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At least 19 recordsLinked to original sources

Effect of increased metabolic rate on oxygen isotopic fractionation.

16O16O is preferentially used over 18O16O (a stable isotope of oxygen comprising about 0.2% of atmospheric O2) as oxygen is consumed during respiration in humans (Epstein and Zeiri, 1988, Proc. Natl. Acad. Sci. USA 85: 1727-1731). To test the hypothesis that oxygen isotopic fractionation is related to the metabolic rate, 8 healthy adults performed 5 min of constant work rate cycle ergometer exercise below and above their anaerobic threshold. Moreover, 3 subjects performed an incremental exercise to the limit of tolerance. Oxygen uptake (VO2) was measured breath by breath. Samples of the exhaled breath for oxygen isotope measurement were obtained at rest and at various times during exercise and recovery. Oxygen isotopic fractionation was determined by isotope ratio mass spectrometry and calculated as the ratio of the degree of fractionation to the oxygen consumed in the breath sample (Z value). For the constant work rate protocol, both low and high intensity exercise resulted in a significant decrease in Z compared to the rest values (P less than 0.01). However, for the high intensity exercise the reduction in fractionation was greater compared to the low intensity protocol (P less than 0.05). For the incremental test, there was a significant negative correlation between oxygen isotopic fractionation and VO2 expressed as percent of the maximal oxygen uptake (r = -0.91, P less than 0.0001). These data suggest that during exercise low-fractionating processes become more important as limiting steps for O2 transport.

Adult↗

Aqueous alteration of the Bali CV3 chondrite: evidence from mineralogy, mineral chemistry, and oxygen isotopic compositions.

A petrographic, geochemical, and oxygen isotopic study of the Bali CV3 carbonaceous chondrite revealed that the meteorite has undergone extensive deformation and aqueous alteration on its parent body. Deformation textures are common and include flattened chondrules, a well-developed foliation, and the presence of distinctive (100) planar defects in olivine. The occurrence of alteration products associated with the planar defects indicates that the deformation features formed prior to the episode of aqueous alteration. The secondary minerals produced during the alteration event include well-crystallized Mg-rich saponite, framboidal magnetite, and Ca-phosphates. The alteration products are not homogeneously distributed throughout the meteorite, but occur in regions adjacent to relatively unaltered material, such as veins of altered material following the foliation. The alteration assemblage formed under oxidizing conditions at relatively low temperatures (<100 degrees C). Altered regions in Bali have higher Na, Ca, and P contents than unaltered regions which suggests that the fluid phase carried significant dissolved solids. Oxygen isotopic compositions for unaltered regions in Bali fall within the field for other CV3 whole-rocks, however, the oxygen isotopic compositions of the heavily altered material lie in the region for the CM and CR chondrites. The heavy-isotope enrichment of the altered regions in Bali suggest alteration conditions similar to those for the petrographic type-2 carbonaceous chondrites.

Calcium Phosphates↗

Oxygen isotope exchange between refractory inclusion in Allende and solar nebula gas.

A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope composition (approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

Crystallization↗

Fractionation of oxygen isotopes due to equilibration of oxygen with hemoglobin.

The aim of the study was to answer the question as to whether the chemical reaction of oxygen with hemoglobin exhibits a source of isotopic fractionation, which could be of significance in forming the overall fractionation effect of respiration recently determined in man. Investigations were performed on bovine hemoglobin solutions adjusted to normal values of Hb concentration and pH. After degassing in vacuo, the hemoglobin solution was equilibrated in a closed system with pure oxygen of suitable pressure so that oxygen saturation levels of 30, 50 and 100% were achieved. After complete equilibration, isotope analysis of oxygen by mass spectrometry resulted in 16O18O/16O2 ratios which were 0.35 +/- 0.02% lower in the oxygen bound to hemoglobin than that of the gas phase during all levels of oxygenation. Model calculations suggest the following: (1) the fractionation during oxygen uptake in the lung at rest is primarily determined by the reaction with hemoglobin, (2) the overall fractionation effect of respiration can be explained as due to single effects of the constituent processes when assuming the oxygen transport to be limited by utilization.

Animals↗

Oxygen isotope exchange between refractory inclusion in allende and solar nebula Gas

A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope compositions ( approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

Journal Article↗

Exchange of oxygen isotopes in carbon dioxide-phosphoric [correction of phosporic] acid systems.

The rate of exchange of isotopes of oxygen between solutions of concentrated phosphoric acid and CO2 was measured as a function of temperature, acid strength (pressure of water in equilibrium with the solution), pressure of CO2, and surface area of the reaction vessel. At 75 degrees C, significant exchange was found to occur even for the "anhydrous" phosphoric acids, those in which the nominal percentage of H3PO4 in solution is equal to or exceeds 100%. Exchange is much slower at 25 degrees C, but isotopic shifts as large as 0.1% can be observed in 95% H3PO4 at equilibration times approaching 1000 hr. Rates of exchange were found to be dependent upon the vapor pressure of water in equilibrium with the acid solutions. Exchange was found to occur primarily on the surface of the reaction vessel above the solution, with no dependence on total CO2 pressure. These observations indicate that phosphoric acids with nominal concentrations of H3PO4 approaching 105% are preferable for the minimization of exchange between CO2 samples and acid solutions during phosphorolyses of carbonate materials. Moreover, with such acids, significant time--temperature trade-offs are possible, allowing rapid preparation of CO2 at elevated temperatures.

Carbon Dioxide↗

Oxygen isotope effects on the ribulosebisphosphate oxygenase reaction.

The oxygen isotope effect at the substrate O2 on the oxygenase reaction of ribulose bisphosphate carboxylase/oxygenase from spinach is pH and metal dependent. The pH dependence between pH 7.4 and 8.9 is different with Mg2+ (steady decrease in this isotope effect from 1.036 to 1.030) and Mn2+ (minimum isotope effect of 1.028 at pH 8.0). Deuteration of the substrate ([3-2H]ribulose bisphosphate) has no influence on the isotope effect. The results are interpreted as a direct participation of the metal ion in the oxygen-sensitive step, i.e. carbon-oxygen bond formation and the stabilization of the intermediates. In the overall reaction oxygen addition is a major rate-limiting step, and the observed isotope effect is probably close to the intrinsic oxygen isotope effect of the reaction. The basic mechanisms for carboxylation and oxygenation of ribulose bisphosphate appear to be the same.

Carbon Isotopes↗

Oxygen-isotope analysis of recent tropical Pacific benthonic Foraminifera.

Analysis by the oxygen-isotope method of samples of benthonic Foraminifera, collected at different depths on the continental shelf and slope of western Cenitral America, yielded isotopic temperatures agreeing closely with the temperatures measured in the field. The validity of the oxygen-isotope method as a means of analysis of paleotemperatures is further supported.

Animals↗

A 14,000-year oxygen isotope record from diatom silica in two alpine lakes on Mt. Kenya.

Oxygen isotopes are sensitive tracers of climate change in tropical regions. Abrupt shifts of up to 18 per mil in the oxygen isotope ratio of diatom silica have been found in a 14,000-year record from two alpine lakes on Mt. Kenya. Interpretation of tropical-montane isotope records is controversial, especially concerning the relative roles of precipitation and temperature. Here, we argue that Holocene variations in delta(18)O are better explained by lake moisture balance than by temperature-induced fractionation. Episodes of heavy convective precipitation dated approximately 11,100 to 8600, 6700 to 5600, 2900 to 1900, and <1300 years before the present were linked to enhanced soil erosion, neoglacial ice advances, and forest expansion on Mt. Kenya.

Diatoms↗

[Localization of the ATPase site of nitrogenase by isotopic oxygen exchange [180]-Pi in equilibrium with H20].

The components of the nitrogenase complex, MoFe-protein and FeMo-cofactor, possessing no ATPase or nitrogen-fixing activity, maintain the 18O-exchange at the level of 1 atom of 18O per molecule of Pi, which is inhibited by ATP. The Fe-protein complex does not catalyze the 18O-exchange. The nitrogenase components do not hydrolyze the substrates for phosphatase (p-nitrophenylphosphate, beta-glycerophosphate, glucose 1-phosphate and ribose 5-phosphate). The artificial albumin-containing MoFe- and Fe-proteins and the carboxyl group-containing proteins (albumin, hemoglobin, lysozyme) as well as sodium molibdate do not catalyze the 18O-exchange. It is assumed that the site of the ATPase center which is subjected to phosphorylation, is located on the MoFe-protein.

Adenosine Triphosphatases↗

Oxygen isotopic abundances in calcium- aluminum-rich inclusions from ordinary chondrites: implications for nebular heterogeneity.

The oxygen isotopic compositions of two calcium-aluminum-rich inclusions (CAIs) from the unequilibrated ordinary chondrite meteorites Quinyambie and Semarkona are enriched in 16O by an amount similar to that in CAIs from carbonaceous chondrites. This may indicate that most CAIs formed in a restricted region of the solar nebula and were then unevenly distributed throughout the various chondrite accretion regions. The Semarkona CAI is isotopically homogeneous and contains highly 16O-enriched melilite, supporting the hypothesis that all CAI minerals were originally 16O-rich, but that in most carbonaceous chondrite inclusions some minerals exchanged oxygen isotopes with an external reservoir following crystallization.

Aluminum↗

Origin of magnetite in oxidized CV chondrites: in situ measurement of oxygen isotope compositions of Allende magnetite and olivine.

Magnetite in the oxidized CV chondrite Allende mainly occurs as spherical nodules in porphyritic-olivine (PO) chondrules, where it is associated with Ni-rich metal and/or sulfides. To help constrain the origin of the magnetite, we measured oxygen isotopic compositions of magnetite and coexisting olivine grains in PO chondrules of Allende by an in situ ion microprobe technique. Five magnetite nodules form a relatively tight cluster in oxygen isotopic composition with delta 18O values from -4.8 to -7.1% and delta 17O values from -2.9 to -6.3%. Seven coexisting olivine grains have oxygen isotopic compositions from -0.9 to -6.3% in delta 18O and from -4.6 to -7.9% in delta 17O. The delta 17O values of the magnetite and coexisting olivine do not overlap; they range from -0.4 to -2.6%, and from -4.0 to -5.7%, respectively. Thus, the magnetite is not in isotopic equilibrium with the olivine in PO chondrules, implying that it formed after the chondrule formation. The delta 17O of the magnetite is somewhat more negative than estimates for the ambient solar nebula gas. We infer that the magnetite formed on the parent asteroid by oxidation of metal by H2O which had previously experienced minor O isotope exchange with fine-grained silicates.

Ferrosoferric Oxide↗

Oxygen isotopes and emerald trade routes since antiquity

Oxygen isotopic compositions of historical emerald artifacts from the Gallo-Roman period to the 18th century indicate that during historical times, artisans worked emeralds originating from deposits supposedly discovered in the 20th century. In antiquity, Pakistani and Egyptian emeralds were traded by way of the Silk Route. Together with Austrian stones, they were the only source of gem-quality emeralds. Immediately after the discovery of the Colombian mines by Spaniards in the 16th century, a new trade route was established, first via Spain to Europe and India and then directly via the Philippines to India. Since then, Colombian emeralds have dominated the emerald trade, and most of the high-quality emeralds cut in the 18th century in India originated from Colombia.

Journal Article↗

[Study of dynein ATPase by oxygen isotope exchange H2(18)O in equilibrium with [16O]-Pi].

The oxygen isotope exchange reactions catalyzed by sea urchin Strongylocentrotus intermedius spermatozoa dynein I were studied with a view of comparing molecular mechanisms of ATP hydrolysis by dynein and myosin ATPases. It was demonstrated that the isotope exchange takes place during ATP hydrolysis and during enzyme incubation with ADP and Pi and is absent when the enzyme is incubated with Pi. It was assumed that the molecular mechanisms of ATP hydrolysis by dynein I and myosin are identical.

Adenosine Triphosphatases↗

Oxygen isotope ratios of PO4: an inorganic indicator of enzymatic activity and P metabolism and a new biomarker in the search for life.

The distinctive relations between biological activity and isotopic effect recorded in biomarkers (e.g., carbon and sulfur isotope ratios) have allowed scientists to suggest that life originated on this planet nearly 3.8 billion years ago. The existence of life on other planets may be similarly identified by geochemical biomarkers, including the oxygen isotope ratio of phosphate (delta(18)O(p)) presented here. At low near-surface temperatures, the exchange of oxygen isotopes between phosphate and water requires enzymatic catalysis. Because enzymes are indicative of cellular activity, the demonstration of enzyme-catalyzed PO(4)-H(2)O exchange is indicative of the presence of life. Results of laboratory experiments are presented that clearly show that delta(18)O(P) values of inorganic phosphate can be used to detect enzymatic activity and microbial metabolism of phosphate. Applications of delta(18)O(p) as a biomarker are presented for two Earth environments relevant to the search for extraterrestrial life: a shallow groundwater reservoir and a marine hydrothermal vent system. With the development of in situ analytical techniques and future planned sample return strategies, delta(18)O(p) may provide an important biosignature of the presence of life in extraterrestrial systems such as that on Mars.

Biomarkers↗

General methods for enriching aldoses with oxygen isotopes.

Synthetic methods are described for enriching 4-, 5-, and 6-carbon aldoses with oxygen isotopes. The general approach includes exchange between H2(1)8O and the aldehyde group of an aldose, exchange of O-1 onto C-2 of both of the 2-epimeric aldoses formed by molybdate-resin epimerization, and chain extension using cyanide addition. These methods make possible the production of all 16 aldohexoses enriched at 5 of the 6 oxygen atoms, all 8 aldopentoses enriched at 4 of the 5 oxygen atoms, and the four aldotetroses enriched at 2 of the 4 oxygen atoms. The general applicability of these methods is illustrated by the synthesis of a group of 22 different, 18O-enriched, biologically important D-aldoses having 4, 5, and 6 carbon atoms. The group includes D-[1-, 2-, 3-, 4-, O]glucose, D-[1-, 2-, 3-, 4-, and 6-18O]mannose, D-[1-, 2-, 3-, and 5-18O]arabinose, D-[1- abd 2- 18O] erythorose, and D-[1- and 2-18O]threose. The g.l.c.-m.s. characterization of these sugars with respect to the position and degree of 18O-enrichment is reported. The potential of the methods for producing aldoses having oxygen labels at multiple positions, or aldoses labeled simultaneously with oxygen, hydrogen, and carbon isotopes is discussed.

Gas Chromatography-Mass Spectrometry↗

Oxygen isotopes and the moon-forming giant impact.

We have determined the abundances of 16O, 17O, and 18O in 31 lunar samples from Apollo missions 11, 12, 15, 16, and 17 using a high-precision laser fluorination technique. All oxygen isotope compositions plot within +/-0.016 per mil (2 standard deviations) on a single mass-dependent fractionation line that is identical to the terrestrial fractionation line within uncertainties. This observation is consistent with the Giant Impact model, provided that the proto-Earth and the smaller impactor planet (named Theia) formed from an identical mix of components. The similarity between the proto-Earth and Theia is consistent with formation at about the same heliocentric distance. The three oxygen isotopes (delta17O) provide no evidence that isotopic heterogeneity on the Moon was created by lunar impacts.

Computer Simulation↗

Pore Fluid Constraints on the Temperature and Oxygen Isotopic Composition of the Glacial Ocean

Pore fluids from the upper 60 meters of sediment 3000 meters below the surface of the tropical Atlantic indicate that the oxygen isotopic composition (delta18O) of seawater at this site during the last glacial maximum was 0.8 &plusmn; 0.1 per mil higher than it is today. Combined with the delta18O change in benthic foraminifera from this region, the elevated ratio indicates that the temperature of deep water in the tropical Atlantic Ocean was 4&deg;C colder during the last glacial maximum. Extrapolation from this site to a global average suggests that the ice volume contribution to the change in delta18O of foraminifera is 1.0 per mil, which partially reconciles the foraminiferal oxygen isotope record of tropical sea surface temperatures with estimates from Barbados corals and terrestrial climate proxies.

Journal Article↗