a lower volumetric proportion transformation to quartz at the coesite–quartz equilibrium, and finally underwent rupture and decompression when T<400°C, facilitating coesite preservation. Type 4 coesite inclusions are interpreted to have suffered minimal transformation to quartz and proceeded to surface temperature conditions along or near the coesite–quartz equilibrium boundary.     

Crustal zircons and mantle sulfides: Archean to Triassic events in the lithosphere beneath south-eastern Sicily

Three types of zircon coexist in an unusual lower crustal xenolith from the Valle Guffari diatreme (Hyblean Plateau, Sicily): igneous Type 1 (near-euhedral, weakly zoned; Ce/Ce > 1); partially recrystallised Type 2 (ovoid, structureless; weak Ce anomaly); hydrothermal Type 3 (sugary, spongy-textured, probably related to F-rich aqueous fluids). U–Pb dating by LAM-ICPMS, supported by in situ Hf-isotope analysis, suggests that both Type 1 and Type 2 zircons were originally Archean (ca 2.7 Ga), though many of these grains have experienced severe Pb loss. The U–Pb ages of the hydrothermal zircons cluster around 246 Ma, interpreted as the timing of the hydrothermal event. Their ε_Hf (+ 8.5 to − 1.2) indicates the mixing of old crustal components and material from a juvenile source.

In situ Os-isotope analyses of sulfides hosted in peridotite xenoliths from Valle Guffari show Paleoproterozoic–Archean T_RD minimum ages, corresponding to the age of the oldest zircon grains in the crustal xenolith. Other peaks of T_RD ages suggest that multiple metasomatic events have affected the lithospheric mantle.

These observations suggest that the lower crust and the upper part of the lithospheric mantle beneath the Hyblean Plateau represent the northernmost portion of the African Plate. These two units have coexisted since at least late Archean time, and have remained linked through several episodes of crustal modification, including the Permo-Triassic hydrothermal event, which was probably related to the onset of rifting in the Ionian Basin.     

Biosorption of Cd(II) from synthetic wastewater using dry biofilms from biotrickling filters

Biofilms wasted from biotrickling filters was dried and used as biosorbent for Cd(II) removal from aqueous solutions. The adsorption condition and effect, adsorption isotherms and kinetics of Cd(II) removal were investigated, and the effects of competitive metal ions on Cd(II) removal were also examined. Results showed that the dry waste biofilms reached the maximum adsorption capacity of 42 mg/g of Cd(II) at 25 °C for 120 min when the initial concentration of Cd(II) and their pH were 50 mg/L and 6.0, respectively. Under these conditions, the removal efficiency of Cd(II) reached to 89.3% when the biosorbent dosage was 2.0 g/L. The Langmuir isotherm model correlated with the isotherm data better than the Freundlich isotherm model, and the pseudo-second-order model fitted the kinetic data better than the pseudo-first-order model. These results indicated that the adsorption was monolayer accompanied with chemical adsorption. In the presence of other metal ions, divalent metal ions of Ca and Zn inhibited the performance of Cd(II) biosorption significantly, while Na(I), K(I) and Fe(III) which had a higher or lower valence than Ca(II) affected slightly when containing 50 mg/L Cd(II), 0.5 g/L adsorbent dosage and pH 6.0. The analyses of scanning electron microscopy and Fourier transform infrared spectroscopy illuminated that the biosorbent had porous structures and the amide group was the majorly responsible for Cd(II) removal. Dry biofilms were novel sorbents for effective removal Cd(II), and it could be reused and recycled if necessary.     

Soil sorption of caesium modelled by the Langmuir and Freundlich isotherm equations

The Langmuir and Freundlich adsorption isotherm equations were used to model Cs sorption in 6 Welsh soils. The pH (in water), of the soils ranged from 3.5 to 6.5, and the estimated organic matter (determined by loss-on-ignition) ranged from 4.8% to 46%. According to the Langmuir adsorption isotherm, highest sorption maxima,b, were displayed by the loams at 102–204 mg kg⁻¹, compared with organic soils at 37–86 mg kg⁻¹. Subsoil horizons (15–30 cm depth) did not always display higher sorption maxima than their topsoil (0–15 cm depth) counterparts. Where an improved fit to the Freundlich model was found over the Langmuir model, it was assumed that either concurrent desorption of other species, or bond-energy heterogeneity in the substrate, were significant for these soils.     

Effect of Fe on garnet–melt trace element partitioning: experiments in FCMAS and quantification of crystal-chemical controls in natural systems

Garnet–melt trace element partitioning experiments were performed in the system FeO–CaO–MgO–Al₂O₃–SiO₂ (FCMAS) at 3 GPa and 1540°C, aimed specifically at studying the effect of garnet Fe²⁺ content on partition coefficients (D^Grt/Melt). D^Grt/Melt, measured by SIMS, for trivalent elements entering the garnet X-site show a small but significant dependence on garnet almandine content. This dependence is rationalised using the lattice strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454], which describes partitioning of an element i with radius r_i and valency Z in terms of three parameters: the effective radius of the site r₀(Z), the strain-free partition coefficient D₀(Z) for a cation with radius r₀(Z), and the apparent compressibility of the garnet X-site given by its Young's modulus E_X(Z). Combination of these results with data in Fe-free systems [Van Westrenen, W., Blundy, J.D., Wood, B.J., 1999. Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am. Mineral. 84, 838–847] and crystal structure data for spessartine, andradite, and uvarovite, leads to the following equations for r₀(3+) and E_X(3+) as a function of garnet composition (X) and pressure (P):

r₀(3+) [Å]=0.930X_Py+0.993X_Gr+0.916X_Alm+0.946X_Spes+1.05(X_And+X_Uv)−0.005(P [GPa]−3.0)(±0.005 Å)

E_X(3+) [GPa]=3.5×10¹²(1.38+r₀(3+) [Å])^−26.7(±30 GPa)

Accuracy of these equations is shown by application to the existing garnet–melt partitioning database, covering a wide range of P and T conditions (1.8 GPa<P<5.0 GPa; 975°C<T<1640°C). D^Grt/Melt for all 3+ elements entering the X-site (REE, Sc and Y) are predicted to within 10–40% at given P, T, and X, when D^Grt/Melt for just one of these elements is known. In the absence of such knowledge, relative element fractionation (e.g. D_Sm^Grt/Melt/D_Nd^Grt/Melt) can be predicted. As an example, we predict that during partial melting of garnet peridotite, group A eclogite, and garnet pyroxenite, r₀(3+) for garnets ranges from 0.939±0.005 to 0.953±0.009 Å. These values are consistently smaller than the ionic radius of the heaviest REE, Lu. The above equations quantify the crystal-chemical controls on garnet–melt partitioning for the REE, Y and Sc. As such, they represent a major advance en route to predicting D^Grt/Melt for these elements as a function of P, T and X.     

Heat transport in serpentinites

The thermal transport properties thermal conductivity and thermal diffusivity were examined for a variety of serpentinites as a function of temperature at ambient pressure. The thermal transport properties of serpentinites show an extraordinary behavior. Besides the common 1/T decrease in thermal transport properties with increasing temperature, which can be related to an increase in phonon–phonon interactions with increasing temperature, an oscillation of thermal conductivity is observed with maxima around 450 and 850 K. This oscillation is linkable to water release of surficially bounded water and water in pores (450 K) and the dehydration of serpentinite (850 K). The oscillations are explained by advective heat transfer during dehydration, reaching up to 30% of the overall heat transport. The dehydration of serpentinites was examined by XRD and Thermo-Gravimetry and Differential Thermal Analysis/Differential Scanning Calorimeters (TG/DSC) investigations, indicating that the dehydration reaction is kinetically hindered and the crystallization of the product phases are observed at ≈1060 K, more than 200 K above the equilibrium of dehydration reactions. The conductive heat transfer by phonons shows a minor temperature variation and dominates thermal diffusivity. Ultrasonic sound velocities as a function of temperature [J. Geophys. Res. 102 (1997) 3051] were used to derive the mean free path length of phonons, which decreases from 0.28 to 0.2 nm at high temperatures. This is in the same order of magnitude as the interatomic distance of O–O, Al–O and Si–O restricting the minimum distance for phononic movement. A high anisotropy in thermal transport properties of single crystallites is concluded from its structure and elastic behaviour. However, the examined samples are macroscopically isotropic. The pressure and temperature dependence of conductive heat transport of an average serpentinite is given by λ=(1/(A+BT))(1+βP) W/m K, with A=0.3638 m K/W, B=0.000244 m/W and β=0.148 GPa⁻¹.     

The geochemical cycle of boron: Constraints from boron isotope partitioning experiments between mica and fluid

The fractionation of boron isotopes between synthetic boromuscovite and fluid was experimentally determined at 3.0 GPa/500 °C and 3.0 GPa/700 °C. For near-neutral fluids Δ¹¹B_(mica-fluid) = δ¹¹B_(mica) − δ¹¹B_(fluid) is − 10.9 ± 1.3‰ at 500 °C, and − 6.5 ± 0.4‰ at 700 °C. This supports earlier assumptions that the main fractionation effect is due to the change from trigonal coordination of boron in neutral fluids to tetrahedrally coordinated boron in micas, clays and melts. The T-dependence of this effect is approximated by the equation Δ¹¹B_{(mica,clay,melt–neutral fluid)} = − 10.69 · (1000/T [K]) + 3.88; R² = 0.992, valid from 25 °C for fluid–clay up to about 1000 °C for fluid–silicate melt. Experiments at 0.4 GPa that used strongly basic fluids produced significantly lower fractionations with Δ¹¹B_{(mica–fluid)} of − 7.4 ± 1.0‰ at 400 °C, and − 4.8 ± 1.0‰ at 500 °C, showing the reduced fractionation effect when large amounts of boron in basic fluids are tetrahedrally coordinated. Field studies have shown that boron concentrations and ¹¹B/¹⁰B-ratios in volcanic arcs systematically decrease across the arc with increasing distance from the trench, thus reflecting the thermal structure of the subducting slab. Our experiments show that the boron isotopic signature in volcanic arcs probably results from continuous dehydration of micas along a distinct P–T range. Continuous slab dehydration and boron transport via fluid into the mantle wedge is responsible for the boron isotopic signature in volcanic arcs.     

Biosorption of cadmium(II) from aqueous solution onto <Emphasis Type="Italic">Hydrilla verticillata</Emphasis>

Biosorption is an effective method to remove heavy metals from wastewater. In this work, the biosorption of Cd(II) onto Hydrilla verticillata was examined in aqueous solution with parameters of initial pH, adsorbent dosage, contact time, initial Cd(II) concentration, temperature, and co-existing ion. Linear Langmuir and Freundlich models were applied to describe the equilibrium isotherms, and both of the two models were fitted well. The monolayer adsorption capacity of Cd(II) was found to be 50 mg/g at pH 6 and 20°C. Dubinin–Radushkevich isotherm model was also applied to the equilibrium data. The mean free energy of adsorption (11.18 kJ/mol) indicated that the adsorption of Cd(II) onto H. verticillata might be carried out via chemical ion-exchange mechanism. Thermodynamic parameters, including free energy (∆G ⁰), enthalpy (∆H ⁰), and entropy (∆S ⁰) of adsorption, were also calculated. These results showed that the biosorption of Cd(II) onto H. verticillata was a feasible, spontaneous, and exothermic process in nature. Desorption experiments indicated that 0.01 mol/L EDTA and HNO₃ were efficient desorbents for the recovery of Cd(II) from biomass. IR spectrum analysis suggested that amido, hydroxyl, C=O and C–O could combine strongly with Cd(II). EDX spectrum analysis suggested that an ion exchange mechanism might be involved.     

Experimental synthesis and phase relations of phengitic muscovite from 6.5 to 11 GPa in a calcareous metapelite from the Dabie Mountains, China

The stability and phase relations of phengitic muscovite in a metapelitic bulk composition containing a mixed H₂O+CO₂ fluid were investigated at 6.5–11 GPa, 750–1050°C in synthesis experiments performed in a multianvil apparatus. Starting material consisted of a natural calcareous metapelite from the coesite zone of the Dabie Mountains, China, ultrahigh-pressure metamorphic complex that had experienced peak metamorphic pressures greater than 3 GPa. The sample contains a total of 2.1 wt.% H₂O and 6.3 wt.% CO₂ bound in hydrous and carbonate minerals. No additional fluid was added to the starting material. Phengite is stable in this bulk composition from 6.5 to 9 GPa at 900°C and coexists with an eclogitic phase assemblage consisting of garnet, omphacite, coesite, rutile, and fluid. Phengite dehydrates to produce K-hollandite between 8 and 11 GPa, 750–900°C. Phengite melting/dissolution occurs between 900°C and 975°C at 6.5–8 GPa and is associated with the appearance of kyanite in the phase assemblage. The formation of K-hollandite is accompanied by the appearance of magnesite and topaz-OH in the phase assemblage as well as by significant increases in the grossular content of garnet (average X_grs=0.52, X_py=0.19) and the jadeite content of omphacite (X_jd=0.92). Mass balance indicates that the volatile content of the fluid phase changes markedly at the phengite/K-hollandite phase boundary. At P≤8 GPa, fluid coexisting with phengite appears to be relatively CO₂-rich (XCO₂/XH₂O=2.2), whereas fluid coexisting with K-hollandite and magnesite at 11 GPa is rich in H₂O (XCO₂/XH₂O=0.2). Analysis of quench material and mass balance calculations indicate that fluids at all pressures and temperatures examined contain an abundance of dissolved solutes (approximately 40 mol% at 8 GPa, 60 mol% at 11 GPa) that act to dilute the volatile content of the fluid phase. The average phengite content of muscovite is positively correlated with pressure and ranges from 3.62 Si per formula unit (pfu) at 6.5 GPa to 3.80 Si pfu at 9 GPa. The extent of the phengite substitution in muscovite in this bulk composition appears to be limited to a maximum of 3.80–3.85 Si pfu at P=9 GPa. These experiments show that phengite should be stable in metasediments in mature subduction zones to depths of up to 300 km even under conditions in which aH₂O1. Other high-pressure hydrous phases such as lawsonite, MgMgAl-pumpellyite, and topaz-OH that may form in subducted sediments do not occur within the phengite stability field in this system, and may require more H₂O-rich fluid compositions in order to form. The wide range of conditions under which phengite occurs and its participation in mixed volatile reactions that may buffer the composition of the fluid phase suggest that phengite may significantly influence the nature of metasomatic fluids released from deeply subducted sediments at depths of up to 300 km at convergent plate boundaries.