The oxygen isotope geochemistry of igneous rocks

Oxygen isotope analyses have been obtained for 443 igneous rock and mineral samples from various localities throughout the world. Detailed studies were made on the Medicine Lake, Newberry, Lassen, Clear Lake, S. E. Guatemala, Hawaii and Easter I. volcanic complexes and on the Bushveld, Muskox, Kiglapait, Guadalupe, Duluth, Nain, Egersund, Lac St. Jean, Laramie, Skaergaard, Mull, Skye, Ardnamurchan and Alta, Utah plutonic complexes, as well as upon several of the zoned ultramafic intrusions of S. E. Alaska. Basalts, gabbros, syenites and andesites are very uniform in O¹⁸/O¹⁶, commonly with δ-values of 5.5 to 7.0 per mil. Many rhyolite obsidians, particularly those from oceanic areas and the Pacific Coast of the United States, also lie in this range; this indicates that such obsidians are differentiates of basaltic or andesitic magma at high temperatures (about 1,000° C). They cannot represent melted sialic crust. The only plutonic granites with such low δ-values are some of the hypersolvus variety, suggesting that these also might form by fractional crystallization. Obsidians from the continental interior, east of the quartz-diorite line, have higher δ-values. This is compatible with their having assimilated O¹⁸-rich sialic crust. A correlation generally exists between the O¹⁸/O¹⁶ ratios of SiO₂-rich differentiates and the chemical trends in volcanic complexes. High O¹⁸/O¹⁶ ratios accompany those trends having the lower Fe/Mg ratios, while ferrogabbro trends are associated with depletion in O¹⁸. Variations in oxygen fugacity may be responsible for these effects, as abundant early precipitation of magnetite should lead to both O¹⁸-enrichment and Fe-depletion in later differentiates. Plutonic granites have higher O¹⁸/O¹⁶ ratios than their volcanic equivalents, because (a) their differentiation occurred at much lower temperatures, or (b) they are in large part derived from O¹⁸-rich sialic crust by partial melting or assimilation. Also, the oxygen isotope fractionations among coexisting minerals are distinctly larger in plutonic rocks than in volcanic rocks. This is in keeping with their lower crystallization temperatures and their longer cooling history, which promotes post-crystallization oxygen isotope exchange. Hydrated obsidians and perlites have δO¹⁸-values that are much different from their primary, magmatic values. A correlation exists between D/H and O¹⁸/O¹⁶ ratios in hydrated volcanic glass from the western U.S.A., proving that the isotopic compositions are a result of exchange with meteoric waters. The O¹⁸ contents of the glasses appear to be about 25 per mil higher than their associated waters; hence, these hydrated glasses have not simply absorbed H₂O, but they have exchanged with large quantities of it. The igneous rocks from Mull, Skye, Ardnamurchan and the Skaergaard intrusion are all abnormally depleted in O¹⁸ relative to “normal” igneous rocks. This is a result of their having exchanged at high temperatures with meteoric water that was apparently abundant in the highly jointed plateau lavas into which these igneous rocks were intruded. In part, this exchange occurred with liquid magma and in part with the crystalline rock; in the latter case the feldspar was more easily exchanged and has become much more depleted in O¹⁸ than has coexisting quartz or pyroxene. The later differentiates of the Muskox intrusion are markedly O¹⁸-rich, but this is not a result of fractional crystallization. It is in large part a result of deuteric exchange between feldspars and an oxygen-bearing fluid (H₂O ?) that was either O¹⁸-rich or had a relatively low temperature. This phenomenon was also observed in a number of granophyres from other localities, particularly those containing brick-red alkali feldspar. The exchanged feldspars in all these examples are turbid or cloudy, and may be filled with hematite dust. It is concluded that most such feldspar in nature is the result of deuteric exchange and is probably drastically out of oxygen isotopic equilibrium with its coexisting quartz.     

Oxygen isotopic studies of the interaction between xenoliths and mafic magma, Voisey’s Bay Intrusion, Labrador, Canada

Sulfide mineralization in the Voisey’s Bay Intrusion, Labrador, Canada, is closely associated with country rock xenoliths that have extensively reacted with basaltic magma. In order to better understand the processes that control the assimilation of country rocks by mafic magma, a detailed study of oxygen isotope systematics related to magma-country rock interaction in the Voisey’s Bay area was undertaken. Protracted interaction of the xenoliths with magma produced refractory mineral assemblages in the xenoliths (2-10 cm in diameter) composed of Ca-rich plagioclase, corundum, hercynite, and minor magnetite. Overgrowth rims of plagioclase and biotite that surround most xenoliths separate the restites from the enclosing igneous matrix. The δ¹⁸O values of minerals from regionally metamorphosed pelitic and quartzofeldspathic protoliths are: plagioclase (8.7-12.3‰), orthoclase (9.5-9.8‰), biotite (5.2-8.7‰), garnet (8.3-10.8‰), pyroxene (8.0-10.1‰), and quartz (9.6-14.0). The δ¹⁸O values of minerals from the hornfels in the contact aureole of the intrusion are consistent with modeling which indicates that as a result of essentially closed system contact metamorphism oxygen isotope values should differ only slightly from those of the protoliths. Hercynite, plagioclase, and corundum separates from the xenoliths have δ¹⁸O values that vary from 2.9‰ to 10.5‰, 5.6‰ to 10.9‰, and 2.0‰ to 6.8‰, respectively. Although a siliceous ¹⁸O-enriched melt has been lost from the xenoliths, corundum, and feldspar δ¹⁸O values are significantly lower than expected through melt loss alone. The relatively low δ¹⁸O values of minerals from the xenoliths may be a function of incomplete isotopic exchange with surrounding mafic magma which had a δ¹⁸O value of ∼5.5‰ to 6.0‰. The high-¹⁸O melt that was released from the xenoliths is partially recorded in the plagioclase overgrowth on the margin of the xenoliths (δ¹⁸O values from 6.2‰ to 10.7‰), and in hercynite that replaced corundum. However, mass balance calculations indicate that a portion of the partial melt must have been transferred to magma that was moving through the conduit system. δ¹⁸O and δD values of biotite surrounding the plagioclase overgrowth range from 5.0‰ to 6.2‰ and −58‰ to −80‰, respectively. These data suggest that the outermost rim associated with many xenoliths has closely approached isotopic equilibrium with uncontaminated mafic magma. The current gabbroic to troctolitic matrix of the xenoliths shows no evidence for contamination by the high-¹⁸O partial melt from the xenoliths. The feldspar and biotite overgrowths on the xenoliths that formed after the motion of the xenoliths relative to the magma had stopped prevented further isotopic exchange between the xenoliths and final magma. The minerals within the xenoliths are not in oxygen isotopic equilibrium with each other, due in part to rapid thermal equilibration, partial melting, and partial exchange with flow through magma.     

Kiglapait Mineralogy I: Apatite, Biotite, and Volatiles

Electron microprobe analyses show that Upper Zone apatites inthe Kiglapait intrusion are fluorine rich and contain minorchlorine and hydroxyl (calculated). Apatite from the Outer BorderZone has a higher Cl content. The refractive indices of UZ apatites have the following ranges: = 1.6345–1.6379, = 1.6326–1.6352, and B = 0.0020–0.0028.The birefringence is low for apatites with these refractiveindices. Some Outer and Upper Border Zone apatites have higherindices of refraction and normal birefringence. Fractional crystallization of the basaltic Kiglapait magma producedcumulus apatite beginning at the 94 per cent solidified levelwhen P₂O₅ reached saturation in the liquid. The amounts of P₂O₅and modal apatite decreased gradually from the 94 per cent tothe 99.99 per cent solidified level as the liquid was depletedin P₂O₅. F and Cl appear to be equally partitioned between theliquid and apatite because no fractionation trends are notedbetween the two halogens. There is a slight decrease in thecalculated ratio OH/F in apatite which suggests possible depletionof OH in the liquid with fractionation. Kiglapait apatites appear to be stoichiometric, based on microprobechemistry, refractive index, and unit cell dimensions. However,infrared absorption analyses show no detectable water, whichleaves approximately 11 per cent of the monovalent anion siteunaccounted for. Anion deficiencies in apatites from low-H₂Oenvironments may be explained either by substitution of O forF, or domains of tetracalcium phosphate. Non-cumulus biotite occurs in minor quantities in the intrusion.Electron microprobe analyses of Upper Zone biotites show thatthey contain an average (by weight) pf 0.4 per cent F, 0.07per cent Cl, and 4.0 per cent H₂O (calculated). The volatile chemistry of the Kiglapait intrusion is calculatedfrom apatite and biotite chemistry. The intrusion contains anestimated 900 ppm P₂O₅, 166 ppm F, and 12 ppm Cl. There is amaximum of 68 ppm H₂O using calculated H₂O from microprobe data,or a minimum of 8 ppm using H₂O from infrared analysis. It isproposed that the anhydrous basaltic Kiglapait magma was a secondpartial melt of amphibole-bearing mantle rock.     

Kiglapait geochemistry VII: Yttrium and the rare earth elements

Based on 51 wholerock analyses by XRF and summation over the layered group, the Kiglapait Intrusion contains 4.7_?1.6^+1.2 ppm Y, which resides principally in augite and apatite. Using liquid compositions calculated by summation, the partition coefficient D^AUG/L_Y is 0.95 ± 0.12 from 84 to 97 PCS (percent solidified) and 1.5 ± 0.4 above 97 PCS. For feldspar, the most likely value for D is 0.028 ± 0.02 (N = 6).REE analyses for 13 whole rocks were interpreted with the aid of yttrium models to yield trends for wholerocks and liquids vs PCS. Summations over the rocks of the layered group gave La = 2.5, Ce = 5.8, Nd = 3.9, Sm = 1.0, Eu = 0.8, Tb = 0.17, Yb = 0.37, and Lu = 0.06 ppm, with 2 s.d. errors near ± 30%. All these elements are highly incompatible until the arrival of augite, which affects chiefly the HREE, and apatite, which affects all (but more strongly, the LREE). The net result is that after apatite arrival at 94 PCS, the liquid compositions are nearly constant, hence D^WR/L_REE ≈ 1.0. These results are compatible with the mineralogy of the intrusion and the estimated partition coefficients for feldspar, olivine, augite, apatite, and Fe-Ti oxide minerals. For pre-apatite liquids, D^FSP/L_REE vary regularly with the normative di content of the liquid and change by an order of magnitude, hence the bulk liquid composition must be considered in any attempt to invert the compositions of feldspars to parent liquids.The Eu anomaly at first decreases in Kiglapait liquids due to plagioclase fractionation, but then increases due to removal of augite and apatite with negative Eu anomalies. The features dominantly responsible for Eu partitioning are liquid structure and, for monoclinic ternary feldspars, crystal structure. The former is best monitored by the augite or diopside content of the liquid and the latter, by the K content of the feldspar.The chondrite-normalized REE pattern for the intrusion has La_N = 7.4, Lu_N = 1.6, (Ce/Yb)_N = 3.6, and Eu/Eu* = 2.4, indicating its feldspar-rich nature. The chilled margin of the nearby Hettasch Intrusion has a similar but more evolved pattern, corresponding roughly to the Kiglapait liquid at 70 PCS. As with other data, those for the REE suggest source differences for the two intrusions rather than a relationship due to fractionation.     

Kiglapait Geochemistry III: Potassium and Rubidium

The regular geometry and completeness of the Kiglapait intrusion permit its bulk composition to be obtained by summation, and the composition of successive liquids to be obtained by subtraction. The summations for K and Rb give 1806 and 1.08 ppm, yielding Rfrsol|K/Rb= 1670 for the intrusion, taken as equal to the parent magma. R increases slightly from this initial value to 2000 at the end of crystallization where MgO approaches zero in the rocks. K and Rb are therefore closely coherent and their distribution coefficients can differ only by a small amount in the Kiglapait system.Apparent feldspar/liquid distribution coefficients (D^F/L) can be estimated from detailed plots of feldspar and liquid compositions against F_L. The Kiglapait data imply that these coefficients are linear 1:1 functions of plagioclase composition within experimental error, having values given by D_KF/L = 1.42? X_AnD_RbF/L = 1.13? X_An with minimum values of 0.75 and 0.49, respectively. The ratio $\text{R}{}^{\mathrm{F}}\text{R}{}^{\mathrm{L}}$ lies in the range of 1.53± 0.03 for the plagioclase composition range X_An= 0.34 to 0.67 showing that high-R rocks such as anorthosite crystallized from high-R liquids.The apparent feldspar distribution coefficients are much closer to 1.0 than common literature values. They can be reduced by assuming that the cumulate pile was continuously recharged by the circulating magma until an advanced stage of differentiation was reached, and assuming that alkalies were exchanged to the feldspars from the magma. When such an ‘aquifer recharge’ model is calibrated using olivine-liquid equilibria as a time marker for the liquid, the inferred minimum equilibrium values of the distribution coefficients are $\text{D}{}_{\mathrm{K}}\text{F}\text{L}$= 0.42, $\text{D}{}_{\mathrm{Rb}}\text{F}\text{L}$ = 0.25 at the base of the intrusion. Their variation is given by $\text{D}{}_{\mathrm{K}}\text{F}\text{L}\text{= 1.66?1.88X}{}_{\mathrm{An}}$, $\text{D}{}_{\mathrm{Rb}}\text{F}\text{L}\text{= 1.17?1.41X}{}_{\mathrm{An}}$, The equilibrium values are considered to be appropriate for deducing liquid compositions in plutonic bodies where alkali exchange can be shown or inferred to have been inhibited, such as in small intrusions. The apparent values are considered to be appropriate, even though they may be artificial, for large intrusions similar to the Kiglapait.The bulk K and Rb concentrations in the Kiglapait intrusion are consistent with a plagioclase-rich abyssal tholeiite magma. Clinopyroxene and olivine fractionation in the mantle may contribute to the production of such high-Rmagmas.     

Assimilation of carbonate country rock by the parent magma of the Panzhihua Fe-Ti-V deposit（SW China）：Evidence from stable isotopes

The Panzhihua intrusion in southwest China is part of the Emeishan Large Igneous Province and host of a large Fe-Ti-V ore deposit.During emplacement of the main intrusion,multiple generations of mafic dykes invaded carbonate wall rocks,producing a large contact aureole.We measured the oxygen-isotope composition of the intrusions,their constituent minerals,and samples of the country rock.Magnetite and plagioclase from Panzhihua intrusion haveδ¹⁸O values that are consistent with magmatic equilibrium, and formed from magmas withδ¹⁸O values that were 1-2‰higher than expected in a mantle-derived magma.The unmetamorphosed country rock has highδ¹⁸O values,ranging from 13.2‰（sandstone） to 24.6-28.6‰（dolomite）.The skarns and marbles from the aureole have lowerδ¹⁸O andδ¹³C values than their protolith suggesting interaction with fluids that were in exchange equilibrium with the adjacent mafic magmas and especially the numerous mafic dykes that intruded the aureole.This would explain the alteration ofδ¹⁸O of the dykes which have significantly higher values than expected for a mantle-derived magma.Depending on the exactδ¹⁸O values assumed for the magma and contaminant, the amount of assimilation required to produce the elevatedδ¹⁸O value of the Panzhihua intrusion was between 8 and 13.7 wt.%,assuming simple mixing.The exact mechanism of contamination is unclear but may involve a combination of assimilation of bulk country rock,mixing with a melt of the country rock and exchange with CO₂-rich fluid derived from decarbonation of the marls and dolomites.These mechanisms,particularly the latter,were probably involved in the formation of the Fe-Ti-V ores.     

O18/O16 Ratios in Rocks and Coexisting Minerals of the Skaergaard Intrusion, East Greenland

The Skaergaard intrusion of East Greenland is a gravitationallystratified gabbroic mass that has undergone extreme fractionalcrystallization. Oxygen-isotopic analyses have been obtainedfor the various rock types of this intrusion and for severalcoexisting minerals of these rocks. The general relationshipsamong the O¹⁸/O¹⁶ ratios of the minerals are the same as havebeen found for other igneous rocks, but the isotopic fracticnationsare smaller, probably as a result of the higher temperatureof formation of the Skaergaard rocks. The later differentiatesare progressively depleted in O¹⁸ to a marked degree relativeto the earlier-formed portions of the layered series; the late-stagegranophyres are 4–5 per mil lower in O¹⁸/O¹⁶ than thelayered Lower Zone gabbros, and are 7–9 per mil lowerthan normal granitic rocks from other localities. This progressivedepletion in O¹⁸ is a result of crystallization and settlingout of minerals that are, on the whole, about 1 per mil higherin O¹⁸/O¹⁶ than the magma liquid. Calculations based on a simplecrystallization model are in agreement with the experimentalresults.     

Kiglapait Mineralogy II: Fe-Ti Oxide Minerals and the Activities of Oxygen and Silica

Cumulus titanomagnetite and subordinate ilmenite first appearin the Upper Zone of the Kiglapait intrusion. They arrive graduallyand then reach abnormal abundances before falling to a sustainedcotectic mode near seven volume per-cent. The most Ti-rich titanomagnetites(to Usp ₆₆) are preserved in ore bands (layers) which solidifiedby adcumulus growth leading to the complete expulsion of interstitialsilicate liquid. Analyses from three of these ore bands, appliedto the solution model of Lindsley (1977), form a single lineararray in f_o2 versus 1/T ?K, with log f_o2 = (–28,283 ?89)/T + 11.03 ? 0.25. This array implies log f_o2 = –9.65at 1094 ?C, the model temperature of the Main Ore Band, consistentwith primary mineral compositions Ilm₈₉, Usp₇₉ and a weightmode of 18 per cent ilmenite. Silicate rocks yield another linear array, i.e. log f_o2 = (–37,910? 102)/T + 22.57 ? 0.61. This array is ascribed to closure ofsubsolidus reactions from initial compositions near Usp_79–80Ilm₉₀. The center of gravity of the data falling on this arraysuggests a primary mode of about 50 per cent ilmenite for thesilicate rocks, implying somewhat more reducing conditions ofcrystallization than for the ore bands. The modal overproductionrepresented by the ore bands is attributed to super-saturationin oxygen, which is demonstrated by the Al-depleted compositionsof titanomagnetite in ore bands, by direct evidence for elevatedf_o2 at the top of the Main Ore Band, and by abnormally magnesiansilicate mineral compositions in and near the ore bands. The primary titanomagnetite composition for average rocks isestimated at Usp₈₀ for the base, and Usp₇₃ for the top of theUpper Zone, from rock and mineral chemistry and observed textures.The idealized magma path for the Upper Zone runs from (T andlog f_o2) 1154 ?C, –9.0 to 960 ?C, –12.2. The orebands lie above this path and are interpreted as lying on themetastable extension of the Lower Zone path, which originatesat 1250 ?C, –8.1, on the WM buffer at 4 kbar total pressure. Silica activity is estimated from mineral compositions nearthe ore bands as applied to the FMQ equilibrium, and mappedfor the Lower Zone by an adjustment downward from the En-Fo-Silequilibrium, with resultant values near 0.55 relative to quartz= 1.0. The logarithmic oxygen/silica activity ratio (OSAR) coincideswith that of the Skaergaard intrusion in the Lower Zones. TheSkaergaard OSAR is offset downward from the Kiglapait trendduring MZ time, and remains below it at the end of crystallization.The more highly silicated Skaergaard magma was initially moreoxidized than the Kiglapait magma, but this relation was reversedafter the loss of olivine in the Skaergaard intrusion, as couldhave been predicted from theory and the mineralogy of the twointrusions.     

Low-O18 basalts from Iceland

The volcanic rocks of Iceland are anomalous in their oxygen isotope content. Recent tholeiitic and transitional alkali basalts from Iceland range in (δO¹⁸ from 1·8 to 5δ7%. Most of the tholeiitic basalts and their phenocrysts are at least 1% lower in δO¹⁸ than unaltered basalts from other oceanic islands or oceanic ridges. The Icelandic basalts that resemble ridge basalts in δO¹⁸ also resemble them in major element chemistry. δO¹⁸ values of alkali olivine basalts are closest to those of other oceanic islands. Secondary alteration processes have lowered as well as raised the δO¹⁸ values of some Icelandic rocks, but such surface mechanisms cannot account for the distribution of oxygen isotopes in the Recent basalts of Iceland. Three mechanisms that could give rise to the low-O¹⁸ magmas are (1) exchange of oxygen between magma and low-O¹⁸ hydrothermally altered rock, (2) exchange with low-O¹⁸ meteoric water, or (3) an exceptional mantle under Iceland. None of the above models can satisfactorily account for all the observations.     

Oxygen isotopic fractionation between oxygen of different sites in hydroxyl-bearing silicate minerals

A method has been developed for extraction of hydroxyl oxygen from hydroxyl-bearing silicate minerals for oxygen isotopic analysis.The δO¹⁸ of oxygen of the OH groups is significantly different from that in the rest of the mineral structure. The isotopic fractionation between the two types of sites has the potential to be a sensitive geothermometer.Several δO¹⁸ values were obtained for oxygen of the OH attached to different silicate structures as well as for two muscovite samples with quantitatively estimated different temperatures of formation.The 1000 ln α (mineral-OH) values ranged from 5.2%. for muscovite to about 12.6%. for kaolinite and chlorite.     

Biogeochemical implications of the isotopic equilibrium fractionation factor between the oxygen atoms of acetone and water

Carbonyl oxygens of organic molecules undergo isotopic exchange with water during reversible hydration reactions. The equilibrium isotopic fractionation factors between the carbonyl oxygen of acetone and water at 15°, 25°, and 35°C are 1.028, 1.028, and 1.026 respectively. The differences between the δ¹⁸O values of the carbonyl oxygen of acetone and of the water with which it is in equilibrium are similar to the differences that have been observed between the δ¹⁸O values of cellulose and the water used in its synthesis by a variety of aquatic plants and animals. Additionally, the identity of the acetone-water fractionation factors at 15° and 25°C parallels the observation that the difference between the δ¹⁸O values of cellulose and water shows no temperature dependence for individual species of plants grown over the same temperature range. These results are discussed in relation to the proposal that the oxygen isotopic relationship between cellulose and water is established by isotopic exchange occurring during the hydration of carbonyl groups of the intermediates of cellulose synthesis.     

sol18O16O of Archean clastic metasedimentary rocks: a petrogenetic indicator for Archean gneisses?

The oxygen isotopic compositions of over 100 Archean clastic metasedimentary, felsic metavolcanic and gneissic rocks from selected areas within the Superior Province have been determined. δ¹⁸O values of low grade, immature clastic metasediments range from 8.0 to 13.3%. and hence are somewhat depleted in ¹⁸O relative to other clastic metasediments. The lower ¹⁸O content is attributed to the large proportion of unaltered rock fragments in the Archean metasediments. Felsic metavolcanics have a similar range of δ¹⁸O values (7.3 to 13.0%..δ¹⁸O values for the middle amphibolite facies Pakwash paragneiss (8.8–11.7%.) are higher than those determined for the amphibolite to granulite facies Twilight paragneiss (7.3–9.2%.). Archean orthogneisses such as the Clay Lake gneiss (7.0–9.0%.), the Cedar Lake gneiss (7.4–8.7%.) and the Footprint gneiss (5.9-8.8%.) have δ¹⁸O values similar to those of the Twilight paragneiss. Therefore, at least at metamorphic grades higher than middle amphibolite facies, Archean metasedimentary gneisses may have δ¹⁸O values that are indistinguishable from those of Archean orthogneisses, and hence are no longer isotopically recognizable as metasedimentary rocks.     

Oxygen isotopes in mammal bone phosphate: A new tool for paleohydrological and paleoclimatological research?

Oxygen isotope analyses of water in blood of humans and domestic pigs indicate that the oxygen isotope fractionation effects between ingested water and body water are the same in all specimens of the same species. The δ¹⁸O of body water has been shown to vary linearly with the mean δ¹⁸O of local meteoric water. This conclusion also holds for the bone phosphate. Thus, δ¹⁸O(PO^3?₄) values of unaltered fossil bones from humans and domestic pigs can be used to reconstruct the δ¹⁸O values of local meteoric waters during the life-times of the mammals. Such data can be used for paleohydrological and paleoclimatological studies both on land and at sea.     

Fractionation of oxygen isotopes between mammalian bone-phosphate and environmental drinking water

The δ¹⁸O of mammalian bone-phosphate varies linearly with δ¹⁸O of environmental water, but is not in isotopic equilibrium with that water. This situation is explained by a model of δ¹⁸O in body water in which the important fluxes of exchangeable oxygen through the body are taken into account. Fractionation of oxygen isotopes between body and environmental drinking water is dependent on the rates of drinking and respiration. Isotopic fractionation can be estimated from physiological data and the estimates correlate very well with observed fractionation. Species whose water consumption is large relatively to its energy expenditure is sensitive to isotopic ratio changes in environmental water.     

Correlation of δ<Superscript>18</Superscript>O and initial<Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr ratios in Kirkpatrick basalt on Mt. Falla,transantarctic mountains

Theδ¹⁸O (SMOW) values of the Kirkpatrick Basalt (Jurassic) on Mt. Falla, Queen Alexandra Range, vary between +6.3‰ and +8.6‰ The apparent enrichment of these rocks in¹⁸O excludes the possibility that they were altered by interaction with aqueous solutions of meteoric origin. Theδ¹⁸O values of the flows correlate significantly with the initial⁸⁷Sr/⁸⁶Sr ratios and all major elements. These correlations confirm the hypothesis that the basalt magma was contaminated by rocks of the continental crust through which it was extruded. Estimates of the chemical composition of the basalt magma and the contaminant, based on extrapolations of the new oxygen data, generally confirm earlier estimates based on extrapolations of initial⁸⁷Sr/⁸⁶Sr ratios. The⁸⁷Sr/⁸⁶Sr ratio of the uncontaminated basalt was 0.7093 which indicates that magma may have originated by melting either in old Rb-enriched lithospheric mantle under Antarctica or in the overlying crust, or both.     

德兴斑岩铜矿成矿热液来源及其演化——花岗闪长斑岩的氧同位素制约

作者研究了德兴铜厂花岗闪长斑岩的氧同位素组成特征在垂直方向上的变化规律,及蚀变作用对花岗闪长斑岩全岩和单矿物氧同位素组成的影响。结果表明,从地表到深部,花岗闪长斑岩全岩和长石单矿物的δ＾１８Ｏ值总体上有逐渐降低的趋势,反映花岗闪长斑岩受到已演化的大气降水水－岩氧同位素交换作用的影响。水－岩交换作用对花岗闪长斑岩氧同位素组成的影响在浅部和深部是不同的,这主要受控于水－岩交换温度和交换水的初始氧同位素组成等因素。石英的氧同位素组成及变化特征不同于全岩和长石,其值与岩石的蚀变作用有关从花岗闪长斑岩的氧同位煮组成及其变化规律可以推论,由大气降水演化为德兴斑岩铜矿成矿热液是可能的。     

The non-mass-dependent oxygen isotope effect in the electrodissociation of carbon dioxide: A step toward understanding NoMaD chemistry

A non-mass dependent (NoMaD) oxygen isotope effect is demonstrated in the dissociation of CO₂ similar to that observed in the electrosynthesis of ozone. The molecular oxygen produced carries the signature of two separate isotopic fractionation processes; a mass-dependent fractionation probably due to CO₂ + O isotopic exchange, and a secondary NoMaD fractionation (δ¹⁷O = 0.97 ± 0.09δ¹⁸O, with the O₂ depleted in ¹⁷O and ¹⁸O). It is suggested that the effect is due to either the formation or relaxation of ozone in an excited electronic state. This represents the latest advance in the understanding of chemical NoMaD effects which may be essential to the explanation of non-mass-dependent fractionations observed in meteorites.     

Transfer and early diagenesis of biogenic silica oxygen isotope signals during settling and sedimentation of diatoms in a temperate freshwater lake (Lake Holzmaar, Germany)

We have investigated the transfer of oxygen isotope signals of diatomaceous silica (δ¹⁸O_diatom) from the epilimnion (0-7 m) through the hypolimnion to the lake bottom (∼20 m) in freshwater Lake Holzmaar, Germany. Sediment-traps were deployed in 2001 at depths of 7 and 16 m to harvest fresh diatoms every 28 days. The 7 m trap collected diatoms from the epilimnion being the main zone of primary production, while the 16 m trap collected material already settled through the hypolimnion. Also a bottom sediment sample was taken containing diatom frustules from approximately the last 25 years. The δ¹⁸O_diatom values of the 7 m trap varied from 29.4‰ in spring/autumn to 26.2‰ in summer according to the temperature dependence of oxygen isotope fractionation and represent the initial isotope signal in this study. Remarkably, despite the short settling distance δ¹⁸O_diatom values of the 7 and the 16 m trap were identical only during spring and autumn seasons while from April to September δ¹⁸O_diatom values of the 16 m trap were roughly ∼1.5‰ enriched in ¹⁸O compared to those of the 7 m trap. Isotopic exchange with the isotopically lighter water of the hypolimnion would shift the δ¹⁸O_diatom value to lower values during settling from 7 to 16 m excluding this process as a cause for the deviation. Dissolution of opal during settling with intact organic coatings of the diatom cells and near neutral pH of the water should only cause a minor enrichment of the 16 m values. Nevertheless, opal from the bottom sediment was found to be 2.5‰ enriched in ¹⁸O compared to the weighted average of the opal from the 7 m trap. Thus, resuspension of bottom material must have contributed to the intermediate δ¹⁸O_diatom signal of the 16 m trap during summer. Dissolution experiments allowed further investigation of the cause for the remarkably enriched δ¹⁸O_diatom value of the bottom sediment. Experiments with different fresh diatomaceous materials show an increase of opaline ¹⁸O at high pH values which is remarkably reduced when organic coatings of the cells still exist or at near neutral pH. In contrast, high pH conditions do not affect the δ¹⁸O_diatom values of sub-fossil and even fossil opal. IR analyses show that the ¹⁸O enrichment of the sedimentary silica is associated with a decrease in Si-OH groups and the formation of Si-O-Si linkages. This indicates a silica dehydroxylation process as cause for the isotopic enrichment of the bottom sediment. Silica dissolution and dehydroxylation clearly induce a maturation process of the diatom oxygen isotope signal presumably following an exponential behaviour with a rapid initial phase of signal alteration. The dynamics of this process is of particular importance for the quantitative interpretation of sedimentary δ¹⁸O_diatom values in terms of palaeothermometry.     

Kiglapait Geochemistry II: Petrography

The mode of the Kiglapait intrusion carries 73 per cent feldspar,but average rocks near the base of the Upper Zone contain aslittle as 48 per cent feldspar. Olivine remained stable throughoutthe crystallization, but was locally suppressed by abundantcrystallization of augite and titano-magnetite. Red biotiteoccurs as rims on Fe–Ti oxide minerals and is probablyfluorine oxybiotite; its frequently similar occurrence in troctoliticrocks may, perversely, indicate dry magmas rather than dampones. Excluded modal components follow Rayleigh fractionation behaviour;their presence in trace amount permits estimation of residualporosity in the Lower Zone. This porosity diminishes directlywith accumulation rate from 0.14 to 0.03 over the first 80 percent of crystallization history. The saturation ratio of excludedmodal components is a well-behaved function of fraction solidified,and implies that the decrease in porosity continues above the80 per cent solidified level. The saturation ratio links withbulk composition, porosity, and F_L, allowing one of these parametersto be estimated from the others. The cumulus arrival of apatite is abrupt, but the earlier arrivalsof augite, oxide minerals, and sulfide each occur over an interval,followed by an interval of overproduction. This behaviour isattributed to feedback on concentration gradients generatedby a long history of plagioclase + olivine extraction, in theabsence of perfect stirring. Diffusion plays a role in the differentiationof large, slowly cooled magma systems because radial mixingby convection is inefficient. Inherited potential supersaturationis the inevitable result. This leads to modal irregularities,and to crystallization effectively on metastable extensionsof field boundaries. The track of the liquid in the Lower Zone is closely parallelto that in the system Fo–Di–An, but offset fromit by the combined effects of Ab and P (toward plagioclase)and Fa (away from plagioclase). The latter effect is important,with the result that the shedding of plagioclase by an ascendingmagma will be much less marked than predicted from iron-freeexperimental systems.     

Oxygen isotope composition of xenoliths from the oceanic crust and volcanic edifice beneath Gran Canaria (Canary Islands): consequences for crustal contamination of ascending magmas

Xenolith samples of marine terrigenous sediments and altered Jurassic MORB from Gran Canaria (Canary Islands) represent samples of sub-island oceanic crust. These samples are postulated to define end-members for crustal contamination of basaltic and felsic ocean island magmas. The meta-igneous rocks show great heterogeneity in oxygen isotope compositions (δ¹⁸O 3.3–8.6‰), broadly correlating with their stratigraphic position in the oceanic crust. Gabbros interpreted as fragments of oceanic crust layer 3 have δ¹⁸O values of 3.3–5.1‰, which is lower than MORB (5.7–6.0‰). Layer 2 lavas and dykes show a broader range of δ¹⁸O of 4.1–8.6‰. Therefore, high-temperature metamorphism seems to have been the dominant process in layer 3, while both high- and low-temperature alteration have variably affected layer 2 rocks. Siliciclastic sediments have high δ¹⁸O values (14.1–16.4‰), indicating diagenesis and low-temperature interaction with seawater. The oxygen isotope stratigraphy of the crust beneath Gran Canaria is typical for old oceanic crust and resembles that in ophiolites. The lithologic boundary between older oceanic crust and the igneous core complex at 8–10 km depth—as postulated from geophysical data—probably coincides with a main magma stagnation level. There, the Miocene shield phase magmas interacted with preexisting oceanic crust. We suggest that the range in δ¹⁸O values (5.2–6.8‰) [Chem. Geol. 135 (1997) 233] found for shield basalts on Gran Canaria, and those in some Miocene felsic units (6.0–8.5‰), are best explained by assimilation of various amounts and combinations of oceanic and island crustal rocks and do not necessarily reflect mantle source characteristics.