Distinct Rare Earth Element Patterns Research Articles

Multistage fluorite mineralization in the southern Black Forest, Germany: evidence from rare earth element (REE) geochemistry

Abstract. The Black Forest hosts a wide range of hydrothermal mineralization, including fluorite–barite vein deposits. In a detailed investigation of the Finstergrund and Tannenboden deposits in the Wieden mining district (southern Black Forest), the diversity, geochemical evolution and relative chronology of multistage fluorite precipitation is tracked on the basis of rare earth element (REE) geochemistry, geologic field relationships and crystal zoning. Geochemical discrimination and mathematical λ coefficients suggest a total of seven fluorite REE groups, at least three distinguishable post-Variscan fluid mobilization events and independent formation histories for the deposits despite their spatial proximity. Fluorite vein mineralization at the Finstergrund deposit evolved over three fluid generations, was derived from gneissic source aquifers and comprises five distinct fluorite REE groups: the first fluid generation is characterized by fluorite precipitation above 200 ∘C (“group III”), below 200 ∘C (“group I”) and after fractional crystallization (“group IV”); the second generation comprises remobilized fluorite (“group II”); and the third generation revealed fluorite precipitation by meteoric water mixing (“group V”). Fluorite vein formation at the Tannenboden deposit is associated with two distinct fluorite REE patterns derived from the same fluid generation: fluorite precipitation above 200 ∘C (“group VII”) and after cooling below 200 ∘C (“group VI”). Its fluid source aquifer lithology best matches migmatites contrary to previous models that suggest either gneissic or granitic aquifer rocks for fluorite vein precipitation in the Black Forest. The decoupled formation history between the deposits is tectonically controlled as suggested by a new genetic model for the Wieden mining district. The model argues for a change in the local fluid percolation network and the termination of hydrothermal activity at the Tannenboden deposit after the first fluid mobilization event. The geochemical evolution of multistage fluorite mineralization, as exemplified by the Tannenboden and Finstergrund deposits in combination with other fluorite mineralizations in the Black Forest, provides unique insights into the lithospheric origin and precipitation behaviour of fluorite by various fluid–rock interaction processes occurring in large hydrothermal systems. The local diversity of REE patterns emphasizes the need for detailed investigations of individual hydrothermal vein deposits.

Apatite trace element geochemistry and cathodoluminescent textures—A comparison between regional magmatism and the Pea Ridge IOAREE and Boss IOCG deposits, southeastern Missouri iron metallogenic province, USA

The southeast Missouri iron metallogenic province contains a remarkable wealth of historically important Fe, Cu, Au, and rare earth element (REE) deposits including the Pea Ridge iron oxide-apatite-rare earth element (IOA-REE) deposit and the Boss iron oxide-copper–gold (IOCG) deposit. These deposits are coeval with silicic and intermediate composition magmatism in the St. Francois Mountains terrane. Magmatism, iron-oxide (±Cu, Au, Co) and apatite formation, and REE mineralization overlapped in space and time, but the specific role of regional magmatism in the metallogenesis of these deposits remains unclear and basic petrogenetic models are still debated.We report results from high-spatial resolution textural and geochemical analyses of apatite from regional igneous and ore rocks to elucidate their petrogenetic histories and evaluate deposit models. Backscattered electron and spectral cathodoluminescence imaging of apatite reveal no primary igneous zoning, but show different domains with intricate rims and dissolution/reprecipitation textures, each with distinctive REE patterns in many samples. Apatite from all samples are nearly endmember fluorapatite containing up to ∼1.3 wt% Cl and F/Cl ratios span nearly three orders of magnitude. Fresh igneous fluorapatite contain low Na2O (≤0.15 wt%) while most Pea Ridge ore samples contain higher Na2O (up to ∼0.45 wt%), and concentrations of sulfur in fluorapatite of all types are generally moderate to low (≤0.3 wt% SO3). Significant amounts of Fe (≤60,000 ppm), Mg (≤30,000 ppm), Mn (≤7000 ppm), and Sr (≤12,000 ppm) are contained in fluorapatite of all sample types, and they also have moderate amounts of As (≤4000 ppm), Ba (≤2000 ppm), Th (≤400 ppm), and U (≤80 ppm). Fluorapatite show an extraordinarily large range of ΣREE (∼0.1–2.0 wt%) and Y (∼100–7000 ppm) concentrations. While fresh igneous fluorapatite share many geochemical features with metasomatized igneous fluorapatite and ore-stage fluorapatite from the Pea Ridge IOA and Boss IOCG ore zones, they also have distinct geochemical signatures that are indicative of unique trace element partitioning and substitution mechanisms. These distinguishing textural and geochemical signatures preclude ore-zone fluorapatite genesis directly from a magma (i.e., crystallization directly from a silicate melt) but are permissive of ore-zone fluorapatite formation by magmatic-hydrothermal fluids derived from the regional magmas. Basinal brines may play an important role in the formation of fluorapatite, especially from the Pea Ridge hematite and Boss magnetite-rich zones. Fluorapatite from different ore zones likely formed by crystallization during pulses of hydrothermal fluids with varying Cl-, Na-, and F-contents, which fundamentally controlled the carrying capacity and solubility of ΣREE + Y and generated geochemically distinctive generations of fluorapatite.Exploration geologists using fluorapatite trace element geochemistry to identify IOA and IOCG deposits should proceed with caution, as more high-quality data from these deposits are needed to improve multivariate discrimination analysis. Fluorapatite from IOA/IOCG deposits can be reasonably discriminated from that of other mineral deposit types (e.g., porphyry/epithermal, skarn, orogenic), but no criteria successfully discriminate yet between IOA and IOCG deposits.

Fluid evolution of Triassic and Jurassic W mineralization in the Xitian ore field, South China: Constraints from scheelite geochemistry and microthermometry

Rare earth element (REE)-enriched scheelite is widely distributed in many ore deposits, and has been utilized in a broad range of geochronological and geochemical studies. In an effort to decipher skarn and quartz vein-hosted W mineralization process, scheelite from Triassic and Jurassic granites, skarn ores and quartz vein-hosted ores in the Xitian ore field (South China) were analyzed for major and minor element content and fluid inclusion microthermometry. All scheelite grains show homogeneous backscatter electron and cathodoluminescence response and uniform W and Ca distribution. The chondrite-normalized REE patterns of scheelite from Triassic granites to skarn ores show similar Pr–Sm-enrichments and negative Eu anomalies but different HREE contents. In contrast, the chondrite-normalized REE patterns of scheelite from Jurassic granites to quartz vein-hosted ores changes from flat with slight LREE enrichment, to concave with remarkable LREE depletion. The homogenization temperatures and salinities of fluid inclusions from the scheelite in Triassic granites and skarn ores are similar, both reduce significantly from the Jurassic granites to quartz vein-hosted ores. Combined with pressure, pH and mineral assemblage analysis, we propose that the REE signatures in the ore-forming fluids of skarn-type W deposits are mainly controlled by crystallization of REE-enriched skarn minerals (e.g., garnet, diopside, epidote). The similarity in LREE patterns and Y/Ho ratios between the Triassic granite and skarn ore scheelite indicates that the skarn ore-forming fluid was derived from the Triassic granite, while the distinct REE patterns and variable Y/Ho ratios in scheelite from Jurassic granites and quartz vein-hosted ores imply possible fluid-mixing for Jurassic W mineralization. In light of these results, REE-rich scheelite could serve to discriminate fluid source and document mineralization processes in a complex ore-forming system.

In situ geochemistry of middle Ordovician dolomites of the upper Mississippi valley

AbstractThe dolomitization and diagenetic history of Ordovician carbonates of southern Wisconsin is complex. Previous studies attributed dolomitization to various diagenetic factors and environments. In this study, high‐resolution, in situ laser ablation inductively coupled mass spectrometry analysis of rare earth element patterns of dolomite was used to assess the diagenetic fluids responsible for dolomitization of the Ordovician Decorah Formation. Integrated geochemical data and petrographic evidence suggest that the dolostones are formed in two different diagenetic realms: shallow burial and hydrothermal. Shallow burial dolomites exhibit three distinct rare earth element patterns. Dolomite from the middle portion of the Guttenberg Member exhibits light rare earth element enrichment consistent with early burial dolomitization. Dolomites of the Carimona, Specht's Ferry and Lower Guttenberg members are often burrow associated and exhibit medium rare earth element enrichment associated with Fe‐oxide desorption in anoxic porewaters. Leaching of Mg from co‐occurring volcanic ash during alteration is a probable source that contributed to the dolomitization. Extensively dolomitized samples in the upper Guttenberg and Ion Member exhibit evidence of hydrothermal dolomitization. The relationship of these heavily dolomitized samples to interbedded limestones provides evidence for a recently proposed hydrothermal dolomitization model invoking pressure solution of calcite and precipitation of dolomite. These early burial and hydrothermal depositional models are consistent with models proposed for overlying and underlying Ordovician dolostones.

Phase equilibria modelling using major and trace element compositions of zoned garnet and clinopyroxene from southwestern Tianshan eclogites, China

We present major and trace element zoning in clinopyroxene and garnet in the low-temperature eclogites from southwestern Tianshan ultrahigh-pressure metamorphic belt. The clinopyroxene crystals in the matrix exhibit three distinct growth zones, including the aegirine-rich core, a transition mantle and the omphacite rim. The aegirine core has weak Ce anomaly, flat light rare earth element pattern, and slightly enriched heavy rare earth element contents. The omphacite rim has lower trace element contents, and is depleted in large-ion lithospheric elements, light and heavy rare earth elements. The garnet zonation is featured by the core-to-rim increase in pyrope and grossular contents, and distinct rare earth element patterns: the core has left-leaning rare earth element patterns and the rim is depleted in both light and heavy rare earth elements. Phase equilibria modelling based on the phase assemblage and mineral zoning patterns reveal that the aegirine eclogite was heated and buried along the ca. 8°C/km geotherm in the cold subduction zone, and reached the peak metamorphic condition of 23–25kbar, 540–560°C. The jadeite content in the clinopyroxene increases along the prograde-to-exhumation P-T path (Jd: from 0.25 to 0.45), with the transitional mantle corresponds to the peak conditions. The omphacite rim with the highest jadeite content (Jd∼45) formed during decompression. For a Fe3+-rich clinopyroxene, the maximum in Jd component does not necessarily represent the peak pressure, so the conventional thermobarometers should be used with caution for mineral assemblages with such complicated zonation patterns. The variation of oxygen fugacity correlates with the changes in mineral assemblage, P-T condition, and the bulk-rock Fe3+/FeT ratio. The oxygen fugacity is not always positively correlated with the Fe3+/(Fe3++Al) or Fe3+/FeT ratio in clinopyroxene. Rare earth element zoning garnet and clinopyroxene are modelled based on mass balance. The modelled growth zonation closely resembles the observed compositional profiles, suggesting that rare earth elements are passively distributed among phases near chemical equilibrium during the mineral growth.

Using geochemistry of rare earth elements to indicate sediment provenance of sand ridges in southwestern Yellow Sea

The Jianggang Harbour-centered radial sand ridge (RSR) is the largest sand body in the Yellow Sea. Its formation and evolution are of interest for scientists of various fields; however, the sediment provenance is uncertain. In this study, rare earth element (REE) geochemical compositions of the RSR sediments together with their potential sources are investigated to identify the provenance of the RSR sediments. The typical parameters ((La/Yb)N, (La/Sm)N and (Gd/Yb)N) as well as the upper continental crust-normalized patterns of REEs can only be associated with source rocks, and thus can be used as effective tracers for the origin and sources of sediments. However, the REE contents of sediments are affected by many factors, such as particle sorting and chemical weathering. Onshore RSR sediments are different in REE geochemical composition from offshore RSR sediments to some extent, suggesting that not all of the offshore RSR sediments have the same sources as the onshore RSR sediments. Meanwhile, the sediments adjacent to the northeast of Cheju Island and at Lian Island near the Lianyun Harbour were not the source of the RSR sediments due to their distinctive REE patterns, δEu, (La/Yb)N, (Gd/Yb)N and (La/Sm)N. The Korean river sediments could be dispersed to the Jiangsu Coast slightly impacting the fine fractions of the RSR sediments, particularly the offshore RSR sediments. Additionally, geochemical comparisons show that the modern Yellow River was responsible for the onshore RSR sediments, whereas the sediment loads from the Yangtze River could serve as a major contributor to the RSR, particularly the offshore RSR. In addition, the offshore RSR could also be partly fed by an unknown source due to some high values of (La/Yb)N, (La/Sm)N and La contents differing from those of the Chinese and Korean river sediments.

Half a billion years of reworking of Hadean mafic crust to produce the Nuvvuagittuq Eoarchean felsic crust

The Nuvvuagittuq greenstone belt is dominated by mafic rocks, called the Ujaraaluk unit, that are mostly composed of cummingtonite–plagioclase–biotite with variable amounts of garnet. While the oldest zircons contained in thin intrusive trondhjemitic bands are ∼3.8 Ga, 146Sm–142Nd systematics suggest that the Ujaraaluk unit is as old as 4.4 Ga. The Nuvvuagittuq greenstone belt is surrounded by Eoarchean TTGs that have geochemical and isotopic compositions consistent with their derivation by partial melting of a source similar in composition and age to the Ujaraaluk unit. New zircon dates reported here show the Nuvvuagittuq TTGs to consist at least of four distinct age units of 3.76 Ga, 3.66 Ga, 3.5–3.4 Ga and 3.35 Ga. The Hf isotopic compositions of zircons from the TTG are consistent with derivation from Hadean mafic crust. The 3.66 Ga to 3.35 Ga TTGs appear to have been formed primarily from melting of a source compositionally similar to the 4.4 Ga Ujaraaluk unit, whereas the more radiogenic Hf of the zircons from the 3.76 Ga TTGs may suggest derivation from melting of a source compositionally similar to 4.1 Ga intrusive gabbros. Alternatively, the distinct rare earth element patterns of the 3.76 Ga and 3.66 Ga TTGs suggest their derivation from sources with variable amounts of residual garnet and hence formation at different depths. The composition of the older TTGs is indicative of a deeper source that may have involved a greater interaction between the melt and the mantle to explain the more radiogenic Hf isotopic compositions of their zircons. Sources compositionally similar to the Ujaraaluk unit and intrusive gabbros appear to be the most likely candidates for the Hadean precursor of the Nuvvuagittuq TTGs.

Rare earths and other trace elements in minerals from skarn assemblages, Hillside iron oxide–copper–gold deposit, Yorke Peninsula, South Australia

The Hillside Cu–(Au) deposit, Yorke Peninsula, South Australia, is a recently-discovered ore system within the 1.6Ga World-class Olympic iron oxide–copper–gold (IOCG) Province. The deposit is characterized by a skarn-style alteration zone. Analyses of feldspar, calcite, skarn minerals (garnet, pyroxene, clinozoisite and actinolite) and accessories (titanite, apatite and allanite), and grain-scale element mapping by laser-ablation inductively-coupled plasma mass spectrometry are used to assess the distributions of rare earth element (REE), incompatible and ore-forming elements in host rocks, prograde and retrograde skarn.Garnet is a major repository of HREE, especially in prograde skarn, whereas LREE-enriched clinozoisite is the principal REE-host in retrograde skarn. REE distribution patterns define a pronounced partitioning of elements among the dominant coexisting minerals. Compositional variation between assemblages, and also within individual grains, defines an evolution from early feldspar–pyroxene skarn through main-stage calcic skarn to the ore-stage. A switch from a prograde, HREE-dominant signature to a LREE-enriched signature is observed in both retrograde and distal skarn. Zr-in-titanite geothermometry supports transition from magmatic to hydrothermal, skarn-forming processes at temperatures of ~660°C; the initiation of ore-stage is about 100°C lower.Understanding REE distributions in all minerals within a complex, multistage ore system assists the development of vectoring tools that use trace element chemistry in exploration for similar IOCG deposits beneath regolith cover across the Olympic Province. Titanite and apatite show particular promise because of their characteristically distinct REE patterns in magmatic and hydrothermal stages, trace element responses to redox changes, and their widespread abundance throughout different lithologies in the area.

Trace element mobility in dolomitic argillites of the Mesoproterozoic Belt-Purcell Supergroup, Western North America

The Belt-Purcell Supergroup comprises dolomite-rich stratigraphic units in a dominantly siliciclastic succession, where sedimentation spans 1400–1470 Ma. Dolomitic units are variable mixtures of co-sedimented argillite and primary carbonate post-depositionally converted to secondary dolomite. Based on rare earth element (REE) relationships three distinct REE patterns are identified in the dolomite-rich units: Type 1 (T1d; d = dolomitic sample) with REE patterns parallel to post-Archean Upper Continental Crust (PA-UCC), albeit at lower absolute abundances due to dilution by carbonate content; Type 2 (T2d) with Heavy REE (HREE) enrichment but Light REE (LREE) depletion relative to T1d; and Type 3 (T3d) with enrichment in LREE and HREE relative to T1d, but erratic Middle REE (MREE) patterns. There is a progressive increase of ΣREE from T1d through T2d to T3d, whereas for ΣLREE/ΣHREE T2d < T1d < T3d. T1d–T2d and T3d represent three different “snapshots” of a continuous process. In terms of timing, dolomitization of calcite primary sediment in all samples likely took place broadly during burial diagenesis, as inferred for most Proterozoic dolomites. T1d is easily explained by provenance: however, T2d and T3d cannot be related to provenance, weathering or sedimentary sorting processes to explain higher concentrations of HREE referenced to PA-UCC and consequently developed in the sediment from a T1d precursor. The same three REE signatures have been described in previous studies in counterpart siliciclastic counterparts throughout the Belt-Purcell Supergroup at three different locations. Mobility of normally stable REE is accompanied by mobility of normally isochemical high field strength elements (HFSE) in T2d and T3d to give REE/REE, HFSE/HFSE, REE/HFSE and Y/HREE fractionations. No specific REE–HFSE signatures are apparent in the carbonate-rich units as compared to their non-dolomitic siliciclastic counterparts. This unusual mobility of REE and HFSE reflected in T2d and T3d is attributed to alkaline oxidizing post-depositional brines. Salinity was derived from seawater–sediment reactions, dissolution of evaporite minerals, and the smectite–illite transformation, whereas alkaline oxidizing conditions were promoted by groundwater interaction with mafic units in the basin, CO 2 introduced into the system during episodic rifting with mantle degassing, and interaction of syn-sedimentary mafic intrusions with carbonate units at early stages of BPS deposition. Intermittent brine activity, inducing T2d and T3d patterns, spanned >1 Ga as recorded by secondary monazite grains with age distributions that correspond to large scale tectono-thermal events in Laurentia. Post-depositional processes and redistribution of carbonate can have an impact on transitional stratigraphic contacts between dolomitic and siliciclastic units which may have been incorrectly described as primary due to sedimentary environment changes.

Volcanic ash in the Lower Cretaceous Chaswood Formation of Nova Scotia: source and implicationsGeological Survey of Canada Contribution 20100082.

Lignites and coals, because of their low sedimentation rates of terrigenous detritus, may preserve a record of volcanic ash fall. Lignite from the Lower Cretaceous Chaswood Formation in central Nova Scotia was studied to identify whether any volcanic ash is present and can be correlated to known Early Cretaceous volcanism in southeastern Canada and adjacent New England. The bulk mineralogy and geochemistry of lignite and lignitic mudstones was determined by X-ray diffraction and whole-rock geochemical analysis of ashed samples; selected samples were examined by electron microprobe and scanning electron microscope. Much of the terrigenous component of some lignites consists of detrital sediments. In some lignites, distinctive rare earth element patterns are due to leaching from monazite and concentration in organic matter. Some lignites, however, lack illite and (or) quartz indicative of detrital sources, but show unusual abundance of stable high-field-strength elements such as Nb, Ta, and Hf, suggesting a volcanic source. Wood or charcoal fragments appear mineralized and diagenetic talc is present. Most of any ash component has been altered to kaolinite. Bulk composition of original ash ranges from basaltic to rhyolitic and matches chemically with subalkaline volcanic rocks on the SW Grand Banks and Orpheus graben. Coeval volcanic rocks on the U.S. continental margin and the New England–Quebec igneous province are more alkaline. Altered ash in lignite in the lower member of the Chaswood Formation correlates with Neocomian volcanism on the SW Grand Banks; and in the middle and upper members with Aptian–Albian volcanism in Orpheus graben.

Geochemistry of South African On- and Off-craton, Group I and Group II Kimberlites: Petrogenesis and Source Region Evolution

Bulk-rock geochemical compositions of hypabyssal kimberlites, emplaced through the Archaean Kaapvaal craton and Proterozoic Namaqua–Natal belt, are used to estimate close-to-primary magma compositions of Group I kimberlites (Mg-number 1⁄4 0 82–0 87; 22–28 wt % MgO; 21–30 wt % SiO2; 10–17 wt % CaO; 0 2–1 7 wt % K2O) and Group II kimberlites (Mgnumber 1⁄4 0 86–0 89; 23–29 wt % MgO; 28–36 wt % SiO2; 8–13 wt % CaO; 1 6–4 6 wt % K2O). Group I kimberlites are distinguished from Group II by their lower Ba/Nb ( 22) ratios. The distinct rare earth element patterns of the two types of kimberlites indicate a more highly metasomatized source for Group II kimberlites, with more residual clinopyroxene and less residual garnet. The similarity of Sr and Nd isotope ratios and diagnostic trace element ratios (Ce/Pb, Nb/U, La/Nb, Ba/Nb, Th/Nb) of Group I kimberlites to ocean island basalts (OIB), but more refractory Mg-numbers and Ni contents, are consistent with derivation of Group I kimberlites from subcontinental lithospheric mantle (SCLM) that has been enriched by OIB-like melts or fluids. Source enrichment ages and plate reconstructions support a direct association of these melts or fluids with Mesozoic upwelling beneath southern Africa of a mantle plume(s), at present located beneath the southern South Atlantic Ocean. In contrast, the geochemical characteristics of both onand off-craton Group II kimberlites show strong similarity to calc-alkaline magmas, particularly in their Nb and Ta depletion and Pb enrichment. It is suggested that Group II kimberlites are derived from both Archaean and Proterozoic lithospheric mantle source regions metasomatized by melts or fluids associated with ancient subduction events, unrelated to mantle plume upwelling. The upwelling of mantle plumes beneath southern Africa during the Mesozoic, at the time of Gondwana break-up, may have acted as a heat source for partial melting of the SCLM and the generation of both Group I and Group II kimberlite magmas.

Rare earth element geochemistry and petrogenesis of miles (IIE) silicate inclusions

An ion probe study of rare earth element (REE) geochemistry of silicate inclusions in the Miles IIE iron meteorite was carried out. Individual mineral phases among inclusions have distinct REE patterns and abundances. Most silicate grains have homogeneous REE abundances but show considerable intergrain variations between inclusions. A few pyroxene grains display normal igneous REE zoning. Phosphates (whitlockite and apatite) are highly enriched in REEs (50 to 2000 × CI) with a relatively light rare earth element (LREE)-enriched REE pattern. They usually occurred near the interfaces between inclusions and Fe host. In Miles, albitic glasses exhibit two distinctive REE patterns: a highly fractionated LREE-enriched (CI normalized La/Sm ∼15) pattern with a large positive Eu anomaly and a relatively heavy rare earth element (HREE)-enriched pattern (CI-normalized Lu/Gd ∼4) with a positive Eu anomaly and a negative Yb anomaly. The glass is generally depleted in REEs relative to CI chondrites. The bulk REE abundances for each inclusion, calculated from modal abundances, vary widely, from relatively depleted in REEs (0.1 to 3 × CI) with a fractionated HREE-enriched pattern to highly enriched in REEs (10 to 100 × CI) with a relatively LREE-enriched pattern. The estimated whole rock REE abundances for Miles are at ∼ 10 × CI with a relatively LREE-enriched pattern. This implies that Miles silicates could represent the product of a low degree (∼10%) partial melting of a chondritic source. Phenocrysts of pyroxene in pyroxene-glassy inclusions were not in equilibrium with coexisting albitic glass and they could have crystallized from a parental melt with REEs of ∼ 10 × CI. Albitic glass appears to have formed by remelting of preexisting feldspar + pyroxene + tridymite assemblage. Yb anomaly played an important role in differentiation processes of Miles silicate inclusions; however, its origin remains unsolved. The REE data from this study suggest that Miles, like Colomera and Weekeroo Station, formed when a molten Fe ball collided on a differentiated silicate regolith near the surface of an asteroid. Silicate fragments were mixed with molten Fe by the impact. Heat from molten Fe caused localized melting of feldspar + pyroxene + tridymite assemblage. The inclusions remained isolated from one another during subsequent rapid cooling.

Geochemical and Sr–Nd–Pb isotopic investigation of Triassic granitoids and basement rocks in the northern Gyeongsang Basin, Korea: Implications for the young basement in the East Asian continental margin

Abstract We present chemical and Sr–Nd–Pb isotopic compositions of three Triassic (226–241 Ma) calc‐alkaline granitoids (the Yeongdeok granite, Yeonghae diorite and Cheongsong granodiorite) and basement rocks in the northern Gyeongsang basin, south‐eastern Korea. These plutons exhibit typical geochemical characteristics of I‐type granitoids generated in a continental magmatic arc. The Yeongdeok and Yeonghae plutons have similar initial Sr, Nd and Pb isotope ratios (87Sr/86Srinitial = 0.7041 ~ 0.7050, ɛNd(t) = 2.3 ~ 4.0, 206Pb/204Pbfeldspar = 18.22 ~ 18.34), but distinct rare earth element patterns, suggesting that the two plutons formed from partial melting of a similar source material at different depths. The Cheongsong pluton has slightly more enriched Sr–Nd–Pb isotopic compositions (87Sr/86Srinitial = 0.7047 ~ 0.7065, ɛNd(t) = 3.9 ~ 2.8, 206Pb/204Pbfeldspar = 18.24 ~ 18.37) than the other two plutons. The Nd model ages of the basement rocks (1.1 ~ 1.4 Ga) are slightly older than those of the plutons (0.6 ~ 1.0 Ga). The initial Sr and Nd isotopic ratios of the plutons can be modeled by the mixing between the mid‐oceanic ridge basalt‐like depleted mantle component and the crustal component represented by basement rocks, which is also supported by Pb isotope data. The Sr and Nd isotope data from granitoids and basement rocks suggest that the Gyeongsang basin, the Hida belt and the inner zone of south‐western Japan share relatively young basement histories (middle Proterozoic), compared with those (early Proterozoic to Archean) of the Gyeonggi and Yeongnam massifs and the Okcheon belt. The Nd isotope data of basement rocks suggest that the Hida belt might be better correlated with the basement of the Gyeongsang basin than the Gyeonggi massif, the Okcheon belt or the Yeongnam massif, although it may represent an older continental margin of East Asia than the Gyeongsang basin considering its slightly older Nd model ages.

Rare earth element geochemistry of hydrothermal deposits from the active TAG Mound, 26°N Mid-Atlantic Ridge

The rare earth element (REE) geochemistry of various phases from the active TAG hydrothermal mound has been examined and related to their mineralogy and fluid chemistry. The mound deposits range from black and white smoker chimneys, massive anhydrite/sulphide mixtures, oxides, and ochres. All phases, except black smoker chimney anhydrite, demonstrate a positive Eu anomaly when normalised to chondrite REE values. REE substitution into sulphide and sulphate phases appears to be strongly influenced by crystallographic control for all REE other than Eu. Precipitation of anhydrite within the TAG mound is the major mechanism for removal of REE during mound circulation and 0.15-0.35 g anhydrite is inferred to precipitate from every kg of fluid venting from the white smoker chimneys. Oxides from the mound fall into three different categories with distinct REE patterns: oxide rims on sulphides, atacamite-bearing oxides, and silica-rich Fe-oxides and ochres. The oxide rim phases contain sulphide and seawater derived REEs whereas the atacamite-bearing oxides and the ochreous material exhibit no seawater signature which suggests precipitation from, or alteration by, a modified hydrothermal fluid.

Distinctive REE patterns for tholiitic and calc-alkaline magma series co-occurring at Adatara volcano, Northeast Japan.

Rare earth element (REE) concentrations were precisely determined by inductively coupled argon plasma/atomic emission spectrometry (ICP) for 9 tholeiitic and 13 associated calc-alkaline rocks from Adatara volcano, located at the volcanic front of Northeast Japan arc. The tholeiitic samples commonly display nearly flat REE patterns, whereas the calc-alkaline samples characteristically show concave light REE-enriched patterns. In both suites, the REEs, with the exception of Eu, are positively correlated to varying extents with K2O and other incompatible elements. Eu concentrations in the calc-alkaline suite do not vary significantly, resulting in significant negative Eu anomalies. In the tholeiitic suite, chondrite-normalized (Ce/Yb)CN ratios are low and show little variation (1.54–1.80) over a significant range in SiO2 content (52–62 wt%). In contrast, (Ce/Yb)CN in the calc-alkaline suite show much greater variation (2.17 to 2.94) over a smaller range in SiO2 content (56 to 62 wt%) and increase systematically with SiO2. REE data for the tholeiitic suite are consistent with a crystal fractionation model that successfully reproduces the observed major and trace-element variations. A similar fractionation model is compatible with major-element and some trace-element variations for the calc-alkaline suite, but results in excessively high heavy REE contents, and fails to reproduce the elevated (Ce/Yb)CN ratios for the most acidic samples. The preferential enrichment of light REEs may reflect additional processes such as: (1) assimilation, (2) incorporation of a differentiated liquid (or evolved magma) that has undergone fractionation of heavy REE-rich minerals, and (3) mixing of primary magma derived by a small degree of partial melting from a common (amphibolitic or hornblende gabbroic) source. Although the tholeiitic and calc-alkaline suites possess distinct 87Sr/86Sr, Rb/Ba and Zr/Nb ratios, different magma sources are not required to produce the distinct REE patterns of the coexisting suites. An equilibrium batch partial melting model can reproduce both the flat (tholeiitic) and concave (calc-alkaline) REE patterns from a common peridotitic source by larger (10–15%) and smaller (5%) degrees of partial melting, respectively. Therefore, both tholeiitic and calc-alkaline suites could have been derived from a common lherzolitic magma source, provided that the calc-alkaline suite underwent incorporation (assimilation) of isotopically distinct (lower crust-derived) materials prior to evolution.

Rare-earth element mobility in alteration pipes below massive CuZn-sulfide deposits

A convincing demonstration of trace-element mobility should satisfy two criteria: (1) the range of trace-element concentrations in the rock before and after alteration must be known with confidence; and (2) the absolute abundances and the ratios of the mobile trace elements should vary between altered and unaltered rocks. These criteria have been applied to the host felsic volcanics and alteration pipes associated with several Canadian massive CuZn-sulfide deposits. Although there is no evidence of rare-earth element (REE) mobility in the pervasive low-grade alteration envelopes adjacent to the deposits, the light and middle REE (LREE and MREE) plus Y have been systematically mobilized relative to the heavy REE (HREE) and other trace elements in the alteration pipes beneath the ore zones. There is evidence of minor LREE and MREE depletion in the most altered rocks at the South Bay Mine (Uchi Lake) and of significant LREE depletion in the alteration pipe beneath the Mattabi Mine (Sturgeon Lake). However, the strongest mobility is found at the Kidd Creek Mine where the LREE were leached from the rocks in the footwall stringer zone and redeposited in a metasomatic chlorite zone directly beneath the massive ore horizon, and the MREE and Y were preferentially lost from the system producing distinctive chondrite-normalized REE patterns with ( Tb Yb ) n ratios less than unity. Eu 2+ was found to be more mobile than the trivalent REE, especially at Kidd Creek where there is a marked increase in the magnitude of the Eu anomaly in the most altered samples. High-field-strength elements such as U, Th, Hf and Zr have not decoupled and apparently remained relatively immobile during all but the most intense alteration (i.e. Kidd Creek). Preliminary data suggest that the degree of REE mobility increases with the size of the deposit. Thus, REE mobility is a potentially useful method of distinguishing between small and large massive sulfide deposits at an early stage in exploration, however, this hypothesis requires further testing.