Rapid Determination of Trace Element Compositions in Peridotites by LA‐ICP‐MS Using an Albite Fusion Method

A rapid sample preparation procedure is described to determine trace element compositions of peridotites using LA‐ICP‐MS. Peridotite powders were fused with albite in a molybdenum–graphite assembly to obtain homogeneous glasses. Best conditions for the fusion procedure (heating at 1500–1550 °C for 10–15 min with a sample‐to‐flux ratio of 1:2) were constrained with melting experiments on two USGS reference materials, PCC‐1 and DTS‐2B. Mass fractions of first series transition elements, Ba and Pb, in quenched glasses of PCC‐1 and DTS‐2B are consistent with published data within 10% RSD. Three spinel peridotite xenoliths from eastern China were analysed following both our method and conventional solution ICP‐MS. Compared with solution ICP‐MS, the relative deviations of our method for most elements were within 10%, while for the REE, Ta, Pb, Th and U, the relative deviations were within 20%. In particular, volatile elements (e.g., Pb and Zn) are retained in the glass. Compared with conventional wet chemistry digestion, our method is faster. Additional advantages are complete sample fusion, especially useful for samples with acid‐resistant minerals (spinel and rutile), and long‐term conservation of glasses allowing unlimited repeated measurements with microbeam techniques. The same approach can be used for analyses of other mantle rocks, such as eclogites and pyroxenites.     

Direct Trace Element Determination in Oil and Gas Produced Waters with Inductively Coupled Plasma‐Optical Emission Spectrometry: Advantages of High‐Salinity Tolerance

Waters co‐produced during petroleum extraction are the largest waste streams from oil and gas development. Reuse or disposal of these waters is difficult due to their high salinities and the sheer volumes generated. Produced waters (PWs) may also contain valuable mineral commodities. While an understanding of produced water trace element composition is required for evaluating the associated resource and waste potential of these materials, measuring trace elements in brines is challenging due to the dilution requirements of typical methods. Alternatively, inductively coupled plasma‐optical emission spectrometry (ICP‐OES) has shown promise as being capable of direct measurements of trace elements within PWs with minimal dilution. Here, we evaluate direct ICP‐OES trace element quantification in PWs for seventeen trace elements (As, Al, Ba, Be, Cd, Cr, Co, Cu, Hg, Mo, Ni, Pb, Rb, Sb, U, V and Zn) within fifteen PWs from five U.S. continuous reservoirs. The total analytical uncertainties associated with the trace element levels determined using ICP‐OES were estimated to be better than ± 30% (2s) except for Rb, which could not be determined due to ionisation interferences. The ICP‐OES results are compared with trace element levels determined using inductively coupled plasma‐mass spectrometry from the same samples. Our results demonstrate the potential for direct analysis of high‐salinity waters using ICP‐OES with minimal dilution and provide trace element concentrations in waters from several important U.S. petroleum‐generating reservoirs where available data are sparse.     

New ICP‐MS Results for Trace Elements in Five Iron‐Formation Reference Materials

Iron formations (IFs) typically contain low mass fractions of most trace elements, including the rare earth elements (REE), and few publications describe analytical methods dedicated to this matrix. In this study, we used bomb and table‐top acid dissolution procedures and ICP‐MS to determine the mass fractions of trace elements in IF reference materials FER‐1, FER‐2, FER‐3, FER‐4 and IF‐G. The full digestion of the IF samples with the bomb procedure required the addition of a small amount of water together with the acids. The results obtained by this method mostly agreed statistically with published values. The most remarkable exception was the higher values obtained for the heavy REE in FER‐3. The recoveries of the REE obtained with the table‐top procedure were slightly higher than those of the bomb digestion, except for the values of the heavy REE in FER‐3 and FER‐4, which were up to 30% lower than published values. Sintering of the samples with sodium peroxide was performed to determine the REE, but the results tended to be lower than those derived following acid digestion. On the whole, the recoveries showed dependence on the conditions of digestion, but subtle differences in trace mineral composition between samples also exerted influence on the analytical results for trace elements.     

Rare Earth and High Field‐Strength Elements in the Multani Mitti Clay: A Study Using INAA

Instrumental neutron activation analysis was used to determine nine rare earth elements (REE), Sc and five high field‐strength elements (HFSE) in the Multani Mitti (MM) clay. Chondrite‐normalised rare earth element patterns for the MM clay compared with those for the Post‐Archaean Australian Shale (PAAS), Upper Continental Crust (UCC) and North American Shale Composite (NASC) showed enrichment of light REEs and depletion of heavy REEs with a slight negative Eu anomaly. The Multani Mitti clay showed close resemblance to PAAS and NASC in its average REE and HFSE contents. Positive correlations between La/Ce, La/Sm, La/Yb, Zr/Hf, Th/U and Th/Ta ratios predict enrichment of LREEs, Zr and Th and depletion of HREEs. A parent source of felsic origin for the MM clay is also endorsed through the high La/Th and low Th/Sc ratios observed.     

Investigating the Influence of Non‐Spectral Matrix Effects in the Determination of Twenty‐Two Trace Elements in Rock Samples by ICP‐QMS

The influence of non‐spectral matrix effects on the determination of twenty‐two trace elements (Rb, Sr, Y, Cs, Ba, lanthanides, Pb, Th and U) in rock samples using ICP‐MS was investigated. Three types of multi‐element solutions were synthesised containing the twenty‐two trace elements, In, Tl and ten major rock‐forming elements with varying mass fractions mimicking the compositions of basalt, peridotite and dolomite. The synthetic solutions were conditioned to have dilution factors (DF) of 1000–10000. The extent of sensitivity suppression relative to the DF = 10000 solution became more significant for smaller DF solutions, which was not constant across different elements in a single solution but displayed general dependence on m/z. This indicates that at least two internal standards (e.g., In and Tl) are required for the correction of sensitivity variation. On the basis of the results, a new isotope dilution‐internal standardisation method for the determination of twenty‐two trace elements with ICP‐MS was developed, in which the sensitivity variation was corrected by monitoring two enriched isotopes, ¹¹³In and ²⁰³Tl. This method, coupled with the quantitative correction of interference from oxides and hydroxides, achieved precise determination of twenty‐two trace elements in some rock reference materials with reproducibilities of ±2% for basaltic to andesitic samples.     

In Situ U‐Th‐Pb Dating and Sr‐Nd Isotope Analysis of Bastnäsite by LA‐(MC)‐ICP‐MS

Bastnäsite is the end member of a large group of carbonate–fluoride minerals with the common formula (REE) CO₃F·CaCO₃. This group is generally widespread and, despite never occurring in large quantities, represents the major economic light rare earth element (LREE) mineral in deposits related to carbonatite and alkaline intrusions. Since bastnäsite is easily altered and commonly contains inclusions of earlier‐crystallised minerals, in situ analysis is considered the most suitable method to measure its U‐Th‐Pb and Sr‐Nd isotopic compositions. Electron probe microanalysis and laser ablation (multi‐collector) inductively coupled plasma‐mass spectrometry of forty‐six bastnäsite samples from LREE deposits in China, Pakistan, Sweden, Mongolia, USA, Malawi and Madagascar indicate that this mineral typically has high Th and LREE and moderate U and Sr contents. Analysis of an in‐house bastnäsite reference material (K‐9) demonstrated that precise and accurate U‐Th‐Pb ages could be obtained after common Pb correction. Moreover, the Th‐Pb age with its high precision is preferable to the U‐Pb age because most bastnäsites have relatively high Th rather than U contents. These results will have significant implications for understanding the genesis of endogenous ore deposits and formation processes related to metallogenic geochronology research.     

榴辉岩退变质过程中的微量元素地球化学行为：对CCSD主孔退变质榴辉岩的研究

对中国大陆科学钻探工程主孔榴辉岩退变质过程中的微量元素地球化学行为进行了研究。对退变质程度连续变化样品的不同部分的对比研究表明，流体作用下的退变质过程中大离子亲石元素（Cs、Rb、Ba、Sr、K、Th、U）和轻稀土元素表现出较大的活动性，重稀土元素和高场强元素变化相对较小。退变质后大离子亲石元素的显著增加和高场强元素、重稀土元素的轻微变化（甚至相对降低），表明与退变质作用有关的流体中的络阴离子含量很少，并不富集高场强元素和重稀土元素。退变质后总体上表现出的Si、大离子亲石元素和轻稀土元素的明显变化，表明外来流体参与了榴辉岩的退变质过程，带入和带出了一些元素。结合榴辉岩中单矿物微量元素组成以及前人对D^Mineral/Fluid的研究成果，对流体-榴辉岩作用形成的退变质分带（富石英条带→角闪岩→退变质榴辉岩→新鲜榴辉岩）的微量元素组成变化进行了详细研究。结果表明在流体作用下的榴辉岩退变质过程中，大离子亲石元素、轻稀土元素和高场强元素含量的变化除了受退变质流体性质的影响外，更大程度上取决于退变质过程中的矿物相（尤其是副矿物）的变化。     

Geochronology, Geochemistry and Sr-Nd-Pb-Hf Isotopes of No. I Complex from the Shitoukengde Ni–Cu Sulfide Deposit in the Eastern Kunlun Orogen, Western China: Implications for the Magmatic Source, Geodynamic Setting and Genesis

The Shitoukengde Ni-Cu deposit, located in the Eastern Kunlun Orogen, comprises three mafic–ultramafic complexes, with the No. I complex hosting six Ni-Cu orebodies found recently. The deposit is hosted in the small ultramafic bodies intruding Proterozoic metamorphic rocks. Complexes at Shitoukengde contain all kinds of mafic-ultramafic rocks, and olivine websterite and pyroxene peridotite are the most important Ni-Cu-hosted rocks. Zircon U-Pb dating suggests that the Shitoukengde Ni-Cu deposit formed in late Silurian(426–422 Ma), and their zircons have εHf(t) values of-9.4 to 5.9 with the older T_(DM1) ages(0.80–1.42 Ga). Mafic-ultramafic rocks from the No. I complex show the similar rare earth and trace element patterns, which are enriched in light rare earth elements and large ion lithophile elements(e.g., K, Rb, Th) and depleted in heavy rare earth elements and high field strength elements(e.g., Ta, Nb, Zr, Ti). Sulfides from the deposit have the slightly higher δ~(34)S values of 1.9–4.3‰ than the mantle(0 ± 2‰). The major and trace element characteristics, and Sr-Nd-Pb and Hf, S isotopes indicate that their parental magmas originated from a metasomatised, asthenospheric mantle source which had previously been modified by subduction-related fluids, and experienced significant crustal contamination both in the magma chamber and during ascent triggering S oversaturation by addition of S and Si, that resulted in the deposition and enrichment of sulfides. Combined with the tectonic evolution, we suggest that the Shitoukengde Ni-Cu deposit formed in the post-collisional, extensional regime related to the subducted oceanic slab break-off after the Wanbaogou oceanic basalt plateau collaged northward to the Qaidam Block in late Silurian.     

西藏班公湖岛弧带含硫化镍超基性岩的源区性质与基底背景

青藏高原班公湖一怒江成矿带上的超基性岩型硫化镍矿化是近年来在西藏地区发现的矿化新类型.文章根据成矿带西段班公湖地区含镍超基性岩体的岩石地球化学和Sr、Pb同位素分析结果,论述了含镍超基性岩浆的源区性质及生成条件,并根据锆石U-Pb LA-ICP-MS年龄测定结果,探讨了藏西北地区的基底背景.研究发现,班公湖地区的含镍超基性岩体以富集大离子不相容元素Rb、Th、U、Sr、Pb,亏损Ba、K为特点,高场强元素亏损Nb、Ti,富集Ta;稀士元素相对球粒陨石亏损强烈,但轻稀土元素相对富集.这些特点一致反映出含矿岩浆产生于受俯冲沉积物熔体交代的富集型岩石圈地幔源区.岩浆的生成深度较浅,为尖晶石二辉橄榄岩相,源区部分熔融程度较低,大体在10%左右.岩石中集中出现一批24.79亿年的残留锆石年龄,标志着当时班公湖中特斯洋盆沉积物的物源区较为单一,主要来自太古代末-元古代初的古老基底,并且推测太古代与元古代之交(25亿年)有可能是藏西北的一个古陆壳快速生长期.     

Determination of Trace Elements in Geological Reference Materials G‐3, GSP‐2 and SGD‐1a by Low‐Dilution Glass Bead Digestion and ICP‐MS

We present a revised alkali fusion method for the determination of trace elements in geological samples. Our procedure is based on simple acid digestion of powdered low‐dilution (flux : sample ≈ 2 : 1) glass beads where large sample dilution demanded by high total dissolved solids, a main drawback of conventional alkali fusion, could be circumvented. Three geological reference materials (G‐3 granite, GSP‐2 granodiorite and SGD‐1a gabbro) decomposed by this technique and routine tabletop acid digestion were analysed for thirty trace elements using a quadrupole ICP‐MS. Results by conventional acid digestion distinctly showed poor recoveries of Zr, Hf and rare earth elements due to incomplete dissolution of resistant minerals. On the other hand, results obtained by our method were in reasonable agreement with reference data for most analytes, indicating that refractory minerals were efficiently dissolved and volatile loss was insignificant.     

Crustal stabilization:Evidence from the geochemistry and U–Pb detrital zircon geochronology of quartzites from Simlipal Complex,Singhbhum Craton,India

Cratonic stabilization was a critical crustal process during the Hadean to Archean for the formation of cratons.The understanding of how and where this process took place is significant to evaluate the architecture of continents.The Singhbhum Craton of eastern India has well preserved Precambrian volcanosedimentary sequences.The Simlipal volcano-sedimentary complex of Singhbhum Craton consists of circular bands of mafic volcanic rocks interlayered with quartzites/shales/phyllites.In the present study,we report petrographic and geochemical characteristics of quartzites from Simlipal Complex coupled with U–Pb ages of detrital zircons and zircon geochemistry to understand the provenance and depositional conditions and its connection with the crustal stabilization in the Singhbhum Craton.The quartzites are texturally mature with sub-angular to sub-rounded quartz grains followed by feldspars embedded in a silty matrix.Based on modal compositions and major element ratios,these quartzites are categorized as quartz arenite and sub-lithic arenites.Trace element abundances normalized to Archean Upper Continental Crust(AUCC)display positive anomalies at U,Zr,Hf and negative anomalies at Nb.REE patterns are characterized by negative Eu anomalies(Eu/Eu^*=0.47–0.97)and flat HREE suggesting felsic provenance.These quartzites show depletion of LILE,enrichment of HFSE and transition metals relative to AUCC.High weathering indices such as CIA,PIA,and ICV are suggestive of moderate to intense chemical weathering.Low trace element ratios such as Th/Cr,Th/Sc,La/Sc,La/Co and Th/Co indicate a predominantly felsic source for these rocks.The overall geochemical signatures indicate passive margin deposition for these quartzites.Detrital zircons from the Simlipal quartzites yield U–Pb ages 3156±31 Ma suggesting Mesoarchean crustal heritage.The trace element geochemistry of detrital zircons suggests that the zircons are magmatic in origin and possibly derived from the 3.1 Ga anorogenic granite/granitoid provenance of Singhbhum Craton.These observations collectively indicate the Mayurbhanj Granite and Singhbhum Granite(SBG-III)provenance for these quartzites,thereby tracking the stabilization of the eastern Indian Shield/Singhbhum Craton back to Mesoarchean.     

Geochemistry and geochronology of mafic rocks from the Vespor suite in the Juruena arc,Roosevelt-Juruena terrain,Brazil: Implications for Proterozoic crustal growth and geodynamic setting of the SW Amazonian craton

This study presents new geochemical data on rocks from the Vespor suite, an important mafic unit from the Juruena arc, Roosevelt-Juruena terrain, SW Amazonian craton, northwest Mato Grosso, Brazil, attempting to define their tectonic setting and type of mantle source. The Juruena arc may be part of a magmatic belt (Jamari and Juruena arcs) at the southwestern Amazonian craton during assembly of the Columbia supercontinent. The investigated rocks represent a Paleoproterozoic subduction-related mafic suite of sigmoidal bodies, composed mainly of gabbro, norite, gabbronorite and diorite, that underwent amphibolite facies metamorphism. Here we present also preliminary petrology aspects and zircon U–Pb geochronology. Geochemical character and variation trends of major and trace elements as well as selected trace element ratios suggest that Vespor suite rocks have a tholeiitic lineage of arc affinity controlled by fractional crystallization with a prominent iron enrichment trend. Gabbros, norites and gabbronorites are characterized by enrichment of LILE and weakly to moderately differentiated HFSE patterns, suggesting their deviation from an enriched heterogeneous lithospheric mantle source. Vespor suite rocks are characterized by depletion of Nb–Ta, P and Ti, with flat distribution of HFSE, markedly large variations in most of the LILE, positive anomalies displayed by Ba, K, Th, Sr, Pb and weak negative anomalies of Hf–Zr. These features reflect limited degrees of crustal contamination associated with a subduction-related magma process where the mantle wedge was chemically modified. In addition, the enrichment in LILE and Pb, low values of the ratios (La_n/Sm_n – 0.83 to 4.58) and (Nb_n/La_n – 0.04 to 0.45), but high Th/Yb ratios, gently to moderately sloping REE profiles (La/Yb_n = 2.53–7.37), negative anomalies in HFSE (Ta, Zr, Hf, and Ti), and positive anomalies in LILE (Th, Ba, Sr), suggest derivation from a metasomatized lithospheric mantle source above a subduction zone with weak crustal contamination. Both the composition of the mantle source and the degree of partial melting that produced the parental magmas of these rocks, determined by using REE abundance and ratios, indicate that gabbroic/dioritic melts were generated at different degrees of melting of the source: about 5–20% partial melting of a garnet-spinel lherzolite, around 1–10% partial melting of spinel lherzolite source, and approximately 1–5% partial melting of intermediate source composition, and crystallizing between 1.773 and 1.764 Ma.     

Trace element composition of continentally subducted slab‐derived melt: insight from multiphase solid inclusions in ultrahigh‐pressure eclogite in the Dabie orogen

The ultrahigh‐pressure (UHP) eclogite in the Dabie orogen preserves petrological evidence for the existence of hydrous silicate melts that formed during continental subduction‐zone metamorphism. This is indicated by occurrence of multiphase solid (MS) inclusions in garnet that primarily consist of K‐feldspar + quartz ± epidote/allanite. All the MS inclusions are euhedral to subhedral in morphology and surrounded with radial cracks in the host garnet. Their trace element compositions were analysed by two different approaches of laser sampling. The mass budget method was used to estimate the trace element abundances of MS inclusions from their mixtures with the host garnet. The results are compared with the direct sampling of MS inclusions, providing a first‐order approximation to the trace element composition of MS inclusions. The MS inclusions exhibit consistent enrichment of LILE, Sr and Pb, but depletion of HFSE in the primitive mantle‐normalized spidergram. Such arc‐like patterns of trace element distribution are common for continental crustal rocks. The melts have variably high K, Rb and Sr abundances, suggesting that breakdown of phengite is a basic cause for partial melting of the UHP eclogite. These MS inclusions also exhibit consistently low HFSE and Y contents, suggesting partial melting of the eclogite in the stability fields of rutile and garnet. Consequently, the trace element composition of MS inclusions provides a proxy for that of hydrous silicate melts derived from dehydration melting of the UHP eclogite during continental collision.     

相山两种不同成因角闪石的地球化学特征对比

通过详细研究相山两种不同成因角闪石的元素及同位素地球化学发现：江西相山铀矿田北部同时存在两种不同成因的角闪石：正变质成因的角闪石，寄主岩石为斜长角闪(片)岩，微量元素以富集大离子亲石元素(LILE)(K,Rb，Th，Ta，U)、稍为富集Ti,Se和相对贫高场强元素(HFSE)(Zr，Hf,Y，Yb，Cr，HREE)为特征，稀土总量低，稀土分布型式为近水平型，δ^18O为7．95～8．58，显示变质火成岩的氧同位素特征；副变质成因的角闪石，寄主岩石为含石榴角闪石英片岩．微量元素以高度富集大离子亲石元素(LILE)(K，Rb，Th，U)、稍为富集Ta,Nb，Ce，Zr，Hf，Sm和相对贫高场强元素(HFSE)(Ti，Y，Yb，Cr)、强烈亏损Sc为特征，稀土总量高．轻重稀土相互分离程度高，轻稀土富集，O同位素组成(δ^18O)较高，为9．95～10．02，显示碎屑沉积变质岩的氧同位素特征。     

The geochemistry of Archaean shales derived from a Mafic volcanic sequence, Belingwe greenstone belt, Zimbabwe: provenance, source area unroofing and submarine versus subaerial weathering

Shales of the ∼2.7 Ga Zeederbergs Formation, Belingwe greenstone belt, Zimbabwe, form thin (0.2-2 m) horizons intercalated with submarine lava plain basalts. Shales of the overlying Cheshire Formation, a foreland basin sedimentary sequence, form 1-100 m thick units intercalated with shallow-water carbonates and deep-water, resedimented basalt pebble conglomerates. Zeederbergs shale is characterized by high contents of MgO and transition metals and low concentrations of K₂O and LILE as compared to average Phanerozoic shale, indicative of an ultramafic to mafic source terrain. Cheshire shales have similar major and trace element contents, but MgO and transition metals are less enriched and the LILE are less depleted. Zeederbergs shales have smoothly fractionated REE patterns (La_N/Yb_N = 2.84-4.45) and no significant Eu anomaly (Eu/Eu* = 0.93-0.96). REE patterns are identical to those of the surrounding basaltic rocks, indicating local derivation from submarine reworking. Cheshire shales have rather flat REE patterns (La_N/Yb_N = 0.69-2.19) and a small, negative Eu anomaly (average Eu/Eu* = 0.85), indicative of a mafic provenance with minor contributions of felsic detritus. A systematic change in REE patterns and concentrations of transition metals and HFSE upwards in the sedimentary succession indicates erosion of progressively more LREE-depleted basalts and ultramafic volcanic rocks, followed by unroofing of granitoid crust. Weathering indices confirm the submarine nature of Zeederbergs shale, whereas Cheshire shale was derived from a source terrain subjected to intense chemical weathering.     

Development of a Matrix‐Matched Sphalerite Reference Material (MUL‐ZnS‐1) for Calibration of In Situ Trace Element Measurements by Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Sphalerite (ZnS) is an abundant ore mineral and an important carrier of elements such as Ge, Ga and In used in high‐technology applications. In situ measurements of trace elements in natural sphalerite samples using LA‐ICP‐MS are hampered by a lack of homogenous matrix‐matched sulfide reference materials available for calibration. The preparation of the MUL‐ZnS1 calibration material containing the trace elements V, Cr, Mn, Co, Ni, Cu, Ga, Ge, As, Se, Mo, Ag, Cd, In, Sn, Sb, Tl and Pb besides Zn, Fe and S is reported. Commercially available ZnS, FeS, CdS products were used as the major components, whereas the trace elements were added by doping with single‐element ICP‐MS standard solutions and natural mineral powders. The resulting powder mixture was pressed to pellets and sintered at 400 °C for 100 h using argon as an inert gas. To confirm the homogeneity of major and trace element distributions within the MUL‐ZnS1 calibration material, measurements were performed using EPMA, solution ICP‐MS, ICP‐OES and LA‐ICP‐MS. The results show that MUL‐ZnS‐1 is an appropriate material for calibrating trace element determination in sphalerite using LA‐ICP‐MS.     

Redistribution of trace elements during prograde metamorphism from lawsonite blueschist to eclogite facies; implications for deep subduction-zone processes

The transfer of fluid and elements from subducting crust to the overlying mantle wedge is a fundamental process affecting arc magmatism and the chemical differentiation of the Earth. While the production of fluid by breakdown of hydrous minerals is well understood, the liberation of trace elements remains generally unconstrained. In this paper, we evaluate the behaviour of trace elements during prograde metamorphism and dehydration using samples of high-pressure, low-temperature metamorphic rocks from New Caledonia. Samples examined include mafic and pelitic rock-types that range in grade from lawsonite blueschist to eclogite facies, and represent typical lithologies of subducting crust. Under lawsonite blueschist facies conditions, the low temperatures of metamorphism inhibit equilibrium partitioning between metamorphic minerals and allow for the persistence of igneous and detrital minerals. Despite this, the most important hosts for trace-elements include lawsonite, (REE, Pb, Sr), titanite (REE, Nb, Ta), allanite (LREE, U, Th), phengite (LILE) and zircon (Zr, Hf). At epidote blueschist to eclogite facies conditions, trace-element equilibrium may be attained and epidote (REE, Sr, Th, U, Pb), garnet (HREE), rutile (Nb, Ta), phengite (LILE) and zircon (Zr, Hf) are the major trace-element hosts. Chlorite, albite, amphibole and omphacite contain very low concentrations of the investigated trace elements. The comparison of mineral trace-element data and bulk-rock data at different metamorphic grades indicates that trace elements are not liberated in significant quantities by prograde metamorphism up to eclogite facies. Combining our mineral trace-element data with established phase equilibria, we show that the trace elements considered are retained by newly-formed major and accessory minerals during mineral breakdown reactions to depths of up to 150 km. In contrast, significant volumes of fluid are released by dehydration reactions. Therefore, there is a decoupling of fluid release and trace element release in subducting slabs. We suggest that the flux of trace elements from the slab is not simply linked to mineral breakdown, but results from complex fluid-rock interactions and fluid-assisted partial melting in the slab.Electronic Supplementary Material Supplementary material is available in the online version of this article at http://dx.doi.org/10.1007/s00410-003-0495-5.Editorial responsibility: J. Hoefs     

内蒙古锡林浩特毛登牧场早石炭世花岗岩锆石U Pb年龄、地球化学特征及其地质意义

通过对内蒙古锡林浩特毛登牧场早石炭世花岗岩体进行野外观察、LA ICP MS锆石U Pb测年以及地球化学测试,讨论其构造环境,进一步为研究古亚洲洋闭合时限提供依据。测年结果表明：花岗闪长岩为(3306±18) Ma,二长花岗岩为(3277±26) Ma,成岩时代为早石炭世。岩石地球化学分析表明:花岗闪长岩为强过铝质、钙碱性系列岩石,具有活动大陆边缘的亲缘性特征。微量元素特征指示花岗闪长岩具有典型下地壳来源特征并伴有部分幔源岩浆混合作用,为弧岩浆岩。二长花岗岩为具高硅、富碱、相对低铝特征的高钾钙碱性系列岩石。两类差异明显的岩石稀土配分曲线表明二长花岗岩具有下地壳岩浆重熔的演化特征。微量元素特征指示样品为大陆弧环境下壳源重熔的成熟弧花岗岩。构造判别图显示花岗闪长岩为代表活动大陆边缘环境的I型花岗岩,而二长花岗岩则为指示活动大陆边缘弧后伸展环境的A2型花岗岩,二者构成I－A型复合岩体,说明研究区在早石炭世仍存在古亚洲洋向西伯利亚板块的俯冲作用,推测古亚洲洋此时尚未闭合。     

中国几个主要煤产地煤中微量元素特征

采用原煤直接溶样和使用ＩＣＰ－ＭＳ方法对我国平朔,大同,六盘水和唐山几个主要煤产地煤的微是元素进行了检测,报道了这几个主要煤产地煤中５１种微量元素含量,并对基含量特征进行了讨论,研究表明,与海水有关的过渡相沉积环境中的煤的Ｌｉ,Ｂｅ,Ｓｃ,Ｔｉ,Ｖ,Ｚｎ,Ｃｕ,Ｇａ,Ａｓ,Ｓｅ,Ｙ,Ｚｒ,Ｓｎ,Ｐｂ,Ｔｈ,Ｕ和稀土元素含量相对较高,内陆湖泊沉积环境中的煤的微量元素含量相对较低。     

Determination of Rare Earth Elements, Sc, Y, Zr, Ba, Hf and Th in Geological Samples by ICP-MS after Tm Addition and Alkaline Fusion

We present a revised method for the determination of concentrations of rare earth (REE) and other trace elements (Y, Sc, Zr, Ba, Hf, Th) in geological samples. Our analytical procedure involves sample digestion using alkaline fusion (NaOH-Na₂O₂) after addition of a Tm spike, co-precipitation on iron hydroxides, and measurement by sector field-inductively coupled plasma-mass spectrometry (SF-ICP-MS). The procedure was tested successfully for various rock types (i.e., basalt, ultramafic rock, sediment, soil, granite), including rocks with low trace element abundances (sub ng g⁻¹). Results obtained for a series of nine geological reference materials (BIR-1, BCR-2, UB-N, JP-1, AC-E, MA-N, MAG-1, GSMS-2, GSS-4) are in reasonable agreement with published working values.