Carbonate complexation of yttrium and the rare earth elements in natural waters

Potentiometric measurements of Yttrium and Rare Earth Element (YREE) complexation by carbonate and bicarbonate indicate that the quality of carbonate complexation constants previously obtained via solvent exchange analyses are superior to characterizations obtained using solubility and adsorptive exchange analyses. The results of our analyses at 25°C are combined with the results of previous solvent exchange analyses to obtain YREE carbonate complexation constants over a wide range of ionic strength (0 ≤ I ≤3 molal). YREE carbonate complexation constants are reported for the following equilibria, M³⁺+nHCO₃⁻?M(CO₃)_n³⁻²ⁿ+nH⁺, where n = 1 or 2. Formation constants written in terms of HCO₃⁻ concentrations require only minor corrections for ion pairing relative to the corrections required for constants expressed in terms of CO₃²⁻ concentrations. Formation constants for the above complexation equilibria, _CO3^Hβ₁=[MCO₃⁺][H⁺][M³⁺]⁻¹[HCO₃⁻]⁻¹ and _CO3^Hβ₂=[M(CO₃)₂⁻][H⁺]²[M³⁺]⁻¹[HCO₃⁻]⁻², have very similar dependencies on ionic strength because the reaction MCO₃⁺+HCO₃⁻?M(CO₃)₂⁻+H⁺ is isocoulombic. Potentiometric analyses indicate that the dependence of log_CO3^Hβ₁ and log_CO3^Hβ₂ on ionic strength at 25°C is given as

(A)     

Variation of the distribution coefficients of rare earth elements in modern coral-lattices: species and site dependencies

Rare earth element (REE) concentrations in the carbonate lattice of four species of coral have been analyzed and compared with the dissolved REE in ambient seawaters. The corals were from two areas of different salinity, marine (34-34.5) and bay (33-34). The measurement of REE in coral was carried out with inductively coupled plasma mass spectrometry (ICP-MS) after meticulous washing of coral samples, digestion with acetic acid and preconcentration of REE. The concentrations of REE in the two ambient seawaters were quite different, being ten-times higher in the bay area and enriched in light REE. However, the average distribution coefficients (D’s) were almost identical in the two areas. Substantial distribution coefficient differences were observed among the four coral species and the magnitude of inter-species variation in D was also species-dependent. Theoretical calculations imply that pH variation could cause variations in D large enough to account for the small differences between the two areas.     

Pyrite oxidation in moist air

The rate of pyrite oxidation in moist air was determined by measuring, over time, the pressure difference between a sealed chamber containing pyrite plus oxygen and a control. The experiments carried out at 25°C, 96.7% fixed relative humidity, and oxygen partial pressures of 0.21, 0.61, and 1.00 atm showed that the rate of oxygen consumption is a function of oxygen partial pressure and time. The rates of oxygen consumption (r, mol/m²sec) fit the expression

(A)     

Oxygen-exchange pathways in aluminum polyoxocations

Using molecular dynamics simulations and electronic structure methods, we postulate a mechanism to explain the complicated reactivity trends that are observed for oxygen isotope exchange reactions between sites in aluminum polyoxocations of the ε-Keggin type and bulk solution. Experimentally, the molecules have four nonequivalent oxygens that differ considerably in reactivity both within a molecule, and between molecules in the series: Al₁₃, GaAl₁₂, and GeAl₁₂ [MO₄Al₁₂(OH)₂₄(H₂O)₁₂ⁿ⁺(aq); with M = Al(III) for Al₁₃, n = 7; M = Ga(III) for GaAl₁₂, n = 7; M = Ge(IV) for GeAl₁₂, n = 8]. We find that a partly dissociated, metastable intermediate molecule of expanded volume is necessary for exchange of both sets of μ₂-OH and that the steady-state concentration of this intermediate reflects the bond strengths between the central metal and the μ₄-O. Thus the central metal exerts extraordinary control over reactions at hydroxyl bridges, although these are three bonds away.This mechanism not only explains the reactivity trends for oxygen isotope exchange in μ₂-OH and η-OH₂ sites in the ε-Keggin aluminum molecules, but also explains the observation that the reactivities of minerals tend to reflect the presence of highly coordinated oxygens, such as the μ₄-O in boehmite, α-, and γ-Al₂O₃ and their Fe(III) analogs. The partial dissociation of these highly coordinated oxygens, coupled with simultaneous activation and displacement of neighboring metal centers, may be a fundamental process by which metals atoms undergo ligand exchanges at mineral surfaces.     

Neodymium isotopes in the Mediterranean Sea: comparison between seawater and sediment signals

Nine depth-profiles of dissolved Nd concentrations and isotopic ratios (ε_Nd) were obtained in the Levantine Basin, the Ionian, the Aegean, the Alboran Seas and the Strait of Gibraltar. Thirteen core-top sediments and Nile River particle samples were also analyzed (leached with 1 N HCl, acetic acid or hydroxylamine hydrochloride). The seawater ε_Nd values become more radiogenic during the eastward circulation in the Mediterranean Sea. The relationship between salinity and the seawater ε_Nd shows that the Nd isotopic signature is more conservative than salinity in the Mediterranean Sea. The water mass with the highest ε_Nd (−4.8) is found at about 200 m in the easternmost Levantine basin. The average ε_Nd value for deep waters is −7.0 in the eastern basin, 2.5 ε-units higher than in the western basin. By examining the sensitivity of seawater ε_Nd to Nd inputs from the Nile, we conclude that the most significant radiogenic Nd source is partially dissolved Nile River particles. The Nd flux from the Nile River water has a minor influence on the Mediterranean seawater ε_Nd. Except for the easternmost Levantine Basin, the leachate ε_Nd values are consistent with the seawater values. In the easternmost Levantine Basin, the leachate ε_Nd values obtained with HCl leaching are systematically higher than the seawater values. The relationship between leachate and residual ε_Nd values indicates that the HCl leaching partially dissolves lithogenic Nd, so the dissolution of Nile River particles is the cause of the observed shift. Some ε_Nd values obtained with hydroxylamine hydrochloride leaching are higher than those obtained with HCl leaching. Although the reason for this shift is not clear, ⁸⁷Sr/⁸⁶Sr successfully detects the presence of a nonmarine component in the leachate. Our results suggest that leaching performance may vary with the mineralogy of marine sediments, at least in the case of the Mediterranean Sea.     

Carbon isotope effects in carbonate systems

Global carbon cycle models require a complete understanding of the δ¹³C variability of the Earth’s C reservoirs as well as the C isotope effects in the transfer of the element among them. An assessment of δ¹³C changes during CO₂ loss from degassing magmas requires knowledge of the melt-CO₂ carbon isotope fractionation. In order to examine the potential size of this effect for silicate melts of varying composition, ¹³C reduced partition functions were computed in the temperature range 275 to 4000 K for carbonates of varying bond strengths (Mg, Fe, Mn, Sr, Ba, Pb, Zn, Cd, Li, and Na) and the polymorphs of calcite. For a given cation and a given pressure the ¹³C content increases with the density of the carbonate structure. For a given structure the tendency to concentrate ¹³C increases with pressure. The effect of pressure (‰/10 kbar) on the size of the reduced partition function of aragonite varies with temperature; in the pressure range 1 to 10⁵ bars the change is given by:

(1)     

Manganese-chromium isotope systematics of enstatite meteorites

We present results of a study of the ⁵³Mn-⁵³Cr isotope systematics in the enstatite chondrites and achondrites (aubrites). The goal of this study was to explore the capabilities of this isotope system to obtain chronological information on these important classes of meteorites and to investigate the original distribution in the inner solar system of the short-lived radionuclide ⁵³Mn. Our earlier work (Lugmair and Shukolyukov, 1998; Shukolyukov and Lugmair, 2000a) has shown that the asteroid belt bodies are characterized by essentially the same initial ⁵³Mn abundance. However, we have found the presence of a gradient in the abundance of the radiogenic ⁵³Cr between the earth-moon system, Mars, and the asteroid Vesta. If this gradient is considered as a function of the heliocentric distance a linear radial dependence is indicated. This can be explained either by an early, volatility controlled Mn/Cr fractionation in the nebula or by an original radially heterogeneous distribution of ⁵³Mn. The enstatite chondrites are suggested to form in the inner zones of the solar nebula, much closer to the Sun than the ordinary chondrites. Therefore, their investigation may be an important test on the hypothesis on a radial heterogeneity in the initial ⁵³Mn.We have studied the bulk samples of the EH4-chondrites Indarch and Abee and the EL6-chondrite Khairpur. Although these meteorites have essentially the same Mn/Cr ratio as the ordinary chondrites, the relative abundance of the radiogenic ⁵³Cr is three times smaller than in the ordinary chondrites. Because these meteorites are primitive (undifferentiated) and no Mn/Cr fractionation had occurred within their parent bodies, this difference is a strong argument in favor of an initially heterogeneous distribution of ⁵³Mn in the early inner solar system. This finding is also consistent with formation of the enstatite chondrites in the inner zones of the solar nebula. Using the characteristic ⁵³Cr excess of the enstatite chondrites and the observed gradient, their place of origin falls at about 1.4 AU or somewhat closer to the Sun (i.e. >1.0-1.4 AU).We also present chronological results for the enstatite chondrites and achondrites. The ‘absolute’ ⁵³Mn-⁵³Cr ages of the EH4-chondrites are old: ∼4565 Ma. The EL6-chondrite Khairpur is ∼4.5 Ma younger, which is in good agreement with the ¹²⁹I-¹²⁹Xe data from the literature. The age of the aubrite Peña Blanca Spring appears to be similar to those of the enstatite chondrites while that of the aubrite Bishopville is at least ∼10 Ma younger, which is also in agreement with the ¹²⁹I-¹²⁹Xe data. The results from bulk samples of aubrites indicate that the last Mn/Cr fractionation in their parent body occurred ∼ 4563 Ma ago and imply an evolution of the Mn-Cr isotope system in an environment with an higher than chondritic Mn/Cr ratio for several millions of years.     

Reversibility of radiocaesium sorption on illite

Adsorption of trace amounts of radiocaesium on NH₄-, K-, and Na-saturated Fithian illite and subsequent desorption by 1 M NH₄ showed that a substantial amount of radiocaesium (44%, 46%, and 91% for NH₄-, K-, and Na-illite, respectively) cannot be desorbed after only 5 min of adsorption. Our results suggest that this instantaneous fixation is caused by the collapse of the frayed edges of the clay mineral and the relatively high concentration of radiocaesium building up in solution in the batch desorption experiments. Consequently, commonly applied high-NH₄ extractions underestimate truly exchangeable amounts of radiocaesium in soils and sediments containing illitic clay minerals. The rate of desorption of trace amounts of radiocaesium from the solids using high NH₄ or Cs concentrations has a half-life of about 2 yr, reflecting radiocaesium desorption from (partially) collapsed interlayers. Extraction of radiocaesium from illite after 5 min of contact time with a Cs-selective adsorbent or a 1 × 10^-6 M CsCl solution shows that 100% of the bound radiocaesium is readily available. The desorption rate in the presence of a Cs-selective adsorbent has a half-life of about 0.2 yr. Desorption of radiocaesium from illite using different ammonium concentrations shows that radiocaesium partitioning follows reversible ion-exchange theory if the NH₄ concentration is below 1 × 10^-4 M, and sufficient time (weeks) is allowed for the reaction to proceed. Thus, radiocaesium sorption reversibility in the natural environment is much higher than generally assumed, and equilibrium solid/liquid partitioning may be assumed for the long-term modelling of radiocaesium mobility in the natural environment. In the particular case of anoxic freshwater sediments with very high NH₄ concentrations in the pore waters (up to several mmol.L^-1), collapse of the frayed edges of illite may occur, influencing radiocaesium partitioning. If collapse occurs before radiocaesium adsorbs to illite, high caesium sorption reversibility as measured by high-NH₄ extraction can be expected because further collapse of the frayed edges during the extraction procedure will be limited. This effect has indeed been observed earlier in the extraction of radiocaesium from anoxic freshwater sediments with high-NH₄ solutions and was as yet unexplained.     

Thermochemistry of jarosite-alunite and natrojarosite-natroalunite solid solutions

The thermochemistry of jarosite-alunite and natrojarosite-natroalunite solid solutions was investigated. Members of these series were either coprecipitated or synthesized hydrothermally and were characterized by XRD, FTIR, electron microprobe analysis, ICP-MS, and thermal analysis. Partial alkali substitution and vacancies on the Fe/Al sites were observed in all cases, and the solids studied can be described by the general formula K_1-x-yNa_y(H₃O)_xFe_zAl_w(SO₄)₂(OH)_6-3(3-z-w)(H₂O)_3(3-z-w). A strong preferential incorporation of Fe over Al in the jarosite/alunite structure was observed. Heats of formation from the elements, ΔH°_f, were determined by high-temperature oxide melt solution calorimetry. The solid solutions deviate slightly from thermodynamic ideality by exhibiting positive enthalpies of mixing in the range 0 to +11 kJ/mol. The heats of formation of the end members of both solid solutions were derived. The values ΔH°_f = −3773.6 ± 9.4 kJ/mol, ΔH°_f = −4912.2 ± 24.2 kJ/mol, ΔH°_f = −3734.6 ± 9.7 kJ/mol and ΔH°_f = −4979.7 ± 7.5kJ/mol were found for K_0.85(H₃O)_0.15Fe_2.5(SO₄)₂(OH)_4.5(H₂O)_1.5, K_0.85(H₃O)_0.15Al_2.5(SO₄)₂(OH)_4.5(H₂O)_1.5, Na_0.7(H₃O)_0.3Fe_2.7(SO₄)₂(OH)_5.1(H₂O)_0.9, and Na_0.7(H₃O)_0.3Al_2.7(SO₄)₂(OH)_5.1(H₂O)_0.9 respectively. To our knowledge, this is the first experimentally-based report of ΔH°_f for such nonstoichiometric alunite and natroalunite samples. These thermodynamic data should prove helpful to study, under given conditions, the partitioning of Fe and Al between the solids and aqueous solution.     

Neodymium isotopic variations in Northwest Pacific waters

Four vertical profiles of the concentration and isotopic composition of Nd in seawater were obtained in the western North Pacific. Two profiles from the Kuroshio Current regime showed congruently that although the Nd concentration increases gradually with depth, its isotopic composition varies significantly with depth depending upon the water mass occupying the water column. The high-salinity Kuroshio waters originating from the North Pacific Tropical Water (NPTW) carry the least radiogenic Nd (?_Nd = −7.4 to −8.7) to this region at ∼250 m from the western margin continental shelves, most likely from the East China Sea. The Nd isotopic compositions in the North Pacific Intermediate Water (NPIW) that occurs at 600 to 1000 m in the subtropical region are fairly uniform at ?_Nd = −3.7. The profile data from the ∼38° to 40°N Kuroshio/Oyashio mixed water region off Sanriku of Honshu, Japan, also suggest that the newest NPIW with ?_Nd = −3.2 is formed there by the mixing of various source waters, and the radiogenic component of Nd is derived mainly from the Oyashio waters.In the Pacific Deep Water (PDW) below ∼1000 m, the Nd isotopic composition is neither vertically nor horizontally homogeneous, suggesting that it serves as a useful tracer for sluggish deep water circulation as well. Two profiles from the Izu-Ogasawara Trench showed a minimum ?_Nd value at ∼2000 m, suggesting that there exists a horizontal advective flow in the vicinity of Honshu, Japan. There is some evidence from other chemical properties to support this observation. The waters below 4000 m including those within the trench in the subtropical region have ?_Nd values of around −5, suggesting that the deep waters are fed from the south along the western boundary, ultimately from the Antarctic Bottom Water (AABW) in the South Pacific. This extends up to ∼40°N along the Japanese Islands. In the subarctic region (>∼42°N), the waters have more radiogenic Nd with ?_Nd > −4.0 throughout the water column, presumably due to the supply of Nd by weathering in such igneous provinces as the Kuril-Kamchatska-Aleutian Island chain. The lateral inhomogeneity of the Nd isotopic composition in PDW suggests that there may be different circulation and mixing regimes in the North Pacific Basin.     

Pb diffusion in monazite: a combined RBS/SIMS study

We report measurements of Pb diffusion in both synthetic (CePO₄) and natural monazites run under dry, 1-atm conditions. Powdered mixtures of prereacted CePO₄ and PbZrO₃ were used as the source of Pb diffusant for “in-diffusion” experiments conducted in sealed Pt capsules for durations ranging from a few hours to several weeks. Following the diffusion anneals, Pb concentration profiles were measured with Rutherford Backscattering Spectroscopy (RBS) and supplemented by measurements with secondary ion mass spectrometry (SIMS). In order to evaluate potential compositional effects upon Pb diffusivity and simulate diffusional Pb loss that might occur in natural systems, we also conducted “out-diffusion” experiments on Pb-bearing natural monazites. In these experiments, monazite grains were surrounded by a synthetic zircon powder to act as a “sink.” Monazites from these experiments were analyzed with SIMS. Over the temperature range 1100 to 1350°C, the Arrhenius relation determined for in-diffusion experiments on synthetic monazite is given by:

     

European vegetation during Marine Oxygen Isotope Stage-3

European vegetation during representative “warm” and “cold” intervals of stage-3 was inferred from pollen analytical data. The inferred vegetation differs in character and spatial pattern from that of both fully glacial and fully interglacial conditions and exhibits contrasts between warm and cold intervals, consistent with other evidence for stage-3 palaeoenvironmental fluctuations. European vegetation thus appears to have been an integral component of millennial environmental fluctuations during stage-3; vegetation responded to this scale of environmental change and through feedback mechanisms may have had effects upon the environment. The pollen-inferred vegetation was compared with vegetation simulated using the BIOME 3.5 vegetation model for climatic conditions simulated using a regional climate model (RegCM2) nested within a coupled global climate and vegetation model (GENESIS-BIOME). Despite some discrepancies in detail, both approaches capture the principal features of the present vegetation of Europe. The simulated vegetation for stage-3 differs markedly from that inferred from pollen analytical data, implying substantial discrepancy between the simulated climate and that actually prevailing. Sensitivity analyses indicate that the simulated climate is too warm and probably has too short a winter season. These discrepancies may reflect incorrect specification of sea surface temperature or sea-ice conditions and may be exacerbated by vegetation-climate feedback in the coupled global model.     

Behavior of Sm and Nd in a lateritic soil profile

A study of lateritic soils and samples of ground and river waters was carried out in the Nsimi-Zoetele, a tropical watershed in the southern Cameroon. The Nd isotopic compositions and concentrations of Nd and Sm were determined. It was found that the Nd isotopic composition of the river waters was much more radiogenic than the parent rocks, and that the Nd in the waters is not homogeneous but is carried by different dissolved and complexed components that are not isotopically homogenized. The soil profile shows a regular increase in ε_Nd going from the parent rock (ε_Nd = −36) to ε_Nd = −18 near the top of the profile. The Nd transported in the river is thus not representative of the parent rock but reflects the results of differential weathering of constituent minerals and the redeposition of REE in phosphates and a significant contribution of radiogenic Nd from dust. The concentration of Nd in the river water is far above that found in temperate climate rivers and thus this type of tropical river may play a dominant role in the marine Nd and REE budget. It is suggested that the correlation of REE with DOC is related to DOC fixing some dissolved REE but that the REE in solution is governed by other mechanisms. No major shifts were found in Sm/Nd; however, a regular progression from the parent rock through the lateritic profile was found. The upper laterite profile shows large, almost uniform depletions in all REE below Tb and enrichment above. Complementary behavior was found in the lower part of the section. The concentration of Nd relative to the immobile elements Zr and Ti in the laterite is depleted by a factor of ∼10. Th, Nd and Sm are enriched in the lowest zone sampled and must reflect redeposition of REE from the upper part of the weathering section and is associated with phosphate formation. It is concluded that the soil evolution involves both differential dissolution of primary phases from the parent rock, significant to major input of REE from atmospheric dust from other regions, and the formation of diagenetic phases, particularly phosphates.     

A stable isotope-based approach to tropical dendroclimatology

We describe a strategy for development of chronological control in tropical trees lacking demonstrably annual ring formation, using high resolution δ¹⁸O measurements in tropical wood. The approach applies existing models of the oxygen isotopic composition of alpha-cellulose (Roden et al., 2000), a rapid method for cellulose extraction from raw wood (Brendel et al., 2000), and continuous flow isotope ratio mass spectrometry (Brenna et al., 1998) to develop proxy chronological, rainfall and growth rate estimates from tropical trees lacking visible annual ring structure. Consistent with model predictions, pilot datasets from the temperate US and Costa Rica having independent chronological control suggest that observed cyclic isotopic signatures of several permil (SMOW) represent the annual cycle of local rainfall and relative humidity. Additional data from a plantation tree of known age from ENSO-sensitive northwestern coastal Peru suggests that the 1997-8 ENSO warm phase event was recorded as an 8‰ anomaly in the δ¹⁸O of α-cellulose. The results demonstrate reproducibility of the stable isotopic chronometer over decades, two different climatic zones, and three tropical tree genera, and point to future applications in paleoclimatology.     

Transient dissolution patterns on stressed crystal surfaces

We present an experimental investigation on the dissolution of uniaxially stressed crystals of NaClO₃ in contact with brine. The crystals are immersed in a saturated fluid, stressed vertically by a piston and monitored constantly in situ with a CCD camera. The experiments are temperature-controlled and uniaxial shortening of the sample is measured with a high-resolution capacitance analyzer. Once the crystal is stressed it develops dissolution grooves on its free surface. The grooves are oriented with their long axis perpendicular to the direction of compressive stress and the initial distance between the parallel grooves is in accordance with the Asaro-Tiller-Grinfeld instability. We observe a novel, transient evolution of this roughness: The grooves on the crystal surface migrate upwards (against gravity), grow in size and the inter-groove distance increases linearly with time. During the coarsening of the pattern this switches from a one-dimensional geometry of parallel grooves to a two-dimensional geometry with horizontal and vertical grooves. At the end of the experiment one large groove travels across the crystal and the surface becomes smooth again. Uniaxial shortening of the crystal by pressure solution creep decays exponentially with time and shows no long term creep within the range of the resolution of the capacitance analyzer (accuracy of 100nm over a period of 14 days). This indicates that, while active, the fast transient processes on the free surface increase the solution concentration and thereby significantly slow down or stop pressure solution at the top of the crystal. This novel feedback mechanism can explain earlier results of cyclic pressure solution creep and demands development of a more complex theory of pressure-solution creep including processes that act on free surfaces.     

Oxygen isotope fractionation in synthetic magnesian calcite

Mg-bearing calcite was precipitated at 25°C in closed system free-drift experiments from solutions containing NaHCO₃, CaCl₂ and MgCl₂. The chemical and isotope composition of the solution and precipitate were investigated during time course experiments of 24-h duration. Monohydrocalcite and calcite precipitated early in the experiments (<8 h), while Mg-calcite was the predominant precipitate (>95%) thereafter. Solid collected at the end of the experiments displayed compositional zoning from pure calcite in crystal cores to up to 23 mol% MgCO₃ in the rims. Smaller excursions in Mg were superimposed on this chemical record, which is characteristic of oscillatory zoning observed in synthetic and natural solid-solution carbonates of differing solubility. Magnesium also altered the predominant morphology of crystals over time from the {104} to {100} and {110} growth forms.The oxygen isotope fractionation factor for the magnesian-calcite-water system (as 10³lnα_Mg-cl-H2O) displayed a strong dependence on the mol% MgCO₃ in the solid phase, but quantification of the relationship was difficult due to the heterogeneous nature of the precipitate. Considering only the Mg-content and δ¹⁸O values for the bulk solid, 10³lnα_Mg-cl-H2O increased at a rate of 0.17 ± 0.02 per mol% MgCO₃; this value is a factor of three higher than the single previous estimate (Tarutani T., Clayton R.N., and Mayeda T. K. (1969) The effect of polymorphims and magnesium substitution on oxygen isotope fractionation between calcium carbonate and water. Geochim. Cosmochim. Acta 33, 987-996). Nevertheless, extrapolation of our relationship to the pure calcite end member yielded a value of 27.9 ± 0.02, which is similar in magnitude to published values for the calcite-water system. Although no kinetic effect was observed on 10³lnα_Mg-cl-H2O for precipitation rates that ranged from 10^3.21 to 10^4.60 μmol · m⁻² · h⁻¹, it was impossible to disentangle the potential effect(s) of precipitation rate and Mg-content on 10³lnα_Mg-cl-H2O due to the heterogeneous nature of the solid.The results of this study suggest that paleotemperatures inferred from the δ¹⁸O values of high magnesian calcite (>10 mol% MgCO₃) may be significantly underestimated. Also, the results underscore the need for additional experiments to accurately characterize the effect of Mg coprecipitation on the isotope systematics of calcite from a chemically homogeneous precipitate or a heterogeneous material that is analyzed at the scale of chemical and isotopic zonation.     

Precise and accurate isotopic measurements using multiple-collector ICPMS

New techniques of isotopic measurements by a new generation of mass spectrometers equipped with an inductively-coupled-plasma source, a magnetic mass filter, and multiple collection (MC-ICPMS) are quickly developing. These techniques are valuable because of (1) the ability of ICP sources to ionize virtually every element in the periodic table, and (2) the large sample throughout. However, because of the complex trajectories of multiple ion beams produced in the plasma source whether from the same or different elements, the acquisition of precise and accurate isotopic data with this type of instrument still requires a good understanding of instrumental fractionation processes, both mass-dependent and mass-independent. Although physical processes responsible for the instrumental mass bias are still to be understood more fully, we here present a theoretical framework that allows for most of the analytical limitations to high precision and accuracy to be overcome. After a presentation of unifying phenomenological theory for mass-dependent fractionation in mass spectrometers, we show how this theory accounts for the techniques of standard bracketing and of isotopic normalization by a ratio of either the same or a different element, such as the use of Tl to correct mass bias on Pb. Accuracy is discussed with reference to the concept of cup efficiencies. Although these can be simply calibrated by analyzing standards, we derive a straightforward, very general method to calculate accurate isotopic ratios from dynamic measurements. In this study, we successfully applied the dynamic method to Nd and Pb as examples. We confirm that the assumption of identical mass bias for neighboring elements (notably Pb and Tl, and Yb and Lu) is both unnecessary and incorrect. We further discuss the dangers of straightforward standard-sample bracketing when chemical purification of the element to be analyzed is imperfect. Pooling runs to improve precision is acceptable provided the pooled measurements are shown to be part of a single population. Second-order corrections seem to be able to improve the precision on ¹⁴³Nd/¹⁴⁴Nd measurements. Finally, after discussing a number of potential pitfalls, such as the consequence of peak shape, correlations introduced by counting statistics, and the effect of memory on double-spike methods, we describe an optimal strategy for high-precision and accurate measurements by MC-ICPMS, which involves the repetitive calibration of cup efficiencies and rigorous assessment of mass bias combined with standard-sample bracketing. We suggest that, when these simple guidelines are followed, MC-ICPMS is capable of producing isotopic data precise and accurate to better than 15 ppm.     

Bond-valence methods for pKa prediction: critical reanalysis and a new approach

Bond-valence methods for the prediction of (hydr)oxide solution monomer and surface functional group acidity constants are examined in light of molecular structures calculated using ab initio methods. A new method is presented that is based on these calculated structures, and it is shown that previously published methods have neglected one or more of four essential features of a generalized model. First, if the apparent pK_a values of solution monomers are to be used to predict intrinsic pK_a values of surface functional groups, similar electrostatic corrections must be applied in both cases. In surface complexation models, electrostatic corrections are applied by representing a charged surface as a uniform plane of charge density, and an analogous correction can be made to solution monomers by treating them as charged spheres. Second, it must be remembered that real surfaces and real monomers are not homogeneous planes or spheres. Rather, charge density is distributed rather unevenly, and a further electrostatic correction (which is often quite large) must be made to account for the proximity of electron density to the point of proton attachment. Third, the unsaturated valence of oxygen atoms in oxyacids, hexaquo cations, and oxide surfaces is strongly correlated with acidity after electrostatic corrections are made. However, calculation of unsaturated valence for oxyacids and oxide surfaces must be based on realistic MeO bond lengths (taking into account bond relaxation), which can be obtained from ab initio structure optimizations. Finally, unsaturated valence must be divided between possible bonds (four for oxygen atoms) to reflect the fact that O-H bonds are localized to particular regions of the O atoms.Empirical models that take all these factors into account are presented for oxyacids and hexaquo cations. These models are applied to the gibbsite (100), (010), (001), and cristobalite (100) surfaces, and it is demonstrated that the model for oxyacids predicts reasonable intrinsic pK_a values for oxide surfaces. However, the prediction of surface pK_a values is complex, because the protonation state of one functional group affects the pK_a values of neighboring groups. Therefore, calculations of larger periodic systems, progressively protonated and reoptimized, are needed.     

Chondrule textures and precursor grain size: an experimental study

Chondrule formation appears to have been a major event in the early solar system, but chondrule properties do not allow us to distinguish between several possible formation mechanisms. The physical nature of the precursors, especially grain size, must affect the textures of the chondrules they yield when heated. We melted precursors of different grain sizes, including extremely fine-grained crystalline aggregates analogous to nebular condensates, to see whether objects resembling most natural chondrules can be crystallized. With one-minute heating and moderate cooling rates, the grain size of the charges depends directly on the grain size of the starting material, for temperatures up to very close to the liquidus temperature. A single rapid heating of condensate-like material thus produces very fine-grained chondrules, like dark-zoned chondrules, for a very wide range of peak temperatures. It is incapable of generating the observed textural distribution of chondrules, which are predominantly porphyritic. The simplest model for chondrules, a single heating of unmodified condensate material, therefore appears unrealistic. Coarse-grained chondrules might be formed from fine-grained precursors by extended heating with evaporation leading to coarsening, or by multiple reheating events, with higher temperatures in subsequent events. Otherwise an origin from annealed condensates, planetary rocks, or by condensation of liquid and crystals is required.     

Imaging and mechanical property measurements of kerogen via nanoindentation

Most analyses of kerogens rely on samples that have been isolated by dissolving the rock matrix. The properties of the kerogen before and after such isolation may be different and all sample orientation information is lost. We report a method of measuring kerogen mechanical properties in the rock matrix without isolation. An atomic force microscope (AFM) based nanoindenter is used to measure the hardness and reduced modulus of the kerogen within Woodford shale. The same instrument also provides useful images of polished rock sections on a submicrometer scale. Measurements were carried out both parallel and perpendicular to the bedding plane.