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Re-Os isotopic evidence for long-lived heterogeneity and equilibration processes in the Earth's upper mantle.

The geochemical composition of the Earth's upper mantle is thought to reflect 4.5 billion years of melt extraction, as well as the recycling of crustal materials. The fractionation of rhenium and osmium during partial melting in the upper mantle makes the Re-Os isotopic system well suited for tracing the extraction of melt and recycling of the resulting mid-ocean-ridge basalt. Here we report osmium isotope compositions of more than 700 osmium-rich platinum-group element alloys derived from the upper mantle. The osmium isotopic data form a wide, essentially gaussian distribution, demonstrating that, with respect to Re-Os isotope systematics, the upper mantle is extremely heterogeneous. As depleted and enriched domains can apparently remain unequilibrated on a timescale of billions of years, effective equilibration seems to require high degrees of partial melting, such as occur under mid-ocean ridges or in back-arc settings, where percolating melts enhance the mobility of both osmium and rhenium. We infer that the gaussian shape of the osmium isotope distribution is the signature of a random mixing process between depleted and enriched domains, resulting from a 'plum pudding' distribution in the upper mantle, rather than from individual melt depletion events.

Journal Article↗

Contrasting origins of the upper mantle revealed by hafnium and lead isotopes from the Southeast Indian Ridge.

The origin of the isotopic signature of Indian mid-ocean ridge basalts has remained enigmatic, because the geochemical composition of these basalts is consistent either with pollution from recycled, ancient altered oceanic crust and sediments, or with ancient continental crust or lithosphere. The radiogenic isotopic signature may therefore be the result of contamination of the upper mantle by plumes containing recycled altered ancient oceanic crust and sediments, detachment and dispersal of continental material into the shallow mantle during rifting and breakup of Gondwana, or contamination of the upper mantle by ancient subduction processes. The identification of a process operating on a scale large enough to affect major portions of the Indian mid-ocean ridge basalt source region has been a long-standing problem. Here we present hafnium and lead isotope data from across the Indian-Pacific mantle boundary at the Australian-Antarctic discordance region of the Southeast Indian Ridge, which demonstrate that the Pacific and Indian upper mantle basalt source domains were each affected by different mechanisms. We infer that the Indian upper-mantle isotope signature in this region is affected mainly by lower continental crust entrained during Gondwana rifting, whereas the isotope signature of the Pacific upper mantle is influenced predominantly by ocean floor subduction-related processes.

Journal Article↗

CO self-shielding as the origin of oxygen isotope anomalies in the early solar nebula.

The abundances of oxygen isotopes in the most refractory mineral phases (calcium-aluminium-rich inclusions, CAIs) in meteorites have hitherto defied explanation. Most processes fractionate isotopes by nuclear mass; that is, 18O is twice as fractionated as 17O, relative to 16O. In CAIs 17O and 18O are nearly equally fractionated, implying a fundamentally different mechanism. The CAI data were originally interpreted as evidence for supernova input of pure 16O into the solar nebula, but the lack of a similar isotope trend in other elements argues against this explanation. A symmetry-dependent fractionation mechanism may have occurred in the inner solar nebula, but experimental evidence is lacking. Isotope-selective photodissociation of CO in the innermost solar nebula might explain the CAI data, but the high temperatures in this region would have rapidly erased the signature. Here we report time-dependent calculations of CO photodissociation in the cooler surface region of a turbulent nebula. If the surface were irradiated by a far-ultraviolet flux approximately 10(3) times that of the local interstellar medium (for example, owing to an O or B star within approximately 1 pc of the protosun), then substantial fractionation of the oxygen isotopes was possible on a timescale of approximately 10(5) years. We predict that similarly irradiated protoplanetary disks will have H2O enriched in 17O and 18O by several tens of per cent relative to CO.

Journal Article↗

Thallium isotopic evidence for ferromanganese sediments in the mantle source of Hawaiian basalts.

Ocean island basalts are generally thought to be the surface expression of mantle plumes, but the nature of the components in the source regions of such mantle plumes is a subject of long-standing debate. The lavas erupted at Hawaii have attracted particular attention, as it has been proposed that coupled 186Os and 187Os anomalies reflect interaction with the Earth's metallic core. It has recently been suggested, however, that such variations could also result from addition of oceanic ferromanganese sediments to the mantle source of these lavas. Here we show that Hawaiian picrites with osmium isotope anomalies also exhibit pronounced thallium isotope variations, which are coupled with caesium/thallium ratios that extend to values much lower than commonly observed for mantle-derived rocks. This correlation cannot be created by admixing of core material, and is best explained by the addition of ferromanganese sediments into the Hawaii mantle source region. However, the lack of correlation between thallium and osmium isotopes and the high thallium/osmium ratios of ferromanganese sediments preclude a sedimentary origin for the osmium isotope anomalies, and leaves core-mantle interaction as a viable explanation for the osmium isotope variations of the Hawaiian picrites.

Journal Article↗

Large primary kinetic isotope effects in the abstraction of hydrogen from organic compounds by a fluorinated radical in water.

Isotope effects have been measured for the abstraction of hydrogen from a series of organic substrates by the perfluoro radical, Na+ -O3SCF2CF2OCF2CF2*, in water. Both primary and secondary deuterium isotope effects were measured, with the primary isotope effects ranging in value from 4.5 for isopropanol to 19.6 for acetic acid. The values for the alpha- and beta-secondary deuterium isotope effects were 1.06 and 1.035, respectively. It was concluded that tunneling contributes significantly to the production of the observed, large primary kinetic isotope effects in these C-H abstraction reactions.

Journal Article↗

[Age-dependency of isotope drainage in diuretic renograms].

OBJECTIVE: The aim of the study was to establish normal values of the isotope drainage in diuretic scintigrams for children of different age-groups. Isotope drainage was determined 30 minutes after the application of technetium- (99m)MAG 3 as well as 15 minutes after the following application of furosemide. METHODS: We analysed the data from 274 investigations in sonographically normal renal units (RU) contralateral to kidneys with ureteropelvic junction obstruction or non-refluxing primary megaureters. RESULTS: There was a significant age-dependency of isotope drainage during the first weeks of life. In 79 RU the results of the first diuretic renogramm were compared with the follow-up examinations. The reliability of the measurements was lowest in children initially investigated during the first six weeks of life. If both the investigations were performed thereafter, no significant difference was found between the results. CONCLUSIONS: The isotope drainage of the sonographically normal contralateral RU seems to be a sufficient marker for the meaningfulness of the diuretic renogram. In urinary tract dilatation, mistakes regarding the interpretation of isotope drainage may be minimized by taking the measurements in the normal contralateral RU in account and by comparing them with age-referred normal values.

Child↗

Quantum-instanton evaluation of the kinetic isotope effects.

A general quantum-mechanical method for computing kinetic isotope effects is presented. The method is based on the quantum-instanton approximation for the rate constant and on the path-integral Metropolis-Monte Carlo evaluation of the Boltzmann operator matrix elements. It computes the kinetic isotope effect directly, using a thermodynamic integration with respect to the mass of the isotope, thus avoiding the more computationally expensive process of computing the individual rate constants. The method should be more accurate than variational transition-state theories or the semiclassical instanton method since it does not assume a single tunneling path and does not use a semiclassical approximation of the Boltzmann operator. While the general Monte Carlo implementation makes the method accessible to systems with a large number of atoms, we present numerical results for the Eckart barrier and for the collinear and full three-dimensional isotope variants of the hydrogen exchange reaction H + H2 --> H2 + H. In all seven test cases, for temperatures between 250 and 600 K, the error of the quantum instanton approximation for the kinetic isotope effects is less than approximately 10%.

Journal Article↗

On the theory of the CO+OH reaction, including H and C kinetic isotope effects.

The effect of pressure, temperature, HD isotopes, and C isotopes on the kinetics of the OH+CO reaction are investigated using Rice-Ramsperger-Kassel-Marcus theory. Pressure effects are treated with a step-ladder plus steady-state model and tunneling effects are included. New features include a treatment of the C isotope effect and a proposed nonstatistical effect in the reaction. The latter was prompted by existing kinetic results and molecular-beam data of Simons and co-workers on incomplete intramolecular energy transfer to the highest vibrational frequency mode in HOCO(*). In treating the many kinetic properties two small customary vertical adjustments of the barriers of the two transition states were made. The resulting calculations show reasonable agreement with the experimental data on (1) the pressure and temperature dependence of the HD effect, (2) the pressure-dependent (12)C(13)C isotope effect, (3) the strong non-Arrhenius behavior observed at low temperatures, (4) the high-temperature data, and (5) the pressure dependence of rate constants in various bath gases. The kinetic carbon isotopic effect is usually less than 10 per mil. A striking consequence of the nonstatistical assumption is the removal of a major discrepancy in a plot of the k(OH+CO)k(OD+CO) ratio versus pressure. A prediction is made for the temperature dependence of the OD+CO reaction in the low-pressure limit at low temperatures.

Journal Article↗

A theoretical study of the chiroptical properties of molecules with isotopically engendered chirality.

There has been a considerable interest in the chiroptical properties of molecules whose chirality is exclusively due to an isotopic substitution and numerous examples for the electronic circular dichroism (CD) spectra of isotopically chiral systems have been reported in literature. Four different explanations have been proposed for the mechanism as to how the isotopic substitution induces a chiral perturbation of the otherwise achiral electronic wave function; however, up to now no conclusive answer has been given about the dominating effect responsible for the experimental observations. In this study we will present, for the first time, fully quantum-mechanical calculations of the CD spectra of three different molecular systems with isotopically engendered chirality. As examples, we consider the spectra of organic molecules with ketone and alpha-diketone carbonyl and diene chromophores. The effect of vibronic couplings for the reorientation of the electric and magnetic transition dipole moments is taken into account within the Herzberg-Teller approximation. The ground and excited state geometries and vibrational normal modes are obtained with (time-dependent) density functional theory [(TD)DFT], while the vibronic coupling effects are calculated at the TDDFT and density functional theory/multireference configuration interaction (DFT/MRCI) levels of theory. Generally, the band shapes of the experimental CD spectra are reproduced very well, and also the absolute CD intensities from the simulations are of the right order of magnitude. The sign and the intensity of the CD band are determined by a delicate balance of the contributions of a large number of individual vibronic transitions, and it is found that the vibrational normal modes with a large displacement are dominant. The separation of the calculated CD spectrum into the different contributions due to the overlap of the in-plane and out-of-plane components (regarding the symmetry plane of the unsubstituted molecule) of the electric and magnetic transition dipole moments yields information about the influence of the vibronic coupling effects for the reorientation of the corresponding transition dipole moments. In conclusion, the calculations clearly show that vibronic effects are responsible or at least dominant for the chiroptical properties of isotopically chiral organic molecules.

Journal Article↗

Anomalous oxygen isotope enrichment in CO2 produced from O+CO: estimates based on experimental results and model predictions.

The oxygen isotope fractionation associated with O+CO-->CO(2) reaction was investigated experimentally where the oxygen atom was derived from ozone or oxygen photolysis. The isotopic composition of the product CO(2) was analyzed by mass spectrometry. A kinetic model was used to calculate the expected CO(2) composition based on available reaction rates and their modifications for isotopic variants of the participating molecules. A comparison of the two (experimental data and model predictions) shows that the product CO(2) is endowed with an anomalous enrichment of heavy oxygen isotopes. The enrichment is similar to that observed earlier in case of O(3) produced by O+O(2) reaction and varies from 70 0/00 to 136 0/00 for (18)O and 41 0/00 to 83 0/00 for (17)O. Cross plot of delta (17)O and delta (18)O of CO(2) shows a linear relation with slope of approximately 0.90 for different experimental configurations. The enrichment observed in CO(2) does not depend on the isotopic composition of the O atom or the sources from which it is produced. A plot of Delta(delta (17)O) versus Delta(delta (18)O) (two enrichments) shows linear correlation with the best fit line having a slope of approximately 0.8. As in case of ozone, this anomalous enrichment can be explained by invoking the concept of differential randomization/stabilization time scale for two types of intermediate transition complex which forms symmetric ((16)O(12)C(16)O) molecule in one case and asymmetric ((16)O(12)C(18)O and (16)O(12)C(17)O) molecules in the other. The delta (13)C value of CO(2) is also found to be different from that of the initial CO due to the mass dependent fractionation processes that occur in the O+CO-->CO(2) reaction. Negative values of Delta(delta (13)C) ( approximately 12.1 0/00) occur due to the preference of (12)C in CO(2)* formation and stabilization. By contrast, at lower pressures (approximately 100 torr) surface induced deactivation makes Delta(delta (13)C) zero or slightly positive.

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Evidence for a 1-electron oxidation mechanism in N-dealkylation of N,N-dialkylanilines by cytochrome P450 2B1. Kinetic hydrogen isotope effects, linear free energy relationships, comparisons with horseradish peroxidase, and studies with oxygen surrogates.

Many enzymes catalyze N-dealkylations of alkylamines, including cytochrome P450 (P450) and peroxidase enzymes. Peroxidases, exemplified by horseradish peroxidase (HRP), are generally accepted to catalyze N-dealkylations via 1-electron transfer processes. Several lines of evidence also support a 1-electron mechanism for many P450 reactions, although this view has been questioned in light of reported trends for kinetic hydrogen isotope effects for N-demethylation with a series of 4-substituted N,N-dimethylanilines. No continuous trend for an increase of isotope effects with the electronic parameters of para-substitution was seen for the P450 2B1-catalyzed reactions in this study. The larger value seen with the 4-nitro derivative is consistent with a shift in mechanism due to either a reversible electron transfer step preceding deprotonation or to a hydrogen atom abstraction mechanism. With HRP, the trend is to lower isotope effects with para electron-withdrawing substituents, due to an apparent shift in rate-limiting steps. Biomimetic model high-valent porphyrins showed reduction rates with variously 4-substituted N,N-dialkylanilines that were consistent with a positively charged intermediate; such relationships were not seen for anisole O-demethylation with P450 2B1. In contrast to the case with the NADPH-supported P450 reactions, high deuterium isotope effects ( approximately 7) were seen in the N-dealkylations supported by the oxygen surrogate iodosylbenzene. With iodosylbenzene, colored aminium radicals were observed in the oxidations of aminopyrine, N,N-dimethyl-4-aminothioanisole, and 4-methoxy-N,N-dimethylaniline. With the latter compound, a substantial intermolecular deuterium isotope effect was observed for N-demethylation. In the N-dealkylation of N-ethyl,N-methylaniline by P450 2B1 (NADPH-supported), the ratio of N-demethylation to N-deethylation was 16. Although it is probably possible for P450s to catalyze amine N-dealkylations via hydrogen atom abstraction when such a course is electronically or sterically favored, we interpret the evidence to favor a 1-electron pathway with N,N-dialkylamines with P450 2B1 as well as HRP and several biomimetic models.

Alkylation↗

Magnetic isotope effects in biology: a marker for radical pair reactions and electromagnetic field effects?

PURPOSE: To explore the possible usefulness of magnetic isotope effects, especially to detect processes affected by magnetic fields. MATERIALS AND METHODS: The theoretical model of Brocklehurst and McLauchlan is used to estimate the effects of isotopic substitution (e.g. 13C for 12C) on the yields of chemical reactions involving radical pairs. RESULTS: It is demonstrated that in some circumstances isotope effects on the yields from initially singlet pairs (bond breaking to give radicals) could be very large and easily detected. The effects on radical pairs formed by random encounters are necessarily much smaller but may be detectable. Illustrative calculations are presented for carbon, hydrogen and oxygen isotopes; deuterium substitution also produces very large mass effects but its study could be useful to support work on carbon. CONCLUSIONS: Effects may be small but worth looking for: distinguishing them from mass effects will be aided by measuring distributions within product molecules. In laboratory experiments (especially tomography) a combination of isotopic substitution and applied fields is a potentially powerful technique.

Electromagnetic Fields↗

Pb-Nd Isotopes Indicate the Origin of Island Arc Terranes in the Early Paleozoic Pacific.

The Takaka Terrane in New Zealand is one of the best exposed arc fragments of the early Paleozoic Australian-Antarctic convergent margin and constitutes one of the most outboard terranes of this margin in paleogeographic reconstructions. Pb-Nd isotope compositions of clinopyroxenes from the Cambrian Devil River Volcanics of the Takaka Terrane enable identification of the location of the terrane in the Paleo-Pacific Ocean. The Devil River Volcanics, a suite of primitive arc and back-arc rocks, are interbedded with the partly continent-derived Haupiri Group sediments. Extremely radiogenic Pb and unradiogenic Nd compositions in the arc rocks cannot be explained by assimilation of the Haupiri Group sediments or a continental basement of such a composition. Pb isotope compositions of the Takaka Terrane sediments are much less radiogenic and overlap with crustal compositions of the Lachlan Fold Belt in Australia, suggesting that both units are derived from one source, the Australian-Antarctic Pacific margin. Pb-Nd isotope compositions in the Devil River Volcanics reflect contamination of their mantle sources by subducted sediments derived from Archean provinces in either Antarctica or Laurentia. Both provinces show characteristically high 207Pb/204Pb500 and were located at the Pacific rim in the Cambrian. Mixing between mantle and Proterozoic continental material from present western South America or eastern Laurentia cannot explain the high 207Pb/204Pb500 in the New Zealand rocks. As in New Zealand, extreme spreads in Pb-Nd isotope compositions in other Cambrian volcano-sedimentary sequences in southeast Australia and Tasmania can be explained by the same model, suggesting that all these fragments originated along the Australian-Antarctic Gondwana margin. Pb isotope compositions of arc rocks, therefore, provide a new tool for terrane analysis in the early Paleozoic Pacific ocean.

Journal Article↗

A simple method for measuring zinc absorption in man using a short-lived isotope (69mZn).

Using a short-lived isotope of zinc (69mZn) with a half-life of 13.9 hr, we have developed a simple test of zinc absorption. After an oral dose of isotope (50 muCi) with 2 mg of elemental zinc a plasma appearance curve was constructed from radioactivity determined in blood samples taken sequentially over 8 hr. Two week later an iv dose of isotope (25 muCi) was administered and a plasma disappearance curve was constructed. Absorption was calculated by computer analysis of appearance and disappearance curves using a deconvolution programme. Mean absorption in five normal subjects was 61% (range 41 to 79%). In three subjects given food with, or 1 hr before the isotope, absorption was delayed and reduced to less than 20% of the oral dose at 8 hr. This test of zinc absorption is simple to perform and, because the isotope has a short half-life, has the advantage of subjecting patients to only limited radiation.

Absorption↗

Calcium fractional absorption and metabolism assessed using stable isotopes differ between postpartum and never pregnant women.

Determining the fractional absorption (FA) of calcium using the incorporation into urine of stable isotopes given intravenously (IV) and orally has become a routine procedure. We investigated the FA of calcium in two groups of (2-3 mo) postpartum women lactating (LACT) (n = 6) and nonlactating (PPNL) (n = 6), and in never pregnant (NP) women (n = 7). The women consumed a controlled diet containing 30-33 mmol/d calcium (Ca) for 21 d. On d 7 of the controlled diet, the women received 0.05 mmol of 42Ca IV and 0.25 mmol 44Ca orally in milk. Urine samples (24-h) were collected for the next 14 d and morning blood samples were collected from fasting subjects before dosing and at 24 and 48 h after receiving the isotopes. Milk samples from the LACT women were collected from each feeding beginning 24 h before to 72 h after dosing. There were no significant differences in the FA of calcium as measured by stable isotope incorporation into urine (23.8 +/- 2.9%), serum (24.0 +/- 3.4%) or milk (23.6 +/- 3.6%) of LACT women. The fractional calcium absorption measured in urine of the postpartum women (LACT and PPNL, 23.8 +/- 2.9% and 25.0 +/- 3.3%, respectively) did not differ but was greater (P < 0.028) than that of the NP women (17.3 +/- 1.3%). The postpartum LACT and PPNL women had a reduced urinary excretion of calcium (P < 0.01) compared with the NP women. There was a significantly greater incorporation (P < 0.001) by LACT women of the oral isotope dose into milk than into urine. Calcium FA can be determined from incorporation of stable isotopes into breast milk and serum as well as urine.

Absorption↗

A rapid and simple method for processing wood to crude cellulose for analysis of stable carbon isotopes in tree rings.

For analysis of carbon isotope discrimination in wood, cellulose or holocellulose is often preferred to whole tissue because of the variability in isotopic composition of different wood components and the relative immobility of cellulose. Most currently used methods for the preparation of wood components for stable isotope analysis (e.g., the Jayme-Wise method) produce a residue of holocellulose. The Jayme-Wise method was initially developed to extract holocellulose from small (~1 g) samples of wood, and, despite subsequent modifications, the method requires specialized glassware, considerable time and entails the risk of sample loss. For carbon isotope analysis, we adapted an acid-catalyzed solvolytic method for preparing crude cellulose by treating wood meal with acidified di-glycol methyl ether (diglyme). The one-step process requires no special glassware, is complete within 24 hours and enables over 100 samples to be processed in a day. This method gives similar delta(13)C values to the Jayme-Wise method for wood of Eucalyptus globulus Labill., Pinus radiata D. Don and Pinus pinaster Ait. The relationship between delta(13)C of wood and crude cellulose is as strong as that observed between wood and alpha-cellulose and stronger than that observed between wood and holocellulose in other species. These relationships suggest that variation in delta(13)C of wood may result from hemicellulose and that analysis of stable carbon isotopes in crude cellulose is preferable. If the consistent -0.3 bias in the value of delta(13)C of cellulose resulting from residual lignin is corrected for, then the relationship between delta(13)C of wood and crude cellulose may be used to predict delta(13)C of cellulose from a small sub-sample. The method is well suited to species with low concentrations of extractives, but further testing is needed to assess its general applicability.

Journal Article↗

Measurement and application of uranium isotopes for human and environmental monitoring.

An improved method is described utilizing extraction chromatography, anion exchange, and alpha spectroscopy for measurement of uranium isotopes in human and environmental surveillance studies. These methods provide a sensitivity of approximately 0.7 mBq per isotope per sample and are generally accurate within the precision of the measurements. The extraction chromatography methods greatly simplify separation of uranium from iron in silicate matrices and provide increased sample throughput and data quality for water, soil, and air filter samples. For bioassay samples, the coprecipitation/anion exchange/alpha spectrometric methods provide rapid throughput and sufficient sensitivity to meet new analytical performance standards in human monitoring studies. In addition, the 234U:238U data can be used as a fingerprint of natural vs. anthropogenic sources of uranium. For 1995 data from our laboratory, a large percentage (79-94% by matrix) of samples appear to be of natural 234U:238U isotopic composition. For all matrices, samples with higher uranium concentration generally have more depleted isotopic composition (smaller 234U:238U). A small percentage of soil (11%), air filter (3%), urine (3%), and water (3%) samples have depleted isotopic signatures at the 95% confidence interval, indicating anthropogenic contributions of uranium to these samples.

Air Pollutants, Radioactive↗

Feasibility of myocardial dual-isotope perfusion imaging combined with gated single photon emission tomography for assessing coronary artery disease.

The clinical feasibility of both dual-isotope single photon emission tomography (SPET) and gated SPET have been described. The present study evaluates the feasibility of combining gated SPET with exercise 201Tl/rest 99mTc-tetrofosmin dual-isotope SPET corrected for scatter. Ninety-one patients with known or suspected coronary artery disease underwent cardiac catheterization and coronary angiography. Twenty-nine of them underwent exercise 201Tl/rest 99mTc-tetrofosmin dual-isotope SPET with a second 201Tl injection 3 h after the initial 201Tl injection (protocol 1). We then segregated a Bull's eye polar map into three coronary artery territories and quantified the relative regional uptake. The remaining 62 patients underwent exercise 201Tl/rest 99mTc-tetrofosmin dual-isotope SPET combined with gated SPET. We visually evaluated exercise and rest images from the three coronary artery territories. Left ventricular (LV) function was assessed globally by means of the LV ejection fraction and regionally by means of visual scoring analysis, compared with left ventriculography (LVG). The correlation between rest 99mTc-tetrofosmin and 201Tl reinjection images in 87 areas of coronary artery territory (r=0.89, P<0.01) and in 13 infarcted areas (r =0.94, P<0.01) was very close in protocol 1. The overall values for vessel-related sensitivity, specificity and accuracy were 88%, 79% and 82%, respectively, in protocol 2. The correlation between gated SPET and LVG was significant and linear with respect to the LV ejection fraction (r=0.77, P<0.01). The wall motion score from visual evaluation in gated SPET revealed a close overall agreement with LVG (concordance rate, 88%; kappa, 0.670). Exercise 201Tl/rest 99mTc-tetrofosmin dual-isotope SPET with scatter correction for assessing the coronary artery disease offers excellent diagnostic accuracy and the additional gated SPET provides useful information about LV function similar to that for LVG. This sequential protocol requires only 2 h to generate much useful clinical information.

Aged↗