Calculation of oxygen isotope fractionation in hydroxyl-bearing silicates

The modified increment method has been applied to the calculation of oxygen isotope fractionation factors for hydroxyl-bearing silicate minerals. The order of ¹⁸O enrichment obtained in common rock-forming minerals is: pyrophyllite > kaolinite > tourmaline talc > prehnite topaz > illite > phengite > lepidolite muscovite staurolite > epidote > glaucophane > serpentine chlorite > tremolite > hornblende > phlogopite biotite > humite > norbergite > ilvaite. Hydroxyl-bearing silicates are enriched in ¹⁸O relative to hydroxyl groups but depleted in ¹⁸O relative to anhydrous counterparts.

Three sets of self-consistent fractionation factors: between quartz and the hydroxyl-bearing silicate minerals, between calcite and the silicate minerals, and between the silicate minerals and water, have been calculated for a temperature range of 0–1200°C. The fractionation factors calculated for mineral pairs are applicable to isotopic geothermometry in igneous, metamorphic and sedimentary petrology. They can be used as a test of isotopic equilibrium or disequilibrium in natural mineral assemblages over all temperature ranges of geological interest. The difference in oxygen isotope composition between the hydroxyl-bearing mineral and the OH group is quantitatively demonstrated to be temperature dependent and, therefore, can be used as a single-mineral geothermometer.     

Oxygen isotope fractionation in dissolved oxygen in the deep sea

¹⁸O variations in dissolved oxygen have been measured at five stations from the eastern equatorial Pacific, at the GEOSECS-I and -II intercalibration stations in the North Pacific and North Atlantic, and along an Antarctic-South Pacific section from MONSOON expedition. Relative to atmospheric oxygen, dissolved oxygen in the ocean is enriched in¹⁸O up to a maximum of 14‰, the extreme enrichments occurring in the oxygen-minimum region of the eastern Pacific. The vertical diffusion-advection model has been used to determine the isotopic fractionation of deep-water in-situ oxygen consumption ascribed to bacterial metabolism. The single-stage enrichment, ε, in Pacific Deep Water below 1 km is 10‰ (α = 0.99,¹⁶O consumed preferentially). The model calculations show that the isotopic data cannot be fit without the introduction of a fractionation factor, just as the dissolved oxygen data cannot be fit without an in-situ consumption parameter. The consistency of the positive sign for ε and the negative source term for O₂, observed in all deep Pacific profiles analyzed to date, provide strong evidence that vertical transport and in-situ consumption terms dominate the horizontal tracer flux terms, and indicate the presence of a significant “deep metabolism” in abyssal ocean waters.     

Iron isotope fractionation during planetary differentiation

The Fe isotope composition of samples from the Moon, Mars (SNC meteorites), HED parent body (eucrites), pallasites (metal and silicate) and the Earth's mantle were measured using high mass resolution MC-ICP-MS. These high precision measurements (δ⁵⁶Fe ≈ ± 0.04‰, 2 S.D.) place tight constraints on Fe isotope fractionation during planetary differentiation.Fractionation during planetary core formation is confined to < 0.1‰ for δ⁵⁶Fe by the indistinguishable Fe isotope composition of pallasite bulk metal (including sulfides and phosphides) and olivine separates. However, large isotopic variations (≈ 0.5‰) were observed among pallasite metal separates, varying systematically with the amounts of troilite, schreibersite, kamacite and taenite. Troilite generally has the lightest (δ⁵⁶Fe ≈ − 0.25‰) and schreibersite the heaviest (δ⁵⁶Fe ≈ + 0.2‰) Fe isotope composition. Taenite is heavier then kamacite. Therefore, these variations probably reflect Fe isotope fractionation during the late stage evolution and differentiation of the S- and P-rich metal melts, and during low-temperature kamacite exsolution, rather than fractionation during silicate-metal separation.Differentiation of the silicate portion of planets also seems to fractionate Fe isotopes. Notably, magmatic rocks (partial melts) are systematically isotopically heavier than their mantle protoliths. This is indicated by the mean of 11 terrestrial peridotite samples from different tectonic settings (δ⁵⁶Fe = + 0.015 ± 0.018‰), which is significantly lighter than the mean of terrestrial basalts (δ⁵⁶Fe = + 0.076 ± 0.029‰). We consider the peridotite mean to be the best estimate for the Fe isotope composition of the bulk silicate Earth, and probably also of bulk Earth. The terrestrial basaltic mean is in good agreement with the mean of the lunar samples (δ⁵⁶Fe = + 0.073 ± 0.019‰), excluding the high-Ti basalts. The high-Ti basalts display the heaviest Fe isotope composition of all rocks measured here (δ⁵⁶Fe ≈ + 0.2‰). This is interpreted as a fingerprint of the lunar magma ocean, which produced a very heterogeneous mantle, including the ilmenite-rich source regions of these basalts.Within uncertainties, samples from Mars (SNC meteorites), HED (eucrites) and the pallasites (average olivine + metal) have the same Fe isotope compositions as the Earth's mantle. This indicates that the solar system is very homogeneous in Fe isotopes. Its average δ⁵⁶Fe is very close to that of the IRMM-014 standard.     

Oxygen isotope fractionation in mantle minerals

The increment method is adopted to calculate oxygen isotope fractionation factors for mantle minerals, particularly for the polymorphic phases of MgSiO₃ and Mg₂SiO₄. The results predict the following sequence of¹⁸O-enrichment:pyroxene (Mg, Fe, Ca)₂Si₂O₆>olivine (Mg, Fe)₂SiO₄ > spinel (Mg, Fe)₂SiO₄> ilmenite (Mg, Fe, Ca) SiO₃>perovskite (Mg, Fe, Ca) SiO₃. The calculated fractionations for the calcite-perovskite (CaTiO₃) System are in excellent agreement with the experimental calibrations. If there would be complete isotopic equilibration in the mantle, the spinel-structured silicates in the transition zone are predicted to be enriched in¹⁸O relative to the perovskite-structured silicates in the lower mantle but depleted in¹⁸O relative to olivines and pyroxenes in the upper mantle. The oxygen isotope layering of the mantle might result from differences in the chemical composition and crystal structure of mineral phases at different mantle depths. Assuming isotopic equilibrium on a whole earth scale, the chemical structure of the Earth’s interior can be described by the following sequence of¹⁸O-enrichment:upper crust>lower crust>upper mantle>transition zone>lower mantle>core. Project supported by the National Natural Science Foundation of China and the Chinese Academy of Sciences.     

Lithium isotope fractionation in the southern Cascadia subduction zone

We present lithium (Li) abundances and isotope compositions for a suite of anhydrous olivine tholeiites (HAOTs) and hydrous basalt-andesitic (BA) lavas from the Mt. Shasta and Medicine Lake regions, California. The values of δ⁷Li vary from + 0.9‰ to + 6.4‰ and correlate inversely with distance from the trench. These data are consistent with continuous isotope fractionation of Li during dehydration of the subducted oceanic lithosphere, an interpretation corroborated by uniformly high pre-eruptive H₂O contents in basaltic andesites accompanied by high Li, Rb, Sr, Ba and Pb abundances. The subduction-derived component that was added to these hydrous magmas is shown to be very similar beneath both Mt. Shasta and Medicine Lake volcanoes despite characteristically distinct Li isotope compositions in the magmas themselves. More evolved andesites and dacites from Mt. Shasta have δ⁷Li from + 2.8 to + 6.9‰ which is identical with the range obtained for HAOTs and BA lavas from Mt. Shasta. Therefore, Li isotopes do not provide evidence for any other crustal component admixed to Mt. Shasta andesites or dacites during magmatic differentiation and magma mixing in the crust.     

Gas hydrates (clathrates) causing pore-water freshening and oxygen isotope fractionation in deep-water sedimentary sections of terrigenous continental margins

The occurrence of gas hydrates in deep-water sections of the continental margins predicted from anomalous acoustic reflectors on seismic profiles has been confirmed by recent deep-sea drilling results. On the Pacific continental slope off Guatemala gas hydrates were brought up for the first time from two holes (497, 498A) drilled during Leg 67 of the DSDP in water depths of 2360 and 5500 m, respectively. The hydrates occur in organic matter-rich Pleistocene to Miocene terrigenous sediments. In the hydrate-bearing zone a marked decrease in interstitial water chlorinities was observed starting at about 10–20 m subbottom depth. Pore waters at the bottom of the holes (near 400 m subbottom) have as little as half the chlorinity of seawater (i.e. 9‰). Similar, but less pronounced, trends were observed during previous legs of the DSDP in other hydrate-prone segments of the continental margins where recharge of fresh water from the continent can be excluded (e.g. Leg 11). The crystallization of hydrates, like ice, excludes salt ions from the crystal structure. During burial the dissolved salts are separated from the solids. Subsidence results in a downward motion of the solids (including hydrates) relative to the pore fluids. Thawing of hydrates during recovery releases fresh water which is remixed with the pore fluid not involved in hydrate formation. The volume of the latter decreases downhole thus causing downward decreasing salinity (chlorinity). Hydrate formation is responsible for oxygen isotope fractionation with¹⁸O-enrichment in the hydrate explaining increasingly more positive δ¹⁸O values in the pore fluids recovered (after hydrate dissociation) with depth.     

Oxygen isotope fractionation in decarbonation metamorphism: the Mottled Zone event

Calculated univariant equilibria and oxygen isotope compositions of silicates and carbonates support the proposal that the “Mottled Zone Event” is a low-pressure (1–25 atm), high-temperature (200° < T < 1300°C) metamorphism of calcareous siliceous sediments in which the thermal energy is provided by combustion of organic matter. δ¹⁸O of silicates decreases systematically with increasing metamorphic grade from averages of 18.1‰ in protolith shales, to 16.6‰ in grossular-diopside-zeolite rocks, 15.6‰ in wollastonite and anorthite-diopside-gehlenite-grossular fels, 14.1‰ in spurrite-brownmillerite marbles and 11.7‰ in the highest-grade larnite-gehlenite-brownmillerite assemblages. Decarbonation is the principal mechanism influencing the oxygen isotope compositions. The progressive decrease of δ¹⁸O in silicates can be modelled as a Rayleigh distillation of CO₂ approximately 16‰ enriched in ¹⁸O relative to whole rock assemblages i.e., of initial isotopic composition 8.5‰ heavier than the parent carbonates. The mineral assemblage of one sample with an unusual granoblastic texture is in apparent isotopic equilibrium at a temperature of 540°C.     

Carbon isotope fractionation during CH4 transport in paddy fields

In this study,to further promote the application of the stable carbon isotope natural abundance(SCINA)method to the study of CH4in paddy fields in China,field experiments were carried out to investigate carbon isotope fractionation during CH4transport in both rice-and non-rice-growing seasons.More importantly,two new methods for the measurement of the CH4transport fractionation factor(εtransport)in paddy fields were introduced.The results indicated that the closed chamber+syringe method was much better for the determination ofεtransport during the non-rice-growing season.Presently,εtransport was calculated using theδ13C value of the CH4emitted from a rice field minus that of the CH4in the floodwater(–6.7‰to–3.0‰).In addition,there were three methods available for estimatingεtransport during the rice-growing season:deduction of theδ13C value of the CH4in the floodwater from that of the CH4emitted from the field(–16.6‰to–15.2‰);deduction of theδ13C value of the CH4in the soil pore water from that of the CH4emitted from the field(–13.2‰to–1.1‰);and deduction of theδ13C value of the CH4in the aerenchyma of plants from that of the CH4emitted from plants(–16.3‰to–10.9‰).Unfortunately,the first two methods showed relatively large uncertainties.Only the last one,the dividing+cutting method,was not only scientific and reliable but also provided accurate measurements.     

Distribution and fractionation mechanism of stable carbon isotope of coalbed methane

The stable carbon isotope values of coalbed methane range widely, and also are gener- ally lighter than that of gases in normal coal-formed gas fields with similar coal rank. There exists strong carbon isotope fractionation in coalbed methane and it makes the carbon isotope value lighter. The correlation between the carbon isotope value and Ro in coalbed methane is less obvious. The coaly source rock maturity cannot be judged by coalbed methane carbon isotope value. The carbon isotopes of coalbed methane become lighter in much different degree due to the hydrodynamics. The stronger the hydrodynamics is, the lighter the CBM carbon isotopic value becomes. Many previous investigations indicated that the desorption-diffusion effects make the carbon isotope value of coalbed methane lighter. However, the explanation has encountered many problems. The authors of this arti- cle suggest that the flowing groundwater dissolution to free methane in coal seams and the free methane exchange with absorbed one is the carbon isotope fractionation mechanism in coalbed methane. The flowing groundwater in coal can easily take more 13CH4 away from free gas and com- paratively leave more 12CH4. This will make 12CH4 density in free gas comparatively higher than that in absorbed gas. The remaining 12CH4 in free gas then exchanges with the adsorbed methane in coal matrix. Some absorbed 13CH4 can be replaced and become free gas. Some free 12CH4 can be ab- sorbed again into coal matrix and become absorbed gas. Part of the newly replaced 13CH4 in free gas will also be taken away by water, leaving preferentially more 12CH4. The remaining 12CH4 in free gas will exchange again with adsorbed methane in the coal matrix. These processes occur all the time. Through accumulative effect, the 12CH4 will be greatly concentrated in coal. Thus, the stable carbon isotope of coalbed methane becomes dramatically lighter. Through simulation experiment on wa- ter-dissolved methane, it had been proved that the flowing water could fractionate the carbon isotope of methane, and easily take heavy carbon isotope away through dissolution.     

Equilibrium and kinetic Si isotope fractionation factors and their implications for Si isotope distributions in the Earth's surface environments

Several important equilibrium Si isotope fractionation factors among minerals,organic molecules and the H_4SiO_4 solution are complemented to facilitate the explanation of the distributions of Si isotopes in Earth's surface environments.The results reveal that,in comparison to aqueous H_4SiO_4,heavy Si isotopes will be significantly enriched in secondary silicate minerals.On the contrary,quadra-coordinated organosilicon complexes are enriched in light silicon isotope relative to the solution.The extent of ~(28)Si-enrichment in hyper-coordinated organosilicon complexes was found to be the largest.In addition,the large kinetic isotope effect associated with the polymerization of monosilicic acid and dimer was calculated,and the results support the previous statement that highly ~(28)Sienrichment in the formation of amorphous quartz precursor contributes to the discrepancy between theoretical calculations and field observations.With the equilibrium Si isotope fractionation factors provided here,Si isotope distributions in many of Earth's surface systems can be explained.For example,the change of bulk soil δ~(30)Si can be predicted as a concave pattern with respect to the weathering degree,with the minimum value where allophane completely dissolves and the total amount of sesquioxides and poorly crystalline minerals reaches their maximum.When,under equilibrium conditions,the well-crystallized clays start to precipitate from the pore solutions,the bulk soil δ~(30)Si will increase again and reach a constant value.Similarly,the precipitation of crystalline smectite and the dissolution of poorly crystalline kaolinite may explain the δ~(30)Si variations in the ground water profile.The equilibrium Si isotope fractionations among the quadracoordinated organosilicon complexes and the H_4SiO_4solution may also shed light on the Si isotope distributions in the Si-accumulating plants.     

Oxygen isotope fractionation between quartz and K-feldspar at 600°C

Quartz and K-feldspar were grown and/or equilibrated in a common fluid at 600°C, and were analyzed mass-spectrometrically as pairs. Various errors that could affect quartz-feldspar oxygen isotope temperature calibrations that are derived from quartz-solution and feldspar-solution data of different studies, are thereby avoided. Using a range of starting materials, we obtained10³ lnα(quartz-K-feldspar) = 1.8 ± 0.15, a value in reasonable agreement with geological data.     

Temperature dependence of the oxygen isotopic fractionation between diatom silica and water

We present a new paleotemperature scale, based on the oxygen isotopic ratio of the non-exchangeable fraction of the oxygen from diatom silica. The equation t = 17.2 − 2.4 (δ¹⁸O_silica − δ¹⁸O_water − 40) − 0.2 (δ¹⁸O_silica − δ¹⁸O_water − 40)² was derived using recent sediment samples from different oceanic areas, the temperature and isotopic composition of the local surface water. Comparison of our results with other relationships established for quartz-water or amorphous silica-water at higher temperature suggests no difference in isotopic fractionation between quartz-water and biogenic silica-water couples.     

Space weathering processes on airless bodies: Fe isotope fractionation in the lunar regolith

Nanophase Fe metal grains (np-Fe°) are a product of space weathering, formed by processes related to meteorite impacts, and solar-wind sputtering on airless planetary bodies, such as the Moon. Iron isotopes of lunar soils are fractionated during these processes, and the np-Fe° in the finest (<10 μm), mature, size fractions of the soil become enriched in heavier isotopes by ∼0.3‰ in ⁵⁶Fe/⁵⁴Fe in comparison to the bulk rocks (0.03±0.05‰), from which the soil was formed. A positive correlation of δ⁵⁶Fe values with the soil maturity index, I_S/FeO, suggests that the high δ⁵⁶Fe values reflect production of nanophase Fe metal that is produced by space weathering that occurs on airless planetary bodies. Furthermore, the enrichment of δ⁵⁶Fe in the smallest size fraction of lunar soils supports a model for creation of np-Fe° through vapor deposition induced by micrometeorites, as well as that by solar-wind sputtering.     

Stable isotope fractionation of fatty acids of Daphnia fed laboratory cultures of microalgae

We tested a comparatively new method of tracing of natural food webs, compound-specific isotope analysis (CSIA) of fatty acids (FA), using laboratory culture of Daphnia galeata fed Chlorella vulgaris and Cryptomonas sp. In general, Daphnia had significantly lighter carbon stable isotope composition of most fatty acids, including essential, than those of their food, microalgae. Thus, our results did not support the pivotal premise of the FA-CSIA application for food web analysis, i.e., transmitting the isotope ‘signal’ of essential FAs to consumers from their food without any modification. Moreover, the values of isotope fractionation of particular FAs in the consumer relative to its food were not constant, but varied from 1.35‰ to 7.04‰. The different isotope fractionation (depletion) values of diverse FAs in consumer were probably caused by different processes of their synthesis, catabolism and assimilation. More work is evidently to be done for correct interpretation of results of FA-CSIA during field studies for tracing of natural food webs.     

Triple oxygen isotope constraints on the origin of ocean island basalts

Understanding the origin of ocean island basalts(OIB) has important bearings on Earth's deep mantle.Although it is widely accepted that subducted oceanic crust, as a consequence of plate tectonics, contributes material to OIB's formation, its exact fraction in OIB's mantle source remains ambiguous largely due to uncertainties associated with existing geochemical proxies. Here we show, through theoretical calculation, that unlike many known proxies, triple oxygen isotope compositions(i.e.D^(17 )O) in olivine samples are not affected by crystallization and partial melting. This unique feature, therefore, allows olivine D^(17 )O values to identify subducted oceanic crusts in OIB's mantle source. Furthermore, the fractions of subducted ocean sediments and hydrothermally altered oceanic crust in OIB's mantle source can be quantified using their characteristic D^(17 )O values. Based on published D^(17 )O data, we estimated the fraction of subducted oceanic crust to be as high as 22.3% in certain OIB, but the affected region in the respective mantle plume is likely to be limited.     

Calculation on sulphur isotope fractionation between sphalerite and galena using lattice dynamics

Increasing use is being made of sulphide minerals in isotope geothermometry. Sulphur isotope fractionation factors for³⁴S exchange between sphalerite (ZnS) and galena (PbS) have been calculated for various temperatures between 0 and 1000°C. The reduced partition function ratios have been calculated using a “shell” model for the forces derived from inelastic neutron scattering studies of the lattice dynamics of sphalerite and galena. A new formalism of the current theory has been developed which enables the accuracy of the calculation to be determined.The Zn³⁴S—Pb³⁴S equilibrium constant obtained by the shell model calculations is 1.0060 to 100°C, 1.0031 at 250°C and 1.0005 at 1000°C, in agreement with experimental determinations.     

Vital effects of K isotope fractionation in organisms: observations and a hypothesis

Compared with the measureable but limited K isotope variation in geological samples,biological samples have much larger variations in δ~(41)K values:from-1.3‰ to+1.1‰ relative to the international K standard NIST SRM 3141a.Notably,higher plants generally have δ~(41)K values that are lower than igneous rocks,whereas sea plants(algae)have δ~(41)K values that are higher than seawater;the range in δ~(41)K values of plants encompasses the δ~(41)K values of both igneous rocks and seawater.Plant cells utilize different K uptake mechanisms in response to highand low-K conditions.In a low-K environment,plant cells use energy-consuming ion pumps for active uptake of K;plant cells in high-K environments use non-energy-consuming ion channels.Based on these facts and on K isotope data from sea and land plants,it is hypothesized that the different K uptake mechanisms are accompanied by distinct K isotope fractionation behaviors or vital effects.The enrichment of light K isotopes in terrestrial plants could be attributed to preferential transport of isotopically light K in the energy-consuming active uptake process by K ion pumps in the membranes of plant root cells.On the other hand,the enrichment of heavy K isotopes in algae may be caused by a combination of the lack of K isotope fractionation during K uptake from seawater via ion channels and the preferential efflux of light K isotopes across the cell membrane back to the seawater.The large variation of K isotope compositions in biological samples therefore may reflect the diversity of isotopic vital effects for K in organisms,which implies the great potential of K isotopes in biogeochemical studies.