Rare earth element abundances in hydrothermal fluids from the Manus Basin, Papua New Guinea: Indicators of sub-seafloor hydrothermal processes in back-arc basins

Rare earth element (REE) concentrations are reported for a large suite of seafloor vent fluids from four hydrothermal systems in the Manus back-arc basin (Vienna Woods, PACMANUS, DESMOS and SuSu Knolls vent areas). Sampled vent fluids show a wide range of absolute REE concentrations and chondrite-normalized (REE_N) distribution patterns (La_N/Sm_N ∼ 0.6-11; La_N/Yb_N ∼ 0.6 - 71; ). REE_N distribution patterns in different vent fluids range from light-REE enriched, to mid- and heavy-REE enriched, to flat, and have a range of positive Eu-anomalies. This heterogeneity contrasts markedly with relatively uniform REE_N distribution patterns of mid-ocean ridge hydrothermal fluids. In Manus Basin fluids, aqueous REE compositions do not inherit directly or show a clear relationship with the REE compositions of primary crustal rocks with which hydrothermal fluids interact. These results suggest that the REEs are less sensitive indicators of primary crustal rock composition despite crustal rocks being the dominant source of REEs in submarine hydrothermal fluids. In contrast, differences in aqueous REE compositions are consistently correlated with differences in fluid pH and ligand (chloride, fluoride and sulfate) concentrations. Our results suggest that the REEs can be used as an indicator of the type of magmatic acid volatile (i.e., presence of HF, SO₂) degassing in submarine hydrothermal systems. Additional fluid data suggest that near-seafloor mixing between high-temperature hydrothermal fluid and locally entrained seawater at many vent areas in the Manus Basin causes anhydrite precipitation. Anhydrite effectively incorporates REE and likely affects measured fluid REE concentrations, but does not affect their relative distributions.     

Geochemistry of hydrothermal fluids from the PACMANUS, Northeast Pual and Vienna Woods hydrothermal fields, Manus Basin, Papua New Guinea

Processes controlling the composition of seafloor hydrothermal fluids in silicic back-arc or near-arc crustal settings remain poorly constrained despite growing evidence for extensive magmatic-hydrothermal activity in such environments. We conducted a survey of vent fluid compositions from two contrasting sites in the Manus back-arc basin, Papua New Guinea, to examine the influence of variations in host rock composition and magmatic inputs (both a function of arc proximity) on hydrothermal fluid chemistry. Fluid samples were collected from felsic-hosted hydrothermal vent fields located on Pual Ridge (PACMANUS and Northeast (NE) Pual) near the active New Britain Arc and a basalt-hosted vent field (Vienna Woods) located farther from the arc on the Manus Spreading Center. Vienna Woods fluids were characterized by relatively uniform endmember temperatures (273-285 °C) and major element compositions, low dissolved CO₂ concentrations (4.4 mmol/kg) and high measured pH (4.2-4.9 at 25 °C). Temperatures and compositions were highly variable at PACMANUS/NE Pual and a large, newly discovered vent area (Fenway) was observed to be vigorously venting boiling (358 °C) fluid. All PACMANUS fluids are characterized by negative δD_H2O values, in contrast to positive values at Vienna Woods, suggesting substantial magmatic water input to circulating fluids at Pual Ridge. Low measured pH (25 °C) values (∼2.6-2.7), high endmember CO₂ (up to 274 mmol/kg) and negative δ³⁴S_H2S values (down to −2.7‰) in some vent fluids are also consistent with degassing of acid-volatile species from evolved magma. Dissolved CO₂ at PACMANUS is more enriched in ¹³C (−4.1‰ to −2.3‰) than Vienna Woods (−5.2‰ to −5.7‰), suggesting a contribution of slab-derived carbon. The mobile elements (e.g. Li, K, Rb, Cs and B) are also greatly enriched in PACMANUS fluids reflecting increased abundances in the crust there relative to the Manus Spreading Center. Variations in alkali and dissolved gas abundances with Cl at PACMANUS and NE Pual suggest that phase separation has affected fluid chemistry despite the low temperatures of many vents. In further contrast to Vienna Woods, substantial modification of PACMANUS/NE Pual fluids has taken place as a result of seawater ingress into the upflow zone. Consistently high measured Mg concentrations as well as trends of increasingly non-conservative SO₄ behavior, decreasing endmember Ca/Cl and Sr/Cl ratios with increased Mg indicate extensive subsurface anhydrite deposition is occurring as a result of subsurface seawater entrainment. Decreased pH and endmember Fe/Mn ratios in higher Mg fluids indicate that the associated mixing/cooling gives rise to sulfide deposition and secondary acidity production. Several low temperature (?80 °C) fluids at PACMANUS/NE Pual also show evidence for anhydrite dissolution and water-rock interaction (fixation of B) subsequent to seawater entrainment. Hence, the evolution of fluid compositions at Pual Ridge reflects the cumulative effects of water/rock interaction, admixing and reaction of fluids exsolved from silicic magma, phase separation/segregation and seawater ingress into upflow zones.     

Controls of fluid chemistry and complexation on rare-earth element contents of anhydrite from the Pacmanus subseafloor hydrothermal system,Manus Basin,Papua New Guinea

Ocean Drilling Program (ODP) leg 193 successfully drilled four deep holes (126 to 386 m) into basement underlying the active dacite-hosted Pacmanus hydrothermal field in the eastern Manus Basin. Anhydrite is abundant in the drill core material, filling veins and vesicles, cementing breccias, and occasionally replacing igneous material. We report rare-earth element (REE) contents of anhydrite from a site of diffuse venting (Site 1188) which show extreme variability, in terms of both absolute concentrations (e.g., 0.08–28.3 ppm Nd) and pattern shape (La_N/Sm_N=0.08–3.78, Sm_N/Yb_N=0.48–23.1, Eu/Eu*=0.59–6.1). The range of REE patterns in anhydrite includes enrichments in the middle and heavy REEs and variable Eu anomalies. The patterns differ markedly from those of anhydrite recovered during ODP Leg 158 from the TAG hydrothermal system at the Mid-Atlantic Ridge which display uniform LREE-enriched patterns with positive Eu anomalies, very similar to TAG vent fluid patterns. As the system is active, the host-rock composition is uniform, and the anhydrite veins appear to relate to the same hydrothermal stage, we can rule out predominant host-rock and transport control. Instead, we propose that the variation in REE content reflects waxing and waning input of magmatic volatiles (HF, SO₂) and variable complexation of REEs in the fluids. REE speciation calculations suggest that increased fluoride and possibly sulfate concentrations at Pacmanus may affect REE complexation in fluids, whereas at TAG only chloride and hydroxide complexes play a significant role. The majority of the anhydrites do not show positive Eu anomalies, suggesting that the fluids were more oxidizing than in typical mid-ocean ridge hydrothermal systems. We use other hydrothermal fluids from the Manus Basin (Vienna Woods and Desmos), which bracket the Pacmanus fluids in terms of acidity and ligand concentrations, to examine the dependence of REE complexation on fluid composition. Geochemical modeling reveals that under the prevailing conditions at Pacmanus (pH~3.5, T=250–300 °C), Eu oxidation state and the relative importance of fluoride versus chloride complexing are very sensitive to small variations in oxygen fugacity, temperature, and pH. Patterns with extreme mid-REE enrichment may reflect speciation effects (free-ion abundance) coupled with crystal chemical control. We conclude that the great variability in REE concentrations and pattern shape is likely due to variable fluid composition and REE complexation in the fluids. Editorial handling: L. Meinert     

Geochemical constraints on the modes of carbonate precipitation in peridotites from the Logatchev Hydrothermal Vent Field and Gakkel Ridge

The ultramafic-hosted Logatchev Hydrothermal Field (LHF) at 15°N on the Mid-Atlantic Ridge and the Arctic Gakkel Ridge (GR) feature carbonate precipitates (aragonite, calcite, and dolomite) in voids and fractures within different types of host rocks. We present chemical and Sr isotopic compositions of these different carbonates to examine the conditions that led to their formation. Our data reveal that different processes have led to the precipitation of carbonates in the various settings. Seawater-like ⁸⁷Sr/⁸⁶Sr ratios for aragonite in serpentinites (0.70909 to 0.70917) from the LHF are similar to those of aragonite from the GR (0.70912 to 0.70917) and indicate aragonite precipitation from seawater at ambient conditions at both sites. Aragonite veins in sulfide breccias from LHF also have seawater-like Sr isotope compositions (0.70909 to 0.70915), however, their rare earth element (REE) patterns show a clear positive europium (Eu) anomaly indicative of a small (< 1%) hydrothermal contribution. In contrast to aragonite, dolomite from the LHF has precipitated at much higher temperatures (~ 100 °C), and yet its ⁸⁷Sr/⁸⁶Sr ratios (0.70896 to 0.70907) are only slightly lower than those of aragonite. Even higher temperatures are calculated for the precipitation of deformed calcite veins in serpentine–talc fault schists form north of the LHF. These calcites show unradiogenic ⁸⁷Sr/⁸⁶Sr ratios (0.70460 to 0.70499) indicative of precipitation from evolved hydrothermal fluids. A simple mixing model based on Sr mass balance and enthalpy conservation indicates strongly variable conditions of fluid mixing and heat transfers involved in carbonate formation. Dolomite precipitated from a mixture of 97% seawater and 3% hydrothermal fluid that should have had a temperature of approximately 14 °C assuming that no heat was transferred. The much higher apparent precipitation temperatures based on oxygen isotopes (~ 100 °C) may be indicative of conductive heating, probably of seawater prior to mixing. The hydrothermal calcite in the fault schist has precipitated from a mixture of 67% hydrothermal fluid and 33% seawater, which should have had an isenthalpic mixing temperature of ~ 250 °C. The significantly lower temperatures calculated from oxygen isotopes are likely due to conductive cooling of hydrothermal fluid discharging along faults. Rare earth element patterns corroborate the results of the mixing model, since the hydrothermal calcite, which formed from waters with the greatest hydrothermal contribution, has REE patterns that closely resemble those of vent fluids from the LHF. Our results demonstrate, for the first time, that (1) precipitation from pure seawater, (2) conductive heating of seawater, and (3) conductive cooling of hydrothermal fluids in the sub-seafloor all can lead to carbonate precipitation within a single ultramafic-hosted hydrothermal system.     

Rare earth element distribution in >400 °C hot hydrothermal fluids from 5°S, MAR: The role of anhydrite in controlling highly variable distribution patterns

Two submarine hydrothermal vent fields at 5°S, Mid-Atlantic Ridge (MAR) - Turtle Pits and Comfortless Cove - emanate vapor-phase fluids at conditions close to the critical point of seawater (407 °C, 298 bars). In this study, the concentration and distribution of rare earth element (REE) and yttrium (Y) has been investigated. Independent of the major element composition, the fluids display a strong temporal variability of their REE + Y concentrations and relative distributions at different time scales of minutes to years. Chondrite-normalized distributions range from common fluid patterns with light REE enrichment relative to the heavy REE, accompanied by positive Eu anomalies (type I), to strongly REE + Y enriched patterns with a concave-downward distribution with a maximum enrichment of Sm and weakly positive or even negative Eu anomalies (type II). The larger the sum of REE, the smaller Ce_CN/Yb_CN and Eu/Eu∗. We also observed a strong variability in fluid flow and changing fluid temperatures, correlating with the compositional variability.As evident by the positive correlation of total REE, Ca, and Sr concentrations in Turtle Pits and Comfortless Cove fluids, precipitation/dissolution of hydrothermal anhydrite controls the variability in REE concentrations and distributions in these fluids and the transformation of one fluid type to the other. The variable distribution of REE can be explained by the accumulation of particulate anhydrite (with concave-downward REE distribution and negative Eu anomaly) into a fluid with common REE distribution (type I), followed by the modification of the REE fluid signature due to dissolution of incorporated anhydrite. A second model, in which the type II fluids represent a primary REE reaction zone fluid pattern, which is variably modified by precipitation of anhydrite, can also explain the observed correlations of total REE, fractionation of LREE/HREE and size of Eu anomaly as well as Ca, Sr. The emanation of such a fluid may be favored in a young hydrothermal system in its high-activity phase with short migration paths and limited exchange with secondary minerals. However, this model is not as well constrained as the other and requires further investigations.The strongly variable REE fluid signature is restricted to the very hot, actively phase-separating hydrothermal systems Turtle Pits and Comfortless Cove at 5°S and has not been observed at the neighboring Red Lion vent field, which continuously emanates 350 °C hot fluid and displays a stable REE distribution (type I).     

Origins of Nd–Sr–Pb isotopic variations in single scheelite grains from Archaean gold deposits,Western Australia

Accessory gangue scheelite (CaWO₄) from the Archaean Mt. Charlotte lode Au deposit can be divided into two types with different rare earth element (REE) signatures. In some scheelite grains, specific REE signatures are reflected by different cathodoluminescence colours, which can be used to map their often complex oscillatory intergrowths. Domains with specific REE contents from two grains were sampled for Sm/Nd, Rb/Sr and Pb isotopic analyses using a micro-drilling technique.Type I scheelite is strongly enriched in middle REE (MREE) and Eu anomalies are either absent or slightly positive. Four fragments collected from Type I regions of two crystals have initial ⁸⁷Sr/⁸⁶Sr and ε_Nd values ranging from 0.70141 to 0.70163 and +2.5 to +3.5, respectively, and Pb isotope ratios reflecting the composition of greenstone sequence. This may indicate that Nd and Pb have their source, either locally or regionally, in the greenstones. Basic greenstone lithologies have ⁸⁷Sr/⁸⁶Sr<0.7015, and the radiogenic Sr signatures indicate that part of the Sr originated from felsic lithologies located either within or beneath the host greenstone pile. Alternatively, the Sr signature may have evolved from preferential leaching of a Rb-rich mineral during hydrothermal alteration of the greenstone.The REE patterns of Type II scheelite are either flat or MREE-depleted and have strong positive Eu anomalies. Three fragments collected from Type II regions of the same two crystals have initial ⁸⁷Sr/⁸⁶Sr ratios and ε_Nd values between 0.70130 and 0.70146, and +1.1 to +2.6, respectively, and Pb isotope signatures that are once again similar to that of the greenstone. This implies that ⁸⁷Sr/⁸⁶Sr ratios in Type II fluids were closer to those of the host dolerite (0.7008–0.7013), due to more extensive fluid interaction with the dolerite.A positive correlation between Na and REE suggests that REE³⁺ are accommodated by the coupled substitution REE³⁺+Na⁺=2 Ca²⁺ into both Type I and Type II scheelite. This is consistent with a fractional crystallisation model to explain the change in REE patterns from Type I to Type II, but not with a model involving different coupled substitutions and fluids from different origins. We propose that the complex REE and isotopic signatures of scheelite at Mt. Charlotte are related to small (<m) to medium (<km) scale processes involving mixing between “fresh” batches of hydrothermal fluid with fluids that had already been involved in extensive wall-rock alteration.The very high-ε_Nd values measured in some scheelites have been previously used to link gold mineralisation with komatiites containing unusually high Sm/Nd ratios. However, tiny (<20 μm) grains of secondary hydroxyl-bastnäsite were found within micro-fractures of one scheelite grain containing an extremely high-ε_Nd signature. The hydroxyl-bastnäsite probably formed during recent REE redistribution within the scheelite as a result of meteoric fluid circulation. The scale of this cryptic low-temperature alteration is sufficient to explain the anomalously high-ε_Ndi values observed in scheelite from Western Australia.     

Geochemical Features of Vein Anhydrite from the Kakkonda Geothermal System, Northeast Japan

Abstract. Cathodoluminescence (CL) color, rare earth element (REE) content, sulfur and oxygen isotopes and fluid inclusions of anhydrite, which frequently filled in hydrothermal veins in the Kakkonda geothermal system, were investigated to elucidate the spatial, temporal and genetical evolution of fluids in the deep reservoir. The anhydrite samples studied are classified into four types based on CL colors and REE contents: type-N (no color), type-G (green color), type-T (tan color) and type-S (tan color with a high REE content). In the shallow reservoir, only type-N anhydrite is observed. In the deep reservoir, type-G anhydrite occurs in vertical veins whereas type-T and -N in lateral veins. Type-S anhydrite occurs in the heat-source Kakkonda Granite. The CL textures revealed that type-G anhydrite deposited earlier than type-T in the deep reservoir, implying that fracture system was changed from predominantly vertical to lateral.
Studies of fluid inclusions and δ³⁴S and δ¹⁸O values of the samples indicate that type-N anhydrite deposited from diluted fluids derived from meteoric water, whereas type-G, -T and -S anhydrites deposited from magmatic brines derived from the Kakkonda Granite with the exception of some of type-G with recrystallization texture and no primary fluid inclusion, which deposited from fossil seawater preserved in the sedimentary rocks. Type-G, -T and -S anhydrites exhibit remarkably different chondrite-normalized REE patterns with a positive Eu anomaly, with a convex shape (peak at Sm or Eu) and with a negative Eu anomaly, respectively. The difference in the patterns might result from the different extent of hydrothermal alteration of the reservoir rocks and contribution of the magmatic fluids.     

Partitioning of rare earth elements between an aqueous chloride fluid phase and melt during the decompression-driven degassing of granite magmas

This paper reports the results of numerical simulation for the behavior of rare earth elements (REE) during decompression degassing of H₂O- and Cl-bearing granite melts at pressures decreasing from 3 to 0.5–0.3 kbar under near isothermal conditions (800 ± 25°C). Fluid phase in equilibrium with the melt contains mainly chloride REE complexes, and their behavior during magma degassing is, therefore, intimately related to the behavior of chlorine. It was shown that the contents and distribution patterns of REE in the aqueous chloride fluid phase formed during decompression vary considerably depending on (1) the contents of volatiles (Cl and H₂O) in the initial melt, (2) the redox state of the magma, and (3) the dynamics of fluid phase separation from magmas during their ascent toward the Earth’s surface. During decompressiondriven degassing, the contents of both Cl and REE in the fluid decrease, especially dramatically under opensystem conditions. The REE patterns of the fluid phase compared with those of the melt are characterized by a higher degree of light to heavy REE fractionation. A weak negative Eu anomaly may be present in the REE patterns of Cl-rich fluids formed during the early stages of degassing at relatively high pressures. At a further decrease in pressure and Cl content in the fluid, it is transformed into a positive Eu anomaly increasing during decompression degassing. Such an anomalous behavior of Eu during degassing is related to its occurrence in magmatic melts in two valence states, Eu³⁺ and Eu²⁺, whereas the other REE occur in melts mainly as (REE)³⁺. The Eu³⁺/Eu²⁺ ratio of melt is controlled by the redox state of the magmatic system. The higher the degree of melt reduction, the more pronounced the anomalous behavior of Eu during decompression degassing. The amount of REE extracted by fluid from melt during various stages of degassing does not significantly influence the content and distribution patterns of REE in the melt.     

Geology,fluid inclusion and sulphur isotope characteristics of the El Cobre VHMS deposit,Southern Cuba

The El Cobre deposit is located in eastern Cuba within the volcanosedimentary sequence of the Sierra Maestra Paleogene arc. The deposit is hosted by tholeiitic basalts, andesites and tuffs and comprises thick stratiform barite and anhydrite bodies, three stratabound disseminated up to massive sulphide bodies produced by silicification and sulphidation of limestones or sulphates, an anhydrite stockwork and a siliceous stockwork, grading downwards to quartz veins. Sulphides are mainly pyrite, chalcopyrite and sphalerite; gold occurs in the stratabound ores. Fluid inclusions measured in sphalerite, quartz, anhydrite and calcite show salinities between 2.3 and 5.7 wt% NaCl eq. and homogenisation temperatures between 177 and 300°C. Sulphides from the stratabound mineralisation display δ ³⁴S values of 0‰ to +6.0‰, whilst those from the feeder zone lie between −1.4‰ and +7.3‰. Sulphides show an intra-grain sulphur isotope zonation of about 2‰; usually, δ ³⁴S values increase towards the rims. Sulphate sulphur has δ ³⁴S in the range of +17‰ to +21‰, except two samples with values of +5.9‰ and +7.7‰. Sulphur isotope data indicate that the thermochemical reduction of sulphate from a hydrothermal fluid of seawater origin was the main source of sulphide sulphur and that most of the sulphates precipitated by heating of seawater. The structure of the deposit, mineralogy, fluid inclusion and isotope data suggest that the deposit formed from seawater-derived fluids with probably minor supply of magmatic fluids.     

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.     

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.     

Different mineralization styles in a volcanic-hosted ore deposit: the fluid and isotopic signatures of the Mt Morgan Au–Cu deposit,Australia

Quantitative laser ablation (LA)-ICP-MS analyses of fluid inclusions, trace element chemistry of sulfides, stable isotope (S), and Pb isotopes have been used to discriminate the formation of two contrasting mineralization styles and to evaluate the origin of the Cu and Au at Mt Morgan.The Mt Morgan Au–Cu deposit is hosted by Devonian felsic volcanic rocks that have been intruded by multiple phases of the Mt Morgan Tonalite, a low-K, low-Al₂O₃ tonalite–trondhjemite–dacite (TTD) complex. An early, barren massive sulfide mineralization with stringer veins is conforming to VHMS sub-seafloor replacement processes, whereas the high-grade Au–Cu ore is associated with a later quartz–chalcopyrite–pyrite stockwork mineralization that is related to intrusive phases of the Tonalite complex. LA-ICP-MS fluid inclusion analyses reveal high As (avg. 8850 ppm) and Sb (avg. 140 ppm) for the Au–Cu mineralization and 5 to 10 times higher Cu concentration than in the fluids associated with the massive pyrite mineralization. Overall, the hydrothermal system of Mt Morgan is characterized by low average fluid salinities in both mineralization styles (45–80% seawater salinity) and temperatures of 210 to 270 °C estimated from fluid inclusions. Laser Raman Spectroscopic analysis indicates a consistent and uniform array of CO₂-bearing fluids. Comparison with active submarine hydrothermal vents shows an enrichment of the Mt Morgan fluids in base metals. Therefore, a seawater-dominated fluid is assumed for the barren massive sulfide mineralization, whereas magmatic volatile contributions are implied for the intrusive related mineralization. Condensation of magmatic vapor into a seawater-dominated environment explains the CO₂ occurrence, the low salinities, and the enriched base and precious metal fluid composition that is associated with the Au–Cu mineralization. The sulfur isotope signature of pyrite and chalcopyrite is composed of fractionated Devonian seawater and oxidized magmatic fluids or remobilized sulfur from existing sulfides. Pb isotopes indicate that Au and Cu originated from the Mt Morgan intrusions and a particular volcanic strata that shows elevated Cu background.     

Biogenic and abiogenic low-Mg calcite (bLMC and aLMC): Evaluation of seawater-REE composition,water masses and carbonate diagenesis

The ΣREE and shale-normalized (PAAS) REE_SN values of modern brachiopods (biogenic low-Mg calcite: bLMC) represented by several species from high- to low latitudes, from shallow- to deep waters and from warm- and cold-water environments, define three distinct average ‘seawater’ trends. The warm- and cold-water brachiopods define two indistinguishable (p < 0.050) groups that mimic open-ocean seawater REE chemistry, exhibiting the typical LREE enrichment with a slightly positive to negative Ce anomaly followed by an otherwise invariant series. Other recent brachiopods from an essentially siliciclastic seabed environment are distinct in both ΣREE and REE_SN trends from the previous two populations, showing a slight enrichment in the MREEs and an increasing trend in the HREEs. Other groups of modern brachiopods are characterized by elevated REE_SN trends relative to the ‘normal’ groups as well as by complexity of the series trends. The most characteristic feature is the decrease in the HREEs in these brachiopods from areas of unusual productivity (i.e., such as upwelling currents, fluvial input and aerosol dust deposition). Preserved brachiopods from the Eocene and Silurian exhibit REE_SN trends and Ce anomalies similar to that of the ‘open-ocean’ modern brachiopods, although, their enriched ΣREE concentrations suggest precipitation of bLMC influenced by extrinsic environmental conditions.Preservation of the bLMC was tested by comparing the ΣREE and REE_SN trends of preserved Eocene brachiopods to those of Oligocene brachiopods that were altered in an open diagenetic system in the presence of phreatic meteoric-water. The altered bLMC is enriched by approximately one order of magnitude in both ΣREE and REE_SN trends relative to that in bLMC of their preserved counterparts. Similarly, the ΣREE and REE_SN of preserved Silurian brachiopod bLMC were compared to those of their enclosing altered lime mudstone, which exhibits features of partly closed system, phreatic meteoric-water diagenesis. Despite these differences in the diagenetic alteration systems and processes, the ΣREEs and REE_SN trends of the bLMC of altered brachiopods and of originally mixed mineralogy lime mudstones (now diagenetic low-Mg calcite) are enriched by about one order of magnitude relative to those observed in the coeval and preserved bLMC.In contrast to the changes in ΣREE and REE_SN of carbonates exposed to phreatic meteoric-water diagenesis, are the REE compositions of late burial calcite cements precipitated in diagenetically open systems from burial fluids. The ΣREE and REE_SN trends of the burial cements mimic those of their host lime mudstone, with all showing slight LREE enrichment and slight HREE depletion, exhibiting a ‘chevron’ pattern of the REE_SN trends. The overall enrichment or depletion of the cement REE_SN trends relative to that of their respective host rock material reflects not only the openness of the diagenetic system, but also strong differences in the elemental and REE compositions of the burial fluids. Evaluation of the (Ce/Ce*)_SN and La = (Pr/Pr*)_SN anomalies suggests precipitation of the burial calcite cements essentially in equilibrium with their source fluids.     

Deducing the source and composition of rare earth mineralising fluids in carbonatites: insights from isotopic (C,O, <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr) data from Kangankunde,Malawi

Carbonatites host some of the largest and highest grade rare earth element (REE) deposits but the composition and source of their REE-mineralising fluids remains enigmatic. Using C, O and ⁸⁷Sr/⁸⁶Sr isotope data together with major and trace element compositions for the REE-rich Kangankunde carbonatite (Malawi), we show that the commonly observed, dark brown, Fe-rich carbonatite that hosts REE minerals in many carbonatites is decoupled from the REE mineral assemblage. REE-rich ferroan dolomite carbonatites, containing 8–15 wt% REE₂O₃, comprise assemblages of monazite-(Ce), strontianite and baryte forming hexagonal pseudomorphs after probable burbankite. The ⁸⁷Sr/⁸⁶Sr values (0.70302–0.70307) affirm a carbonatitic origin for these pseudomorph-forming fluids. Carbon and oxygen isotope ratios of strontianite, representing the REE mineral assemblage, indicate equilibrium between these assemblages and a carbonatite-derived, deuteric fluid between 250 and 400 °C (δ¹⁸O + 3 to + 5‰_VSMOW and δ¹³C ? 3.5 to ? 3.2‰_VPDB). In contrast, dolomite in the same samples has similar δ¹³C values but much higher δ¹⁸O, corresponding to increasing degrees of exchange with low-temperature fluids (< 125 °C), causing exsolution of Fe oxides resulting in the dark colour of these rocks. REE-rich quartz rocks, which occur outside of the intrusion, have similar δ¹⁸O and ⁸⁷Sr/⁸⁶Sr to those of the main complex, indicating both are carbonatite-derived and, locally, REE mineralisation can extend up to 1.5 km away from the intrusion. Early, REE-poor apatite-bearing dolomite carbonatite (beforsite: δ¹⁸O + 7.7 to + 10.3‰ and δ¹³C ?5.2 to ?6.0‰; ⁸⁷Sr/⁸⁶Sr 0.70296–0.70298) is not directly linked with the REE mineralisation.     

Multi-isotope approach for the identification of metal and fluid sources of the Arroyo Rojo VMS deposit,Tierra del Fuego,Argentina

The Arroyo Rojo deposit, located in Tierra del Fuego, is the most important polymetallic, volcanic-hosted massive sulphide in the rhyolitic belt of the Fuegian Andes. The best intercepts in drill holes indicate a true thickness of 18.6 m and concentrations of 2.2% Cu, 3.9% Pb, 14.5% Zn, 140 g/t Ag, 1.1 g/t Au). This deposit, located near the town of Ushuaia, is hosted in a Middle Jurassic volcanic and volcanoclastic sequence. Massive and semimassive bodies display stacked lenticular morphologies with disseminated mineralization in both the footwall and hanging wall. The associated hydrothermal alteration system is partially conformable with the layering of the volcanic rocks. The ores and host rocks display a penetrative tectonic foliation and were metamorphosed to greenschist facies.Previous studies have not resulted in a consensus regarding the nature and the source of ore-forming fluids and the style of deposition of the sulphides at Arroyo Rojo. In this study, both stable and radiogenic isotopes were used develop a better understanding of these aspects of the deposit.Hydrogen and oxygen isotopes indicate that an evolved seawater mixed with significant contributions from other fluid reservoirs such as magmatic and/or metamorphic waters was the most likely source of the ore-forming fluids. These fluids underwent significant interaction with the underlying volcanic and sedimentary rocks, which promoted partial (Sr isotopes) or full (Pb isotopes) homogenization of radiogenic isotopes. δ³⁴S_CDT values suggest that the sulphur was derived from several sources: biogenic reduction of seawater sulphate (BSR) in a restricted to closed basin was mixed with a heavier component derived from inorganic reduction of seawater sulphate (TRS) and possibly from sulphur leached from igneous footwall rocks and/or direct contribution from magmatic fluids.Lateral infiltration of hydrothermal fluids resulted in the formation of a halo of semimassive to disseminated ore due to the replacement of porous, reactive glassy and breccia tuffs.As a result of the hydrothermal circulation, two styles of mineralization are observed in the Arroyo Rojo deposit: a stringer zone and a halo of semimassive to disseminated ore corresponding to sub-seafloor replacement, and syn-sedimentary mineralization consisting of massive sulphides.This model is consistent with the geodynamic context of the study area: a narrow, deep-marine volcano-tectonic rift parallel to the Andean side of South America and related to the initial break-up of Gondwana (ca. 145 Ma).     

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.     

Characteristics of rare-earth elements （REE）, strontium and neodymium isotopes in hydrothermal fluorites from the Bailashui tin deposit in the Furong ore field,southern Hunan Province,China

In this paper the authors present the REE concentrations and Sr and Nd isotopic compositions of fluorites from the Bailashui tin deposit of the Furong ore field, southern Hunan Province. The results showed that the total amount of REE in fluorites is usually low, ranging from 0.705 to 8.785 μg/g with the chondrite-normalized REE distribution patterns similar to those of the Qitianling granites in the study area, characterized by LREE-enrichment patterns with pronounced negative Eu anomalies. The fluorites vary in Sr isotopic composition within the range of 0.7083-0.7091, the values are lower than those of the granites and higher than those of the host carbonate rocks in this area. The εNd（t） values of fluorites vary between -9.4 and ＋10.3, revealing that both the crust- and mantle-source materials were involved in the ore-forming hydrothermal fluids. Combined with previous studies on this ore deposit, the Bailashui tin deposit is temporally and spatially closely related with granitic magmatism in this area. The hydrothermal fluorites are the product of fluid/rock interactions between granitic magmatic hydrothermal fluid and marine carbonate rocks. The REE and F in the ore-forming fluid were derived from the granites, whereas Sr in the ore-forming fluid came mainly from the granitic magmatic hydrothermal fluid and marine carbonate rocks, although variations in Sr isotopic composition cannot be explained by a simple mixture of these two end-members. Evidence demonstrated that the ore-forming fluids are of crustal-mantle mixing origin, but that the fluids were probably incompletely homogenized and this may be caused by inhomogeneous mixing of the fluids of different sources.     

Chemical compositions of mussels and clams from the Tangyin and Yonaguni Knoll IV hydrothermal fields in the southwestern Okinawa Trough

Studies of the chemical characteristics of mussels and clams in seafloor hydrothermal fields are important for understanding mass fluxes and elemental partitioning from hydrothermal vents into the biosphere, metal bioaccumulation of seafloor hydrothermal ecosystems, and the sources and sinks of biogeochemical and fluid cycles. We are the first to measure the mineral, major, trace and rare earth element, and carbon and oxygen isotope compositions of mussels (Bathymodiolus platifrons) and clams (Conchocele bisecta) from the Tangyin and Yonaguni Knoll IV hydrothermal fields in the southwestern Okinawa Trough. Mineralogical analysis shows that the carbonate shells of the mussel and clam samples are mainly composed of calcite and aragonite. Metal elements exhibit linear correlations in the shells (e.g., V and U) and tissues (e.g., Li and Rb) of the mussels and clams, suggesting that not all positive correlations of elements in tissues are inherited by the shells. V/As, Ca/Sr, and Fe/Cr ratios in the mussels and clams are close to those in the seawater, indicating that element ratios of seawater might be inherited by the mussels and clams. In addition, the Fe/Cr ratio of the shells of both mussels and clams can be used to trace the local seawater composition.The total LREE concentrations of mussel and clam tissue samples are higher than those of the mussel and clam shell samples, are similar to the hydrothermal fluids, exhibit LREE enrichment (La_CN/Nd_CN ratios = 1.86-32.1), and no or only slightly negative Eu anomalies, indicating that benthic animals are a sink of LREEs from hydrothermal fluids, and that the Eu/Eu* ratios of fluids change when fluids are incorporated into the tissues of the mussels and clams. In addition, the δ¹³C values of mussel shell samples are heavier than those of the clam shell samples in the hydrothermal field, indicating that more than one carbon source may be involved in defining the δ¹³C compositions of the shells. The majority of the δ¹⁸O values of clam shell samples fall in the range of δ¹⁸O values of the mussel shell samples, and are close to the hydrothermal fluid δ¹⁸O_H2O values, implying that the δ¹⁸O values of mussel and clam shell carbonate is influenced by the hydrothermal environment (magmatic water and fluid dilution with seawater).     

Mechanisms for anhydrite and gypsum formation in the Kuroko massive sulfide–sulfate deposits,north Japan

The Sr, Ba, and rare earth elements (REEs) concentrations and Sr isotopic composition of anhydrite and gypsum have been determined for samples from the Matsumine, Shakanai, and Hanaoka Kuroko-type massive sulfide–sulfate deposits of northern Japan to evaluate the mechanisms of sekko (anhydrite and gypsum) ore formation. The Sr isotopic compositions of the samples fall in the range of 0.7077–0.7087, intermediate between that for middle Miocene (13–15 Ma) seawater (0.7088) (Peterman et al., Geochim Cosmochim Acta, 34:105–120, 1970) and that for country rocks (e.g., 0.7030–0.7050) (Shuto, Assn Geol Collab Japan Monograph 18:91–105, 1974). The Kuroko anhydrite samples exhibit two types of chondrite-normalized REE patterns: one with a decrease from light REEs (LREEs) to heavy REEs (HREEs) (type I), and another with a LREE-depleted pattern (type II). Based on the Sr content and isotopic ratio (assuming an Sr/Ca (mM/M) of 8.7 for seawater), anhydrite is considered to have formed by mixing of preheated seawater with a hydrothermal solution of Sr/Ca (mM/M) = ca. 0.59–1.36 under the condition in which the partition coefficient (Kd) ranges between ca. 0.5 and 0.7. This results in the formation of anhydrite with higher Sr content with an Sr isotopic value close to that of seawater under seawater-dominant conditions. Larger crystals of type II anhydrite are partly replaced by smaller ones, indicating that anhydrite dissolution and recrystallization occurred after or during the formation of sekko ore. Gypsum, which partially replaces anhydrite in the Kuroko deposits, also exhibits two distinct chondrite-normalized REE patterns. Because LREEs are likely to be more readily mobilized during dissolution and recrystallization, it is hypothesized that LREEs are leached from type I anhydrite, resulting in the formation of type II anhydrite with LREE-depleted profiles.