Silicon isotopes in the inner Solar System: Implications for core formation, solar nebular processes and partial melting

We report Si isotopic data on a suite of terrestrial mantle-derived samples, meteorites and a lunar sample. Our data on co-existing mantle minerals, peridotites and basalts demonstrate lack of any resolvable high temperature fractionation during igneous processes. We show that the δ³⁰Si of the bulk silicate Earth (BSE) is identical, within analytical uncertainties, to carbonaceous and ordinary chondrites (CHUR). Based on our data the difference between δ³⁰Si_BSE and δ³⁰Si_CHUR is 0.035 ± 0.035. Whole-rock differentiated meteorites from different parent bodies (Mars, Vesta) and a lunar breccia sample also show similar δ³⁰Si suggesting broad-scale Si isotope homogeneity in the inner Solar System with an average δ²⁹Si = −0.20 ± 0.01 and δ³⁰Si = −0.39 ± 0.02 relative to the NBS28 Si isotope standard.A difference between δ³⁰Si_BSE and δ³⁰Si_CHUR of 0.035, as observed in our study, translates to less than 1.67 wt.% Si in the core considering a continuous accretion model whereas estimates using a batch model are even lower. Within uncertainties (±0.035‰) in the δ³⁰Si difference between the BSE and CHUR, a maximum of 3.84 wt.% Si could be present in the Earth’s core whereas at δ³⁰Si_BSE-δ³⁰Si_CHUR = 0, there is no requirement of Si in the Earth’s core. Such low Si in the core necessitates the presence of other light elements in the core to explain its density deficit. Our data also places constraints on the oxidation state of the Earth’s mantle during core segregation. The uncertainties in estimating the concentration of oxidized Fe in the mantle during the first 90% of accretion arise from uncertainties in the estimates of the equilibrium partition coefficient of silicon between metal and silicate at conditions relevant to core formation. For δ³⁰Si_BSE-δ³⁰Si_CHUR = 0.035 ± 0.035, the concentration of oxidized Fe in the mantle during the first 90% of accretion could be as low as ∼1%. However, at δ³⁰Si_BSE-δ³⁰Si_CHUR = 0, the Si isotope data do not require any change in the mantle concentration of oxidized Fe during accretion from the present day value of 6.26%.     

Variations of δSi and Ge/Si with weathering and biogenic input in tropical basaltic ash soils under monoculture

In soils, silicon released by mineral weathering can be retrieved from soil solution through clay formation, Si adsorption onto secondary oxides and plant uptake, thereby impacting the Si-isotopic signature and Ge/Si ratio of dissolved Si (DSi) exported to rivers. Here we use these proxies to study the contribution of biogenic Si (BSi) in a soil-plant system involving basaltic ash soils differing in weathering degree under intensive banana cropping. δ³⁰Si and Ge/Si ratios were determined in bulk soils (<2 mm), sand (50-2000 μm), silt (2-50 μm), amorphous Si (ASi, 2-50 μm) and clay (<2 μm) fractions: δ³⁰Si by MC-ICP-MS Nu Plasma in medium resolution, operating in dry plasma with Mg doping (δ³⁰Si vs. NBS28 ± 0.12‰ ± 2σ_SD), Ge/Si computed after determination of Ge and Si concentrations by HR-ICP-MS and ICP-AES, respectively. Components of the ASi fraction were quantified by microscopic counting (phytoliths, diatoms, ashes). Compared to fresh ash (δ³⁰Si = −0.38‰; Ge/Si = 2.21 μmol mol⁻¹), soil clay fractions (<2 μm) were enriched in light Si isotopes and Ge: with increasing weathering degree, δ³⁰Si decreased from −1.19 to −2.37‰ and Ge/Si increased from 4.10 to 5.25 μmol mol⁻¹. Sand and silt fractions displayed δ³⁰Si values close to fresh ash (−0.33‰) or higher due to saharian dust quartz deposition, whose contribution was evaluated by isotopic mass balance calculation. Si-isotopic signatures of bulk soils (<2 mm) were strongly governed by the relative proportions of primary and secondary minerals: the bulk soil Si-isotopic budget could be closed indicating that all the phases involved were identified. Microscopic counting highlighted a surface accumulation of banana phytoliths and a stable phytolith pool from previous forested vegetation. δ³⁰Si and Ge/Si values of clay fractions in poorly developed volcanic soils, isotopically heavier and Ge-depleted in surface horizons, support the occurrence of a DSi source from banana phytolith dissolution, available for Si sequestration in clay-sized secondary minerals (clay minerals formation and Si adsorption onto Fe-oxide). In the soil-plant system, δ³⁰Si and Ge/Si are thus highly relevant to trace weathering and input of DSi from phytoliths in secondary minerals, although not quantifying the net input of BSi to DSi.     

The oxygen-isotope composition of chondrules and isolated forsterite and olivine grains from the Tagish Lake carbonaceous chondrite

The oxygen-isotope compositions (obtained by laser fluorination) of hand-picked separates of isolated forsterite, isolated olivine and chondrules from the Tagish Lake carbonaceous chondrite describe a line (δ¹⁷O = 0.95 * δ¹⁸O − 3.24; R² = 0.99) similar to the trend known for chondrules from other carbonaceous chondrites. The isolated forsterite grains (Fo_99.6-99.8; δ¹⁸O = −7.2‰ to −5.5‰; δ¹⁷O = −9.6‰ to −8.2‰) are more ¹⁶O-rich than the isolated olivine grains (Fo_39.6-86.8; δ¹⁸O = 3.1‰ to 5.1‰; δ¹⁷O = −0.3‰ to 2.2‰), and have chemical and isotopic characteristics typical of refractory forsterite. Chondrules contain olivine (Fo_97.2-99.8) with oxygen-isotope compositions (δ¹⁸O = −5.2‰ to 5.9‰; δ¹⁷O = −8.1‰ to 1.2‰) that overlap those of isolated forsterite and isolated olivine. An inverse relationship exists between the Δ¹⁷O values and Fo contents of Tagish Lake isolated forsterite and chondrules; the chondrules likely underwent greater exchange with ¹⁶O-poor nebular gases than the forsterite. The oxygen-isotope compositions of the isolated olivine grains describe a trend with a steeper slope (1.1 ± 0.1, R² = 0.94) than the carbonaceous chondrite anhydrous mineral line (CCAM_slope = 0.95). The isolated olivine may have crystallized from an evolving melt that exchanged with ¹⁶O-poor gases of somewhat different composition than those which affected the chondrules and isolated forsterite. The primordial components of the Tagish Lake meteorite formed under conditions similar to other carbonaceous chondrite meteorite groups, especially CMs. Its alteration history has its closest affinities to CI carbonaceous chondrites.     

Impact of soil weathering degree on silicon isotopic fractionation during adsorption onto iron oxides in basaltic ash soils, Cameroon

The sequestration of silicon in soil clay-sized iron oxides may affect the terrestrial cycle of Si. Iron oxides indeed specifically adsorb aqueous monosilicic acid (H₄SiO₄⁰), thereby influencing Si concentration in soil solution. Here we study the impact of H₄SiO₄⁰ adsorption on the fractionation of Si isotopes in basaltic ash soils differing in weathering degree (from two weathering sequences, Cameroon), hence in clay and Fe-oxide contents, and evaluate the potential isotopic impact on dissolved Si in surrounding Cameroon rivers. Adsorption was measured in batch experiment series designed as function of time (0-72 h) and initial concentration (ic) of Si in solution (0.61-1.18 mM) at 20 °C, constant pH (5.5) and ionic strength (1 mM). After various soil-solution contact times, the δ³⁰Si vs. NBS28 compositions were determined in selected solutions by MC-ICP-MS (Nu Plasma) in medium resolution, operating in dry plasma with Mg doping with an average precision of ±0.15‰ (±2σ_SEM). The quantitative adsorption of H₄SiO₄⁰ by soil Fe-oxides left a solution depleted in light Si isotopes, which confirms previous study on synthetic Fe-oxides. Measured against its initial composition (δ³⁰Si = +0.02 ± 0.07‰ (±2σ_SD)), the solutions were systematically enriched in ³⁰Si reaching maximum δ³⁰Si values ranging between +0.16‰ and +0.95‰ after 72 h contact time. The enrichment of the solution in heavy isotopes increased with increasing values of three parameters: soil weathering degree, iron oxide content, and proportion of short-range ordered Fe-oxide. The Si-isotopic signature of the solution was partly influenced by Si release, possibly through mineral dissolution and Si desorption from oxide surfaces, depending on soil type, highlighting the complex pattern of natural soils. Surrounding Cameroon rivers displayed a mean Si-isotopic signature of +1.19‰. Our data imply that in natural environments, H₄SiO₄⁰ adsorption by soil clay-sized Fe-oxides at least partly impacts the Si-isotopic signature of the soil solution exported to water streams.     

Silicon isotopic fractionation during adsorption of aqueous monosilicic acid onto iron oxide

The quantification of silicon isotopic fractionation by biotic and abiotic processes contributes to the understanding of the Si continental cycle. In soils, light Si isotopes are selectively taken up by plants, and concentrate in secondary clay-sized minerals. Si can readily be retrieved from soil solution through the specific adsorption of monosilicic acid () by iron oxides. Here, we report on the Si-isotopic fractionation during adsorption on synthesized ferrihydrite and goethite in batch experiment series designed as function of time (0-504 h) and initial concentration (ic) of Si in solution (0.21-1.80 mM), at 20 °C, constant pH (5.5) and ionic strength (1 mM). At various contact times, the δ²⁹Si vs. NBS28 compositions were determined in selected solutions (ic = 0.64 and 1.06 mM Si) by MC-ICP-MS in dry plasma mode with external Mg doping with an average precision of ±0.08‰ (±2σ_SEM). Per oxide mass, ferrihydrite (74-86% of initial Si loading) adsorbed more Si than goethite (37-69%) after 504 h of contact over the range of initial Si concentration 0.42-1.80 mM. Measured against its initial composition (δ²⁹Si = +0.01 ± 0.04‰ (±2σ_SD)), the remaining solution was systematically enriched in ²⁹Si, reaching maximum δ²⁹Si values of +0.70 ± 0.07‰ for ferrihydrite and +0.50 ± 0.08‰ for goethite for ic 1.06 mM. The progressive ²⁹Si enrichment of the solution fitted better a Rayleigh distillation path than a steady state model. The fractionation factor ²⁹ε (±1σ_SD) was estimated at −0.54 ± 0.03‰ for ferrihydrite and −0.81 ± 0.12‰ for goethite. Our data imply that the sorption of onto synthetic iron oxides produced a distinct Si-isotopic fractionation for the two types of oxide but in the same order than that generated by Si uptake by plants and diatoms. They further suggest that the concentration of light Si isotopes in the clay fraction of soils is partly due to sorption onto secondary clay-sized iron oxides.     

Oxygen isotopic compositions of chondrules from the metal-rich chondrites Isheyevo (CH/CBb), MAC 02675 (CBb) and QUE 94627 (CBb)

It has been recently suggested that (1) CH chondrites and the CB_b/CH-like chondrite Isheyevo contain two populations of chondrules formed by different processes: (i) magnesian non-porphyritic (cryptocrystalline and barred) chondrules, which are similar to those in the CB chondrites and formed in an impact-generated plume of melt and gas resulted from large-scale asteroidal collision, and (ii) porphyritic chondrules formed by melting of solid precursors in the solar nebula. (2) Porphyritic chondrules in Isheyevo and CH chondrites are different from porphyritic chondrules in other carbonaceous chondrites ( [Krot et al., 2005], [Krot et al., 2008a] and [Krot et al., 2008b]). In order to test these hypotheses, we measured in situ oxygen isotopic compositions of porphyritic (magnesian, Type I and ferroan, Type II) and non-porphyritic (magnesian and ferroan cryptocrystalline) chondrules from Isheyevo and CB_b chondrites MAC 02675 and QUE 94627, paired with QUE 94611, using a Cameca ims-1280 ion microprobe.On a three-isotope oxygen diagram (δ¹⁷O vs. δ¹⁸O), compositions of chondrules measured follow approximately slope-1 line. Data for 19 magnesian cryptocrystalline chondrules from Isheyevo, 24 magnesian cryptocrystalline chondrules and 6 magnesian cryptocrystalline silicate inclusions inside chemically-zoned Fe,Ni-metal condensates from CB_b chondrites have nearly identical compositions: Δ¹⁷O = −2.2 ± 0.9‰, −2.3 ± 0.6‰ and −2.2 ± 1.0‰ (2σ), respectively. These observations and isotopically light magnesium compositions of cryptocrystalline magnesian chondrules in CB_b chondrites (Gounelle et al., 2007) are consistent with their single-stage origin, possibly as gas-melt condensates in an impact-generated plume. In contrast, Δ¹⁷O values for 11 Type I and 9 Type II chondrules from Isheyevo range from −5‰ to +4‰ and from −17‰ to +3‰, respectively. In contrast to typical chondrules from carbonaceous chondrites, seven out of 11 Type I chondrules from Isheyevo plot above the terrestrial fractionation line. We conclude that (i) porphyritic chondrules in Isheyevo belong to a unique population of objects, suggesting formation either in a different nebular region or at a different time than chondrules from other carbonaceous chondrites; (ii) Isheyevo, CB and CH chondrites are genetically related meteorites: they contain non-porphyritic chondrules produced during the same highly-energetic event, probably large-scale asteroidal collision; (iii) the differences in mineralogy, petrography, chemical and whole-rock oxygen isotopic compositions between CH and CB chondrites are due to various proportions of the nebular and the impact-produced materials.     

Iron and magnesium isotopic compositions of peridotite xenoliths from Eastern China

We present high-precision measurements of Mg and Fe isotopic compositions of olivine, orthopyroxene (opx), and clinopyroxene (cpx) for 18 lherzolite xenoliths from east central China and provide the first combined Fe and Mg isotopic study of the upper mantle. δ⁵⁶Fe in olivines varies from 0.18‰ to −0.22‰ with an average of −0.01 ± 0.18‰ (2SD, n = 18), opx from 0.24‰ to −0.22‰ with an average of 0.04 ± 0.20‰, and cpx from 0.24‰ to −0.16‰ with an average of 0.10 ± 0.19‰. δ²⁶Mg of olivines varies from −0.25‰ to −0.42‰ with an average of −0.34 ± 0.10‰ (2SD, n = 18), opx from −0.19‰ to −0.34‰ with an average of −0.25 ± 0.10‰, and cpx from −0.09‰ to −0.43‰ with an average of −0.24 ± 0.18‰. Although current precision (∼±0.06‰ for δ⁵⁶Fe; ±0.10‰ for δ²⁶Mg, 2SD) limits the ability to analytically distinguish inter-mineral isotopic fractionations, systematic behavior of inter-mineral fractionation for both Fe and Mg is statistically observed: Δ⁵⁶Fe_ol-cpx = −0.10 ± 0.12‰ (2SD, n = 18); Δ⁵⁶Fe_ol-opx = −0.05 ± 0.11‰; Δ²⁶Mg_ol-opx = −0.09 ± 0.12‰; Δ²⁶Mg_ol-cpx = −0.10 ± 0.15‰. Fe and Mg isotopic composition of bulk rocks were calculated based on the modes of olivine, opx, and cpx. The average δ⁵⁶Fe of peridotites in this study is 0.01 ± 0.17‰ (2SD, n = 18), similar to the values of chondrites but slightly lower than mid-ocean ridge basalts (MORB) and oceanic island basalts (OIB). The average δ²⁶Mg is −0.30 ± 0.09‰, indistinguishable from chondrites, MORB, and OIB. Our data support the conclusion that the bulk silicate Earth (BSE) has chondritic δ⁵⁶Fe and δ²⁶Mg.The origin of inter-mineral fractionations of Fe and Mg isotopic ratios remains debated. δ⁵⁶Fe between the main peridotite minerals shows positive linear correlations with slopes within error of unity, strongly suggesting intra-sample mineral-mineral Fe and Mg isotopic equilibrium. Because inter-mineral isotopic equilibrium should be reached earlier than major element equilibrium via chemical diffusion at mantle temperatures, Fe and Mg isotope ratios of coexisting minerals could be useful tools for justifying mineral thermometry and barometry on the basis of chemical equilibrium between minerals. Although most peridotites in this study exhibit a narrow range in δ⁵⁶Fe, the larger deviations from average δ⁵⁶Fe for three samples likely indicate changes due to metasomatic processes. Two samples show heavy δ⁵⁶Fe relative to the average and they also have high La/Yb and total Fe content, consistent with metasomatic reaction between peridotite and Fe-rich and isotopically heavy melt. The other sample has light δ⁵⁶Fe and slightly heavy δ²⁶Mg, which may reflect Fe-Mg inter-diffusion between peridotite and percolating melt.     

Sources and biological fractionation of Silicon isotopes in the Eastern Equatorial Pacific

Silicon isotopes in dissolved silicic acid were measured in the upper four kilometers between 4°N and 3°S latitude at 110°W longitude in the eastern Equatorial Pacific. Silicon isotopes became progressively heavier with silicic acid depletion of surface water as expected from biological fractionation. The value of ε estimated by applying a steady-state isotope fractionation model to data from all stations between 4°N and 3°S was −0.77 ± 0.12‰ (std. err.). When the analysis was restricted to those stations whose temperature and salinity profiles indicated that they were directly influenced by upwelling of the Equatorial Undercurrent (EUC), the resulting value of ε was −1.08 ± 0.27‰ (std. err.) similar to the value established in culture studies (−1.1‰). When the non steady state Rayleigh model was applied to the same restricted data set the resulting value of ε was significantly more positive, −0.61 ± 0.16‰ (std. err.). To the extent that the equatorial system approximates a steady state these results support a value of −1.1‰ for the fractionation factor for isotopes of Si in the sea. Without the assumption of steady state the value of ε can only be constrained to be between −0.6 and −1.1‰. Silicic acid in Equatorial Pacific Deep Water below 2000 m had a near constant δ³⁰Si of +1.32 ± 0.05‰. That value is significantly more positive than obtained for North Pacific Deep Water at similar depths at stations to the northwest of our study area (0.9-1.0‰) and it is slightly less positive than new measures of the δ³⁰Si of silicic acid from the silicic acid plume centered over the Cascadia basin in the Northeast Pacific (Si(OH)₄ > 180  μM, δ³⁰Si = +1.46 ± 0.12‰ (SD, n = 4). We show that the data from the equator and Cascadia basin fit a general trend of increasing δ³⁰Si(OH)₄ with increasing silicic acid concentration in the deep sea, but that the isotope values from the Northeast Pacific are anomalously light. The observed level of variation in the silicon isotope composition of deep waters from this single ocean basin is considerably larger than that predicted by current models based on fractionation during opal formation with no isotope effect during dissolution. Confirmation of such high variability in deep water δ³⁰Si(OH)₄ within individual ocean basins will require reassessment of the mechanisms controlling the distribution of isotopes of silicon in the sea.     

SIMS analyses of silicon and oxygen isotope ratios for quartz from Archean and Paleoproterozoic banded iron formations

Banded iron formations (BIFs) are chemical marine sediments dominantly composed of alternating iron-rich (oxide, carbonate, sulfide) and silicon-rich (chert, jasper) layers. Isotope ratios of iron, carbon, and sulfur in BIF iron-bearing minerals are biosignatures that reflect microbial cycling for these elements in BIFs. While much attention has focused on iron, banded iron formations are equally banded silica formations. Thus, silicon isotope ratios for quartz can provide insight on the sources and cycling of silicon in BIFs. BIFs are banded by definition, and microlaminae, or sub-mm banding, are characteristic of many BIFs. In situ microanalysis including secondary ion mass spectrometry is well-suited for analyzing such small features. In this study we used a CAMECA IMS-1280 ion microprobe to obtain highly accurate (±0.3‰) and spatially resolved (∼10 μm spot size) analyses of silicon and oxygen isotope ratios for quartz from several well known BIFs: Isua, southwest Greenland (∼3.8 Ga); Hamersley Group, Western Australia (∼2.5 Ga); Transvaal Group, South Africa (∼2.5 Ga); and Biwabik Iron Formation, Minnesota, USA (∼1.9 Ga). Values of δ¹⁸O range from +7.9‰ to +27.5‰ and include the highest reported δ¹⁸O values for BIF quartz. Values of δ³⁰Si have a range of ∼5‰ from −3.7‰ to +1.2‰ and extend to the lowest δ³⁰Si values for Precambrian cherts. Isua BIF samples are homogeneous in δ¹⁸O to ±0.3‰ at mm- to cm-scale, but are heterogeneous in δ³⁰Si up to 3‰, similar to the range in δ³⁰Si found in BIFs that have not experienced high temperature metamorphism (up to 300 °C). Values of δ³⁰Si for quartz are homogeneous to ±0.3‰ in individual sub-mm laminae, but vary by up to 3‰ between multiple laminae over mm-to-cm of vertical banding. The scale of exchange for Si in quartz in BIFs is thus limited to the size of microlaminae, or less than ∼1 mm. We interpret differences in δ³⁰Si between microlaminae as preserved from primary deposition. Silicon in BIF quartz is mostly of marine hydrothermal origin (δ³⁰Si < −0.5‰) but silicon from continental weathering (δ³⁰Si ∼ 1‰) was an important source as early as 3.8 Ga.     

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.     

Stable silicon isotopes of groundwater, feldspars, and clay coatings in the Navajo Sandstone aquifer, Black Mesa, Arizona, USA

We present some of the first analyses of the stable isotopic composition of dissolved silicon (Si) in groundwater. The groundwater samples were from the Navajo Sandstone aquifer at Black Mesa, Arizona, USA, and the Si isotope composition of detrital feldspars and secondary clay coatings in the aquifer were also analyzed. Silicon isotope compositions were measured using high-resolution multi-collector inductively coupled mass spectrometry (HR-MC-ICP-MS) (Nu1700 & NuPlasma HR). The quartz dominated bulk rock and feldspar separates have similar δ³⁰Si of −0.09 ± 0.04‰ and −0.15 ± 0.04‰ (±95% SEM), respectively, and clay separates are isotopically lighter by up to 0.4‰ compared to the feldspars. From isotopic mass-balance considerations, co-existing aqueous fluids should have δ³⁰Si values heavier than the primary silicates. Positive δ³⁰Si values were only found in the shallow aquifer, where Si isotopes are most likely fractionated during the dissolution of feldspars and subsequent formation of clay minerals. However, δ³⁰Si decreases along the flow path from 0.56‰ to −1.42‰, representing the most negative dissolved Si isotope composition so far found for natural waters. We speculate that the enrichment in ²⁸Si is due to dissolution of partly secondary clay minerals and low-temperature silcretes in the Navajo Sandstone. The discovery of the large range and systematic shifts of δ³⁰Si values along a groundwater flow path illustrates the potential utility of stable Si isotopes for deciphering the Si cycling in sedimentary basins, tracing fluid flow, and evaluating global Si cycle.     

Variations of Li and Mg isotope ratios in bulk chondrites and mantle xenoliths

We present whole rock Li and Mg isotope analyses of 33 ultramafic xenoliths from the terrestrial mantle, which we compare with analyses of 30 (mostly chondritic) meteorites. The accuracy of our new Mg isotope ratio measurement protocol is substantiated by a combination of standard addition experiments, the absence of mass independent effects in terrestrial samples and our obtaining identical values for rock standards using two different separation chemistries and three different mass-spectrometric introduction systems. Carbonaceous, ordinary and enstatite chondrites have irresolvable mean stable Mg isotopic compositions (δ²⁵Mg = −0.14 ± 0.06; δ²⁶Mg = −0.27 ± 0.12‰, 2SD), but our enstatite chondrite samples have lighter δ⁷Li (by up to ∼3‰) than our mean carbonaceous and ordinary chondrites (3.0 ± 1.5‰, 2SD), possibly as a result of spallation in the early solar system. Measurements of equilibrated, fertile peridotites give mean values of δ⁷Li = 3.5 ± 0.5‰, δ²⁵Mg = −0.10 ± 0.03‰ and δ²⁶Mg = −0.21 ± 0.07‰. We believe these values provide a useful estimate of the primitive mantle and they are within error of our average of bulk carbonaceous and ordinary chondrites. A fuller range of fresh, terrestrial, ultramafic samples, covering a variety of geological histories, show a broad positive correlation between bulk δ⁷Li and δ²⁶Mg, which vary from −3.7‰ to +14.5‰, and −0.36‰ to + 0.06‰, respectively. Values of δ⁷Li and δ²⁶Mg lower than our estimate of primitive mantle are strongly linked to kinetic isotope fractionation, occurring during transport of the mantle xenoliths. We suggest Mg and Li diffusion into the xenoliths is coupled to H loss from nominally anhydrous minerals following degassing. Diffusion models suggest that the co-variation of Mg and Li isotopes requires comparable diffusivities of Li and Mg in olivine. The isotopically lightest samples require ∼5-10 years of diffusive ingress, which we interpret as a time since volatile loss in the host magma. Xenoliths erupted in pyroclastic flows appear to have retained their mantle isotope ratios, likely as a result of little prior degassing in these explosive events. High δ⁷Li, coupled with high [Li], in rapidly cooled arc peridotites may indicate that these samples represent fragments of mantle wedge that has been metasomatised by heavy, slab-derived fluids. If such material is typically stirred back into the convecting mantle, it may account for the heavy δ⁷Li seen in some oceanic basalts.     

Note on the isotopic geochemistry of fossil-lacustrine tufas in carbonate plateau—A study from Dungul region (SW Egypt)

Lithological, chemical, and stable isotope data are used to characterize lacustrine tufas dating back to pre-late Miocene and later unknown times, capping different surfaces of a Tertiary carbonate (Sinn el-Kedab) plateau in Dungul region in the currently hyperarid south-western Egypt. These deposits are composed mostly of calcium carbonate, some magnesium carbonate and clastic particles plus minor amounts of organic matter. They have a wide range of (Mg/Ca)_molar ratios, from 0.03 to 0.3. The bulk-tufa carbonate has characteristic isotope compositions: (δ¹³C_mean = −2.49 ± 0.99‰; δ¹⁸O_mean = −9.43 ± 1.40‰). The δ¹³C values are consistent with a small input from C4 vegetation or thinner soils in the recharge area of the tufa-depositing systems. The δ¹⁸O values are typical of fresh water carbonates. Covariation between δ¹³C and δ¹⁸O values probably is a reflection of climatic conditions such as aridity. The tufas studied are isotopically similar to the underlying diagenetic marine chalks, marls and limestones (δ¹³C_mean = −2.06 ± 0.84‰; δ¹⁸O_mean = −10.06 ± 1.39‰). The similarity has been attributed to common meteoric water signatures. This raises large uncertainties in using tufas (Mg/Ca)_molar, δ¹³C and δ¹⁸O records as proxies of paleoclimatic change and suggests that intrinsic compositional differences in material sources within the plateau may mask climatic changes in the records.     

Tissue N content and N natural abundance in epilithic mosses for indicating atmospheric N deposition in the Guiyang area,SW China

Tissue N contents and δ¹⁵N signatures in 175 epilithic mosses were investigated from urban to rural sites in Guiyang (SW China) to determine atmospheric N deposition. Moss N contents (0.85–2.97%) showed a significant decrease from the urban area (mean = 2.24 ± 0.32%, 0–5 km) to the rural area (mean = 1.27 ± 0.13%, 20–25 km), indicating that the level of N deposition decreased away from the urban environment, while slightly higher N contents re-occurred at sites beyond 30 km, suggesting higher N deposition in more remote rural areas. Moss δ¹⁵N ranged from −12.50‰ to −1.39‰ and showed a clear bimodal distribution (−12‰ to −6‰ and −5‰ to −2‰), suggesting that there are two main sources for N deposition in the Guiyang area. More negative δ¹⁵N (mean = −8.87 ± 1.65‰) of urban mosses mainly indicated NH₃ released from excretory wastes and sewage, while the less negative δ¹⁵N (from −3.83 ± 0.82‰ to −2.48 ± 0.95‰) of rural mosses were mainly influenced by agricultural NH₃. With more negative values in the urban area than in the rural area, the pattern of moss δ¹⁵N variation in Guiyang was found to be opposite to cities where N deposition is dominated by NO_x–N. Therefore, NH_x–N is the dominant N form deposited in the Guiyang area, which is supported by higher NH_x–N than NO_x–N in local atmospheric deposition. From the data showing that moss is responding to NH_x–N/NO_x–N in deposition it can be further demonstrated that the variation of moss δ¹⁵N from the Guiyang urban to rural area was more likely controlled by the ratio of urban-NH_x/agriculture-NH_x than the ratio of NH_x–N/NO_x–N. The results of this study have extended knowledge of atmospheric N sources in city areas, showing that urban sewage discharge could be important in cities co-generic to Guiyang.     

Silicon isotopic composition of dissolved silicon and suspended particulate matter in the Yellow River, China, with implications for the global silicon cycle

The silicon isotopic composition of dissolved silicon and suspended particulate matter (SPM) were systematically investigated in water samples from the mainstem of the Yellow River and 4 major tributaries. The SPM content of the Yellow River varied from 1.4 to 38,560 mg/L, averaging 3568 mg/L, and the δ³⁰Si of suspended particulate matter (δ³⁰Si_SPM) varied from 0.3‰ to −0.4‰, averaging −0.02‰. The major factors affecting the SPM content and the δ³⁰Si_SPM values in the Yellow River were inferred to be the mineralogical, chemical and isotopic characteristics of the sediments from the Loess Plateau and a combination of the climate and the flow discharge of the river.The major ions in the Yellow River water were Na⁺, Ca²⁺, Mg²⁺, HCO₃⁻, SO₄²⁻ and Cl⁻. High salt concentration was observed in samples from the middle and lower reaches, likely reflecting the effects of evaporation and irrigation because the Na⁺, Mg²⁺, SO₄²⁻ and K⁺ concentrations were correlated with the Cl⁻ concentration. The dissolved Si concentration (D_Si) increased downstream, varying from 0.016 to 0.323 mM. The δ³⁰Si of dissolved Si (δ³⁰Si_Diss) varied from 0.4‰ to 2.5‰, averaging 1.28‰. The major processes controlling the D_Si and δ³⁰Si_Diss of the Yellow River are (a) the weathering of silicate rocks, (b) the formation of phytoliths in plants, (c) the evaporation of water from and the addition of meteoric water to the river system, which only affects concentrations, (d) the adsorption and desorption of aqueous monosilicic acid on iron oxide, and (e) the dissolution of phytoliths in soils.The D_Si and δ³⁰Si_Diss values of global rivers vary spatially and temporally in response to changes in climate, chemical weathering intensity and biological activity. The moderately positive δ³⁰Si_Diss values observed in the Yellow River may be attributed to the higher rates of chemical weathering and biological activities that have been observed in this catchment in comparison with those of other previously studied catchments, excluding the Yangtze River. Human activities may also potentially influence chemical weathering and biological activities and affect the D_Si and δ³⁰Si_Diss values of the major rivers of the world. Further river studies should be performed to gain a better understanding of the global Si isotope budget.     

Silicon isotope fractionation during magmatic differentiation

The Si isotopic composition of Earth’s mantle is thought to be homogeneous (δ³⁰Si = −0.29 ± 0.08‰, 2 s.d.) and not greatly affected by partial melting and recycling. Previous analyses of evolved igneous material indicate that such rocks are isotopically heavy relative to the mantle. To understand this variation, it is necessary to investigate the degree of Si isotopic fractionation that takes place during magmatic differentiation. Here we report Si isotopic compositions of lavas from Hekla volcano, Iceland, which has formed in a region devoid of old, geochemically diverse crust. We show that Si isotopic composition varies linearly as a function of silica content, with more differentiated rocks possessing heavier isotopic compositions. Data for samples from the Afar Rift Zone, as well as various igneous USGS standards are collinear with the Hekla trend, providing evidence of a fundamental relationship between magmatic differentiation and Si isotopes. The effect of fractionation has been tested by studying cumulates from the Skaergaard Complex, which show that olivine and pyroxene are isotopically light, and plagioclase heavy, relative to the Si isotopic composition of the Earth’s mantle. Therefore, Si isotopes can be utilised to model the competing effects of mafic and felsic mineral fractionation in evolving silicate liquids and cumulates.At an average SiO₂ content of ∼60 wt.%, the predicted δ³⁰Si value of the continental crust that should result from magmatic fractionation alone is −0.23 ± 0.05‰ (2 s.e.), barely heavier than the mantle. This is, at most, a maximum estimate, as this does not take into account weathered material whose formation drives the products toward lighter δ³⁰Si values. Mass balance calculations suggest that removal of continental crust of this composition from the upper mantle will not affect the Si isotopic composition of the mantle.     

Copper isotope fractionation in acid mine drainage

We measured the Cu isotopic composition of primary minerals and stream water affected by acid mine drainage in a mineralized watershed (Colorado, USA). The δ⁶⁵Cu values (based on ⁶⁵Cu/⁶³Cu) of enargite (δ⁶⁵Cu = −0.01 ± 0.10‰; 2σ) and chalcopyrite (δ⁶⁵Cu = 0.16 ± 0.10‰) are within the range of reported values for terrestrial primary Cu sulfides (−1‰ < δ⁶⁵Cu < 1‰). These mineral samples show lower δ⁶⁵Cu values than stream waters (1.38‰ ? δ⁶⁵Cu ? 1.69‰). The average isotopic fractionation (Δ_aq-min = δ⁶⁵Cu_aq − δ⁶⁵Cu_min, where the latter is measured on mineral samples from the field system), equals 1.43 ± 0.14‰ and 1.60 ± 0.14‰ for chalcopyrite and enargite, respectively. To interpret this field survey, we leached chalcopyrite and enargite in batch experiments and found that, as in the field, the leachate is enriched in ⁶⁵Cu relative to chalcopyrite (1.37 ± 0.14‰) and enargite (0.98 ± 0.14‰) when microorganisms are absent. Leaching of minerals in the presence of Acidithiobacillus ferrooxidans results in smaller average fractionation in the opposite direction for chalcopyrite (Δ_aq-min^o=-0.57±0.14‰, where min^o refers to the starting mineral) and no apparent fractionation for enargite (Δ_aq-min^o=0.14±0.14‰). Abiotic fractionation is attributed to preferential oxidation of ⁶⁵Cu⁺ at the interface of the isotopically homogeneous mineral and the surface oxidized layer, followed by solubilization. When microorganisms are present, the abiotic fractionation is most likely not seen due to preferential association of ⁶⁵Cu_aq with A. ferrooxidans cells and related precipitates. In the biotic experiments, Cu was observed under TEM to occur in precipitates around bacteria and in intracellular polyphosphate granules. Thus, the values of δ⁶⁵Cu in the field and laboratory systems are presumably determined by the balance of Cu released abiotically and Cu that interacts with cells and related precipitates. Such isotopic signatures resulting from Cu sulfide dissolution should be useful for acid mine drainage remediation and ore prospecting purposes.     

Abundance of mass 47 CO2 in urban air, car exhaust, and human breath

Atmospheric carbon dioxide is widely studied using records of CO₂ mixing ratio, δ¹³C and δ¹⁸O. However, the number and variability of sources and sinks prevents these alone from uniquely defining the budget. Carbon dioxide having a mass of 47 u (principally ¹³C¹⁸O¹⁶O) provides an additional constraint. In particular, the mass 47 anomaly (Δ₄₇) can distinguish between CO₂ produced by high temperature combustion processes vs. low temperature respiratory processes. Δ₄₇ is defined as the abundance of mass 47 isotopologues in excess of that expected for a random distribution of isotopes, where random distribution means that the abundance of an isotopologue is the product of abundances of the isotopes it is composed of and is calculated based on the measured ¹³C and ¹⁸O values. In this study, we estimate the δ¹³C (vs. VPDB), δ¹⁸O (vs. VSMOW), δ47, and Δ₄₇ values of CO₂ from car exhaust and from human breath, by constructing ‘Keeling plots’ using samples that are mixtures of ambient air and CO₂ from these sources. δ47 is defined as , where is the R⁴⁷ value for a hypothetical CO₂ whose δ¹³C_VPDB = 0, δ¹⁸O_VSMOW = 0, and Δ₄₇ = 0. Ambient air in Pasadena, CA, where this study was conducted, varied in [CO₂] from 383 to 404 μmol mol⁻¹, in δ¹³C and δ¹⁸O from −9.2 to −10.2‰ and from 40.6 to 41.9‰, respectively, in δ47 from 32.5 to 33.9‰, and in Δ₄₇ from 0.73 to 0.96‰. Air sampled at varying distances from a car exhaust pipe was enriched in a combustion source having a composition, as determined by a ‘Keeling plot’ intercept, of −24.4 ± 0.2‰ for δ¹³C (similar to the δ¹³C of local gasoline), δ¹⁸O of 29.9 ± 0.4‰, δ47 of 6.6 ± 0.6‰, and Δ₄₇ of 0.41 ± 0.03‰. Both δ¹⁸O and Δ₄₇ values of the car exhaust end-member are consistent with that expected for thermodynamic equilibrium at∼200 °C between CO₂ and water generated by combustion of gasoline-air mixtures. Samples of CO₂ from human breath were found to have δ¹³C and δ¹⁸O values broadly similar to those of car exhaust-air mixtures, −22.3 ± 0.2 and 34.3 ± 0.3‰, respectively, and δ47 of 13.4 ± 0.4‰. Δ₄₇ in human breath was 0.76  ± 0.03‰, similar to that of ambient Pasadena air and higher than that of the car exhaust signature.     

Controls on the D/H ratios of plant leaf waxes in an arid ecosystem

The extent to which leaf water D-enrichment (transpiration) and soil water D-enrichment (evaporation) affect the D/H ratio of plant leaf waxes remains a contentious issue, with important implications for paleohydrologic reconstructions. In this study we measure δD values of precipitation (δD_p), groundwater (δD_gw), plant xylem water (δD_xw) and leaf water (δD_lw) to understand their impact on the δD values of plant leaf wax n-alkanes (δD_wax) in an arid ecosystem. Our survey includes multiple species at four sites across an aridity gradient (80-30% relative humidity) in southern California.We find that many species take up groundwater or precipitation without significant fractionation. D-enriched soil water is a minor source even in species known to perform and utilize waters from hydraulic lift, such as Larrea tridentata (+10‰). Measurements of leaf water isotopic composition demonstrate that transpiration is an important mechanism for D-enrichment of leaf waters (+74 ± 20‰, 1σ), resulting in the smallest net fractionation yet reported between source water and leaf waxes (L. tridentata −41‰; multi-species mean value is −94 ± 21‰, 1σ). We find little change in leaf water D-enrichment or net fractionation across the climatic gradient sampled by our study, suggesting that a net fractionation of ca. −90‰ may be appropriate for paleohydrologic reconstructions in semi-arid to arid environments. Large interspecies offsets in net fractionations (1σ = 21‰) are potentially troublesome, given the observed floristic diversity and the likelihood of species assemblage changes with climate shifts.     

Quadruple sulfur isotope analysis of ca. 3.5 Ga Dresser Formation: New evidence for microbial sulfate reduction in the early Archean

Multiple sulfur isotope system is a powerful new tracer for atmospheric, volcanic, and biological influences on sulfur cycles in the anoxic early Earth. Here, we report high-precision quadruple sulfur isotope analyses (³²S/³³S/³⁴S/³⁶S) of barite, pyrite in barite, and sulfides in related hydrothermal and igneous rocks occurring in the ca. 3.5 Ga Dresser Formation, Western Australia. Our results indicate that observed isotopic variations are mainly controlled by mixing of mass-dependently (MD) and non-mass-dependently fractionated (non-MD) sulfur reservoirs. Based on the quadruple sulfur isotope systematics (δ³⁴S-Δ³³S-Δ³⁶S) for these minerals, four end-member sulfur reservoirs have been recognized: (1) non-MD sulfate (δ³⁴S = −5 ± 2‰; Δ³³S = −3 ± 1‰); (2) MD sulfate (δ³⁴S = +10 ± 3‰); (3) non-MD sulfur (δ³⁴S > +6‰; Δ³³S > +4‰); and (4) igneous MD sulfur (δ³⁴S = Δ³³S = 0‰). The first and third components show a clear non-MD signatures, thus probably represent sulfate and sulfur aerosol inputs. The MD sulfate component (2) is enriched in ³⁴S (+10 ± 3‰) and may have originated from microbial and/or abiotic disproportionation of volcanic S or SO₂. Our results reconfirm that the Dresser barites contain small amounts of pyrite depleted in ³⁴S by 15-22‰ relative to the host barite. These barite-pyrite pairs exhibit a mass-dependent relationship of δ³³S/δ³⁴S with slope less than 0.512, which is consistent with that expected for microbial sulfate reduction and is significantly different from that of equilibrium fractionation (0.515). The barite-pyrite pairs also show up to 1‰ difference in Δ³⁶S values and steep Δ³⁶S/Δ³³S slopes, which deviate from the main Archean array (Δ³⁶S/Δ³³S = −0.9) and are comparable to isotope effects exhibited by sulfate reducing microbes (Δ³⁶S/Δ³³S = −5 to −11). These new lines of evidence support the existence of sulfate reducers at ca. 3.5 Ga, whereas microbial sulfur disproportionation may have been more limited than recently suggested.