Zirconium and hafnium fractionation in differentiation of alkali carbonatite magmatic systems

Zirconium and hafnium are valuable strategic metals which are in high demand in industry. The Zr and Hf contents are elevated in the final products of magmatic differentiation of alkali carbonatite rocks in the Polar Siberia region (Guli Complex) and Ukraine (Chernigov Massif). Early pyroxene fractionation led to an increase in the Zr/Hf ratio in the evolution of the ultramafic–alkali magmatic system due to a higher distribution coefficient of Hf in pyroxene with respect to Zr. The Rayleigh equation was used to calculate a quantitative model of variation in the Zr/Hf ratio in the development of the Guli magmatic system. Alkali carbonatite rocks originated from rare element-rich mantle reservoirs, in particular, the metasomatized mantle. Carbonated mantle xenoliths are characterized by a high Zr/Hf ratio due to clinopyroxene development during metasomatic replacement of orthopyroxene by carbonate fluid melt.     

The brevity of carbonatite sources in the mantle: evidence from Hf isotopes

Hf, Zr and Ti in carbonatites primarily reside in their non-carbonate fraction while the carbonate fraction dominates the Nd and Sr elemental budget of the whole rock. A detailed investigation of the Hf, Nd and Sr isotopic compositions shows frequent isotopic disequilibrium between the carbonate and non-carbonate fractions. We suggest that the trace element and isotopic composition of the carbonate fraction better represents that of the carbonatite magma, which in turn better reflects the composition of the carbonatitic source. Experimental partitioning data between carbonatite melt and peridotitic mineralogy suggest that the Lu/Hf ratio of the carbonatite source will be equal to or greater than the Lu/Hf ratio of the carbonatite. This, combined with the Hf isotope systematics of carbonatites, suggests that, if carbonatites are primary mantle melts, then their sources must be short-lived features in the mantle (maximum age of 10–30 Ma), otherwise they would develop extremely radiogenic Hf compositions. Alternatively, if carbonatites are products of extreme crystal fractionation or liquid immiscibility then the lack of radiogenic initial Hf isotope compositions also suggests that their sources do not have long-lived Hf depletions. We present a model in which the carbonatite source is created in the sublithospheric mantle by the crystallization of earlier carbonatitic melts from a mantle plume. This new source melts shortly after its formation by the excess heat provided by the approaching hotter center of the plume and/or the subsequent ascending silicate melts. This model explains the HIMU-EMI isotope characteristics of the East African carbonatites, their high LREE/HREE ratios as well as the rarity of carbonatites in the oceanic lithosphere.     

New carbonatite complex in the western Baikal area,southern Siberian craton: Mineralogy,age, geochemistry,and petrogenesis

A dike–vein complex of potassic type of alkalinity recently discovered in the Baikal ledge, western Baikal area, southern Siberian craton, includes calcite and dolomite–ankerite carbonatites, silicate-bearing carbonatite, phlogopite metapicrite, and phoscorite. The most reliable ⁴⁰Ar–³⁹Ar dating of the rocks on magnesioriebeckite from alkaline metasomatite at contact with carbonatite yields a statistically significant plateau age of 1017.4 ± 3.2 Ma. The carbonatite is characterized by elevated SiO₂ concentrations and is rich in K₂O (K₂O/Na₂O ratio is 21 on average for the calcite carbonatite and 2.5 for the dolomite–ankerite carbonatite), TiO₂, P₂O₅ (up to 9 wt %), REE (up to 3300 ppm), Nb (up to 400 ppm), Zr (up to 800 ppm), Fe, Cr, V, Ni, and Co at relatively low Sr concentrations. Both the metapicrite and the carbonatite are hundreds of times or even more enriched in Ta, Nb, K, and LREE relative to the mantle and are tens of times richer in Rb, Ba, Zr, Hf, and Ti. The high (Gd/Yb)_CN ratios of the metapicrite (4.5–11) and carbonatite (4.5–17) testify that their source contained residual garnet, and the high K₂O/Na₂O ratios of the metapicrite (9–15) and carbonatite suggest that the source also contained phlogopite. The Nd isotopic ratios of the carbonatite suggest that the mantle source of the carbonatite was mildly depleted and similar to an average OIB source. The carbonatites of various mineral composition are believed to be formed via the crystallization differentiation of ferrocarbonatite melt, which segregated from ultramafic alkaline melt.     

Metasomatism in mantle xenoliths from the Letlhakane kimberlites: estimation of element fluxes

A suite of metasomatised xenoliths from the Letlhakane kimberlite (Botswana) forms a metasomatic sequence from garnet peridotite to garnet phlogopite peridotite to phlogopite peridotite. Before the modal metasomatism, most of the Letlhakane xenoliths were depleted harzburgites that had been subjected to an earlier cryptic metasomatic event. Modal phlogopite and clinopyroxene - Cr-spinel increase at the expense of garnet and orthopyroxene with increasing degrees of metasomatism. The most metasomatised xenolith is a wehrlite. With progressive modal metasomatism, the clinopyroxene becomes enriched in Sr, Sc and the LREE, orthopyroxene becomes depleted in Ca and Ni, but enriched in Al and Mn, and olivine becomes depleted in Al and V. Garnet chemical composition largely remains unchanged. The garnet replacement reaction seen in most xenoliths allows the measurement of the flux of trace elements through detailed modal analysis of the pseudomorphs. Mass balance calculations show that the modally metasomatised rocks became enriched in incompatible elements such as Sr, Na, K, the LREE and the HFSE (Ti, Zr and Nb). Major elements (Al, Cr and Fe) and garnet-compatible trace elements (V, Y, Sc, and the HREE) were removed during this metasomatic process. The modal metasomatism caused a strong depletion in Al, and the results challenge previous suggestions that this metasomatic process merely occurred within an Al-poor environment. The data suggest that the xenoliths represent the mantle wallrock adjacent to a major conduit for an alkaline basic silicate melt (with high contents of volatile and incompatible elements). The volatile and incompatible element-enriched component of this melt percolated into the wallrock along a strong temperature gradient and caused the observed range of metasomatism.     

四川木洛稀土矿床碳酸岩地球化学

木洛稀土矿床成因上与碳酸岩-碱性杂岩密切相关。碳酸岩主要由方解石组成,CaO/（CaO＋MgO＋FeO＋Fe2O3＋MnO）比值在95.7%～99.6%,为方解石碳酸岩。碳酸岩相对富集大离子亲石元素Ba、Sr、LREE,亏损高场强元素Nb、Ta、Ti、Zr、P,高Zr/Hf和La/Nb值,低Sm/Nd和Rb/Sr值,暗示岩石来自富集地幔EMI。地质、地球化学研究表明,木洛碳酸岩是在峨眉山地幔柱地幔遗存物经喜马拉雅造山运动再次活化的产物,但碳酸岩熔浆在上侵过程中受到地壳物质混染。碳酸岩-碱性岩熔浆带来大量稀土元素,并在喜马拉雅造山期造山运动派生的局部引张部位成矿。     

Experimental cpx/melt partitioning of 24 trace elements

Cpx/melt partition coefficients have been determined by ion probe for 24 trace elements at natural levels in an alkali basalt experimentally equilibrated at 1,380°C and 3 GPa. One goal was to intercompare Ds for both high-field-strength elements and rare earth elements (REE) in a single experiment. Relative to the REE spidergram, Hf and Ti show virtually no anomaly, whereas Zr exhibits a major negative anomaly. Other incompatible elements (Ba, K, Nb) fall in the range of published values, as do elements such as Sr, Y, Sc, Cr and V. Pb shows a value intermediate between La and Ce. Values for Be, Li and Ga are reported for the first time, and show that Be is as incompatible as the light REEs whereas Li and Ga are somewhat more compatible than the heavy REE.     

Equivocal carbonatite markers in the mantle xenoliths of the Patagonia backarc: the Gobernador Gregores case (Santa Cruz Province,Argentina)

Amphibole ± phlogopite ± apatite-bearing mantle xenoliths at Gobernador Gregores display modal, bulk-rock and phase geochemical characteristics held as indicators of carbonatitic metasomatism. However, part of these xenoliths has high TiO₂/Al₂O₃ and those displaying the most pronounced carbonatitic geochemical markers modally trend towards harzburgite. Bulk-rock, clinopyroxene and amphibole show Zr, Hf and Ti negative anomalies, which increase at decreasing Na₂O and high field strength elements (HFSE) concentrations. Steady variation trends between xenoliths which have and do not have carbonatitic characteristics suggest a control by reactive porous flow of only one agent, inferred to be initially a ne-normative hydrous basalt (because of the presence of wehrlites) evolving towards silica saturation. Variation trends exhibit cusps when amphibole appears in the mode. Appearance of amphibole may explain the Ti anomaly variations, but not those of Zr and Hf. Numerical modelling [Plate Model (Vernières et al. in J Geophys Res 102:24771–24784, 1997)] gives results consistent with the observed geochemical features by assuming the presence of loveringite. Modest HFSE anomalies in the infiltrating melt may be acquired during percolation in the garnet-facies.In memory of Carlo Rivalenti     

橄榄石微量元素原位分析的现状及其应用

随着高精度EMPA和LA-ICP-MS分析技术的发展和矿物微量元素测试精度的提高,利用橄榄石中的微量元素示踪地幔部分熔融、地幔交代作用、岩浆早期结晶过程等地质问题成为近年来一个新兴的研究方向。一系列开拓性的研究发现也被陆续的发表,主要涉及橄榄石中Ni、Co、Al、Cr、Zn、Ti、Li、V、Sc、Mn、Ca和P等元素的示踪使用。一些卓有成效的示踪方法为:Ca、Al、Ti、Ni及Mn能够很好的用于区分橄榄石捕掳晶和斑晶;橄榄石-尖晶石地幔演化趋势线(OSMA:olivine-spinel mantle array)图解可以用于表征岩浆源区的亏损程度;玄武岩中橄榄石斑晶的Li同位素及Li含量可以很有效地指示岩浆源区是否存在地壳物质再循环及地幔交代作用;橄榄石斑晶中Ni、Ca、Mn、Cr和Al协变关系图解可以识别岩浆的辉石岩源区;利用橄榄石捕掳晶中Zr和Sc的含量差异特征可将橄榄岩中三种最主要的类型(尖晶石橄榄岩、石榴石橄榄岩以及尖晶石-石榴石橄榄岩)区分开来;一些元素的比值或组合(例如Ni/Co、Fe/Mn、V/Sc、Zr和Sc、Ca和Ti)可以指示源区交代作用、岩浆作用过程及氧化状态;基于橄榄石中Al、Cr及Ca的地质温度计可以为推算地幔热状态提供新方法;基于橄榄石分离结晶Fo-NiO演化线的原始岩浆计算模型可以较好的推算原始岩浆成分;利用橄榄石的环带及微量元素的扩散机制可以判别更多岩石成因信息,如识别交代介质、熔体类型以及地质构造背景等。基于上述最新研究的相关资料和已有成果,本文对橄榄石微量元素的地球化学示踪方法做系统性的归纳整理,并对橄榄石微量元素赋存状况、橄榄石微量元素测试方法、橄榄石微量元素的使用条件及需注意的问题等进行讨论,为读者在做相关研究时提供参考。     

Trace Element Residence and Partitioning in Mantle Xenoliths Metasomatized by Highly Alkaline, Silicate- and Carbonate-rich Melts (Kerguelen Islands, Indian Ocean)

Mantle xenoliths in alkaline lavas of the Kerguelen Islandsconsist of: (1) protogranular, Cr-diopside-bearing harzburgite;(2) poikilitic, Mg-augite-bearing harzburgite and cpx-poor lherzolite;(3) dunite that contains clinopyroxene, spinel phlogopite, andrarely amphibole. Trace element data for rocks and mineralsidentify distinctive signatures for the different rock typesand record upper-mantle processes. The harzburgites reflectan initial partial melting event followed by metasomatism bymafic alkaline to carbonatitic melts. The dunites were firstformed by reaction of a harzburgite protolith with tholeiiticto transitional basaltic melts, and subsequently developed metasomaticassemblages of clinopyroxene + phlogopite ± amphiboleby reaction with lamprophyric or carbonatitic melts. We measuredtwo-mineral partition coefficients and calculated mineral–meltpartition coefficients for 27 trace elements. In most samples,calculated budgets indicate that trace elements reside in theconstituent minerals. Clinopyroxene is the major host for REE,Sr, Y, Zr and Th; spinel is important for V and Ti; orthopyroxenefor Ti, Zr, HREE, Y, Sc and V; and olivine for Ni, Co and Sc. KEY WORDS: mantle xenoliths; mantle metasomatism; partition coefficients; Kerguelen Islands; trace elements     

The lithospheric mantle beneath the southwestern Tianshan area, northwest China

A suite of spinel peridotite xenoliths in Mesozoic basalts of the Tuoyun basin in the Tianshan area of northwest China has a high proportion of amphibole/mica-bearing lherzolites, with high Cpx/Opx ratios (mean 0.74). Many aspects of mineral chemistry in the Tuoyun peridotites are intermediate between those of refractory Archean cratonic mantle and fertile Phanerozoic mantle. These include Ni/Cr and the contents of transition metals and Y in olivine and orthopyroxene and the abundances of elements such as Na, Al, Ti, Y, Sr and LREE in clinopyroxene. The data suggest that the mantle in Tuoyun is moderately depleted in basaltic components relative to both the refractory Archean mantle and the fertile Phanerozoic mantle. The wide variations in the CaO/Al₂O₃ (0.9–3.5) of whole rocks and LREE/HREE (0.8–14.2) and Ti/Eu (971–5,765) of clinopyroxenes in the Tuoyun peridotites are interpreted as the metasomatism of hydrous carbonatitic and potassic melt or the cumulative effects of mantle metasomatism by different agents (carbonatite and small-volume silicate melts) through time. The Tuoyun mantle shows closer affinity to the type of mantle found beneath the Proterozoic Cathaysia block, and especially to that beneath the East Central Asia Orogenic Belt (ECAOB), than to the mantle beneath the Archean North China Craton. This implies that the Tianshan subcontinental lithospheric mantle may have been generated during the accretion of the ECAOB. The high proportion of fine-grained microstructures, high Cpx/Opx ratio, obvious Ca enrichment and lower overall depletion in the Tuoyun mantle relative to that in other parts of the ECAOB reflect stronger mechanical and chemical modification of the Tuoyun mantle, near the translithospheric Talas-Ferghana strike-slip fault, which played a major role in controlling the strength of the mantle lithosphere and has channeled the upwelling mantle.     

Constraints from eclogite and MARID xenoliths on origins of mantle Zr/Hf–Nb/Ta variability

New trace-element data of rutile in kimberlite-borne ~1.85 Ga eclogite and pyroxenite xenoliths from the central Slave craton, as well as ~110 Ma MARID xenoliths from the Kaapvaal craton, provide constraints on the origins of lithospheric and sublithospheric mantle variability in high field strength element ratios. Rutiles in eclogites and pyroxenites have Zr/Hf ranging from 20 to 62 and Nb/Ta ranging from 10 to 40. Rutiles in MARID xenoliths have Zr/Hf from 24 to 33 and Nb/Ta from 10 to 41. Calculated whole-rock Zr/Hf is suprachondritic for eclogites with suggested gabbroic protoliths and subchondritic for boninite-like eclogites; the latter is consistent with cpx-controlled depletion in the protolith source. Within each eclogite type, positive correlations of Zr/Hf with La/Lu and negative correlations with Lu/Hf likely reflect fractionation of cpx and/or plagioclase during crystallisation of the protoliths. Zr/Hf–Nb/Ta relationships of some MARID-type rocks, which are products of lithospheric mantle metasomatism, and eclogite xenoliths plot on a silicate differentiation trend, whereas other samples have higher Nb/Ta at a given Zr/Hf. Fractionation of a few percent rutile from an HFSE-rich mafic melt can generate a trend towards strongly increased Nb/Ta at minimally changed Zr/Hf in the residual melt. Superposition of rutile fractionation on the effects of silicate differentiation, which fractionates Zr/Hf more strongly than Nb/Ta, can explain the Zr/Hf–Nb/Ta relationships of most eclogites from the central Slave craton as well as those of MARID rocks, metasomatised peridotites and group II kimberlites. By contrast, Zr/Hf–Nb/Ta relationships suggest that Group I kimberlites are mixtures between depleted peridotite and carbonatite. Thus, high Nb/Ta is a signature of lithospheric processes and may not be important in deeply subducted eclogites that bypass extended residence in the lithosphere. Conversely, considerable primary Zr/Hf variability was inherited by the eclogites, which is indicative of the compositional diversity of ancient subducted oceanic crust, which is expected to have generated substantial heterogeneity in sublithospheric basalt sources.     

Distribution of high field strength and rare earth elements in mantle and lower crustal xenoliths from the Southwestern United States: The role of grain-boundary phases

Spinel lherzolite and harzburgite xenoliths from the Basin and Range and Colorado Plateau Provinces in the southwestern United States (SWUS) show a broad range in incompatible element distributions from depleted to enriched, both within and between sites. The most fertile xenoliths occur in the Basin and Range Province and the most refractory in the Colorado Plateau or Transition Zone. Mass balance calculations indicate that up to 80% of the high field strength (Nb, Ta, Zr, Hf, Th, Ti) and rare earth elements (50% for Yb) in these xenoliths occur in phases along grain boundaries (or in microfractures). In lower crustal and eclogite xenoliths, up to 90% of these elements occur in grain-boundary phases. Nb/Ta, Zr/Hf, La/Sm and Nb/Th ratios and Nb-Ta anomalies in both types of xenoliths are also controlled by grain-boundary phases. To interpret these ratios in whole-rock analyses, it is critical to understand the timing and origin of the grain-boundary components in the xenoliths. Most of the enriched mantle xenoliths appear to have been enriched by metasomatic fluids related to silicate magmas and not to carbonatite magmas.Because of a complex multi-event history that affected the composition of the xenoliths, there is no simple geochemical relationship between magmatic or metamorphic history of the lower crust and upper mantle in the SWUS as reflected by the xenolith populations.     

OUTLINE OF THE GEOLOGY OF KOREA

A database on a number of elements in oceanic volcanic rocks is presented, including the principal major-element oxides-SiO₂, TiO₂, Al₂O₃, Fe₂O₃(T), MnO, MgO, CaO, Na₂O, K₂O, and P₂O₅ (where T refers to total iron)–and the trace elements–Ba, Ce, Cr, Cu, Ni, Sc, Sr, V, Pb (mainly by isotope dilution), Yb, Zn, and Zr. Interpretations are given for transition metals, with emphasis on Mn, Sc, and V, in order to determine the concentration of the elements in primitive melts and assess their trends in magmatic differentiation. Transition metals are not enriched in plagioclase, so all are incompatible with pure plagioclase removal–that is, they become enriched in the melt. Both Cr and Ni are known to be highly compatible with olivine separation-i.e., they are depleted in the melt early in differentiation. Also, Sc is compatible with clinopyroxene (Cpx) removal from the melt and is depleted by separation of Cpx. Copper does not fit well in any of the principal silicates, but Cu, like Ni, is greatly enriched in sulfides that may remain in the source or separate from the magma. Decreasing Ni abundances and increasing Cu contents during differentiation are a sign of olivine separation. In the analysis presented herein, V–in the absence of Cpx separation–is found to behave remarkably like the moderately incompatible element Zn, and these two elements add to the list of element pairs of similar incompatibility whose ratios are insensitive to differentiation and to submarine weathering as well. Both are enhanced in titanomagnetite, so both would be compatible during titanomagnetite separation. When Cpx separates, however, V becomes compatible like Sc, but Zn remains incompatible. Thus, decreasing V (and Sc) contents and increasing Zn contents during differentiation are a sign of Cpx separation. Manganese often behaves much like Zn and therefore is moderately incompatible, but Mn is less compatible than Zn and V in titanomagnetite. Thus, decreasing Zn and V with increasing Mn is an indication of titanomagnetite removal. Dual compatible and incompatible trends with differentiation are found chiefly for Cu, Sc, and Sr. Distinguishing mid-ocean ridge basalts (MORB), oceanic-island volcanic rocks (OIV), and island-arc volcanic rocks (IAV) may be accomplished by plots of Ce/Yb versus Ba/Ce, where OIV plot to higher values of Ce/Yb than do MORB, and IAV data plot to higher values of Ba/Ce than do those of MORB. These ratios do not seem to be significantly affected by submarine weathering.     

Trace elemental and PGE geochemical constraints of Mesozoic and Cenozoic peridotitic xenoliths on lithospheric evolution of the North China Craton

Whole-rock major, trace, and platinum-group elemental (PGE) data, and major and trace element compositions of diopsides are reported for peridotite xenoliths from (1) early Mesozoic volcanic breccias in Xinyang, located at the southern margin of the North China Craton, and (2) Cenozoic basalts in Hebi and Shanwang, both of which are situated within the craton and lie on the North-South Gravity Line and the Tanlu fault zone, respectively. The early Mesozoic Xinyang xenoliths are harzburgites containing <2% Cpx with high Cr^# and enriched in LREE but depleted in HFSE. These xenoliths have chondritic Pd/Ir (1.9-6.6) and Ru/Ir (3.5-4.0) ratios and high Ni and low CaO, Al₂O₃, and S contents, indicating derivation from a highly refractory mantle that experienced carbonatitic metasomatism. Negative Ce (mean δCe = 0.50) and low Mg/Si ratios of the Xinyang peridotites record the addition of crustal components likely produced from subducted continental material of the Yangtze Craton in the early Mesozoic. The subduction-related modification of the lithospheric mantle was limited to the area close to the collision zone rather than being pervasive throughout the craton. The Cenozoic Hebi peridotite xenoliths are harzburgites with ≤4.5% Cpx and have low CaO and Al₂O₃ but high Ni contents, chondritic Ru/Ir ratios (2.5-5.4), and a wide range of CaO/Al₂O₃, Na₂O/TiO₂, Pt/Ir (0.4-2.3), and Pd/Pt (1.1-8.5) ratios. These peridotites are interpreted as the shallow relics of the cratonic mantle. In contrast, the Cenozoic Shanwang xenoliths are lherzolites (5.6%-19.5% Cpx), which have low Ni contents and low Ni/Cu and Mg/Si ratios, but high CaO, Al₂O₃, S, and HREE contents, and relatively high Ru/Ir and Pd/Ir ratios. The Shanwang peridotites show pronounced positive Ti and Sr, negative Th, and slightly negative Y, Zr, and Hf anomalies. They are believed to represent newly accreted fertile lithospheric mantle derived from cooling of upwelling asthenosphere. The documented temporal and spatial variations in the Mesozoic-Cenozoic mantle support the previous suggestion that the buoyant refractory continental keel in the eastern part of the North China Craton was heterogeneously replaced by younger fertile lithospheric mantle in the late Cretaceous-early Tertiary.     

Partitioning of elements between majorite garnet and melt and implications for petrogenesis of komatiite

Partitioning of elements between majorite garnet and ultrabasic melt has been studied at 16 GPa and 1950° C. Ca, Ti, La, Sm, Gd, Zr, Hf, Fe, Ni, Mn, K, and Na are enriched in the melt, whereas Al, Cr, V, Sc and Yb are concentrated in majorite garnet. Thus, majorite garnet fractionation by partial melting could produce chemical heterogeneities in these elements deviating from chondritic abundance. Using the partitioning behaviour of elements between majorite garnet and ultrabasic melt, the petrogenesis of komatiite is discussed. A simple model to explain the chemical varieties of komatiites is as follows. Aluminadepleted komatiite was generated by partial melting of the primitive mantle at 200–650 km depth, and alumina-enriched komatiite is the product of remelting of the residual solid at the same depths, whereas alumina-undepleted komatiite was formed by partial melting of the primitive upper mantle at depths shallower than 200 km. We suggest the possibility of large-scale chemical layering or heterogeneity in the early Archean upper mantle as an alternative model for komatiite genesis; shallower mantle depleted in majorite garnet and the underlying mantle enriched in majorite garnet. Alumina-depleted and alumina-enriched komatiites in the early Archean might be generated by a high degree of partial melting of the layered mantle. Such chemical layering could have been homogenized by the late Archean. This explains the observations that alumina-depleted and alumina-enriched komatiites were generally formed in the early Archean but alumina-undepleted komatiite was erupted in the late Archean.     

Fractionation of zirconium and hafnium during processes of mantle metasomatism

For the first time, fractionation of zirconium and hafnium in carbonatized mantle xenoliths from the eastern Antarctic has been studied. An elevation relative to the chondrite values of Zr/Hf in the metasomatized xenoliths has been revealed. The main reactions of the carbonate metasomatism lead to replacement of primary orthopyroxene by secondary clinopyroxene. A substantial broadening of the clinopyroxene crystallization field results in an increase of Zr/Hf in an equilibrated melt due to a higher partition coefficient of Hf in clinopyroxene, relative to that of Zr. Migration of reaction-active carbonate and carbonate–silicate melts, equilibrated to metasomatic wehrlite, causes an increase in the Zr/Hf value in the carbonatized mantle substrate.     

Trace element composition of parental magmas from mafic–ultramafic cumulates determined by in situ mineral analyses: The Juquiá mafic–ultramafic alkaline–carbonatite massif,SE Brazil

Major and trace element analyses of relict cores of cumulus minerals (olivine and clinopyroxene) from primitive rocks of the Juquiá mafic–ultramafic alkaline–carbonatite complex (Early Cretaceous) in the Ponta Grossa Arch Alkaline Province, southeastern Brazil, were used to calculate the equilibrium melt compositions. Olivine relict cores are compositionally restricted to the Fo_83–74 interval, and they exhibit significant concentrations of Mn (2220–3001 ppm), Ni (1188–2327 ppm), Ca (175–649 ppm), Co (169–216 ppm), Zn (115–215 ppm), Ti (55–305 ppm), Cr (4–320 ppm) and P (31–154 ppm). Clinopyroxene relict cores are essentially diopside, with minor amounts of hedenbergite and tschermakite components. The trace element contents found in clinopyroxene cores are Ni (196–339 ppm), V (99–318 ppm), Sr (110–260 ppm), Zr (12–163 ppm), Sc (50–78 ppm), P (16–118 ppm), Zn (16–48 ppm) and Co (25–43 ppm). The rare earth element (REE) concentrations are variable (28–240 ppm), with the lighter elements present in the greatest abundance, particularly Ce (up to 83 ppm).The melt compositions in equilibrium with olivine and clinopyroxene cores from different samples suggest that distinct basanite magma batches have played a role in the formation of the Juquiá cumulate rocks. These calculated liquids have compositions that are quite similar to those of the nearby lamprophyre dikes. The CaO/Al₂O₃ values (>0.8) from the lamprophyre dikes and the high La/Zr and low Ti/Eu values from the calculated liquids point to a previous carbonatite metasomatic event in the magmatic source that lead to the formation of wehrlite veins in a peridotitic mantle. The variation in the Hf/Y ratio implies differences in cpx/gt modal proportions in the source. Non-modal mantle batch-melting models indicate that a homogeneous source with little variation in the degree of partial melting cannot explain the trace element differences among the calculated liquids. The models suggest that the geochemical differences represent (1) mixing between metasomatic vein partial melt and garnet lherzolite partial melt and (2) clinopyroxene/garnet modal ratios of the residual mantle.     

西藏松多榴辉岩的矿物原位微量元素地球化学研究

对松多榴辉岩中单矿物进行的LA-ICP-MS原位微区微量元素分析研究结果表明,石榴石主要富集中、重稀土元素和Y,同时具有高丰度的Sc、V、Cr和Co等元素;绿辉石中的微量元素以中稀土元素、Sr、Sc、V、Cr、Co、Ni和Ti为主,含有一定量的Zr、Hf等。石榴石、绿辉石、角闪石和绿帘石中均显示轻稀土元素亏损的特点,表明在退变质过程中没有发生明显的富轻稀土元素的外来流体交代作用,因而其微量元素矿物地球化学的某些特点不同于苏鲁地区的榴辉岩。石榴石变斑晶中某些元素(如Ti、Zr)的分带性暗示了榴辉岩在紧随峰期变质之后的折返过程中发生了降压增温过程。榴辉岩主要变质矿物中微量元素的分配显然受到矿物主量元素的分配所控制,如MgO在石榴石和绿辉石之间的分配对Ni、Co、Ti分配的控制以及CaO的分配对Sr、Y、REE分配的控制等。退变质过程中矿物的形成或分解以及物理化学条件的改变都可以引起矿物间微量元素的重新分配。由绿辉石退变质而形成的角闪石,较之原先的绿辉石,其微量元素配分曲线总体特征会发生变化,但元素总体丰度相近,某些元素特点相似,又反映了绿辉石和角闪石之间的成生联系。金红石是Ti、Nb、Ta、Zr、Hf的主要赋存矿物,而与之共生的绿帘石所表现出来的高场强元素的亏损特征表明了金红石的存在所带来的影响。     

Ti-rich komatiites from northern Norway

Komatiites of the Karasjok Greenstone Belt, northern Norway, show two unusual features: they have certain compositional differences compared with other komatiites, and they are largely volcaniclastic in origin. Their geological setting suggests that the komatiites were crupted into shallow water, thus permitting phreatomagmatic eruption, in a small ocean basin that opened in the Baltic Shield. The major oxides (except for TiO₂), the trace elements Y, Sc, V, heavy rare earth elements (HREE), Cr, Co, Ni and the platinum group elements (PGE) cover similar ranges to those observed in other komatiites, but TiO₂, Sm, Zr and Hf (Ti-associated elements, TAE) are enriched compared with abundances commonly reported for komatiites. Thus, the Karasjok komatiites have interelement ratios 2 to 3 times greater than chondritic between the TAE and the HREE, PGE, Sc, V, Y, Al (HRE-associated elements, HAE). The light rare earth elements (LREE), Ta and Th are enriched in some samples relative to Ti, Sm, Zr, and Hf, but are depleted in others. One group of rocks that is similar to the Karasjok komatiites both in terms of geological setting and geochemistry is the Baffin Bay picrites. The reason for the high concentrations of TAE in the Karasjok komatiites could be that they formed at lower degrees of partial melting than most komatiites. The greater-than-chondritic TAE/HAE ratios indicate that garnet was a residual phase during their formation, requiring that the melt formed at a pressure greater than 40 kb. A model involving decompression melting of a mantle plume rising in a rifting environment, can explain the main features of the Karasjok komatiites.     

内蒙古集宁橄榄岩包体微区微量元素与Sr同位素特征及其岩石圈地幔演化的指示意义

为完整了解华北克拉通的破坏程度和机制,加深对其西部陆块岩石圈地幔的研究十分重要,而位于华北克拉通西部集宁新生代碱性玄武岩中的地幔橄榄岩包体,为研究人员认识该地区的岩石圈地幔的性质和演化起到指示作用.运用LA-ICP-MS和LA-MC-ICP-MS对集宁地区橄榄岩矿物进行原位微区测试,获得其主量、微量元素和Sr同位素成分的数据.根据矿物组成,可以将集宁地区的橄榄岩分为两类:第一类为贫单斜辉石橄榄岩 (单斜辉石体积分数小于8%),它们经历了高程度的部分熔融,可能是古老难熔岩石圈地幔的残留;第二类为二辉橄榄岩 (单斜辉石体积分数大于13%),其熔融程度低,代表了新生饱满的岩石圈地幔.第一类橄榄岩中单斜辉石REE含量整体偏低且轻微富集LREE,第二类橄榄岩中单斜辉石具有LREE富集和轻微亏损两种配分模式,大部分样品的核边有一定的强不相容元素及Sr同位素组成变化.这些微量元素和同位素特征都表明集宁橄榄岩包体经历过交代作用.(La/Yb)_N和Ti/Eu比值特征表明它们经历过多阶段的交代作用,交代介质有硅酸盐、碳酸盐熔/流体,这些交代介质可能为来源于古亚洲洋板块俯冲时释放的熔/流体.