Origin of major dissolved ions in groundwater within the Lower Pra Basin using groundwater geochemistry,source-rock deduction and stable isotopes of 2H and 18O

Hydrochemical and stable isotopes (¹⁸O and ²H) analyses of groundwater samples were employed to establish the origin of major dissolved ions in groundwater within the Lower Pra Basin. Results showed that, the major processes responsible for chemical evolution of groundwater include: silicate (SiO₄)^4? dissolutions, ion exchange reactions, sea aerosol spray and pyrite (FeS₂) and arsenopyrite (FeAsS) oxidations. The groundwater is strongly acidic to neutral, with pH generally range from 3.5 to 7.0 pH units and mean 5.9 (±0.5). Approximately 89 % of boreholes had pH values outside the World Heath Organization (WHO, Guidelines for drinking water quality, 2004) guideline value for drinking water due principally to natural biogeochemical processes and therefore, not suitable for potable purposes. Electrical conductivity (EC) range from 57.6 to 1,201 μS/cm with mean 279.3 (±198.8) μS/cm. Total dissolved solids (TDS) range from 32 to 661 mg/L with mean 151.7 (±106.8) mg/L, with 98.6 % of groundwater as fresh (TDS < 500 mg/L). The chemical constituents generally have low concentrations and are within the WHO (Guidelines for drinking water quality, 2004) guideline value for drinking water. The relative abundance of cations and anions is in the order: Na⁺ > Ca²⁺> Mg²⁺ > K⁺ and HCO₃ ^? > Cl^? > SO₄ ^2?, respectively. A plot of ?¹⁸O ‰ against ²H ‰ showed that, ground and surface waters clustered on or closely along the Global Meteoric Water Line, suggesting that, the waters emanated principally from meteoric source with evaporation playing an insignificant role on the infiltrating water.     

Episodic fluid migration in the Fennoscandian Shield recorded by stable isotopes, rare earth elements and fluid inclusions in fracture minerals at Forsmark, Sweden

Drilling through the Palaeoproterozoic bedrock at Forsmark, central Sweden, during the site investigation for a potential geological repository of highly radioactive nuclear waste has provided high quality drill-core material from the upper 1 km of the Fennoscandian Shield. Analyses of stable isotopes (δ¹³C, δ¹⁸O, δ³⁴S, ⁸⁷Sr/⁸⁶Sr), rare earth elements and fluid inclusions in fracture filling calcite and pyrite from these drill cores have resulted in the discrimination of several episodes of fracture mineralisations. These events represent migration of fluids during a wide range of conditions, ranging from high-temperature hydrothermal to present-day groundwater circulation. Four major events have been distinguished: 1) Precipitation of epidote, chlorite and quartz under hydrothermal conditions (T > 150–200 °C) during the Proterozoic, sometime between 1.8 and 1.1 Ga. 2) Hydrothermal circulation at temperatures close to 200 °C with precipitation of adularia, albite, prehnite, laumontite, calcite and chlorite. Most of these minerals precipitated during a tectonothermal event between 1.1 and 1.0 Ga, possibly in response to far-field effects of the Sveconorwegian orogeny. 3) Precipitation of mainly quartz, calcite, pyrite and asphaltite occurred during the Palaeozoic, at temperatures between 60 and 190 °C (mainly at < 100 °C). Mixing of a fluid emanating from an organic rich overlying sedimentary cover and a deep basinal fluid from the crystalline bedrock is suggested to have caused this precipitation, possibly as a far-field response to the Caledonian orogeny and/or the development of the Caledonian foreland basin. 4) The youngest generation of fracture minerals is associated with formation of clay minerals and calcite with minor occurrences of pyrite and goethite. These minerals have probably precipitated episodically during a long time period (possibly from the Late Palaeozoic to the present) from various fluids at low temperature conditions (< 50 °C). Few calcites in equilibrium with the present groundwater suggest that the ongoing precipitation of calcite is very limited.     

Partitioning of rare earth elements, yttrium, and some major elements among source rocks, liquid and vapor of Larderello-Travale geothermal field, Tuscany (Central Italy)

Rare earth elements (REE), yttrium and some major element concentrations have been measured in the high-enthalpy fluids (HEF) of several geothermal wells and the fluid′s source rocks in the Larderello-Travale area (Tuscany/Central Italy). The REE and Y abundances in the HEF range from 0.1 to about 10 pmol/kg and are slightly higher in the HEF originating from evaporite/carbonate sequences (Calcare Cavernoso) than in those from phyllites. The resulting REY distribution factors between HEF and source rocks, ^appKdsource-rockHEF defined as the ratios of REY/Ca in both phases, range from <0.01 to 0.03 and 0.03 to 0.1 for phyllites and evaporite-limestone sequences (Calcare Cavernoso), respectively. REE+Y are more retained by the source rocks than Ca. HEF show no inherited and, with exception of a small Y anomaly, no acquired anomalies. This indicates a static equilibrium between HEF and the source rocks. The absence of any Eu anomalies points to temperatures less than 250°C in the source region. The small negative Y anomalies are the result of Y depletion in the rock fractions taking part in the water-rock interaction.Due to depressurization of the HEF to about 120°C and 2 bars, a liquid and a vapor phase is produced, which were sampled for the determination of the REE+Y partitioning between the two phases. The apparent partition factors between vapor and liquid ^appDliquidvapor of REE+Y range between 0.05 to 0.2 and about 3 for HEF originating from the phyllites and evaporites/carbonates, respectively. Among all ionic species determined, only NH₄⁺ has an apparent partition factor ^appDliquidvapor above one. In general, REY partition more easily into the vapor phase than the earth alkaline and alkaline elements. No significant correlation of REE+Y in the vapor phase with any of the determined ionic species could be detected. This probably points to the dominant presence of ion pairing such as REY(OH)₃^o or REYO(OH)^o.     

Calculating groundwater mixing ratios in groundwater-inrushing aquifers based on environmental stable isotopes (D, 18O) and hydrogeochemistry

Conventional hydrogeochemical data and environmental stable isotopes are used to identify the recharge sources and the water–rock interactions in the groundwater-flowing direction within the multilayer groundwater system of the Sulin coal-mining district in the north Anhui province in China. δD and δ ¹⁸O of groundwater in the mining district decrease along the groundwater-flowing direction in the recharge areas, yet in the runoff or discharge areas, they rise and fall along average δ values (δ ¹⁸O = ?8.68 ‰, δD = ?67.4 ‰), which are lower than average δ values of local atmospheric precipitation (δ ¹⁸O = ?7.80 ‰, δD = ?52.4 ‰). Principal component analysis is used to analyze the conventional hydrogeochemical data (K⁺ + Na⁺, Mg²⁺, Ca²⁺, Cl^?, SO₄ ^2?, HCO₃ ^?, CO₃ ^2?) in the groundwater. The first and second principal components have large variance contributions, and represent “pyrite oxidation or groundwater hardening” and “desulfurization or cation exchange and adsorption,” respectively. From conventional hydrogeochemical data and environmental stable isotopes, it is demonstrated that groundwater of the Sulin coal-mining district is characterized by a mixing type, which is confirmed by three recharge end-members: fresh groundwater, leaching groundwater, and retained groundwater. By means of a sample dot-encompassed triangle in the scatter diagram of load scores for Component 1–Component 2, whose vertexes stand for the three end-members, a model for calculating groundwater mixing ratio is established and applied successfully to the evaluation and management of groundwater hazards in the coal-mining districts.     

岩石—土壤—铁芒萁系统中稀土元素的分布、迁移和累积

在赣南非稀土矿区和四处不同稀土矿区内取样,用ICP-MS法测定岩石-土壤-铁芒萁系统中15个稀土元素的含量,并对其分布、迁移、累积特征进行了研究。结果表明:稀土元素在岩石、土壤各层含量由高到低的顺序为C(心土层)>A(表土层)>B(底土层)>D(成土母岩);在铁芒萁植物体内的分布规律是:轻稀土元素含量为叶>根>茎>叶柄;重稀土元素含量为根>叶>茎>叶柄;稀土元素演化、迁移的难易是由稀土元素的重轻所决定的;岩-土-芒萁系统各环节间稀土元素的含量模式基本相似,表征元素在岩石→土壤→植物大系统中存在着向量(非均衡性)关系。     

Hydrogeological and hydrochemical investigation of groundwater using environmental isotopes (18O, 2H, 3H, 14C) and chemical tracers: a case study of the intermediate aquifer,Sfax, southeastern Tunisia

Major element concentrations and stable (δ¹⁸O and δ²H) and radiogenic (³H and ¹⁴C) isotopes in groundwater have proved useful tracers for understanding the geochemical processes that control groundwater mineralization and for identifying recharge sources in the semi-arid region of Sfax (southeastern Tunisia). Major-ion chemical data indicate that the origins of the salinity in the groundwater are the water–rock interactions, mainly the dissolution of evaporitic minerals, as well as the cation exchange with clay minerals. The δ¹⁸O and δ²H relationships suggest variations in groundwater recharge mechanisms. Strong evaporation during recharge with limited rapid water infiltration is evident in the groundwater of the intermediate aquifer. The mixing with old groundwater in some areas explains the low stable isotope values of some groundwater samples. Groundwaters from the intermediate aquifer are classified into two main water types: Ca-Na-SO₄ and Ca-Na-Cl-SO₄. The high nitrate concentrations suggest an anthropogenic source of nitrogen contamination caused by intensive agricultural activities in the area. The stable isotopic signatures reveal three water groups: non-evaporated waters that indicate recharge by recent infiltrated water; evaporated waters that are characterized by relatively enriched δ¹⁸O and δ²H contents; and mixed groundwater (old/recent) or ancient groundwater, characterized by their depleted isotopic composition. Tritium data support the existence of recent limited recharge; however, other low tritium values are indicative of pre-nuclear recharge and/or mixing between pre-nuclear and contemporaneous recharge. The carbon-14 activities indicate that the groundwaters were mostly recharged under different climatic conditions during the cooler periods of the late Pleistocene and Holocene.

     

Climatic variations in MIS 11 recorded by stable isotopes and trace elements in a French tufa (La Celle,Seine Valley)

Marine Isotope Stage (MIS) 11 palaeoclimate has so far been documented in marine and ice sheet isotopic records. However, excepting some lacustrine pollen records, very little is known about palaeoclimatic conditions in continental areas. This study uses geochemical records in calcareous tufa deposits from rivers as a basis for reconstructing temperate palaeoclimatic conditions. Tufa deposits are now proven to record high‐quality palaeoclimatic information in recent to Holocene deposits. Work on older interglacial tufas is just starting and in this paper we present the first comprehensive results from a MIS 11 tufa. The tufa comes from the Seine Valley (La Celle, northern France). Geochemical data in the tufa calcite are interpreted to record primarily air temperature (δ¹⁸O) and humidity (δ¹³C and Mg/Ca and Sr/Ca). The combined data identify a warm and wet climatic optimum followed by two temperature decreases associated with oscillations in humidity. These marked climatic variations recorded through the La Celle profile are strongly coherent with the palaeoenvironmental reconstructions from malacological data. The abrupt climatic and environmental events recorded could be related to short‐term degradation of vegetation cover in Europe, which is itself controlled by global palaeoclimatic events. Copyright © 2012 John Wiley & Sons, Ltd.     

Spatio-temporal variation of stable isotopes of river waters, water source identification and water security in the Heishui Valley (China) during the dry-season

Spatial variations of δD and δ¹⁸O among seven tributaries and their water sources were investigated in the Heishui Valley of the Yangtze River, China during the dry-season in 2004. A one-way ANOVA (analysis of variation) test showed that both δD (p?18O (p?=?0.045) spatially varied among the seven tributaries. The plot of δ¹⁸O versus δD for the river water collected at different locations showed that isotopic fractionation occurred during the snow and glacial melting process. The depleted δ¹⁸O and δD in the tributary waters distributed above the local meteoric water line (LMWL) suggested that the glacial and early snowpack meltwater largely recharged these streams during the early spring. The meltwater was isotopically distinguishable from the precipitation and river water, which had been evaporated during warmer and drier times. If glaciers and snow accumulation diminish with future climate warming, the recharge of these tributaries’ baseflow will decline and the security of the water resource in this watershed will be threatened.     

Environmental isotopes (18O, 2H, and 87Sr/86Sr) as a tool in groundwater investigations in the Keta Basin, Ghana

Analyses of environmental isotopes (¹⁸O, ²H, and ⁸⁷Sr/⁸⁶Sr) are applied to groundwater studies with emphasis on saline groundwater in aquifers in the Keta Basin, Ghana. The ⁸⁷Sr/⁸⁶Sr ratios of groundwater and surface water of the Keta Basin primarily reflect the geology and the mineralogical composition of the formations in the catchments and recharge areas. The isotopic compositions of ¹⁸O and ²H of deep groundwater have small variations and plot close to the global meteoric water line. Shallow groundwater and surface water have considerably larger variations in isotopic compositions, which reflect evaporation and preservation of seasonal fluctuations. A significant excess of chloride in shallow groundwater in comparison to the calculated evaporation loss is the result of a combination of evaporation and marine sources. Groundwaters from deep wells and dug wells in near-coastal aquifers are characterized by relatively high chloride contents, and the significance of marine influence is evidenced by well-defined mixing lines for strontium isotopes, and hydrogen and oxygen stable isotopes, with isotopic compositions of seawater as one end member. The results derived from environmental isotopes in this study demonstrate that a multi-isotope approach is a useful tool to identify the origin and sources of saline groundwater. Electronic Publication     

Trace elements (REE) and isotopes (O,C, Sr) to characterize the metasomatic fluid sources: evidence from the skarn deposit (Fe,W, Cu) of Traversella (Ivrea,Italy)

The skarn complex of Traversella was formed at the expense of various rock types (calcic hornfels, gneiss, dolomitic marble) occurring in the contact aureole of the dioritic intrusion of Traversella (30±5 Ma). Application of phase equilibria has fixed the temperature of the primary stage of skarn formation between 550° C to 625° C. Similar applications indicate a larger range of temperature (525° C to 300° C) for the secondary stage. The different types of skarn (primary stage) are enriched in REE relative to the corresponding precursor rock (T.R.=126 ppm (protolith) to 228 ppm (inner zone) for the skarn on gneisses; T.R.=14 ppm to 71 ppm for the skarn on calcic hornfelses; T.R.=12 ppm to 200 ppm for the skarn on dolomitic marbles), but all the inner zones of these different types of skarn show a similar REE distribution with a slight LREE fractionation and no Eu anomaly. It is inferred that the primary metasomatic fluid has a parallel REE pattern. The oxygen isotope composition of water in equilibrium with the early stage of skarn at T=600° C ranges from 8.3 per mil to 8.9 per mil. At the beginning of the first hydroxylation stage (secondary stage), the fluid σ ¹⁸O remains in the range observed in the primary stage but within it, there is a sharp decrease from 8.0 per mil to 5.0 per mil. During the sulphidation stage, the fluid σ ¹⁸O decreases more gradually from 5.0 per mil to 3.0 per mil. The I _Sr of the early skarn silicates ranges from the values observed in the dolomitic marbles (0.70874 to 0.70971) to the I _Sr of the intrusion (0.70947 to 0.71064). During the secondary stage, there is a progressive increase of the minerals I _Sr up to 0.71372. The REE pattern of the primary metasomatic fluid does not put any precise constraint on the primary fluid source. On the other hand, both stable and radiogenic isotopes suggest that the early high-temperature metasomatic fluid was isotopically equilibrated with the dioritic intrusion. This implies that this early fluid is either exsolved from the crystallizing intrusion or a metamorphic water previously equilibrated with the intrusion. During the secondary stage, the replacement of the early anhydrous phases by hydrated parageneses is accompanied by the mixing with meteoric fluid as indicated by stable (σ ¹⁸O) and radiogenic (⁸⁷Sr/⁸⁶Sr) isotopes.     

Behaviour of rare earth elements at the freshwater–seawater interface of two acid mine rivers: the Tinto and Odiel (Andalucia, Spain)

The concentrations of dissolved and suspended particulate rare-earth elements (REE) are reported in acid-sulphate waters from the Odiel and Tinto rivers. Shale normalized patterns are typically convex and high REE concentrations (e.g., Ce=0.43–65 μg.l⁻¹) are present in the waters. The REE content of the suspended load is greater by a factor of up to 3000. In the Odiel river, REE patterns of the particulates are essentially convex and sub-parallel to those of the waters; speciation calculations indicate that SO₄ complexes play a dominant role in controlling the REE distributions. In the Tinto river, the REE patterns of the suspended load are slightly fractionated and a negative Ce anomaly is apparent in several samples, reflecting the local influence of phosphogypsum deposits.Contrasting with normal estuaries, REE are not intensely removed in the low chlorinity zone. A remobilization in relation to Fe reduction is observed in the Tinto river.     

Solubility of rare earth elements in carbonatite magmas,indicated by the liquidus surface in CaCO3Ca(OH)2La(OH)3 at 1 kbar pressure

The system CaCO₃Ca(OH)₂(CCCH) represents a synthetic analog to a carbonatite magma. Addition of a light rare earth (RE) component La(OH)₃ (LH) gives a simple analog of a rare earth carbonatite. Liquidus relations for two joins were studied at 1 kbar pressure; CHLH and (CC₅₅CH₄₅)LH. CHLH is binary with a eutectic at CH₇₉LH₂₁ and 710°C. Thejoin CC₅₅ + CH₄₅)LH has a liquidus piercing point between CC and LH, at (CC₅₅CH₄₅)₆₀LH₄₀ and 700°C. Combining the new results with known results for CCCH allows construction of a liquidus diagram for part of the join CCCHLH. A ternary eutectic between the primary liquidus fields for CH, CC and LH occurs near 610°C with estimated composition CC= 33%,CH= 47%,LH= 20%. The solubility of La(OH)₃ in the synthetic carbonatite magma increases with increase of CO₂/H₂O from 20% at the eutectic to 40% at the piercing point on the join (CC₅₅CH₄₅)LH. The solubility of La in synthetic carbonatite is high compared with that of silicates. P₂O₅, and S. The results show that REE can become concentrated to high levels by fractionation of carbonatites, as long as they are not removed by high temperature crystallization of apatite and monazite.     

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.     

The system NaAlSi3O8−H2O−H2 (1200° C, 2 kbar): the solubility and interaction mechanism of fluid species with melt

The H₂O and H₂ solubilities in an albite melt at 1200° C and 2 kbar over the entire range of gas phase composition, from pure hydrogen to pure water were studied in gas-media pressure vessels. The water solubility initially increases with increasing hydrogen content until a maximum of 9.19 wt% H₂O atXH ₂ ^v =0.1 is reached, withXH ₂ ^v >0.1 the water solubility decreases. The hydrogen solubility curve has a maximum atXH ₂ ^v =0.42 where the concentration reaches 0.206 wt% H₂O. Over the entire compositional range¹H NMR (nuclear magnetic resonance) spectra show distinct absorption lines due to protons bound to OH groups and to isolated firmly bound water molecules. In NMR and Raman spectra there were no bands attributable to the H–H vibrations of molecular hydrogen. The X-ray photo-electronic spectra of hydrogen-bearing glasses show the Si2p (99 eV) band which corresponds to the zero-valency silicon. The formation of OH groups and molecular water during interaction between hydrogen-bearing fluids and melts under reducing conditions has a qualitative effect, the same as for water dissolution. Another point of interest is that hydrogen-bearing melts undergo more depolymerization than do hydrous melts.     

Evolution of an ancient (Lower Cretaceous) marginal‐marine system from tide‐dominated to wave‐dominated deposition,McMurray Formation

Regionally extensive parasequences in the upper McMurray Formation, Grouse Paleovalley, north‐east Alberta, Canada, preserve a shift in depositional processes in a paralic environment from tide domination, with notable fluvial influence, through to wave domination. Three stacked parasequences form the upper McMurray Formation and are separated by allogenic flooding surfaces. Sediments within the three parasequences are grouped into three facies associations: wave‐dominated/storm‐dominated deltas, storm‐affected shorefaces to sheltered bay‐margin and fluvio‐tidal brackish‐water channels. The two oldest parasequences comprise dominantly tide‐dominated, wave‐influenced/fluvial‐influenced, shoreface to bay‐margin deposits bisected by penecontemporaneous brackish‐water channels. Brackish‐water channels trend approximately north‐west/south‐east, which is perpendicular to the interpreted shoreline trend; this implies that the basinward and progradational direction was towards the north‐west during deposition of the upper McMurray Formation in Grouse Paleovalley. The youngest parasequence is interpreted as amalgamated wave‐dominated/storm‐dominated delta lobes. The transition from tide‐dominated deposition in the oldest two parasequences to wave‐dominated deposition in the youngest is attributed mainly to drowning of carbonate highlands to the north and north‐west of the study area, and potentially to relative changes in accommodation space and deposition rate. The sedimentological, ichnological and regional distribution of the three facies associations within each parasequence are compared to modern and Holocene analogues that have experienced similar shifts in process dominance. Through this comparison it is possible to consider how shifts in depositional processes are expressed in the rock record. In particular, this study provides one of few ancient examples of preservation of depositional process shifts and showcases how topography impacts the character and architecture of marginal‐marine systems.     

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.