Rare earth element distribution in some hydrothermal minerals: evidence for crystallographic control

Rare earth element (REE) abundances were measured by neutron activation analysis in anhydrite (CaSO₄), barite (BaSO₄), siderite (FeCO₃) and galena (PbS). A simple crystal-chemical model qualitatively describes the relative affinities for REE substitution in anhydrite, barite, and siderite. When normalized to ‘crustal’ abundances (as an approximation to the hydrothermal fluid REE pattern), log REE abundance is a surprisingly linear function of (ionic radius of major cation—ionic radius of REE)² for the three hydrothermal minerals, individually and collectively. An important exception, however, is Eu, which is anomalously enriched in barite and depleted in siderite relative to REE of neighboring atomic number and trivalent ionic radius. In principle, REE analyses of suitable pairs of co-existing hydrothermal minerals, combined with appropriate experimental data, could yield both the REE content and the temperature of the parental hydrothermal fluid.The REE have only very weak chalcophilic tendencies, and this is reflected by the very low abundances in galena—La, 0.6 ppb; Sm, 0.06 ppb; the remainder are below detection limits.     

Rare earth element and stable isotope (O, S) geochemistry of barite from the Bijgan deposit, Markazi Province, Iran

The Bijgan barite deposit, which is located northeast of Delijan in Markazi Province of Iran, occurs as a small lenticular body at the uppermost part of an Eocene volcano-sedimentary rock unit. The presence of fossiliferous and carbonaceous strata suggests that the host rocks were deposited in a quiet marine sedimentary environment. Barite, calcite, iron oxides and carbonaceous clay materials are found as massive patches as well as thin layers in the deposit. Barite is marked by very low concentrations of Sr (1–2%) and total amounts of rare earth elements (REEs) (6.25–17.39?ppm). Chondrite-normalized REE patterns of barite indicate a fractionation of light REEs (LREEs) from La to Sm, similar to those for barite of different origins from elsewhere. The La_CN/Lu_CN ratios and chondrite-normalized REE patterns reveal that barite in the Bijgan deposit is enriched in LREE relative to heavy rare earth elements (HREEs). The similarity between the Ce/La ratios in the barite samples and those found in deep-sea barite supports a marine origin for barite. Lanthanum and Gd exhibit positive anomalies, which are common features of marine chemical sediments. Cerium shows a negative anomaly in most samples that was inherited from the negative Ce anomaly of hydrothermal fluid that mixed with seawater at the time of barite precipitation. The δ¹⁸O values of barites show a narrow range of 9.1–11.4‰, which is close to or slightly lower than that of contemporaneous seawater at the end of the Eocene. This suggests a contribution of oxygen from seawater in the barite-forming solution. The δ³⁴S values of barites (9.5–15.3‰) are lower than that of contemporaneous seawater, which suggests a contribution of magmatic sulfur to the ore-forming solution. The oxygen and sulfur isotope ratios indicate that submarine hydrothermal vent fluids are a good analog for solutions that precipitated barite, due to similarities in the isotopic composition of the sulfates. The available data including tectonic setting, host rock characteristics, REE geochemistry, and oxygen and sulfur isotopic compositions support a submarine hydrothermal origin for the Bijgan barite deposit. At the seafloor, barite deposition occurred where ascending Ba-bearing hydrothermal fluids encountered seawater. Sulfate was derived from the sulfate-bearing marine waters, and, to a lesser extent, by oxidized H₂S, which was derived from magmatic hydrothermal fluids.     

Speciation of rare earth elements in natural terrestrial waters: assessing the role of dissolved organic matter from the modeling approach

Humic Ion-Binding Model V, which focuses on metal complexation with humic and fulvic acids, was modified to assess the role of dissolved natural organic matter in the speciation of rare earth elements (REEs) in natural terrestrial waters. Intrinsic equilibrium constants for cation-proton exchange with humic substances (i.e., pK_MHA for type A sites, consisting mainly of carboxylic acids), required by the model for each REE, were initially estimated using linear free-energy relationships between the first hydrolysis constants and stability constants for REE metal complexation with lactic and acetic acid. pK_MHA values were further refined by comparison of calculated Model V “fits” to published data sets describing complexation of Eu, Tb, and Dy with humic substances. A subroutine that allows for the simultaneous evaluation of REE complexation with inorganic ligands (e.g., Cl⁻, F⁻, OH⁻, SO₄²⁻, CO₃²⁻, PO₄³⁻), incorporating recently determined stability constants for REE complexes with these ligands, was also linked to Model V. Humic Ion-Binding Model V’s ability to predict REE speciation with natural organic matter in natural waters was evaluated by comparing model results to “speciation” data determined previously with ultrafiltration techniques (i.e., organic acid-rich waters of the Nsimi-Zoetele catchment, Cameroon; dilute, circumneutral-pH waters of the Tamagawa River, Japan, and the Kalix River, northern Sweden). The model predictions compare well with the ultrafiltration studies, especially for the heavy REEs in circumneutral-pH river waters. Subsequent application of the model to world average river water predicts that organic matter complexes are the dominant form of dissolved REEs in bulk river waters draining the continents. Holding major solute, minor solute, and REE concentrations of world average river water constant while varying pH, the model suggests that organic matter complexes would dominate La, Eu, and Lu speciation within the pH ranges of 5.4 to 7.9, 4.8 to 7.3, and 4.9 to 6.9, respectively. For acidic waters, the model predicts that the free metal ion (Ln³⁺) and sulfate complexes (LnSO₄⁺) dominate, whereas in alkaline waters, carbonate complexes (LnCO₃⁺ + Ln[CO₃]₂⁻) are predicted to out-compete humic substances for dissolved REEs. Application of the modified Model V to a “model” groundwater suggests that natural organic matter complexes of REEs are insignificant. However, groundwaters with higher dissolved organic carbon concentrations than the “model” groundwater (i.e., >0.7 mg/L) would exhibit greater fractions of each REE complexed with organic matter. Sensitively analysis indicates that increasing ionic strength can weaken humate-REE interactions, and increasing the concentration of competitive cations such as Fe(III) and Al can lead to a decrease in the amount of REEs bound to dissolved organic matter.     

Pressure-Dependence of Rare Earth Element Distribution in Amphibolite- and Granulite- Grade Garnets. A LA-ICP-MS Study

Using an excimer (KrF) laser ablation ICP-MS system, we studied the distribution of REE in garnets from metapelites and metabasites from Ivrea-Verbano (Western Alps, Italy) and from the Peña Negra Anatectic Complex (Central Iberia), finding systematic variations that correlate well with the metamorphic grade. Chondrite-normalized REE patterns of garnets from amphibolite-grade metapelites have lower-than-chondrite levels from La to Sm, a very small or no Eu anomaly, and a steep rise in the abundance of heavy REE as the atomic number increases. Metapelitic garnets from the amphibolite-granulite transition have a marked Eu negative anomaly and are enriched in MREE such that Sm is 10-15 times chondrite and the pattern is almost flat from Dy to Yb-Lu. In garnets from granulite-grade metapelites, the intensity of the Eu anomaly and the relative concentration of Nd, Sm, Gd and Tb increase, with almost flat chondrite-normalized patterns from Sm to Lu. Garnets from mafic granulites are remarkably similar to those of metapelitic garnets equilibrated at the same pressure, except for the Eu anomaly. The apparent paradox of enhanced uptake of larger REE ions with increasing pressure is attributed to the 3M²⁺ 2REE³⁺+ vacancy substitution, which produces a net decrease in the dimensions of the unit-cell of garnet. Variations in REE patterns depend essentially on the pressure and have little dependence on either temperature, bulk-composition of garnet, or REE whole-rock composition, so they could represent a new approach for geobarometric studies. The best numerical parameter to express pressure-related variations of REE distribution in garnets is the Gd/Dy ratio which does not seem perceptibly affected by disequilibrium partitioning. The regression equation between GASP pressure and the average Gd/Dy^garnet is P = 3.6 + 5.6 Gd/Dy. This equation seems to be reliable for garnets: (1)equilibrated within a pressure range of 4-9 kbar, (2) coexisting with modal monazite; and (3) with unit-cell dimensions under 11.46 Å.     

Mobility and fractionation of rare earth elements during supergene weathering and gossan formation and chemical modification of massive sulfide gossan

Primary massive sulfide gossans (MSG) in the Bathurst Mining Camp (BMC), New Brunswick, Canada, are characterized by relative enrichment of Au, Sb, and As, formation of jarosite group minerals (jarosite, plumbojarosite, and argentojarosite) and little or no fractionation in the rare earth elements (REE), including preservation of large positive Eu anomalies (average [Eu/Eu*]_NASC = 4.14 in MSG; 6.61 in massive sulfide mineralization; 0.60 in host rocks). The chemical and mineralogical characteristics of MSG (e.g., Halfmile Lake deposit) imply low pH (<3) and relatively oxidizing conditions during gossan formation; oxidation of a volcanogenic massive sulfide body (comprising pyrite, pyrrhotite, sphalerite, galena, and chalcopyrite) with a falling water table. The lack of light REE or heavy REE fractionation and preservation of positive Eu anomalies characteristic of the original (465 Ma) hydrothermal fluid is consistent with relatively large water-rock ratios during massive sulfide mineralization oxidation, and removal of the REE predominantly as sulfate complexes (LnSO₄⁺, Ln(SO₄)₂⁻). Low pH groundwaters recovered from past producing mines in the BMC display REE patterns reflecting those inferred to have occurred during gossan formation. Gossan at the Restigouche deposit, in contrast to the Halfmile Lake deposit, displays mineralogical and chemical evidence for having been chemically reworked since primary gossan formation. Evidence for chemical reworking includes loss of primary massive sulfide mineralization textures, replacement of plumbojarosite with anglesite, almost complete removal of jarosite minerals, loss of Au, Sb, and As and apparent preferential removal of Eu, resulting in loss of positive Eu anomalies for most samples (average [Eu/Eu*]_NASC = 1.21 in the gossan, with many displaying strong negative anomalies; 3.65 in massive sulfide mineralization; 0.54 in host rocks). Based on geochemical modeling, conditions inferred for the chemical reworking of the Restigouche deposit include near neutral conditions and either relatively oxidizing conditions with Eu²⁺ hosted in a preferentially weathered mineral host (possibly through substitution for Pb in plumbojarosite and beudantite) or cycling between reduced and oxidized conditions during gossan reworking.     

A new occurrence of thorianite from syenitic pegmatite near Bhaluchuan,Odisha

We report a new occurrence of thorianite from syenitic pegmatite near Bhaluchuan, Sambalpur district, Odisha. The thorianite is brown to deep-brown with round grains of 2 to 10 mm size. The chemical analysis of the investigated thorianite reveals 64.8% ThO₂, 25% U₃O₈, 3.81% PbO and 1.7% Fe₂O₃. Calculated structural formula of the thorianite is (Th⁺⁴ _0.61U⁺⁴ _0.14U⁺⁶ _0.08ΣREE⁺³ _0.017Pb⁺² _0.04Ca⁺² _0.01Mn⁺² _0.001Fe⁺³ _0.05Al⁺³ _0.003Sc⁺² _0.002K⁺¹ _0.005Na⁺¹ _0.008 Si⁺⁴ _0.04Ti⁺⁴ _0.02)O_2.08. Chondrite-normalised rare-earth element (REE) plot of the thorianite reveals enrichment of light REE (LREE) over heavy REE (HREE) with pronounced negative Eu-anomaly (Eu/Eu* = 0.35). The (ΣLREE/ΣHREE)_N ratio is perceptibly high (2.76). The (La/Lu)_N (42.31), (La/Yb)_N (27.49) and (Ce/Yb)_N (21.58) ratios are also very high. X-ray diffraction (XRD) pattern of the investigated thorianite displays sharply-defined reflections. Corresponding interplanar spacings (d-spacings) of all the reflections are in very close agreement with those published for thorianite standard in International Centre for Diffraction Data (ICDD) Card No. 4-556. However, I/Io of two reflections (1.9694Å and 1.6787Å) are lower than those published for thorianite standard. The unit cell parameter (a_o) of the investigated thorianite (a_o 5.5750Å) is also less than a_o of thorianite standard (a_o 5.6000Å and V 175.62ų), which is because of extensive substitution of Th by U.     

Rare earth elements (REE) and yttrium in stream waters, stream sediments, and Fe-Mn oxyhydroxides: Fractionation, speciation, and controls over REE + Y patterns in the surface environment

We have collected ∼500 stream waters and associated bed-load sediments over an ∼400 km² region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into “dissolved” (<0.45 μm), labile (hydroxylamine) and detrital sediment fractions to investigate REE fractionation, and in particular, with respect to the development of Ce and Eu anomalies in oxygenated surface environments. Surface waters are typically LREE depleted ([La/Sm]_NASC ranges from 0.16 to 5.84, average = 0.604, n = 410; where the REE are normalized to the North America Shale Composite), have strongly negative Ce anomalies ([Ce/Ce^∗]_NASC ranges from 0.02 to 1.25, average = 0.277, n = 354), and commonly have positive Eu anomalies ([Eu/Eu^∗]_NASC ranges from 0.295 to 1.77, average = 0.764, n = 84). In contrast, the total sediment have flatter REE + Y patterns relative to NASC ([La/Sm]_NASC ranges from 0.352 to 1.12, average = 0.778, n = 451) and are slightly middle REE enriched ([Gd/Yb]_NASC ranges from 0.55 to 3.75, average = 1.42). Most total sediments have negative Ce and Eu anomalies ([Ce/Ce^∗]_NASC ranges from 0.097 to 2.12, average = 0.799 and [Eu/Eu^∗]_NASC ranges from 0.39 to 1.43, average = 0.802). The partial extraction sediments are commonly less LREE depleted than the total sediments ([La/Sm]_NASC ranges from 0.24 to 3.31, average = 0.901, n = 4537), more MREE enriched ([Gd/Yb]_NASC ranges from 0.765 to 6.28, average = 1.97) and Ce and Eu anomalies (negative and positive) are more pronounced.The partial extraction recovered, on average ∼20% of the Fe in the total sediment, ∼80% of the Mn, and 21-29% of the REEs (Ce = 19% and Y = 32%). Comparison between REEs in water, partial extraction and total sediment analyses indicates that REEs + Y in the stream sediments have two primary sources, the host lithologies (i.e., mechanical dispersion) and hydromorphically transported (the labile fraction). Furthermore, Eu appears to be more mobile than the other REE, whereas Ce is preferentially removed from solution and accumulates in the stream sediments in a less labile form than the other REEs + Y. Despite poor statistical correlations between the REEs + Y and Mn in either the total sediment or partial extractions, based on apparent distribution coefficients and the pH of the stream waters, we suggest that either sediment organic matter and/or possibly δ-MnO₂/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.     

Genesis for Rare Earth Elements Enrichment in the Permian Manganese Deposits in Zunyi,Guizhou Province,SW China

The Zunyi manganese deposits, which formed during the Middle to Late Permian period and are located in northern Guizhou and adjacent areas, are the core area of a series of large-medium scale manganese enrichment minerogenesis in the southern margin and interior of the Yangtze platform, Southern China. This study reports the universal enrichment of rare earth elements(REEs) in Zunyi manganese deposits and examines the enrichment characteristics, metallogenic environment and genesis of REEs. The manganese ore bodies present stratiform or stratoid in shape, hosted in the silicon–mud–limestones of the Late Permian Maokou Formation. The manganese ores generally present lamellar, massive, banded and brecciated structures, and mainly consist of rhodochrosite, ropperite, tetalite, capillitite, as well as contains paragenetic gangue minerals including pyrite, chalcopyrite, rutile, barite, tuffaceous clay rock, etc. The manganese ores have higher ΣREE contents range from 158 to 1138.9 ppm(average 509.54 ppm). In addition, the ΣREE contents of tuffaceous clay rock in ore beds vary from 1032.2 to 1824.5 ppm(average 1396.42 ppm). The REEs from manganese deposits are characterized by La, Ce, Nd and Y enriched, and existing in the form of independent minerals(e.g., monazite and xenotime), indicating Zunyi manganese deposits enriched in light rare earth elements(LREE). The Ce_(anom) ratios(average-0.13) and lithofacies and paleogeography characteristics indicate that Zunyi manganese deposits were formed in a weak oxidation-reduction environment. The(La/Yb)_(ch), Y/Ho,(La/Nd)_N,(Dy/Yb)_N, Ce/Ce* and Eu/Eu* values of samples from the Zunyi manganese deposits are 5.53–56.92, 18–39, 1.42–3.15, 0.55–2.20, 0.21–1.76 and 0.48–0.86, respectively, indicating a hydrothermal origin for the manganese mineralization and REEs enrichment. The δ~(13) C_(V-PDB)(-0.54 to-18.1‰) and δ~(18) O_(SMOW)(21.6 to 26.0‰) characteristics of manganese ores reveal a mixed source of magmatic and organic matter. Moreover, the manganese ore, tuffaceous clay rock and Emeishan basalt have extremely similar REE fractionation characteristic, suggesting REEs enrichment and manganese mineralization have been mainly origin from hydrothermal fluids.     

Geochemistry and petrogenesis of Proterozoic granitic rocks from northern margin of the Chotanagpur Gneissic Complex (CGC)

This study presents the geochemical characteristics of granitic rocks located on the northern margin of Chotanagpur Gneissic Complex (CGC), exposed in parts of Gaya district, Bihar and discusses the possible petrogenetic process and source characteristics. These granites are associated with Barabar Anorthosite Complex and Neo-proterozoic Munger–Rajgir group of rocks. The granitic litho-units identified in the field are grey, pink and porphyritic granites. On the basis of geochemical and petrographic characteristics, the grey and pink granites were grouped together as GPG while the porphyritic granites were named as PG. Both GPG and PG are enriched in SiO₂, K₂O, Na₂O, REE (except Eu), Rb, Ba, HFSE (Nb, Y, Zr), depleted in MgO, CaO, Sr and are characterised by high Fe* values, Ga/Al ratios and high Zr saturation temperatures (GPG_avg～ 861 ^°C and PG_avg～ 835 ^°C). The REE patterns for GPG are moderately fractionated with an average (La/Yb)_N～ 4.55 and Eu/Eu* ～ 0.58, than PG which are strongly fractionated with an average (La/Yb)_N～ 31.86 and Eu/Eu* ～ 0.75. These features indicate that the granites have an A-type character. On the basis of geochemical data, we conclude that the granites are probably derived from a predominant crustal source with variable mantle involvement in a post-collisional setting.     

Hydrochemical,isotopic, and reservoir characterization of the Pasinler (Erzurum) geothermal field,eastern Turkey

The reservoir temperature and conceptual model of the Pasinler geothermal area, which is one of the most important geothermal areas in Eastern Anatolia, are determined by considering its hydrogeochemical and isotope properties. The geothermal waters have a temperature of 51 °C in the geothermal wells and are of Na–Cl–HCO₃ type. The isotope contents of geothermal waters indicate that they are of meteoric origin and that they recharge on higher elevations than cold waters. The geothermal waters are of immature water class and their reservoir temperatures are calculated as 122–155 °C, and their cold water mixture rate is calculated as 32%. According to the δ¹³C_VPDB values, the carbon in the geothermal waters originated from the dissolved carbon in the groundwaters and mantle-based CO₂ gases. According to the δ³⁴S_CDT values, the sources of sulfur in the geothermal waters are volcanic sulfur, oil and coal, and limestones. The sources of the major ions (Na⁺, Ca²⁺, Mg²⁺, Cl^?, and HCO₃ ^?) in the geothermal waters are ion exchange and plagioclase and silicate weathering. It is determined that the volcanic rocks in the area have effects on the water chemistry and elements like Zn, Rb, Sr, and Ba originated from the rhyolite, rhyolitic tuff, and basalts. The rare earth element (REE) content of the geothermal waters is low, and according to the normalized REE diagrams, the light REE are getting depleted and heavy REE are getting enriched. The positive Eu and negative Ce anomalies of waters indicate oxygen-rich environments.     

Determination of zircon/melt trace element partition coefficients from SIMS analysis of melt inclusions in zircon

Partition coefficients (^zircon/meltD_M) for rare earth elements (REE) (La, Ce, Nd, Sm, Dy, Er and Yb) and other trace elements (Ba, Rb, B, Sr, Ti, Y and Nb) between zircon and melt have been calculated from secondary ion mass spectrometric (SIMS) analyses of zircon/melt inclusion pairs. The melt inclusion-mineral (MIM) technique shows that D_REE increase in compatibility with increasing atomic number, similar to results of previous studies. However, D_REE determined using the MIM technique are, in general, lower than previously reported values. Calculated D_REE indicate that light REE with atomic numbers less than Sm are incompatible in zircon and become more incompatible with decreasing atomic number. This behavior is in contrast to most previously published results which indicate D > 1 and define a flat partitioning pattern for elements from La through Sm. The partition coefficients for the heavy REE determined using the MIM technique are lower than previously published results by factors of ≈15 to 20 but follow a similar trend. These differences are thought to reflect the effects of mineral and/or glass contaminants in samples from earlier studies which employed bulk analysis techniques.D_REE determined using the MIM technique agree well with values predicted using the equations of Brice (1975), which are based on the size and elasticity of crystallographic sites. The presence of Ce⁴⁺ in the melt results in elevated D_Ce compared to neighboring REE due to the similar valence and size of Ce⁴⁺ and Zr⁴⁺. Predicted ^zircon/meltD values for Ce⁴⁺ and Ce³⁺ indicate that the Ce⁴⁺/Ce³⁺ ratios of the melt ranged from about 10⁻³ to 10⁻². Partition coefficients for other trace elements determined in this study increase in compatibility in the order Ba < Rb < B < Sr < Ti < Y < Nb, with Ba, Rb, B and Sr showing incompatible behavior (D_M < 1.0), and Ti, Y and Nb showing compatible behavior (D_M > 1.0).The effect of partition coefficients on melt evolution during petrogenetic modeling was examined using partition coefficients determined in this study and compared to trends obtained using published partition coefficients. The lower D_REE determined in this study result in smaller REE bulk distribution coefficients, for a given mineral assemblage, compared to those calculated using previously reported values. As an example, fractional crystallization of an assemblage composed of 35% hornblende, 64.5% plagioclase and 0.5% zircon produces a melt that becomes increasingly more enriched in Yb using the D_Yb from this study. Using D_Yb from Fujimaki (1986) results in a melt that becomes progressively depleted in Yb during crystallization.     

Origin of natural sulfur-metal chimney in the Tangyin hydrothermal field,Okinawa Trough: constraints from rare earth element and sulfur isotopic compositions

For the first time, we present the rare earth element (REE) and sulfur isotopic composition of hydrothermal precipitates recovered from the Tangyin hydrothermal field (THF), Okinawa Trough at a water depth of 1206 m. The natural sulfur samples exhibit the lowest ΣREE concentrations (ΣREE= 0.65×10^–6–4.580×10^–6) followed by metal sulfides (ΣREE=1.71×10^–6–11.63×10^–6). By contrast, the natural sulfur-sediment samples have maximum ΣREE concentrations (ΣREE=11.54×10^–6–33.06×10^–6), significantly lower than those of the volcanic and sediment samples. Nevertheless, the δEu, δCe, (La/Yb)_N, La/Sm, (Gd/Yb)_N and normalized patterns of the natural sulfur and metal sulfide show the most similarity to the sediment. Most hydrothermal precipitate samples are characterized by enrichments of LREE (LREE/HREE=10.09–24.53) and slightly negative Eu anomalies or no anomaly (δEu=0.48–0.99), which are different from the hydrothermal fluid from sediment-free mid-oceanic ridges and back-arc basins, but identical to the sulfides from the Jade hydrothermal field. The lower temperature and more oxidizing conditions produced by the mixing between seawater and hydrothermal fluids further attenuate the leaching ability of hydrothermal fluid, inducing lower REE concentrations for natural sulfur compared with metal sulfide; meanwhile, the negative Eu anomaly is also weakened or almost absent. The sulfur isotopic compositions of the natural sulfur (δ³⁴S=3.20‰–5.01‰, mean 4.23‰) and metal sulfide samples (δ³⁴S=0.82‰–0.89‰, mean 0.85‰) reveal that the sulfur of the chimney is sourced from magmatic degassing.     

Partition of Sr,Ba, Ca,Y, Eu2+, Eu3+, and other REE between plagioclase feldspar and magmatic liquid: an experimental study

Plagioclase feldspar/magmatic liquid partition coefficients for Sr, Ba, Ca, Y, Eu²⁺, Eu³⁺ and other REE have been determined experimentally at 1 atm total pressure in the temperature range 1150–1400°C. Natural and synthetic melts representative of basaltic and andesitic bulk compositions were used, crystallizing plagioclase feldspar in the composition range An₃₅–An₈₅. Partition coefficients for Sr are greater than unity at all geologically reasonable temperatures, and for Ba are less than unity above approximately 1060°C. Both are strongly dependent upon temperature. Partition coefficients for the trivalent REE are relatively insensitive to temperature. At fixed temperature they decrease monotonically from La to Lu. The partition of Eu is a strong function of oxygen fugacity. Under extreme reducing conditions D_Eu approaches the value of D_Sr.     

Adsorption of rare earth elements onto Carrizo sand: Experimental investigations and modeling with surface complexation

Rare earth element (REE) adsorption onto sand from a well characterized aquifer, the Carrizo Sand aquifer of Texas, has been investigated in the laboratory using a batch method. The aim was to improve our understanding of REE adsorption behavior across the REE series and to develop a surface complexation model for the REEs, which can be applied to real aquifer-groundwater systems. Our batch experiments show that REE adsorption onto Carrizo sand increases with increasing atomic number across the REE series. For each REE, adsorption increases with increasing pH, such that when pH >6.0, >98% of each REE is adsorbed onto Carrizo sand for all experimental solutions, including when actual groundwaters from the Carrizo Sand aquifer are used in the experiments. Rare earth element adsorption was not sensitive to ionic strength and total initial REE concentrations in our batch experiments. It is possible that the differences in experimental ionic strength conditions (i.e., 0.002-0.01 M NaCl) chosen were insufficient to affect REE adsorption behavior. However, cation competition (e.g., Ca, Mg, and Zn) did affect REE adsorption onto Carrizo sand, especially for light rare earth elements (LREEs) at low pH. Rare earth element adsorption onto Carrizo sand can be successfully modeled using a generalized two-layer surface complexation model. Our model calculations suggest that REE complexation with strong surface sites of Carrizo sand exceeds the stability of the aqueous complexes LnOH²⁺, LnSO₄⁺, and LnCO₃⁺, but not that of Ln(CO₃)₂^- or LnPO₄^o in Carrizo groundwaters. Thus, at low pH (<7.3), where major inorganic ligands did not effectively compete with surface sites for dissolved REEs, free metal ion (Ln³⁺) adsorption was sufficient to describe REE adsorption behavior. However, at higher pH (>7.3) where solution complexation of the dissolved REEs was strong, REEs were adsorbed not only as free metal ion (Ln³⁺) but also as aqueous complexes (e.g., as Ln(CO₃)₂^- in Carrizo groundwaters). Because heavy rare earth elements (HREEs) were preferentially adsorbed onto Carrizo sand compared to LREEs, original HREE-enriched fractionation patterns in Carrizo groundwaters from the recharge area flattened along the groundwater flow path in the Carrizo Sand aquifer due to adsorption of free- and solution-complexed REEs.     

Geology,geochemistry, sulfur isotope composition,and fluid inclusion data of Farsesh barite deposit,Lorestan Province,Iran

Farsesh barite in the central part of Iranian Sanandaj-Sirjan zone is a sample of epigenetic hydrothermal mineralization in dolomitized limestone, which provides appropriate chemicophysical conditions making the passage of mineral-bearing fluids possible. Barite veins may range from a few centimeters to 2 m in thickness that increases downward. The microthermometry measurements obtained from more than 30 fluid inclusions show relative homogenization temperatures ranging from 125 to 200 °C with an average of 110 °C for Farsesh barite deposits. The mean salinity measured proves 16 times as much as weight percentage of NaCl for barite. Coexistence of liquid- and vapor-rich fluid inclusions in barite minerals may provide an evidence of boiling in ore veins. Moreover, occurrence of bladed calcite, high-grade ore zones, and presence of hydrothermal breccia are all consistent with boiling. Thermometric studies indicate that homogenization temperatures (Th) for primary and pseudosecondary fluid inclusions in barite range from 125 to 200 °C with an average of 1,100 °C. The δ³⁴S values of barite also lie between 8.88 and 16.6 %. The relatively narrow spread in δ³⁴S values may suggest uniform environmental conditions throughout the mineralization field. Thus, δ³⁴S values are lower than those of contemporaneous seawater, which indicates a contribution of magmatic sulfur to the ore-forming solution. Barite is marked by total amounts of rare Earth elements (REEs) (6.25–17.39 ppm). Moreover, chondrite-normalized REE patterns of barite indicate a fractionation of light REEs (i.e., LREEs) from La to Sm, similar to those for barite from different origins. The La_CN/Lu_CN ratios and chondrite-normalized REE patterns reveal that barite in Farsesh deposit is enriched in LREEs compared with heavy rare Earth elements (HREEs). Similarity between Ce/La ratios in barite samples and those found in deep-sea barite supports its marine origin. Lanthanum and Gd exhibit positive anomalies, which are common features of chemical marine sediments. Cerium shows a negative anomaly in most samples inherited from the negative Ce anomaly of hydrothermal fluid that is mixed with seawater at barite precipitation. The available data including tectonic setting, host rock characteristics, REE geochemistry, and sulfur isotopic compositions may support a hydrothermal submarine origin for Farsesh barite deposit.     

Geochemical and hydrogeochemical evolution of groundwater in Ferdows area, northeast of Iran

The chemical analysis of 19 water wells in Ferdows area, Northeastern Iran, has been evaluated to determine the hydrogeochemical processes and ion concentration background in the region. In the study area, the order of cation and anion abundance is Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ and Cl^? > SO ₄ ^?2  > HCO₃ ^? > NO₃ ^?, respectively, and the dominating hydrochemical types are Na–Cl. Most metal concentrations in water depend on the mineral solubility, and pH, Eh, and salinity of the solution. Their ΣREE concentrations showed excellent correlations with parameters such as TDS and pH. North American Shale Composite (NASC)-normalized REE patterns are enriched in the HREEs relative to the LREEs for all groundwaters. They all have positive Eu anomalies (Eu/Eu* = 0.752–3.934) and slightly negative Ce anomalies (Ce/Ce* = 0.019–1.057). Reduction–oxidation, complexation, desorption, and re-adsorption alter groundwater REE concentrations and fractionation patterns. The positive Eu anomalies in groundwaters are probably due to preferential mobilization of Eu²⁺ relative to the trivalent REEs in the reducing condition.     

Fluid-rock interaction during progressive migration of carbonatitic fluids, derived from small-scale trace element and Sr, Pb isotope distribution in hydrothermal fluorite

Associated with the Cretaceous Okorusu carbonatite complex (Namibia) is a hydrothermal fluorite mineralization hosted in Pan-African country rock marbles, which resulted from fluid-rock reaction between the marbles and orthomagmatic, carbonatitic fluids expelled from the carbonatite. Yellow fluorite I was deposited in veins up to 5 cm away from the wallrock contact, followed by purple and colorless fluorite II, smoky quartz and barite, a Mn-rich crust on early calcite, and pure calcite. This clear-cut sequence of mineral growth allows an investigation into fluid-rock interaction processes between the marble and the migrating carbonatitic fluid, and element fractionation patterns between the fluid and subsequent hydrothermal precipitates.Fluorite I shows a progressive change in color from dark yellow to colorless with purple laminations over time of deposition. Subsequent fluorite I precipitates show an increase in Ca, and a continuous decrease in F, Sr, REE, Y, Th, U and Pb contents. The ratios (Eu/Eu*)_cn, Th/Pb and U/Pb increase whereas Y/Ho, Th/U and (La/Yb)_cn decrease. The Sr-isotopic composition remains constant at ⁸⁷Sr/⁸⁶Sr = 0.70456-0.70459, but with varying, highly radiogenic Pb (²⁰⁶Pb/²⁰⁴Pb = 32-190, ²³⁸U/²⁰⁴Pb = 7-63). Fluorite II has ⁸⁷Sr/⁸⁶Sr = 0.70454-0.70459, ²⁰⁶Pb/²⁰⁴Pb = 18.349, and ²⁰⁷Pb/²⁰⁴Pb = 15.600, and a chemical composition similar to youngest fluorite I. The Mn-rich crust on early calcite accumulated REE, Ba, Pb, Zr, Cs, Th and U, developing into pure calcite with a prominent negative Ce anomaly and successively more radiogenic Sr. The calculated degrees of fluid-rock interaction, f = weight fraction of fluid/(fluid + marble), decrease from fluorite I and most fluorite II (f = 0.5) to calcite (f = 0.2-0.3) and hydrothermal quartz (f ? 0.1). A crush-leach experiment for fluid inclusions in the hydrothermal quartz yielded a Rb-Sr isochron age of 103 ± 12 Ma. Crush-leach analysis for the carbonatitic fluid trapped in the wallrock yielded a trend from the fluid leachate to the host quartz (²⁰⁶Pb/²⁰⁴Pb = 18.224 and 18.602, ²⁰⁷Pb/²⁰⁴Pb = 15.616 and 15.636, respectively) extending from carbonatite towards crustal rocks.Calculated trace element distribution coefficients fluorite/fluid are below unity throughout, and increase from La to Yb. Elements largely excluded from fluorite (Ba, Pb, LREE relative to HREE) were incorporated later into the Mn-rich crust on calcite. The trace element patterns of the hydrothermal minerals are related to changing aCO₂ and aF⁻ in the fluid during continued fluid-marble reaction. A predominance of carbonate over fluoride complexing in the fluid as reactions proceeded controlled the Y/Ho, Th/U and REE patterns in the fluid and the crystallizing phases. Deviations from these trends indicate discontinuous processes of fluid-rock reaction.     

新疆喀喇昆仑阿然保泰二叠纪OIB型玄武岩地球化学特征及其地质意义

位于喀喇昆仑山喀喇昆仑断裂(塔什库尔干断裂)西侧的阿然保泰一带发育一套中二叠统灰岩-凝灰岩-枕状玄武岩地层。枕状玄武岩分布在北西向长约12km,宽约4.5km范围内。该套玄武岩枕状构造十分典型,岩石具气孔、杏仁状构造。玄武岩SiO2含量为44.14%～48.81%、TiO2为1.11%～1.83%,在Si2O-(Na2O+K2O)图中落入苦橄玄武岩、玄武岩和碱玄岩交界区,属于碱性岩石。稀土元素含量较高(54.40×10-6～139.9×10-6),Eu、Ce无异常,(La/Yb)N比值为2.87～6.29,配分模式为右倾型。大离子亲石元素富集(K、Rb、Ba等),但含量变化较大,高场强元素(Nb、Ta、Zr、Hf和P)相对亏损,Ti出现弱的负异常。玄武岩的地球化学特征显示阿然保泰玄武岩具洋岛玄武岩特征,源区为尖晶石二辉橄榄岩,其形成构造环境为板内拉张环境。阿然保泰OIB型玄武岩的发现证实了喀喇昆仑阿然保泰地区属于古特提斯主洋盆一部分。     

Rare earth element and strontium isotope geochemistry in Dujiali Lake,central Qinghai-Tibet Plateau,China: Implications for the origin of hydromagnesite deposits

Rare earth element (REE) and strontium isotope data (⁸⁷Sr/⁸⁶Sr) are presented for hydromagnesite and surface waters that were collected from Dujiali Lake in central Qinghai-Tibet Plateau (QTP), China. The goal of this study is to constrain the solute sources of hydromagnesite deposits in Dujiali Lake. All lake waters from the area exhibit a slight LREE enrichment (average [La/Sm]_PAAS = 1.36), clear Eu anomalies (average [Eu/Eu*]_PAAS = 1.31), and nearly no Ce anomalies. The recharge waters show a flat pattern (average [La/Sm]_PAAS = 1.007), clear Eu anomalies (average [Eu/Eu*] _PAAS = 1.83), and nearly no Ce anomalies (average [Ce/Ce*]_PAAS = 1.016). The REE+Y data of the surface waters indicate the dissolution of ultramafic rock at depth and change in the hydrogeochemical characteristics through fluid-rock interaction. These data also indicate a significant contribution of paleo-groundwater to the formation of hydromagnesite, which most likely acquired REE and Sr signatures from the interaction with ultramafic rocks. The ⁸⁷Sr/⁸⁶Sr data provide additional insight into the geochemical evolution of waters of the Dujiali Lake indicating that the source of Sr in the hydromagnesite does not directly derive from surface water and may have been influenced by both Mg-rich hydrothermal fluids and meteoric water. Additionally, speciation modeling predicts that carbonate complexes are the most abundant dissolved REE species in surface water. This study provides new insights into the origins of hydromagnesite deposits in Dujiali Lake, and contributes to the understanding of hydromagnesite formation in similar modern and ancient environments on Earth.     

蒙古-鄂霍茨克洋俯冲的记录：额尔古纳地区八大关变质杂岩的证据

本文对额尔古纳地块西缘八大关杂岩进行了锆石LA-ICP-MS U-Pb定年和岩石地球化学分析,以确定该套杂岩的形成时代及其构造属性。原定义为"佳疙瘩组"的八大关杂岩主要由黑云角闪斜长片麻岩和花岗质糜棱岩组成。LA-ICP MS锆石U-Pb研究表明,3个样品的锆石发育典型的岩浆振荡环带,高Th/U(0.13~1.42),轻稀土元素亏损,重稀土元素富集,具有强烈的正Ce异常和强烈的负Eu异常等特征,表明锆石均属于岩浆成因。测年结果表明2个黑云角闪斜长片麻岩形成时代分别为210±2Ma、214±2Ma,花岗质糜棱岩的原岩年龄为203±3Ma;样品中同时存在~501Ma和~795Ma的捕获/继承锆石。上述结果显示八大关杂岩的形成时代应为晚三叠世而不是前人认为的新元古代,而捕获锆石则显示与东北其它地块具有相同的构造演化历史。地球化学研究显示,八大关杂岩具有高钠、铝等特点,A/CNK=0.86~1.05,A/NK=1.53~1.97,为准铝质到弱过铝质钙碱性系列;轻稀土元素富集、重稀土元素亏损(La/Yb)N=6~31,Eu弱亏损(Eu/Eu*=0.50~1.01),具有较高的Sr含量(在378×10-6~598×10-6之间)及低的Yb含量(在0.71×10-6~3.50×10-6之间);微量元素原始地幔标准化蛛网模式图显示,富集Rb、Ba、K及Sr等大离子亲石元素、强烈亏损Nb、Ta、P、Ce及Ti等高场强元素。这些地球化学特征表明八大关杂岩形成于活动大陆边缘的岛弧环境。因此,八大关杂岩应形成于蒙古-鄂霍茨克洋向额尔古纳地块俯冲的大地构造背景,为蒙古-鄂霍茨克洋在三叠纪晚期南向俯冲提供了关键证据。