Cadmium and lead interaction with diatom surfaces: A combined thermodynamic and kinetic approach

This work is devoted to the physico-chemical study of cadmium and lead interaction with diatom-water interfaces for two marine planktonic (Thalassiosira weissflogii, TW; Skeletonema costatum, SC) and two freshwater periphytic species (Achnanthidium minutissimum, AMIN; Navicula minima, NMIN) by combining adsorption measurements with surface complexation modeling. Adsorption kinetics was studied as a function of pH and initial metal concentration in sodium nitrate solution and in culture media. Kinetic data were consistent with a two-step mechanism in which the loss of a water molecule from the inner coordination sphere of the metal is rate limiting. Reversible adsorption experiments, with 3 h of exposure to metal, were performed as a function of pH (2-9), metal concentration in solution (10⁻⁹-10⁻³ M), and ionic strength (10⁻³-1.0 M). While the shape of pH-dependent adsorption edge is similar among all four diatom species, the constant-pH adsorption isotherm and maximal binding capacities differ. Measurements of electrophoretic mobilities (μ) revealed negative surface potential for AMIN diatom, however, the absolute value of μ decreases with increase of [Pb²⁺]_aq suggesting the metal adsorption on negative surface sites. These observations allowed us to construct a surface complexation model (SCM) for cadmium and lead binding by diatom surfaces that postulates the Constant Capacitance of the electric double layer and considers Cd and Pb complexation with mainly carboxylic and, partially, silanol groups. In the full range of investigated Cd concentration, the SCM is able to describe the concentration of adsorbed metal as a function of [Cd²⁺]_aq without implying the presence of high affinity, low abundance sites, that are typically used to model the metal interactions with natural multi-component organic substances. At the same time, Cd fast initial reaction requires the presence of “highly reactive sites” those concentration represents only 2.5-3% of the total amount of carboxylic sites. For reversible adsorption experiments, the dominating carboxylic groups, whose concentration is allowed to vary within the uncertainty of experimental acid-base titrations, are sufficient to reproduce the metal adsorption isotherms. Results of this study strongly suggest that laboratory experiments performed in a wide range of metal to biomass ratios, represent robust and relatively simple method for assessing the distribution of metals between aqueous solution and planktonic and periphytic biomass in natural settings.     

Interaction between zinc and freshwater and marine diatom species: Surface complexation and Zn isotope fractionation

This work is devoted to characterization of zinc interaction in aqueous solution with two marine planktonic (Thalassiosira weissflogii = TW, Skeletonema costatum = SC) and two freshwater periphytic species (Achnanthidium minutissimum = AMIN, Navicula minima = NMIN) by combining adsorption and electrophoretic measurements with surface complexation modeling and by assessing Zn isotopes fractionation during both long term uptake and short term adsorption on diatom cells and their frustules. Reversible adsorption experiments were performed at 25 and 5 °C as a function of exposure time (5 min to 140 h), pH (2 to 10), zinc concentration in solution (10 nM to 1 mM), ionic strength (I = 0.001 to 1.0 M) and the presence of light. While the shape of pH-dependent adsorption edge is almost the same for all four species, the constant-pH adsorption isotherm and maximal Zn binding capacities differ by an order of magnitude. The extent of adsorption increases with temperature from 5 to 25 °C and does not depend on light intensity. Zinc adsorption decreases with increase of ionic strength suggesting competition with sodium for surface sites. Cell number-normalized concentrations of sorbed zinc on whole cells and their silica frustules demonstrated only weak contribution of the latter (10-20%) to overall zinc binding by diatom cell wall. Measurements of electrophoretic mobilities (μ) revealed negative diatoms surface potential in the full range of zinc concentrations investigated (0.15-760 μmol/L), however, the absolute value of μ decreases at [Zn] > 15 μmol/L suggesting a change in surface speciation. These observations allowed us to construct a surface complexation model for Zn binding by diatom surfaces that postulates the constant capacitance of the electric double layer and considers Zn complexation with carboxylate and silanol groups. Thermodynamic and structural parameters of this model are based on previous acid-base titration and spectroscopic results and allow quantitative reproduction of all adsorption experiments. Although Zn adsorption constants on carboxylate groups are almost the same, Zn surface adsorption capacities are very different among diatom species which is related to the systematic differences in their cell wall composition and thickness. Measurements of Zn isotopic composition (⁶⁶Zn/(⁶⁴Zn)) performed using a multicollector ICP MS demonstrated that irreversible incorporation of Zn in cultured diatom cells produces enrichment in heavy isotope compared to growth media (Δ⁶⁶Zn(solid-solution) = 0.27 ± 0.05, 0.08 ± 0.05, 0.21 ± 0.05, and 0.19 ± 0.05‰ for TW, SC, NMIN, and AMIN species, respectively). Accordingly, an enrichment of cells in heavy isotopes (Δ⁶⁶Zn(solid-solution) = 0.43 ± 0.1 and 0.27 ± 0.1‰ for NMIN and AMIN, respectively) is observed following short-term Zn sorption on freshwater cells in nutrient media at pH ∼ 7.8. Finally, diatoms frustules are enriched in heavy isotopes compared to solution during Zn adsorption on silica shells at pH ∼ 5.5 (Δ⁶⁶Zn(solid-solution) = 0.35 ± 0.10‰). Measured isotopes fractionation can be related to the structure and stability of Zn complexes formed and they provide a firm basis for using Zn isotopes for biogeochemical tracing.     

Uranyl adsorption and surface speciation at the imogolite-water interface: Self-consistent spectroscopic and surface complexation models

Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ∼7-8 (I = 0.1 M NaNO₃ solution, suspension density = 0.4 g/L [U(VI)]_i = 0.01-30 μM, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and β charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in controlling U(VI) mobility in low-temperature geochemical environments over a wide pH range (∼5-9), even at the partial pressure of carbon dioxide of ambient air (p_CO2 = 10^−3.45 atm).     

Diatom community response to multiple scales of Holocene climate variability in a small lake on Victoria Island, NWT, Canada

A lake sediment core spanning 9900 years, collected from a small lake on western Victoria Island, NWT, Canada, provides a high-resolution record of diatom community dynamics over the Holocene. Ten radiocarbon dates and ²¹⁰Pb dating provided the core chronology. Loss-on-ignition (LOI), magnetic susceptibility, biogenic silica content, and diatom concentrations provided information on changes in the sedimentary environment. LOI gradually increased over the Holocene whereas magnetic susceptibility showed an inverse trend. Biogenic silica content showed three distinct peaks spaced approximately 3000 years apart. Major shifts in diatom assemblages occurred at 8100–8000, 5800–5700, and 3800–3500 cal yr BP. There is evidence of diatom community response to centennial-scale variations such as the ‘Medieval Warm Period’ (1000–700 cal yr BP), ‘Little Ice Age’ (800–150 cal yr BP) and recent warming. Although recent changes in diatom community composition, productivity, and species richness are apparent they were surpassed at other periods throughout the Holocene. Variations of the taxa within the genera Staurosira, Pseudostaurosira, Fragilaria, and Staurosirella, usually combined into one genus in Arctic lake sediment studies, suggest these taxa provide useful insight into paleonvironmental questions.     

U(VI) adsorption on natural iron-coated sands: comparison of approaches for modeling adsorption on heterogeneous environmental materials

Adsorption of U(VI) on 6 samples of natural Fe-rich sands from Oyster, VA was studied over a range of U(VI) concentrations (0.1–100 μM), pH values (3–7.6), and dithionite–citrate–bicarbonate (DCB) extractable amounts of Fe (3.1–12.3 μmol/g). Four modeling approaches were applied to represent the U(VI) adsorption data. Model I was a two-site, diffuse double layer, surface complexation model based on data for synthetic ferrihydrite [Geochim. Cosmochim. Acta 58 (1994) 5465–5478]. Considering the magnitude of approximations necessary for application of the laboratory-based model to natural sands, Model I was surprisingly accurate, as determined by the goodness of fit parameter, χ²/N of 53.1–22.2. Model II was based on the reactions and diffuse double layer treatment of Model I, but was calibrated to a portion of U(VI) adsorption data for each sand, and then used to predict adsorption data for the same sand under different experimental conditions. Model II did not increase the accuracy of the predictions made with Model I, χ²/N of 42.4–27.6. Models III and IV were four-site affinity spectrum models, without an explicit electric double layer model or explicit surface hydrolysis reactions. Model III was based on a discrete log K spectrum approach, and Model IV was obtained from adjusting all surface stability constants and site concentrations for all surface sites. Models III and IV represented the U(VI) adsorption data with the greatest accuracy, χ²/N ranged from 13.8 to 4.4. Model I provides evidence supporting the practice of using pure phase thermodynamic reaction constants for describing the adsorption characteristics of environmentally important sorbents in certain simple cases. Yet, affinity spectrum approaches (Models III and IV) become increasingly important as more accurate interpolation of adsorption data is necessary, the sorbent becomes increasingly complex, or the range of experimental conditions expands.     

Cd adsorption onto Anoxybacillus flavithermus: Surface complexation modeling and spectroscopic investigations

Several recent studies have applied surface complexation theory to model metal adsorption behaviour onto mesophilic bacteria. However, no investigations have used this approach to characterise metal adsorption by thermophilic bacteria. In this study, we perform batch adsorption experiments to quantify cadmium adsorption onto the thermophile Anoxybacillus flavithermus. Surface complexation models (incorporating the Donnan electrostatic model) are developed to determine stability constants corresponding to specific adsorption reactions. Adsorption reactions and stoichiometries are constrained using spectroscopic techniques (XANES, EXAFS, and ATR-FTIR). The results indicate that the Cd adsorption behaviour of A. flavithermus is similar to that of other mesophilic bacteria. At high bacteria-to-Cd ratios, Cd adsorption occurs by formation of a 1:1 complex with deprotonated cell wall carboxyl functional groups. At lower bacteria-to-Cd ratios, a second adsorption mechanism occurs at pH > 7, which may correspond to the formation of a Cd-phosphoryl, CdOH-carboxyl, or CdOH-phosphoryl surface complex. X-ray absorption spectroscopic investigations confirm the formation of the 1:1 Cd-carboxyl surface complex, but due to the bacteria-to-Cd ratio used in these experiments, other complexation mechanism(s) could not be unequivocally resolved by the spectroscopic data.     

Geochemical, Sr–Nd and zircon U–Pb–Hf isotopic studies of Late Carboniferous magmatism in the West Junggar, Xinjiang: Implications for ridge subduction?

Voluminous granitic intrusions are distributed in the West Junggar, NW China, and they can be classified as the dioritic rocks, charnockite and alkali-feldspar granite groups. The dioritic rocks (SiO₂ = 50.4–63.8 wt.%) are calc-alkaline and Mg enriched (average MgO = 4.54 wt.%, Mg^# = 0.39–0.64), with high Sr/Y ratios (average = 21.2), weak negative Eu (average Eu/Eu = 0.80) and pronounced negative Nb–Ta anomalies. Their Sr–Nd and zircon Hf isotopic compositions ((⁸⁷Sr/⁸⁶Sr)_i = 0.7035–0.7042, ε_Nd(t) = 4.5–7.9, ε_Hf(t) = 14.1–14.5) show a depleted mantle-like signature. These features are compatible with adakites derived from partial melting of subducted oceanic crust that interacted with mantle materials. The charnockites (SiO₂ = 60.0–65.3 wt.%) show transitional geochemical characteristics from calc-alkaline to alkaline, with weak negative Eu (average Eu/Eu = 0.75) but pronounced negative Nb–Ta anomalies. Sr–Nd and zircon Hf isotopic compositions ((⁸⁷Sr/⁸⁶Sr)_i = 0.7037–0.7039, ε_Nd(t) = 5.2–8.0, ε_Hf(t) = 13.9–14.7) also indicate a depleted source, suggesting melts from a hot, juvenile lower crust. Alkali-feldspar granites (SiO₂ = 70.0–78.4 wt.%) are alkali and Fe-enriched, and have distinct negative Eu and Nb–Ta anomalies (average Eu/Eu = 0.26), low Sr/Y ratios (average = 2.11), and depleted Sr–Nd and zircon Hf isotopic compositions ((⁸⁷Sr/⁸⁶Sr)_i = 0.7024–0.7045, ε_Nd(t) = 5.1–8.9, ε_Hf(t) = 13.7–14.2). These characteristics are also comparable with those of rocks derived from juvenile lower crust. Despite of the differences in petrology, geochemistry and possibly different origins, zircon ages indicate that these three groups of rocks were coevally emplaced at ~ 305 Ma.A ridge subduction model can account for the geochemical characteristics of these granitoids and coeval mafic rocks. As the “slab window” opened, upwelling asthenosphere provided enhanced heat flux and triggered voluminous magmatisms: partial melting of the subducting slab formed the dioritic rocks; partial melting of the hot juvenile lower crust produced charnockite and alkali-feldspar granite, and partial melting in the mantle wedge generated mafic rocks in the region. These results suggest that subduction was ongoing in the Late Carboniferous and, thus support that the accretion and collision in the Central Asian Orogenic Belt took place in North Xinjiang after 305 Ma, and possibly in the Permian.     

New observational information on the precursory accelerating and decelerating strain energy release

Recent reliable data are used to study the behavior of seismic activity before 46 strong shallow earthquakes (M ≥ 6.0), which correspond to five complete samples of mainshocks. These samples include 6 mainshocks (M = 6.0–7.1) that occurred in western Mediterranean since 1980, 17 mainshocks (M = 6.0–7.2) which occurred in the Aegean (Greece and surrounding area) since 1980, 5 mainshocks (M = 6.4–7.5) that occurred in Anatolia since 1980, 12 mainshocks (M = 6.0–7.3) that occurred in California since 1980 and 6 mainshocks (M = 7.0–8.3) that occurred in Japan since 1990. In all 46 cases, a similar precursory seismicity pattern is observed. Specifically, it is observed that accelerating Benioff strain (square root of seismic energy) release caused by preshocks occurs in a broad circular region (critical region), with a radius about eight times larger than the fault length of the mainshock, in agreement with results obtained by various research groups during the last two decades. However, in a much smaller circular region (seismogenic region), with a radius about four times the fault length, the corresponding preshock strain decelerates with the time to the mainshock. The time variation of the strain follows in both cases a power law but the exponent power is smaller than unit (m ¯ = 0.3) in the case of the accelerating preshock strain and larger than unit (m ¯ = 3.0) in the case of the decelerating preshock strain. Predictive properties of this “Decelerating In–Accelerating Out Strain” model are expressed by empirical relations. The possibility of using this model for intermediate-term earthquake prediction is discussed and the relative model uncertainties are estimated.     

Aqueous cadmium uptake by calcite: a stirred flow-through reactor study

Uptake of cadmium ions from solution by a natural Mg-containing calcite was investigated in stirred flow-through reactor experiments. Input NaCl solutions were pre-equilibrated with calcite (pH 8.0) or not (pH 6.0), prior to being spiked with CdCl₂. For water residence times in the reactor less than 0.5 h, irreversible uptake of Cd by diffusion into the bulk crystal had a minor effect on the measured cadmium breakthrough curves, hence allowing us to quantify “fast” Cd²⁺ adsorption. At equal aqueous activities of Cd²⁺, adsorption was systematically lower for the pre-equilibrated input solutions. The effect of variable solution composition on Cd²⁺ adsorption was reproduced by a Ca²⁺-Cd²⁺ cation exchange model and by a surface complexation model for the calcite-aqueous solution interface. For the range of experimental conditions tested, the latter model predicted binding of aqueous Ca²⁺ and Cd²⁺ to the same population of carbonate surface sites. Under these circumstances, both adsorption models were equivalent. Desorption released 80 to 100% of sorbed cadmium, confirming that fast uptake of Cd²⁺ was mainly due to binding at surface sites. Slow, irreversible cadmium uptake by the solid phase was measured in flow-through reactor experiments with water residence times exceeding 0.7 h. The process exhibited first-order kinetics with respect to the concentration of adsorbed Cd²⁺, with a linear rate constant at 25°C of 0.03 h⁻¹. Assuming that diffusion into the calcite lattice was the mechanism of slow uptake, a Cd²⁺ solid-state diffusion coefficient of 8.5×10⁻²¹ cm² s⁻¹ was calculated. Adsorbed Cd²⁺ had a pronounced effect on the dissolution kinetics of calcite. At maximum Cd²⁺ surface coverage (∼10⁻⁵ mol m⁻²), the calcite dissolution rate was 75% slower than measured under initially cadmium-free conditions. Upon desorption of cadmium, the dissolution rate increased again but remained below its initial value. Thus, the calcite surface structure and reactivity retained a memory of the adsorbed Cd²⁺ cations after their removal.     

Single and binary adsorption of lead and cadmium ions from aqueous solution using the clay mineral beidellite

Beidellite, a low-cost, locally available and natural mineral was used as an adsorbent for the removal of lead and cadmium ions from aqueous solutions in batch experiments. The kinetics of adsorption process was tested for the pseudo first-order, pseudo second-order reaction and intra-particle diffusion models. The rate constants of adsorption for all these kinetic models were calculated. Comparison amongst the models showed that the sorption kinetics was best described by the pseudo second-order model. Langmuir and Freundlich isotherm models were applied to the experimental equilibrium data for different temperatures. The adsorption capacities (Q°) of beidellite for lead and cadmium ions were calculated from the Langmuir isotherm. It was found that adsorption capacity was in the range of 83.3–86.9 for lead and 42–45.6 mg/g for cadmium at different temperatures. Thermodynamic studies showed that the metal uptake reaction by beidellite was endothermic in nature. Binary metal adsorption studies were also conducted to investigate the interactions and competitive effects in binary adsorption process. Based on the optimum parameters found, beidellite can be used as adsorbent for metal removal processes.     

Upper mantle structure of the Northern Eurasia from peaceful nuclear explosion data

Several long-range seismic profiles were carried out in Russia with Peaceful Nuclear Explosions (PNE). The data from 25 PNEs recorded along these profiles were used to compile a 3-D upper mantle velocity model for the central part of the Northern Eurasia. 2-D crust and upper mantle models were also constructed for all profiles using a common methodology for wavefield interpretation. Five basic boundaries were traced over the study area: N1 boundary (velocity level, V = 8.35 km/s; depth interval, D = 60–130 km), N2 (V = 8.4 km/s; D = 100–140 km), L (V = 8.5 km/s; D = 180–240 km) and H (V = 8.6 km/s; D = 300–330 km) and structural maps were compiled for each boundary. Together these boundaries describe a 3-D upper mantle model for northern Eurasia. A map characterised the velocity distribution in the uppermost mantle down to a depth of 60 km is also presented. Mostly horizontal inhomogeneity is observed in the uppermost mantle, and the velocities range from the average 8.0–8.1 km/s to 8.3–8.4 km/s in some blocks of the Siberian Craton. At a depth of 100–200 km, the local high velocity blocks disappear and only three large anomalies are observed: lower velocities in West Siberia and higher velocities in the East-European platform and in the central part of the Siberian Craton. In contrast, the depths to the H boundary are greater beneath the craton and lower beneath in the West Siberian Platform. A correlation between tectonics, geophysical fields and crustal structure is observed. In general, the old and cold cratons have higher velocities in the mantle than the young platforms with higher heat flows.Structural peculiarities of the upper mantle are difficult to describe in form of classical lithosphere–asthenosphere system. The asthenosphere cannot be traced from the seismic data; in contrary the lithosphere is suggested to be rheologically stratified. All the lithospheric boundaries are not simple discontinuities, they are heterogeneous (thin layering) zones which generate multiphase reflections. Many of them may be a result of fluids concentrated at some critical P–T conditions which produce rheologically weak zones. The most visible rheological variations are observed at depths of around 100 and 250 km.     

Adsorption of oleate on fluorite surface as revealed by atomic force microscopy

The adsorption of oleic acid / oleate on fluorite surface could be visualized using tapping mode of atomic force microscopy (AFM). The natural fluorite crystals were equilibrated with 10^− 3 to 10^− 7 M oleate solutions and their AFM images at each concentration along with height profiles were recorded. Even at low oleate concentration of 1 × 10^− 7 M, concomitant monolayer and bilayer structures were observed. It suggests that normal–normal bonding of hydrocarbon chains takes place before the surface is completely covered by the monolayer. Multi-layer adsorption of oleate was observed at oleate concentrations of above 10^− 4 M. The tapping mode AFM can be utilized to visualize the topography of surfaces adsorbed with surfactant molecules.     

High-pressure and ultrahigh-temperature metamorphism at Komateri, northern Madurai Block, southern India

We report for the first time the evidence for prograde high-pressure (HP) metamorphism preceding a peak ultrahigh-temperature (UHT) event in the northernmost part of the Madurai Block in southern India. Mg–Al-rich Grt–Ged rocks from Komateri in Karur district contain poikiloblastic garnet with numerous multi-phase inclusions. Although most of the inclusion assemblages are composed of gedrite, quartz, and secondary biotite, rare staurolite + sapphirine and spinel + quartz are also present. The X_Mg (=Mg/[Fe+Mg]) of staurolite (0.45–0.49) is almost consistent with that reported previously from Namakkal district in the Palghat–Cauvery Shear Zone system (X_Mg = 0.51–0.52), north of the Madurai Block. The HP event was followed by peak UHT metamorphism at T = 880–1040 °C and P = 9.8–12.5 kbar as indicated by thermobarometric computations in the Grt–Ged rock and associated mafic granulite. Symplectic intergrowth of spinel (X_Mg = 0.50–0.59, ZnO < 1.7 wt.%) and quartz, a diagnostic indicator of UHT metamorphism, probably formed by decompression at UHT conditions. The rocks subsequently underwent retrograde metamorphism at T = 720–760 °C and P = 4.2–5.1 kbar. The P–T conditions and clockwise exhumation trajectory of the Komateri rocks, comparable to similar features recorded from the Palghat–Cauvery Shear Zone system, suggest that the Madurai Block and the Palghat–Cauvery Shear Zone system underwent similar HP and UHT metamorphic history probably related to the continent–continent collision during the final stage of amalgamation of Gondwana supercontinent.     

Adsorption of rare earth elements onto Carrizo sand: Experimental investigations and modeling with surface complexation

Rare earth element (REE) adsorption onto sand from a well characterized aquifer, the Carrizo Sand aquifer of Texas, has been investigated in the laboratory using a batch method. The aim was to improve our understanding of REE adsorption behavior across the REE series and to develop a surface complexation model for the REEs, which can be applied to real aquifer-groundwater systems. Our batch experiments show that REE adsorption onto Carrizo sand increases with increasing atomic number across the REE series. For each REE, adsorption increases with increasing pH, such that when pH >6.0, >98% of each REE is adsorbed onto Carrizo sand for all experimental solutions, including when actual groundwaters from the Carrizo Sand aquifer are used in the experiments. Rare earth element adsorption was not sensitive to ionic strength and total initial REE concentrations in our batch experiments. It is possible that the differences in experimental ionic strength conditions (i.e., 0.002-0.01 M NaCl) chosen were insufficient to affect REE adsorption behavior. However, cation competition (e.g., Ca, Mg, and Zn) did affect REE adsorption onto Carrizo sand, especially for light rare earth elements (LREEs) at low pH. Rare earth element adsorption onto Carrizo sand can be successfully modeled using a generalized two-layer surface complexation model. Our model calculations suggest that REE complexation with strong surface sites of Carrizo sand exceeds the stability of the aqueous complexes LnOH²⁺, LnSO₄⁺, and LnCO₃⁺, but not that of Ln(CO₃)₂^- or LnPO₄^o in Carrizo groundwaters. Thus, at low pH (<7.3), where major inorganic ligands did not effectively compete with surface sites for dissolved REEs, free metal ion (Ln³⁺) adsorption was sufficient to describe REE adsorption behavior. However, at higher pH (>7.3) where solution complexation of the dissolved REEs was strong, REEs were adsorbed not only as free metal ion (Ln³⁺) but also as aqueous complexes (e.g., as Ln(CO₃)₂^- in Carrizo groundwaters). Because heavy rare earth elements (HREEs) were preferentially adsorbed onto Carrizo sand compared to LREEs, original HREE-enriched fractionation patterns in Carrizo groundwaters from the recharge area flattened along the groundwater flow path in the Carrizo Sand aquifer due to adsorption of free- and solution-complexed REEs.     

Experimental Study on Surface Reactions of Heavy Metal Ions With Quartz—Aqueous Ion Concentration Dependence

Adsorption of divalent metal ions, including Cu²⁺, Pb²⁺, Zn²⁺, Cd²⁺ and Ni²⁺, on quartz surface was measured as a function of metal ion concentration at 30°C under conditions of solution pH= 6. 5 and ion strength I = 0. 1mol/L. Results of the experimental measurements can be described very well by adsorption isotherm equations of Freudlich. The correlation coefficients (r) of adsorption isotherm lines are > 0. 96. Moreover, the experimental data were interpreted on the basis of surface complexation model. The experimental results showed that the monodentate-coordinated metal ion surface complex species (SOM⁺) are predominant over the bidentate-coordinated metal ion surface complex species [(SO)₂M] formed only by the ions Cu²⁺, Zn²⁺ and Ni²⁺. And the relevant apparent surface complexation constants are lgK_M = 2.2–3.3 in order of K_Cd≥K_Pb > K_Zn > K_Ni≥K_Cu, and lgβ_M = 5.9-6.8 in order of β_Ni > β_Zn > β_Cu. Therefore, the reactive ability of the ions onto mineral surface of quartz follows the order of Cd > Pb > Zn > Ni> Cu under the above-mentioned solution conditions. The apparent surface complexation constants, influenced by the surface potential, surface species and hydrolysis of metal ions, depend mainly on the Born solvation coefficient of the metal ions. This project was financially supported by the National Natural Science Foundation of China (No. 49572091).     

Graphite oxidation in the Apollo 17 orange glass magma: Implications for the generation of a lunar volcanic gas phase

An Apollo 17 picritic orange glass composition has been used to experimentally investigate the conditions at which graphite would oxidize to form a CO-rich gas, and ultimately produce lunar fire-fountain eruptions. Isothermal decompression experiments run above the A17 orange glass liquidus temperature (>1350 °C) suggest that the initial CO-rich gas phase produced by graphite oxidation would be generated during magma ascent at a pressure of 40 MPa, 8.5 km beneath the lunar surface. Additional experiments with 2000 ppm S and 1000 ppm Cl showed that the presence of these dissolved gas species would not affect the depth of graphite oxidation, verifying that the first volcanic gas phase would be generated by the oxidation of graphite.A simple ideal chemical mixing model for calculating melt FeO activity in a Fe-metal/silicate melt system was tested with a series of 0.1 MPa controlled oxygen fugacity experiments. Agreement between the model and experiments allows the model to be used to calculate oxygen fugacity in picritic lunar glass compositions such as the A17 orange glass. Using this model in a reanalysis of chemical equilibria between the natural A17 orange glass melt and the metal spherules (Fe₈₅Ni₁₄Co₁) trapped within the glass beads indicates a log oxygen fugacity of −11.2, 0.7 log units, more oxidized than previous estimates. At the A17 orange glass liquidus temperature (1350 ± 5 °C), this f_O2 corresponds to a minimum pressure of 41 MPa on the graphite–C–O surface. The fact that the same critical graphite oxidation pressure was determined in decompression experiments and from the Fe–FeO activity model for the natural A17 orange glass–metal assemblage strongly supports this pressure (8.5 km depth) for volcanic gas formation in lunar basalts. Generation of a gas by oxidation of C in ascending magma is likely to have been important in getting dense lunar magmas to the surface as well as in generating fire-fountain eruptions. The vesicles common in many lunar basalts and the ubiquitous Fe-metal in these rocks are also likely generated by the oxidation of carbon. The presence of carbon in the lunar basalts and the recent discovery of ppm levels of water in lunar basalts indicate that at least parts of the lunar interior still contained volatiles at 3.9 bybp.     

Quantitative reconstruction of Holocene precipitation changes in southern Patagonia

Holocene variations in annual precipitation (P_ann) were reconstructed from pollen data from southern Argentinian Patagonia using a transfer function developed based on a weighted-averaging partial least squares (WA-PLS) regression. The pollen–climate calibration model consisted of 112 surface soil samples and 59 pollen types from the main vegetation units, and modern precipitation values obtained from a global climate database. The performance (r² = 0.517; RMSEP = 126 mm) of the model was comparable or slightly lower than in other comparable pollen–climate models. Fossil pollen data were obtained from a sediment core from Cerro Frias site (50°24'S, 72°42'W) located at the forest-steppe ecotone. Reconstructed P_ann values of about 200 mm suggest dry conditions during the Pleistocene–Holocene transition (12,500–10,500 cal yr BP). P_ann values were about 300–350 mm from 10,500 to 8000 cal yr BP and increased to 400–500 mm between 8000 and 1000 cal yr BP. An abrupt decrease in P_ann at about 1000 cal yr BP was associated with a Nothofagus decline. The reconstructed P_ann suggests a weakening and southward shift of the westerlies during the early Holocene and intensification, with no major latitudinal shifts, during the mid-Holocene at high latitudes in southern Patagonia.     

A high-resolution diatom-inferred palaeoconductivity and lake level record of the Aral Sea for the last 1600 yr

Formerly the world's fourth largest lake by area, the Aral Sea is presently undergoing extreme desiccation due to large-scale irrigation strategies implemented in the Soviet era. As part of the INTAS-funded CLIMAN project into Holocene climatic variability and the evolution of human settlement in the Aral Sea basin, fossil diatom assemblages contained within a sediment core obtained from the Aral Sea have been applied to a diatom-based inference model of conductivity (r² = 0.767, RMSEP = 0.469 log₁₀ μS cm^− 1). This has provided a high-resolution record of conductivity and lake level change over the last ca. 1600 yr. Three severe episodes of lake level regression are indicated at ca. AD 400, AD 1195–1355 and ca. AD 1780 to the present day. The first two regressions may be linked to the natural diversion of the Amu Darya away from the Aral Sea and the failure of cyclones formed in the Mediterranean to penetrate more continental regions. Human activity, however, and in particular the destruction of irrigation facilities are synchronous with these early regressions and contributed to the severity of the observed low stands.