Hydration of rhyolitic glass during weathering as characterized by IR microspectroscopy

The mechanism and rate of hydration of rhyolitic glass during weathering were studied. Doubly polished thin sections of two rhyolites with different duration of weathering (Ohsawa lava: 26,000 yr, Awanomikoto lava: 52,000 yr) were prepared. Optical microscope observation showed that altered layers had developed along the glass surfaces. IR spectral line profile analysis was conducted on the glass sections from the surface to the interior for a length of 250 μm and the contents of molecular H₂O (H₂O_m), OH species (OH) and total water (H₂O_t) were determined. The diffusion profile of H₂O_m in Ohsawa lava extends beyond the layer observed by optical microscope. The content of H₂O_m in the hydrated region is much higher than that of OH species. Thus, the reaction from H₂O_m to OH appears to be little and H₂O_m is the dominant water species moving into the glass during weathering. Based on the concentration profiles, the diffusion coefficients of H₂O_m(D_H2Om) and H₂O_t(D_H2Ot) were determined to be 2.8 × 10⁻¹⁰ and 3.4 × 10⁻¹⁰ μm² s⁻¹ for Ohsawa lava, and 5.2 × 10⁻¹¹ and 4.1 × 10⁻¹¹ μm² s⁻¹ for Awanomikoto lava, respectively. The obtained D_H2Om during weathering are more than 2-3 orders of magnitude larger than the diffusion coefficient at ∼20 °C that is extrapolated from the diffusivity data for >400 °C. This might suggest that the mechanism of water transport is different at weathering conditions and >400 °C.     

The thermal history of equilibrated ordinary chondrites and the relationship between textural maturity and temperature

The compositions and textures of phases in eleven equilibrated ordinary chondrites from the H, L, and LL groups spanning petrographic types 4-6 were studied and used to constrain the thermal histories of their parent bodies. Based on Fe-Mg exchange between olivine and spinel, average equilibration temperatures for type 4-6 chondrites encompass a small range, 586-777 °C, relative to what is commonly assumed for peak temperatures (600-950 °C). The maximum temperatures recorded by individual chondrites, which are minima relative to peak metamorphic temperatures, increase subtly but systematically with metamorphic type and are tightly clustered for H4-6 (733-754 °C) and LL4-6 (670-777 °C). For the Ls, Ausson (L5) records a higher maximum olivine-spinel temperature (761 °C) than does the L4 chondrite Saratov (673 °C) or the L6 chondrite Glatton (712 °C). Our data combined with olivine-spinel equilibration temperatures calculated for other equilibrated ordinary chondrites using mineral compositions from the literature demonstrate that, in general, type 4 chondrites within each chemical group record temperatures lower than or equal to those of types 5-6 chondrites.For H chondrites, the olivine-spinel closure temperature is a function of spinel grain size, such that larger grains, abundant in types 5-6 chondrites, record temperatures of ∼740 °C or more while smaller grains, rare in types 5-6 but abundant in type 4 chondrites, record lower temperatures. Olivine-spinel temperatures in the type 6 chondrites Guareña and Glatton are consistent with rapid (50-100 °C/Myr) cooling from high temperatures in the ordinary chondrite parent bodies. With one exception (∼500 °C/Myr), olivine-spinel data for St.-Séverin (LL6) are consistent with similar cooling rates. Cooling rates of order 100 °C/Myr at ∼750 °C for type 6 chondrites are considerably higher than previously determined cooling rates for lower temperatures (?550 °C) based on metallography, fission tracks, and geochronology. For H chondrites, current thermal models of an “onion shell” parent body are inconsistent with a small range of peak temperatures based on olivine-spinel and two pyroxene thermometry combined with a wide dispersion of cooling rates at low temperatures. Equilibrated chondrites may have sampled regions near a major transition in physical properties such as near the base of a regolith pile.     

Ammonium in aqueous fluids to 600 °C, 1.3 GPa: A spectroscopic study on the effects on fluid properties, silica solubility, and K-feldspar to muscovite reactions

The behavior of ammonium, NH₄⁺, in aqueous systems was studied based on Raman spectroscopic experiments to 600 °C and about 1.3 GPa. Spectra obtained at ambient conditions revealed a strong reduction of the dynamic three-dimensional network of water with addition of ammonium chloride, particularly at small solute concentrations. The differential scattering cross section of the ν₁-NH₄⁺ Raman band in these solutions was found to be similar to that of salammoniac.The Raman band of silica monomers at ∼780 cm⁻¹ was present in all spectra of the fluid at high temperatures in hydrothermal diamond-anvil cell experiments with H₂O ± NH₄Cl and quartz or the assemblage quartz + kyanite + K-feldspar ± muscovite/tobelite. However, these spectra indicated that dissolved silica is less polymerized in ammonium chloride solutions than in comparable experiments with water. Quantification based on the normalized integrated intensity of the H₄SiO₄⁰ band showed that the silica solubility in experiments with H₂O + NH₄Cl was significantly lower than that in equimolal NaCl solutions. This suggests that ammonium causes a stronger decrease in the activity of water in chloridic solutions than sodium.The Raman spectra of the fluid also showed that a significant fraction of ammonium was converted to ammonia, NH₃, in all experiments at temperatures above 300 °C. This indicates a shift towards acidic conditions for experiments without a buffering mineral assemblage. The estimated pH of the fluid was ∼2 at 600 °C, 0.26 GPa, 6.6 m initial NH₄Cl, based on the ratio of the integrated ν₁-NH₃ and ν₁-NH₄⁺ intensities and the HCl⁰ dissociation constant. The NH₃/NH₄⁺ ratio increased with temperature and decreased with pressure. This implies that more ammonium should be retained in K-bearing minerals coexisting with chloridic fluids upon high-P low-T metamorphism. At 500 °C, 0.73 GPa, ammonium partitions preferentially into the fluid, as constrained from infrared spectroscopy on the muscovite and from mass balance.The conversion of K-feldspar to muscovite proceeded much faster in experiments with NH₄Cl solutions than in comparable experiments with water. This is interpreted as being caused by enhancement of the rate-limiting alumina solubility, suggesting complexation of Al with NH₄. Nucleation and growth of mica at the expense of K-feldspar and NH₄⁺/K⁺ exchange between fluid and K-feldspar occurred simultaneously, but incorporation of NH₄⁺ into K-feldspar was distinctly faster than K-feldspar consumption.     

Intra-shell oxygen isotope ratios in the benthic foraminifera genus Amphistegina and the influence of seawater carbonate chemistry and temperature on this ratio

Using secondary ion mass spectrometry (SIMS) we looked at the natural variability in the oxygen isotope ratio of the shallow water, symbionts-bearing foraminiferan Amphistegina lobifera. Live foraminifera were collected in February 2005 in the Gulf of Eilat, Israel. Vertical section exposing the knob area of this species represents the growth history of this species from August 2004 to February 2005. SIMS profile at a resolution of ∼15 μm (representing about 2 weeks considering the size of the knob area and the life span of ≈6 months of this foraminifera species) yielded δ¹⁸O changes of ∼1.5‰ that are compatible with the known temperature changes for the Gulf of Eilat for this period (21-27 °C). Natural variability between primary and secondary calcite at the knob area were obtained on horizontal section of the upper knob area. This section is semi-tangential to the growth lines and exposes relatively wide belts of the primary calcite which could be analysed using the SIMS (beam size of 10 × 20 μm). The primary calcite δ¹⁸O value is on average more than 3‰ lower than the secondary calcite that represents the bulk of the skeleton (more than 95% by weight). A vertical profile at the knob was obtained by rastering an area of 50 × 50 μm at vertical steps of roughly 1 μm. The profile revealed a narrow zone of lower δ¹⁸O compared to the higher values above and below it. The difference between the lowest δ¹⁸O and the highest one was also close to 2‰. The δ¹⁸O in the margin - keel area of A. lobifera is also lower compared to the bulk secondary calcite. Specimens that were cultured in the laboratory at a constant temperature and inorganic carbon but at different pH have increased their CaCO₃ weight by roughly a factor of 8. Single specimen from each pH (ranging between 7.90 and 8.45) were investigated with the SIMS at the knob area. While there is some variability within each specimen (perhaps related to the primary calcite), the general trend was a decrease in δ¹⁸O with increasing pH (or CO₃²⁻ concentration), in agreement with previous studies on planktonic foraminifera. Some other specimens grown at different temperatures (between 21 and 33 °C) were also measured with the SIMS at the knob area. For each temperature, we observed also some variability, nevertheless the trend of −0.2‰/°C in δ¹⁸O is observed.     

Ar and Ar recoil loss during neutron irradiation of sanidine and plagioclase

The ⁴⁰Ar/³⁹Ar dating technique requires the activation of ³⁹Ar via neutron irradiation. The energy produced by the reaction is transferred to the daughter atom as kinetic energy and triggers its displacement, known as the recoil effect. Significant amounts of ³⁹Ar and ³⁷Ar can be lost from minerals leading to spurious ages and biased age spectra. Through two experiments, we present direct measurement of the recoil-induced ³⁹Ar and ³⁷Ar losses on Fish Canyon sanidine and plagioclase. We use multi-grain populations with discrete sizes ranging from 210 to <5 μm. One population consists of a mixture between sanidine and plagioclase, and the other includes pure sanidine.We show that ³⁹Ar loss (depletion factor) for sanidine is ∼3% for the smallest fraction. Age spectra of fractions smaller than ∼50 μm show slight departure from flat plateau-age spectrum usually observed for large sanidine. This departure is roughly proportional to the size of the grain but does not show typical ³⁹Ar loss age spectra. The calculated thickness of the total depletion layer d₀(sanidine) is 0.035 ± 0.012 (2σ). This is equivalent to a mean depth of the partial depletion layer (x₀) of 0.070 ± 0.024 μm. The latter value is indistinguishable from previous values of ∼0.07-0.09 μm obtained by argon implantation experiments and simulation results.We show that it is possible to adequately correct ages from ³⁹Ar ejection loss provided that the d₀-value and the size range of the minerals are sufficiently constrained. As exemplified by similar calculations performed on results obtained in a similar study of GA1550 biotite [Paine J. H., Nomade S., and Renne P. R. (2006) Quantification of ³⁹Ar recoil ejection from GA1550 biotite during neutron irradiation as a function of grain dimensions. Geochim. Cosmochim. Acta70, 1507-1517.], the d₀(biotite) is 0.46 ± 0.06 μm. The significant difference between empirical results on biotite and sanidine, along with different simulation results, suggests that for biotite, crystal structures and lattice defects of the stopping medium and possibly subsequent thermal degassing (due to ∼150-200 °C temperature in the reactor or extraction line bake out) must play an important role in ³⁹Ar loss.The second experiment suggests that ³⁷Ar recoil can substantially affect the age via the interference corrections with results that suggest up to ∼98% of ³⁷Ar can be ejected from the ∼5 μm grain dimension.Further investigation of silicates of various compositions and structures are required to better understand (and correct) the recoil and recoil-induced effects on both ³⁹Ar and ³⁷Ar and their influences on ⁴⁰Ar/³⁹Ar dating.     

How depositional conditions control input, composition, and degradation of organic matter in sediments from the Chilean coastal upwelling region

In a comprehensive study, we compared depositional conditions, organic matter (OM) composition, and organic carbon turnover in sediments from two different depositional systems along the Chilean continental margin: at ∼23° S off Antofagasta and at ∼36° S off Concepción. Both sites lie within the Chilean coastal upwelling system and have an extended oxygen minimum zone in the water column. However, the northern site (23° S) borders the Atacama Desert, while the southern site (36° S) has a humid hinterland. Eight surface sediment cores (up to 30 cm long) from water depths of 126-1350 m were investigated for excess ²¹⁰Pb (²¹⁰Pb_xs) activity, total organic and total inorganic carbon concentrations (TOC and TIC, respectively), C/N-ratios, organic carbon isotopic compositions (δ¹³C), chlorin concentrations, Chlorin Indices (CI), and sulfate reduction rates (SRR). Sediment accumulation rates obtained from ²¹⁰Pb-analysis were similar in both regions (0.04-0.15 cm yr⁻¹ at 23° S, 0.10-0.19 cm yr⁻¹ at 36° S), although total ²¹⁰Pb_xs fluxes indicated that the vertical particle flux was higher at 36° S than at 23° S. We propose that sediment focusing in isolated deposition centers led to high sediment accumulation rates at 23° S. Furthermore, there were no indications for sediment mixing at 23° S, while bioturbation was intense at 36° S. δ¹³C-values (−24.5‰ to −20.1‰ vs. VPDB) and C/N-ratios (molar, 8.6-12.8) were characteristic of a predominantly marine origin of the sedimentary OM in both investigated areas. The extent of OM alteration in the water column was partly reflected in the surface sediments as chlorin concentrations decreased and C/N-ratios and CI increased with increasing water depth of the sampling site. SRR were lower at 23° S (areal SRR 0.12-0.60 mmol m⁻² d⁻¹) than at 36° S (areal SRR 0.82-1.18 mmol m⁻² d⁻¹), which was partly due to the greater water depth of most of the sediments investigated in the northern region and consistent with a lower quality of the sedimentary OM at 23° S. Reaction rate constants for TOC degradation that were obtained from measured SRR (k_SRR; 0.0004-0.0022 yr⁻¹) showed a good correspondence to k_TOC that were derived from the depth profiles of TOC (0.0003-0.0014 yr⁻¹). Both, k_SRR and k_TOC, reflect differences in OM composition. At 36° S they were related to the degradation state of bulk OM (represented by C/N-ratios), whereas near 23° S they were related to the freshness of a small fraction of labile OM (represented by CI). Our study shows that although rates of organic carbon accumulation were similar in both investigated sites, the extent and kinetics of organic carbon degradation were closely linked to differing depositional conditions.     

Silver isotope variations in chondrites: Volatile depletion and the initial Pd abundance of the solar system

The extinct radionuclide ¹⁰⁷Pd decays to ¹⁰⁷Ag (half-life of 6.5 Ma) and is an early solar system chronometer with outstanding potential to study volatile depletion in the early solar system. Here, a comprehensive Ag isotope study of carbonaceous and ordinary chondrites is presented. Carbonaceous chondrites show limited variations (ε¹⁰⁷Ag = −2.1 to +0.8) in Ag isotopic composition that correlate with the Pd/Ag ratios. Assuming a strictly radiogenic origin of these variations, a new initial ¹⁰⁷Pd/¹⁰⁸Pd of 5.9 (±2.2) × 10⁻⁵ for the solar system can be deduced. Comparing the Pd-Ag and Mn-Cr data for carbonaceous chondrites suggests that Mn-Cr and Pd-Ag fractionation took place close to the time of calcium-aluminium-rich inclusion (CAI) and chondrule formation ∼4568 Ma ago. Using the new value for the initial ¹⁰⁷Pd abundance, the revised ages for the iron-rich meteorites Gibeon (IVA, 8.5 +3.2/−4.6 Ma), Grant (IIIAB, 13.0 +3.5/−4.9 Ma) and Canyon Diablo (IA, 19.5 +24.1/−10.4 Ma) are consistent with cooling rates and the closure temperature of the Pd-Ag system. In contrast to carbonaceous chondrites, ordinary chondrites show large stable isotope fractionation of order of 1 permil for ¹⁰⁷Ag/¹⁰⁹Ag. This indicates that different mechanisms of volatile depletion were active in carbonaceous and ordinary chondrites. Nebular processes and accretion, as experienced by carbonaceous chondrites, did not led to significant Ag isotope fractionation, while the significant Ag isotope variations in ordinary chondrites are most likely inflicted by open system parent body metamorphism.     

Evidence for the nucleation and epitaxial growth of Zn phyllosilicate on montmorillonite

Zinc uptake in suspensions (?3.7 g L⁻¹) of MX80 montmorillonite was investigated at pH 4.0 and 7.3, a total Zn concentration ([Zn]_total) of 500 μM, and dissolved Si concentrations ([Si]_aq) of ∼70 and ∼500 μM in 0.5 M NaCl, by kinetics experiments and polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy. Differential thermogravimetric analysis verified the cis-vacant character of the montmorillonite. No Zn uptake occurred at pH 4.0, confirming that cation exchange was hampered by the high ionic strength of the suspension. At pH 7.3 and low [Si]_aq (∼70 μM), Zn uptake occurred rapidly during the first hour of reaction, and then leveled off to 50 μmol/g montmorillonite at 168 h. The uptake rate is consistent with Zn sorption on pH-dependent edge sites. At pH 7.3 and high [Si]_aq (∼500 μM), the initial sorption rate was similar, but Zn sorption continued, reaching 130 μmol/g at 168 h, and was paralleled by Si uptake with a Si/Zn uptake ratio of 1.51(10), suggesting formation of a Zn (hydrous) silicate. P-EXAFS data indicated that the first oxygen coordination shell of sorbed Zn is split into two subshells at 1.97(2) and 2.08(3)-2.12(2) Å for all EXAFS samples. These two distances are assigned to a mixture of tetrahedral (^IVZn) and octahedral (^VIZn) Zn complexes. The proportion of ^IVZn was lower in the high [Si]_aq samples and decreased with reaction time. Al low [Si]_aq and 216 h of reaction, nearest cationic shells of 0.6(4) Al in the film plane and 0.5(4) Si out of the film plane were detected at 3.00(2) and 3.21(2) Å, respectively, and were interpreted as the formation of ^IVZn and ^VIZn mononuclear complexes at the edges of montmorillonite platelets, in structural continuity to the (Al, Mg) octahedral sheets. At high [Si]_aq, in-plane Zn and Al and out-of-plane Si neighbors were detected at 4 h, indicating the formation of Zn phyllosilicate nuclei at the layer edges. At 313 h, Zn-Al pairs were no longer detected, and Zn atoms were surrounded on average by 3.4(5) in-plane Zn at 3.10(1) Å and 1.7(9) out-of-plane Si at 3.30(2) Å, supporting the precipitation of a Zn phyllosilicate. Thus, dioctahedral Al phyllosilicate may act as a nucleating surface for the heterogeneous formation of trioctahedral Zn phyllosilicate at [Si]_aq relevant to natural systems.     

The effect of phytostabilization on Zn speciation in a dredged contaminated sediment using scanning electron microscopy, X-ray fluorescence, EXAFS spectroscopy, and principal components analysis

The maintenance of waterways generates large amounts of dredged sediments, which are deposited on adjacent land surfaces. These sediments are often rich in metal contaminants and present a risk to the local environment. Understanding how the metals are immobilized at the molecular level is critical for formulating effective metal containment strategies such as phytoremediation. In the present work, the mineralogical transformations of Zn-containing phases induced by two graminaceous plants (Agrostis tenuis and Festuca rubra) in a contaminated sediment ([Zn] = 4700 mg kg⁻¹, [P₂O₅] = 7000 mg kg⁻¹, pH = 7.8), untreated or amended with hydroxylapatite (AP) or Thomas basic slag (TS), were investigated after two yr of pot experiment by scanning electron microscopy coupled with energy-dispersive spectrometry (SEM-EDS), synchrotron-based X-ray microfluorescence (μ-SXRF), and powder and laterally resolved extended X-ray absorption fine structure (μ-EXAFS) spectroscopy. The number and nature of Zn species were evaluated by principal component (PCA) and least-squares fitting (LSF) analysis of the entire set of μ-EXAFS spectra, which included up to 32 individual spectra from regions of interest varying in chemical composition. Seven Zn species were identified at the micrometer scale: sphalerite, gahnite, franklinite, Zn-containing ferrihydrite and phosphate, (Zn-Al)-hydrotalcite, and Zn-substituted kerolite-like trioctahedral phyllosilicate. Bulk fractions of each species were quantified by LSF of the powder EXAFS spectra to linear combinations of the identified Zn species spectra.In the untreated and unvegetated sediment, Zn was distributed as ∼50% (mole ratio of total Zn) sphalerite, ∼40% Zn-ferrihydrite, and ∼10 to 20% (Zn-Al)-hydrotalcite plus Zn-phyllosilicate. In unvegetated but amended sediments (AP and TS), ZnS and Zn-ferrihydrite each decreased by 10 to 20% and were replaced by Zn-phosphate (∼30∼40%). In the presence of plants, ZnS was almost completely dissolved, and the released Zn bound to phosphate (∼40-60%) and to Zn phyllosilicate plus (Zn,Al)-hydrotalcite (∼20-40%). Neither the plant species nor the coaddition of mineral amendment affected the Zn speciation in the vegetated sediment. The sediment pore waters were supersaturated with respect to Zn-containing trioctahedral phyllosilicate, near saturation with respect to Zn-phosphate, and strongly undersaturated with respect to (Zn,Al)-hydrotalcite. Therefore, the formation of (Zn,Al)-hydrotalcite in slightly alkaline conditions ought to result from heterogeneous precipitation on mineral surface.     

O/O and D/H ratios of pedogenic kaolinite in a North American Cenomanian laterite: Paleoclimatic implications

Kaolinite, gibbsite and quartz are the dominant minerals in samples collected from two outcrops of a Cenomanian (∼95 Ma) laterite in southwestern Minnesota. A combination of measured yields and isotope ratios permitted mass balance calculations of the δD and δ¹⁸O values of the kaolinite in these samples. These calculations yielded kaolinite δD values of about −73‰ and δ¹⁸O values of about +18.7‰. The δD and δ¹⁸O values appear to preserve information on the ancient weathering system.If formed in hydrogen and oxygen isotope equilibrium with water characterized by the global meteoric water line (GMWL), the kaolinite δD and δ¹⁸O values indicate a crystallization temperature of 22 (±5) °C. A nominal paleotemperature of 22 °C implies a δ¹⁸O value for the corresponding water of −6.3‰. The combination of temperature and meteoric water δ¹⁸O values is consistent with relatively intense rainfall at that mid-paleolatitude location (∼40°N) on the eastern shore of the North American Western Interior Seaway. The inferred Cenomanian paleosol temperature of ∼22 °C is in general accord with published mid-Cretaceous continental mean annual temperatures (MAT) estimated from leaf margin analyses of fossil plants.When compared with results from a published GCM-based Cenomanian climate simulation which specifies a latitudinal sea surface temperature (SST) gradient that was either near modern or smaller-than-modern, the kaolinite paleotemperature of 22 °C is closer to the GCM-predicted MAT for a smaller equator-to-pole temperature difference in the mid-Cretaceous. Moreover, the warm, kaolinite-derived, mid-paleolatitude temperature of 22 °C is associated with proxy estimates of high concentrations of atmospheric CO₂ in the Cenomanian. The overall similarity of proxy and model results suggests that the general features of Cenomanian continental climate in that North American locale are probably being revealed.     

Late Quaternary glaciation and equilibrium-line altitudes of the Mayan Ice Cap, Guatemala, Central America

The Sierra los Cuchumatanes (3837 m), Guatemala, supported a plateau ice cap and valley glaciers around Montaña San Juan (3784 m) that totaled ∼ 43 km² in area during the last local glacial maximum. Former ice limits are defined by sharp-crested lateral and terminal moraines that extend to elevations of ∼ 3450 m along the ice cap margin, and to ca. 3000-3300 m for the valley glaciers. Equilibrium-line altitudes (ELAs) estimated using the area-altitude balance ratio method for the maximum late Quaternary glaciation reached as low as 3470 m for the valley glaciers and 3670 m for the Mayan Ice Cap. Relative to the modern altitude of the 0°C isotherm of ∼ 4840 m, we determined ELA depressions of 1110-1436 m. If interpreted in terms of a depression of the freezing level during maximal glaciation along the modern lapse rate of − 5.3°C km^− 1, this ΔELA indicates tropical highland cooling of ∼ 5.9 to 7.6 ± 1.2°C. Our data support greater glacial highland cooling than at sea level, implying a high tropical sensitivity to global climate changes. The large magnitude of ELA depression in Guatemala may have been partially forced by enhanced wetness associated with southward excursions of the boreal winter polar air mass.     

Characteristics of alkenone distributions in suspended and sinking particles in the northwestern North Pacific

We investigated alkenones recorded in suspended particles and a settling particle time series collected at three stations, 40N (40°N, 165°E), KNOT (44°N, 155°E), and 50N (50°N, 165°E), in the northwestern North Pacific from December 1997 to May 1999. Emiliania huxleyi, the most abundant alkenone producer in this area, is present in surface to subsurface (to ∼50 m depth) waters. The alkenone concentrations recorded in the suspended particles indicated that the seasonal alkenone particle distribution differed significantly interannually. Alkenone export fluxes at the three sediment-trap stations ranged from 0.16 to 49.3 μg m⁻² day⁻¹, and the maximum export flux, which occurred in summer to fall (July-November), was associated with a high organic carbon export flux. The amount of alkenone produced during the maximum export season accounted for 60-80% of the total annual amount of alkenone, and the alkenones accumulated in the sediment below the traps had characteristics corresponding to subsurface waters during the summer-autumn season. Alkenone-derived temperatures recorded in suspended particles corresponded to the in situ temperature within ∼2 °C. Although alkenone-derived temperatures corresponded approximately to the temperatures observed in the stratified subsurface waters at the three trap stations during the high-export season, large differences were observed during the low-export (winter-spring) period. For example, the alkenone-derived temperatures observed at stations KNOT and 50N were much higher than the in situ subsurface temperatures reported in the World Ocean Atlas 2001. Relatively large differences between alkenone-derived temperatures and in situ temperatures in the subarctic might be due to (1) a low-light limitation or (2) contributions of allochthonous alkenones in particulate material transported from subtropical areas within a warm-core ring.     

Solubility of cyclooctasulfur in pure water and sea water at different temperatures

The solubility of cyclooctasulfur in water and sea water at various temperatures in the range between 4 and 80 °C was determined. Cyclooctasulfur in equilibrium with rhombic sulfur reacted with hot acidic aqueous potassium cyanide to form thiocyanate anion which was measured by anion chromatography. Sulfur solubility in pure water was found to increase with temperature by more than 78 times: from 6.1 nM S₈ at 4 °C to 478 nM S₈ at 80 °C. The following thermodynamic values for solubilisation of S₈ in water were calculated from the experimental data: K° = 3.01 ± 1.04 × 10⁻⁸, ΔG_r° = 42.93 ± 0.73 kJ mol⁻¹, ΔH_r° = 47.4 ± 3.6 kJmol⁻¹, ΔS_r° = 15.0 ± 11.7 J mol⁻¹ K⁻¹). Solubility of cyclooctasulfur in sea water was found to be 61 ± 13% of the solubility in pure water regardless of the temperature.     

Origin and chronology of chondritic components: A review

Mineralogical observations, chemical and oxygen-isotope compositions, absolute ²⁰⁷Pb-²⁰⁶Pb ages and short-lived isotope systematics (⁷Be-⁷Li, ¹⁰Be-¹⁰B, ²⁶Al-²⁶Mg, ³⁶Cl-³⁶S, ⁴¹Ca-⁴¹K, ⁵³Mn-⁵³Cr, ⁶⁰Fe-⁶⁰Ni, ¹⁸²Hf-¹⁸²W) of refractory inclusions [Ca,Al-rich inclusions (CAIs) and amoeboid olivine aggregates (AOAs)], chondrules and matrices from primitive (unmetamorphosed) chondrites are reviewed in an attempt to test (i) the x-wind model vs. the shock-wave model of the origin of chondritic components and (ii) irradiation vs. stellar origin of short-lived radionuclides. The data reviewed are consistent with an external, stellar origin for most short-lived radionuclides (⁷Be, ¹⁰Be, and ³⁶Cl are important exceptions) and a shock-wave model for chondrule formation, and provide a sound basis for early Solar System chronology. They are inconsistent with the x-wind model for the origin of chondritic components and a local, irradiation origin of ²⁶Al, ⁴¹Ca, and ⁵³Mn. ¹⁰Be is heterogeneously distributed among CAIs, indicating its formation by local irradiation and precluding its use for the early solar system chronology. ⁴¹Ca-⁴¹K, and ⁶⁰Fe-⁶⁰Ni systematics are important for understanding the astrophysical setting of Solar System formation and origin of short-lived radionuclides, but so far have limited implications for the chronology of chondritic components. The chronological significance of oxygen-isotope compositions of chondritic components is limited. The following general picture of formation of chondritic components is inferred. CAIs and AOAs were the first solids formed in the solar nebula ∼4567-4568 Myr ago, possibly within a period of <0.1 Myr, when the Sun was an infalling (class 0) and evolved (class I) protostar. They formed during multiple transient heating events in nebular region(s) with high ambient temperature (at or above condensation temperature of forsterite), either throughout the inner protoplanetary disk (1-4 AU) or in a localized region near the proto-Sun (<0.1 AU), and were subsequently dispersed throughout the disk. Most CAIs and AOAs formed in the presence of an ¹⁶O-rich (Δ¹⁷O ∼ −24 ± 2‰) nebular gas. The ²⁶Al-poor [(²⁶Al/²⁷Al)₀ < 1 × 10⁻⁵], ¹⁶O-rich (Δ¹⁷O ∼ −24 ± 2‰) CAIs - FUN (fractionation and unidentified nuclear effects) CAIs in CV chondrites, platy hibonite crystals (PLACs) in CM chondrites, pyroxene-hibonite spherules in CM and CO chondrites, and the majority of grossite- and hibonite-rich CAIs in CH chondrites—may have formed prior to injection and/or homogenization of ²⁶Al in the early Solar System. A small number of igneous CAIs in ordinary, enstatite and carbonaceous chondrites, and virtually all CAIs in CB chondrites are ¹⁶O-depleted (Δ¹⁷O > −10‰) and have (²⁶Al/²⁷Al)₀ similar to those in chondrules (<1 × 10⁻⁵). These CAIs probably experienced melting during chondrule formation. Chondrules and most of the fine-grained matrix materials in primitive chondrites formed 1-4 Myr after CAIs, when the Sun was a classical (class II) and weak-lined T Tauri star (class III). These chondritic components formed during multiple transient heating events in regions with low ambient temperature (<1000 K) throughout the inner protoplanetary disk in the presence of ¹⁶O-poor (Δ¹⁷O > −5‰) nebular gas. The majority of chondrules within a chondrite group may have formed over a much shorter period of time (<0.5-1 Myr). Mineralogical and isotopic observations indicate that CAIs were present in the regions where chondrules formed and accreted (1-4 AU), indicating that CAIs were present in the disk as free-floating objects for at least 4 Myr. Many CAIs, however, were largely unaffected by chondrule melting, suggesting that chondrule-forming events experienced by a nebular region could have been small in scale and limited in number. Chondrules and metal grains in CB chondrites formed during a single-stage, highly-energetic event ∼4563 Myr ago, possibly from a gas-melt plume produced by collision between planetary embryos.     

Contributors to chromium isotope variation of meteorites

We report the results of a comprehensive, high precision survey of the Cr isotopic compositions of primitive chondrites, along with some differentiated meteorites. To ensure complete dissolution of our samples, they were first fused with lithium borate-tetraborate at 1050-1000 °C. Relative to the NIST Cr standard SRM 3112a, carbonaceous chondrites exhibit excesses in ⁵⁴Cr/⁵²Cr from 0.4 to 1.6ε (1ε = 1 part in 10,000), and ordinary chondrites display a common ⁵⁴Cr/⁵²Cr deficit of ∼0.4ε. Analyses of acid-digestion residues of chondrites show that carbonaceous and ordinary chondrites share a common ⁵⁴Cr-enriched carrier, which is characterized by a large excess in ⁵⁴Cr/⁵²Cr (up to 200ε) associated with a very small deficit in ⁵³Cr/⁵²Cr (<2ε). We did not find ⁵⁴Cr anomalies in either bulk enstatite chondrites or in leachates of their acid-digestion residues. This either requires that the enstatite chondrite parent bodies did not incorporate the ⁵⁴Cr anomaly carrier phase during their accretion, or the phase was destroyed by parent body metamorphism. Chromium in the terrestrial rocks and lunar samples analyzed here show no deviation from the NIST SRM 3112a Cr standard. The eucrite and Martian meteorites studied exhibit small deficits in ⁵⁴Cr/⁵²Cr. The ⁵⁴Cr/⁵²Cr variations among different meteorite classes suggest that there was a spatial and/or temporal heterogeneity in the distribution of a ⁵⁴Cr-rich component in the inner Solar System.We confirm the correlated excesses in ⁵⁴Cr/⁵²Cr and ⁵³Cr/⁵²Cr for bulk carbonaceous chondrites, but the new data yield a steeper slope (∼6.6) than that reported in Shukolyukov and Lugmair (2006). The correlated excesses may affect the use of the Mn-Cr chronometer in carbonaceous chondrites. We could not confirm the bulk carbonaceous chondrite Mn-Cr isochron reported by Shukolyukov and Lugmair (2006) and Moynier et al. (2007), mostly because we find much smaller total variations in ε⁵³Cr (∼0.2). All bulk chondrites have small ε⁵³Cr excesses (up to 0.3) relative to the Earth, most likely reflecting the sub-chondritic Mn/Cr ratio of the Earth. The ε⁵³Cr variations in chondrites do seem to grossly correlate with Mn/Cr and yield an initial Solar System ⁵³Mn/⁵⁵Mn value of 5.4(±2.4) × 10⁻⁶, corresponding to an absolute age of 4566.4 (±2.2) Ma.Nuclear interactions with cosmic rays result in coupled excesses in ε⁵⁴Cr and ε⁵³Cr with a ∼4:1 ratio in phases with high Fe/Cr. These are most dramatically demonstrated in the iron meteorite Carbo, showing excesses in ε⁵⁴Cr of up to 140ε. These new results show that the Mn-Cr chronometer should be used with caution in samples/minerals with high Fe/Cr and long cosmic ray exposure ages.     

Sulfur speciation in natural hydrothermal waters, Iceland

The speciation of aqueous dissolved sulfur was determined in hydrothermal waters in Iceland. The waters sampled included hot springs, acid-sulfate pools and mud pots, sub-boiling well discharges and two-phase wells. The water temperatures ranged from 4 to 210 °C, the pH_T was between 2.20 and 9.30 at the discharge temperature and the SO₄ and Cl concentrations were 0.020-52.7 and <0.01-10.0 mmol kg⁻¹, respectively. The analyses were carried out on-site within ∼10 min of sampling using ion chromatography (IC) for sulfate (SO₄²⁻), thiosulfate (S₂O₃²⁻) and polythionates (S_xO₆²⁻) and titration and/or colorimetry for total dissolved sulfide (S²⁻). Sulfite (SO₃²⁻) could also be determined in a few cases using IC. Alternatively, for few samples in remote locations the sulfur oxyanions were stabilized on a resin on site following elution and analysis by IC in the laboratory. Dissolved sulfate and with few exceptions also S²⁻ were detected in all samples with concentrations of 0.02-52.7 mmol kg⁻¹ and <1-4100 μmol kg⁻¹, respectively. Thiosulfate was detected in 49 samples of the 73 analyzed with concentrations in the range of <1-394 μmol kg⁻¹ (S-equivalents). Sulfite was detected in few samples with concentrations in the range of <1-3 μmol kg⁻¹. Thiosulfate and SO₃²⁻ were not detected in <100 °C well waters and S₂O₃²⁻ was observed only at low concentrations (<1-8 μmol kg⁻¹) in ∼200 °C well waters. In alkaline and neutral pH hot springs, S₂O₃²⁻ was present in significant concentrations sometimes corresponding to up to 23% of total dissolved sulfur (S_TOT). In steam-heated acid-sulfate waters, S₂O₃²⁻ was not a significant sulfur species. The results demonstrate that S₂O₃²⁻ and SO₃²⁻ do not occur in the deeper parts of <150 °C hydrothermal systems and only in trace concentrations in ∼200-300 °C systems. Upon ascent to the surface and mixing with oxygenated ground and surface waters and/or dissolution of atmospheric O₂, S²⁻ is degassed and oxidized to SO₃²⁻ and S₂O₃²⁻ and eventually to SO₄²⁻ at pH >8. In near-neutral hydrothermal waters the oxidation of S²⁻ and the interaction of S²⁻ and S⁰ resulting in the formation of S_x²⁻ are considered important. At lower pH values the reactions seemed to proceed relatively rapidly to SO₄²⁻ and the sulfur chemistry of acid-sulfate pools was dominated by SO₄²⁻, which corresponded to >99% of S_TOT. The results suggest that the aqueous speciation of sulfur in natural hydrothermal waters is dynamic and both kinetically and source-controlled and cannot be estimated from thermodynamic speciation calculations.     

Nature of volatile depletion and genetic relationships in enstatite chondrites and aubrites inferred from Zn isotopes

Enstatite meteorites include the undifferentiated enstatite chondrites and the differentiated enstatite achondrites (aubrites). They are the most reduced group of all meteorites. The oxygen isotope compositions of both enstatite chondrites and aubrites plot along the terrestrial mass fractionation line, which suggests some genetic links between these meteorites and the Earth as well.For this study, we measured the Zn isotopic composition of 25 samples from the following groups: aubrites (main group and Shallowater), EL chondrites, EH chondrites and Happy Canyon (impact-melt breccia). We also analyzed the Zn isotopic composition and elemental abundance in separated phases (metal, silicates, and sulfides) of the EH4, EL3, and EL6 chondrites. The different groups of meteorites are isotopically distinct and give the following values (‰): aubrite main group (−7.08 < δ⁶⁶Zn < −0.37); EH3 chondrites (0.15 < δ⁶⁶Zn < 0.31); EH4 chondrites (0.15 < δ⁶⁶Zn < 0.27); EH5 chondrites (δ⁶⁶Zn = 0.27 ± 0.09; n = 1); EL3 chondrites (0.01 < δ⁶⁶Zn < 0.63); the Shallowater aubrite (1.48 < δ⁶⁶Zn < 2.36); EL6 chondrites (2.26 < δ⁶⁶Zn < 7.35); and the impact-melt enstatite chondrite Happy Canyon (δ⁶⁶Zn = 0.37).The aubrite Peña Blanca Spring (δ⁶⁶Zn = −7.04‰) and the EL6 North West Forrest (δ⁶⁶Zn = 7.35‰) are the isotopically lightest and heaviest samples, respectively, known so far in the Solar System. In comparison, the range of Zn isotopic composition of chondrites and terrestrial samples (−1.5 < δ⁶⁶Zn < 1‰) is much smaller ( [Luck et al., 2005] and [Herzog et al., 2009]).EH and EL3 chondrites have the same Zn isotopic composition as the Earth, which is another example of the isotopic similarity between Earth and enstatite chondrites. The Zn isotopic composition and abundance strongly support that the origin of the volatile element depletion between EL3 and EL6 chondrites is due to volatilization, probably during thermal metamorphism. Aubrites show strong elemental depletion in Zn compared to both EH and EL chondrites and they are enriched in light isotopes (δ⁶⁶Zn down to −7.04‰). This is the opposite of what would be expected if Zn elemental depletion was due to evaporation, assuming the aubrites started with an enstatite chondrite-like Zn isotopic composition. Evaporation is therefore not responsible for volatile loss from aubrites. On Earth, Zn isotopes fractionate very little during igneous processes, while differentiated meteorites show only minimal Zn isotopic variability. It is therefore very unlikely that igneous processes can account for the large isotopic fractionation of Zn in aubrites. Condensation of an isotopically light vapor best explains Zn depletion and isotopically light Zn in these puzzling rocks. Mass balance suggests that this isotopically light vapor carries Zn lost by the EL6 parent body during thermal metamorphism and that aubrites evolved from an EL6-like parent body. Finally, Zn isotopes suggest that Shallowater and aubrites originate from distinct parent bodies.     

The continental shelf benthic iron flux and its isotope composition

Benthic iron fluxes from sites along the Oregon-California continental shelf determined using in situ benthic chambers, range from less than 10 μmol m⁻² d⁻¹ to values in excess of ∼300 μmol m⁻² d⁻¹. These fluxes are generally greater than previously published iron fluxes for continental shelves contiguous with the open ocean (as opposed to marginal seas, bays, or estuaries) with the highest fluxes measured in the regions around the high-sediment discharge Eel River and the Umpqua River. These benthic iron fluxes do not covary with organic carbon oxidation rates in any systematic fashion, but rather seem to respond to variations in bottom water oxygen and benthic oxygen demand. We hypothesize that the highest rates of benthic iron efflux are driven, in part, by the greater availability of reactive iron deposited along these river systems as compared to other more typical continental margin settings. Bioirrigation likely plays an important role in the benthic Fe flux in these systems as well. However, the influence of bottom water oxygen concentrations on the iron flux is significant, and there appears to be a threshold in dissolved oxygen (∼60-80 μM), below which sediment-ocean iron exchange is enhanced. The isotope composition of this shelf-derived benthic iron is enriched in the lighter isotopes, and appears to change by ∼3‰ (δ⁵⁶Fe) during the course of a benthic chamber experiment with a mean isotope composition of −2.7 ± 1.1‰ (2 SD, n = 9) by the end of the experiment. This average value is slightly heavier than those from two high benthic Fe flux restricted basins from the California Borderland region where δ⁵⁶Fe is −3.4 ± 0.4‰ (2 SD, n = 3). These light iron isotope compositions support previous ideas, based on sediment porewater analyses, suggesting that sedimentary iron reduction fractionates iron isotopes and produces an isotopically light iron pool that is transferred to the ocean water column. In sum, our data suggest that continental shelves may export a higher efflux of iron than previously hypothesized, with the likelihood that along river-dominated margins, the benthic iron flux could well be orders of magnitude larger than non-river dominated shelves. The close proximity of the continental shelf benthos to the productive surface ocean means that this flux is likely to be essential for maintaining ecosystem micronutrient supply.     

Environmental memory and a possible seasonal bias in the stable isotope composition of (U-Th)/He-dated goethite from the Canadian Arctic

Goethite (Ax-2) from Axel Heiberg Island (∼80°N) on the margin of the Arctic Ocean is the dominant mineral in a sample of “petrified” Eocene wood, but U, Th, and He measurements suggest that the goethite (α-FeOOH) crystallized in the latest Miocene/Pliocene (ca. 5.5 to 2.8 Ma). Measured δD and δ¹⁸O values of Ax-2 are −221 (±6)‰ and −9.6 (±0.5)‰, respectively. The inferred δD and δ¹⁸O values of the ancient water were about −139‰ and −18.6‰, respectively, with a calculated temperature of crystallization of 3 (±5)°C, which compares with the modern summer (J-J-A) temperature of 3 °C and contrasts with a modern MAT of −19 °C. Published results from various biological proxies on nearby Ellesmere Island indicate a Pliocene (∼4 Ma) MAT of either −6 or −0.4 °C and corresponding seasonal amplitudes of about 18 or 13 °C. A conductive heat flow model suggests that a temperature of 3 °C could represent goethite crystallization at depths of ∼100-200 cm (for MAT = −6 °C) or ∼250-450 cm (for MAT = −0.4 °C) over seasonally restricted intervals of time.The δ¹⁸O value of the Ax-2 water (−18.6‰) is more positive than the modern J-J-A precipitation (−22‰). In combination, the paleotemperatures and δ¹⁸O values of ancient waters (from Ax-2 and published results from three Eocene or Pliocene proxy sites on Axel Heiberg and Ellesmere Islands) are consistent with a warm season bias in those isotopic proxies. The results are also consistent with higher proportions of J-J-A precipitation in the annual total. If so, this emphasizes the importance of seasonality at high latitudes even in times of warmer global climates, and suggests that the Arctic hydrologic cycle, as expressed in the seasonal distribution and isotopic composition of precipitation (perhaps modified by a warmer Arctic Ocean), differed from modern.The δ¹³C value of the Fe(CO₃)OH component in the Ax-2 goethite is +6.6‰, which is much more positive than expected if crystallizing goethite incorporated CO₂ derived primarily from oxidation of relict Eocene wood with δ¹³C values of about −24‰. This apparent paradox may be resolved if the goethite is a product of oxidation of ¹³C-rich siderite, which had previously replaced wood in an Eocene methanogenic burial environment. Thus, the goethite retains a carbon isotope “memory” of a diagenetic Eocene event, but a δD and δ¹⁸O record of the latest Miocene/Pliocene Arctic climate.     

Oxygen- and magnesium-isotope compositions of calcium-aluminum-rich inclusions from Rumuruti (R) chondrites

We report oxygen- and magnesium-isotope compositions of Ca,Al-rich inclusions (CAIs) from several Rumuruti (R) chondrites measured in situ using a Cameca ims-1280 ion microprobe. On a three-isotope oxygen diagram, δ¹⁷O vs. δ¹⁸O, compositions of individual minerals in most R CAIs analyzed fall along a slope-1 line. Based on the variations of Δ¹⁷O values (Δ¹⁷O = δ¹⁷O − 0.52 × δ¹⁸O) within individual inclusions, the R CAIs are divided into (i) ¹⁶O-rich (Δ¹⁷O ∼ −23-26‰), (ii) uniformly ¹⁶O-depleted (Δ¹⁷O ∼ −2‰), and (iii) isotopically heterogeneous (Δ¹⁷O ranges from −25‰ to +5‰). One of the hibonite-rich CAIs, H030/L, has an intermediate Δ¹⁷O value of −12‰ and a highly fractionated composition (δ¹⁸O ∼ +47‰). We infer that like most CAIs in other chondrite groups, the R CAIs formed in an ¹⁶O-rich gaseous reservoir. The uniformly ¹⁶O-depleted and isotopically heterogeneous CAIs subsequently experienced oxygen-isotope exchange during remelting in an ¹⁶O-depleted nebular gas, possibly during R chondrite chondrule formation, and/or during fluid-assisted thermal metamorphism on the R chondrite parent asteroid.Three hibonite-bearing CAIs and one spinel-plagioclase-rich inclusion were analyzed for magnesium-isotope compositions. The CAI with the highly fractionated oxygen isotopes, H030/L, shows a resolvable excess of ²⁶Mg (²⁶Mg^∗) corresponding to an initial ²⁶Al/²⁷Al ratio of ∼7 × 10⁻⁷. Three other CAIs show no resolvable excess of ²⁶Mg (²⁶Mg^∗). The absence of ²⁶Mg^∗ in the spinel-plagioclase-rich CAI from a metamorphosed R chondrite NWA 753 (R3.9) could have resulted from metamorphic resetting. Two other hibonite-bearing CAIs occur in the R chondrites (NWA 1476 and NWA 2446), which appear to have experienced only minor degrees of thermal metamorphism. These inclusions could have formed from precursors with lower than canonical ²⁶Al/²⁷Al ratio.