Rare Earth Element Profiles Research Articles

Interpretation of vertical migration and enrichment processes of rare earth elements (REEs) in ion-adsorption-type mineralization in Japan based on REE speciation analyses

Typical vertical profiles of ion-adsorption-type rare earth element (REE) deposits discovered in southwest Japan were studied by conducting speciation analyses, including X-ray absorption fine structure and laser-induced fluorescence spectroscopy combined with transmission electron microscopy and adsorption/desorption experiments. The results revealed that REE speciation, migration, and enrichment in weathered granite is largely controlled by soil pH, which in turn controls the variable charges of kaolinite, the REE host phase. Both the distribution coefficient Kd and the soil pH increase with depth. As a result, (i) REE dissolution and migration occur in the near-surface acidic environment of the upper layers, where hydroxyls of kaolinite basal surfaces and edges are deprotonated to a lesser degree, and (ii) REEs accumulate in the relatively high-pH environment below the surface, where hydroxyls of kaolinite basal surfaces and edges are deprotonated to a larger degree, producing REE adsorption sites with variable charges. An increase of soil pH to greater than 6 in deeper layers promotes inner-sphere complexation of REEs. Although inner-sphere complexation inhibits the ion-exchange extraction of REEs, the inner-sphere complexes can be still extracted by lowering the pH of the extraction solution. This fact, which indicates that the adsorption of both inner- and outer-sphere complexes is reversible, is important in terms of both (i) understanding vertical REE profiles in which the pH varies and (ii) the efficient recovery of REEs from REE-enriched layers at all depths in weathered granite.

Retentiveness of rare earth elements in garnet with implications for garnet Lu‐Hf chronology

AbstractIncorporation of rare earth elements (REE) in garnet enables garnet chronology (Sm‐Nd, Lu‐Hf), and imparts a garnet‐stable signature on cogenetic phases, which allows petrochronology and general petrogenetic tracing of garnet stability in minerals and melts. Constraints on the uptake and redistribution mechanisms, as well as on the diffusive behaviour of REE in garnet are required for allowing accurate interpretation of REE signatures and ages. Garnet REE profiles are often measured to gain insight into the nature and cause of REE zoning. Interpretation of such profiles is nevertheless complicated by poor constraints on the extent of diffusive relaxation. This is especially relevant for Lu, which, according to experiments, has a relatively high diffusivity and thus may re‐equilibrate with possible consequences for Lu‐Hf chronology. To provide new insight into the REE systematics of garnet, we applied quantitative trace‐element mapping of garnet grains from metamorphic rocks that record peak temperatures above 750°C and cooling rates as low as 1.5°C Ma−1. Garnet in all samples preserves Rayleigh‐type or oscillatory growth zoning with sharply defined interfacial angles that match the garnet habit. Re‐equilibration of REE compositions appears restricted to domains with nebulous and patchy zoning, which likely form by interface‐coupled dissolution and re‐precipitation reactions mediated by fluids or melts, rather than REE volume diffusion. The possible effect of Lu diffusion in the analysed grains was investigated by comparing the observations to the results from 2D numerical modelling using Lu diffusivities from recent diffusion experiments. This test indicates that Lu diffuses significantly slower in natural garnet than experiments predict. The retentiveness of REE in garnet demonstrates the reliability of REE signatures in magmatic tracing and petrochronology and establishes Lu‐Hf chronology as a robust means of dating garnet growth and recrystallization in metamorphic rocks, including those that underwent high‐ or ultrahigh‐temperature conditions.

Trophic Transfer and Toxic Potency of Rare Earth Elements along a Terrestrial Plant-Herbivore Food Chain.

Extensive rare earth element (REE) mining activities have caused REE contamination of ambient agricultural soils, posing threats to associated food webs. Here, a simulated lettuce-snail food chain was conducted to evaluate the trophic transfer characteristics and the consequent effects of REEs on consumers. After 50-day exposure to soil, lettuce roots dose-dependently accumulated 9.4-76 mg kg-1 REEs and translocated 3.7-20 mg kg-1 REEs to shoots. Snails feeding on REE-contaminated shoots accumulated 3.0-6.7 mg kg-1 REEs with trophic transfer factors of 0.20-0.98, indicating trophic dilution in the lettuce-snail system. REE profiles in lettuce and snails indicated light REE (LREE) enrichment only in snails and the varied REE profiles along the food chain. This was corroborated by toxicokinetics. Estimated uptake (Ku) and elimination (Ke) parameters were 0.010-2.9 kgshoot kgsnail-1 day-1 and 0.010-1.8 day-1, respectively, with higher Ku values for LREE and HREE. The relatively high Ke, compared to Ku, indicating a fast REE elimination, supports the trophic dilution. Dietary exposure to REEs dose-dependently affected gut microbiota and metabolites in snails. These effects are mainly related to oxidative damage and energy expenditure, which are further substantiated by targeted analysis. Our study provides essential information about REE bioaccumulation characteristics and its associated risks to terrestrial food chains near REE mining areas.

Identification of lentils (Lens culinaris Medik) from Eglouvi (Lefkada, Greece) based on rare earth elements profile combined with chemometrics

An analytical approach has been developed to verify the authenticity of premium lentils originating from Eglouvi, Lefkada, Greece. The method relies on the digestion of samples followed by the analysis of their rare earth elements (REEs) content. Lentils originating from Eglouvi exhibit higher content in most REEs compared to lentils from other regions as well as distinct Sc/Y and Sc/Yb concentration ratios. Principal component analysis effectively segregates “Eglouvi” lentils into a distinct cluster. Soft Independent Modelling of Class Analogy (SIMCA) successfully models “Eglouvi” lentils. Significant enhancement in model specificity was achieved upon inclusion of Sc/Y and Sc/Yb concentration ratios as additional variables. The model is capable of detecting adulteration in blends of Eglouvi lentils, with a minimum rejection threshold of 4.6% w/w for Greek lentil adulterants and 6.0% w/w for imported lentil adulterants.

Hydrothermal monazite and xenotime chemistry as genetic discriminators for intrusion-related and orogenic gold deposits: implications for an orogenic origin of the Pogo gold deposit, Alaska

Attempts to geochemically distinguish between metamorphic-hydrothermal systems that form orogenic gold deposits and both reduced and oxidized magmatic-hydrothermal systems using isotopes or metal associations have proven ambiguous, particularly for orogenic gold and reduced intrusion-related gold systems. The absence of conclusive geochemical discriminators and the overlap in geologic characteristics have led to gold deposit models being potentially incorrectly applied, which in turn negatively affect regional mineral exploration and mine planning. In this study, in situ electron microprobe geochemical analyses of hydrothermal monazite and xenotime crystals associated with different types of gold-bearing deposits are shown to be effective geochemical discriminators. There are notable differences in mineral chemistry such as rare earth element (REE) profiles, total light REE, Dy, Er, Pr, Y, Nd/Sm, and La/Sm that distinguish monazite precipitated from metamorphic-hydrothermal fluids that form orogenic gold deposits and those precipitated from magmatic-hydrothermal fluids that form both porphyry Cu-Mo-Au and reduced intrusion-related gold deposits. Notable differences in overall xenotime abundances and concentrations of heavy REEs, Ca, and Sc are distinctive between the different deposit classes for xenotime. The origin of the controversially classified Pogo gold deposit, Tintina gold province, Alaska, which has been characterized as both a reduced intrusion-related and an orogenic gold deposit, is tested based upon the noted chemical differences associated with these hydrothermal phosphates. The findings of this study have implications for exploration and mine development in the Tintina gold province and other areas that contain deposits that are controversially classified as either orogenic or as magmatic-hydrothermal gold deposits.

The use of rare earth element profiles as a proxy for a fractionation source and mine-waste provenance

Rare earth elements (REEs) have been determined in acid mine drainage samples from the Wiśniówka area, south-central Poland. Two benchmark acid pit ponds, i.e., Podwiśniówka (PwIIb) and Wiśniówka Duża (WD), have shown diverse contents of sulfates, phosphates, REEs and metal(loid)s. Moreover, these ponds exhibit different NASC-normalized REE concentration patterns: (i) a positive middle REE anomaly in PwIIb and (ii) a positive heavy REE anomaly in WD, regardless of sampling time. This MREE anomaly has also been highlighted in a small tailings pile pool showing high contents of metal(loid)s, including As (3.86 g/L) and REEs (90.1 mg/L). In contrast, the light REE (LaEu)-rich profiles are recorded in all Upper Cambrian rock series of the study area. However, the Pw geologic section is distinctly enriched in pyrite, goethite/hematite and carbonaceous clayey-silty shales compared to its WD counterpart that contains a lesser amount of these components, but many more quartzite/sandstone beds. The Pw mineral-lithologic pattern favors selective partitioning of heavy REEs to abundant Fe- and Al-oxyhydroxides and organic matter. Both very short solute transport from sheer rock faces to pit ponds and a low pH of acid waters (mean of 2.3 to 3.0) indicate that scavenging/adsorption and mineral co-precipitation of REEs in a water column may be negligible. This inference is also backed up by overlapping REE profiles at different depths of acid pit ponds. Taken together, this implies that preferential fractionation of REEs takes place primarily during on-site weathering of pyrite and REE-bearing minerals in different rock media thus leading to changes in the Pw- and WD shale-normalized REE concentration patterns at source. The characteristic Pw roof-shaped (convex-up) profile in water samples has been used as a proxy for tracing the most detrimental Podwiśniówka As-bearing mine-waste that were scattered within the mining area a couple of years ago.

Igneous Rock Associations 29. The Nenana Magnetitite Lava Flow, Alaska Range, Alaska

Magnetitite deposits like El Laco (Chile) are rare and have controversial origins. An unusual magnetitite lava flow overlying a rhyolite unit occurs in the north-central Alaska Range and originally covered ~ 750 km2 of the Miocene Nenana basin. Dating of the rhyolite and relationships between the magnetitite and sedimentary rocks indicate that both are of Late Miocene age. The magnetitite flow is mainly magnetite with some post-eruptive alteration to hematite. Both the rhyolite flow and the magnetitite flow are vesicular, but the magnetitite flow also has small, millimetre-scale columnar jointing. The vesicular zones in the magnetitite flow grade into massive rock on the scale of a thin section, suggesting a degassing lava origin. Samples of the magnetitite flow contain between 12 and 26 wt.% SiO2 and between 45 and 75 wt.% FeO. Rare earth elements (REE) and trace elements from the magnetitite and rhyolite have similar patterns but with lesser abundance in the magnetitite. Both the rhyolite and the magnetitite have light-REE-enriched REE profiles with negative Eu anomalies. Electron microscopic analysis shows that most of the silica and trace element content of the magnetitite flow comes from very finely disseminated silicate minerals and glass in the magnetite. This suggests that the magnetitite was derived from a magma that had undergone unmixing into a silica-rich phase and an iron-rich phase prior to its eruption. Fractures and vesicles within the magnetitite flow contain minor rhyolitic glass and minerals suggesting that the rhyolite magma invaded columnar joints in the solidified magnetitite flow, and is a subvolcanic sill-like body at the studied locality. The magnetitite flow erupted prior to the emplacement of the rhyolite, which may be extrusive on a regional scale. The features of the Nenana magnetitite, and its geological relationships, are consistent with genetic models that invoke unmixing of magma into immiscible Fe-rich and Si-rich liquids during ascent.

The history of ice-sheet retreat on North America during Termination 5: Implications for the origin of the sea-level highstand during interglacial stage 11

Termination (T) 5, ∼424 ka, involved the biggest deglaciation of land-ice mass during the Quaternary. Warming and ice-sheet retreat during T5 led to an exceptionally long period of interglacial warmth known as Marine Isotope Stage (MIS) 11, ∼424–395 ka. A detailed understanding of the history of continental ice-sheet decay during T5 is required to disentangle regional contributions of ice-sheet retreat to sea-level rise (that range between ∼1 and 13 m above present day) and to correct it for glacio-isostatic adjustments (GIA). Yet little is known about the timing and magnitude of retreat during this time of the volumetrically most important continental ice sheet in the Northern Hemisphere, the Laurentide Ice Sheet (LIS). Here we present new authigenic Fe-Mn oxyhydroxide-derived high-resolution records of Pb isotope data and associated rare earth element profiles for samples spanning T5 from Labrador Sea IODP Site U1302/3. These records feature astronomically-paced radiogenic Pb isotope excursions that track increases in chemical weathering of North American bedrock and freshwater routing to the Labrador Sea via Hudson Straits associated with LIS retreat. Our records show that LIS retreat during T5 began 429. 2 ± 7.9 ka (2σ) and likely occurred over a longer timescale (by ∼10 to 5 kyr) than that observed for T2 and T1. They also show that Hudson Bay Ice Saddle collapse (and therefore LIS break-up) occurred ∼419 ± 4.7 ka (2σ), around the same time as best estimates of southern Greenland deglaciation, but ∼12 kyr before LIS deglaciation and the sea-level high-stand associated with the latter half of MIS 11 likely occurred. Our findings therefore highlight that ice-mass loss on North America likely played an important role in the seemingly protracted nature of T5 sea-level rise. A comparison of the deglaciation histories of the LIS and the southern Greenland Ice Sheet during T5, T2 and T1 also demonstrates that the well-constrained history of regional ice-sheet retreat during T1 is not always applicable as a template for older late Pleistocene terminations in GIA modelling.

Geochemical characterization, U–Pb apatite geochronology, and geodynamic significance of olivine minette dykes from the Julian Alps, NE Italy

AbstractWe investigated olivine minette dykes from the Rio Colan Valley of the Julian Alps (NE Italy) to provide new constraints on the mantle geochemistry underneath this extreme sector of the Italian Southern Alps. Petrographic observations, high Mg#s, high Cr and Ni contents, low Dy/YbCN ratios and flat heavy rare earth element (REE) profiles imply these are primary magmas derived from a depleted peridotite with olivine and garnet as possible residual phases. However, high K2O and incompatible trace element contents, coupled with superchondritic Nb/Ta ratios, suggest that the source was modified into a rutile–phlogopite-bearing carbonated peridotite by multiple metasomatic events such as recycling of crustal material and carbonatitic metasomatism related to an old orogenic event and rutile-rich metasomatism linked to the Pangaea break-up. Laser ablation – multi-collector – inductively coupled plasma – mass spectrometer (LA-MC-ICP-MS) U–Pb geochronology of apatites from two dykes yielded differences between unforced and forced discordia ages up to ∼45 Ma, likely due to the initial 207Pb/206Pb correction adopted. Nonetheless, because forced discordia and 206Pb/238U weighted mean ages are overall similar within the uncertainty, our preferred interpretation is that olivine minettes intruded and crystallized at ∼67 Ma. The age and anorogenic signature of these magmas are consistent with the regional extensional tectonics in the Julian Alps due to the advance of the external Dinaric front following Adria plate eastward subduction. Eventually, we show also that Rio Colan magmas are geochemically hybrid products between lamprophyres and lamproites compared with similar Italian and Western Mediterranean volcanics.

Geochemical and radiometric data for mafic rocks from the Guleman Ophiolite (SE, Turkey): New insights on the geodynamic evolution of the southern Neo-Tethyan ocean

The Guleman Ophiolite is located in the southeast of Turkey and mainly consists of harzburgites and dunites hosting economically viable chromitite bodies, and lesser amounts of cumulate and isotropic gabbro, diabase dykes, pyroxenite and locally plagiogranite. This study reports the combined whole-rock geochemical and radiogenic isotope (Sr and Nd) data for gabbro and diabase dykes, and in-situ zircon U-Pb geochronological data for plagiogranite and gabbro from the Guleman Ophiolite. Two different geochemical groups were determined based on immobile minor and trace elements, and radiogenic isotope characteristics of gabbro and diabase dykes investigated here. The first group is represented by boninites and displays highly depleted elemental patterns compared to NMORB, and spoon-shaped rare earth element profiles. Contrarily, the second group resembles back-arc basin basalts and is characterized by NMORB-like rare earth element patterns associated with negative Nb anomalies. The boninitic samples are characterized by less radiogenic 143Nd/144Nd(i) (0.51229 to 0.51267; ƐNd = −4.8 to +2.7) and more radiogenic 87Sr/86Sr(i) (0.70549 to 0.70758) isotope compositions compared to the back-arc basin basalt-like samples (143Nd/144Nd(i) = 0.51289 to 0.51296; ƐNd = +7.0 to +8.4; 87Sr/86Sr(i) = 0.70496 to 0.70629), indicating derivation from distinct and/or heterogeneous mantle source regions within a supra-subduction zone. The LA–ICP–MS zircon U-Pb analyses yielded concordant late Cretaceous ages for gabbro (82 ± 2.9 Ma) and plagiogranite (79.9 ± 0.8 Ma) samples. The overall geochemical, isotopic and geochronological data presented here suggest that the Guleman Ophiolite consists of forearc and initial back-arc spreading sections of oceanic crust, which may have been formed in an intra-oceanic subduction zone within the Berit Ocean (northern branch of the southern Neo-Tethyan ocean). Moreover, the generation of continental arc magmatism (i.e. Baskil and Esence Granitoids) was well-documented on the active margin of the Malatya-Keban Metamorphics to the north. Therefore the closure of this oceanic basin should have resulted in multiple coeval northward subduction events during the late Cretaceous.

Early dolomitization and subsequent hydrothermal modification of the middle Permian Qixia Formation carbonate in the northwest Sichuan Basin

High-quality dolomite reservoir are widely developed in Permian Qixia Formation in northwest Sichuan Basin. Understanding the genesis of dolomite is significant to predicting high-quality reservoir distribution. Based on the petrographical and geochemical characteristics, three types of dolomites and one type of dolomite cement were identified in the Qixia Formation in northwest Sichuan Basin: micritic to fine-crystalline dolomites (D1), medium-crystalline dolomite (D2), medium-to coarse-crystalline dolomite (D3) and saddle dolomite cement.Type D1 dolomites are characterized by micritic to fine-sized crystals, lamellar structure, generally dull to no luminescence, and relatively high strontium (Sr) concentrations. These characteristics suggest that type D1 dolomites were initially formed during the penecontemporaneous phase. The wide range of depleted δ18O values, slightly higher 87Sr/86Sr ratios and slightly positive europium (Eu) anomalies indicate that type-D1 dolomites were subsequently subjected to hydrothermal modification. Type D2 dolomite is characterized by unimodal middle-sized crystals and crystal texture dominated by nonplanar crystals. It usually occurs as thin or thick layers in the study area. The δ18O and δ13C values of type D2 dolomite generally fall within the estimated Middle Permian marine dolomite and show a significantly positive offset compared to those of coeval seawater. The 87Sr/86Sr ratios of type D2 dolomite are slightly higher than the coeval seawater. These features combined with the flat rare earth element (REE) profile and relatively high Sr concentrations (both are similar to the host limestone) indicate that type D2 dolomites first precipitated in the slightly evaporated Middle Permian seawater during the near-surface to shallow burial phase. Type D3 dolomites are mainly characterized by interlocking mosaic crystals with crystal sizes varying from 300 μm to 900 μm. It mainly occurs as patches in type D2 dolomites or as a thick layer sandwiched by type D2 dolomites. These features combined with its high 87Sr/86Sr ratios, δ18O depletion and positive Eu anomalies (which are very similar to those of the saddle dolomites) demonstrate that it is formed by hydrothermal recrystallization upon type D2 dolomites. Saddle dolomite generally occurs as the filling cement of pores, vugs, and fractures and is usually combined with matrix dolomite to form zebra dolomite and hydrothermal dolomite breccia. It has a curve crystal face, demonstrates wavy extinction under cross-polarization and red luminescence under a cathodoluminescence microscope. These features, together with the highest Th, most negative δ18O value and highest 87Sr/86Sr ratio compared to those of all types of dolomites in the study area as well as the positive Eu anomalies suggest that it should have been formed by hydrothermal fluid precipitation.Type D1 and type D3 dolomites are volumetrically minor and the pores are poorly developed. Saddle dolomite cemented and filled the pores and vugs of matrix dolomite, resulting in reservoir damage. Type D2 dolomites constitute the main body of high-quality reservoir in Qixia Formation. It precipitated in the slightly evaporated penesaline Middle Permian seawater during the near-surface to shallow burial phase. Potential high-quality reservoirs may occur in the shoal around the limited inter-shoal sea.

Significant contribution of seamounts to the oceanic rare earth elements budget

The rare earth elements (REEs) are a crucial resource frequently used as proxies for reconstructing paleomarine environmental conditions. However, there is limited understanding regarding the marine REEs cycling. In addition, the relationship between benthic diffusion of REEs and seamounts, remain unclear. Here we present the concentration profiles of REEs and trace elements in porewater and seawater from both the seamounts area and abyssal plain. Our results evidenced that the concentration of dissolved porewater REEs, Mn and Al in sediments in proximity of seamount are much higher than those at the abyssal plain. This is attributed to the substantial benthic diffusion of REEs to the ocean. The REEs enrichment processes in porewater at uneven seafloor are based mainly on re-suspension associated with the strong currents and/ or partial dissolution of detrital from seamounts. We suspect this process may occur in other world regions with seamounts and infer that these sediments may account for a significant contributor to the oceanic REEs budget.

Hyperspectral cathodoluminescence, trace element, and U-Pb geochronological characterization of apatite from the Ernest Henry iron oxide copper-gold (IOCG) deposit, Cloncurry district, Queensland

Hyperspectral cathodoluminescence (CL), geochemical, and geochronological characterization of a series of apatite-bearing samples from within and around the Ernest Henry IOCG deposit, NW Queensland, Australia, have revealed complex mineral parageneses and a spectrum of U-Pb ages that point to the effects of multiple geological processes. No two samples are identical, either in geochemistry or texture, despite their relative proximity to one another (all samples within 5 km from Ernest Henry). Hyperspectral CL maps reveal diverse internal textures and emissions ranging from near infrared (NIR) to near ultraviolet (UV) with a complex series of spectra in all samples, requiring the fitting more than 40 individual peaks (both sharp and broad) to capture the observed variability. Imaging analyses via LA-ICPMS show that apatite from the Ernest Henry district is enriched above background in a variety of trace elements, including Na, Mg, Al, Si, V, Mn, As, Sr, Y, the rare Earth elements (REEs), Pb, Th, and U. Samples outside the ore zone display chondrite-normalized REE profiles that are consistent with either a magmatic or hydrothermal origin, whereas ore zone apatite exhibits profiles that are decidedly hydrothermal in nature. Moreover, specific zones within ore zone apatite grains are very As-rich (up to 7 wt% As2O5), and the effect of such high As on the hyperspectral CL signature of these zones is a pronounced dampening of CL emission, regardless of REE concentrations. Uranium-Pb dating of the same samples (via LA-ICPMS) has yielded a diverse array of overlapping Mesoproterozoic ages ranging from 1,580 ± 34 Ma to 1,533 ± 61 Ma. These results correlate to published ages that constrain hydrothermal alteration in the Ernest Henry area, both before and during Cu-Au mineralization. Collectively, these data highlight the complexity of apatite studies at Ernest Henry, the broader Cloncurry district, and probably analogous terranes elsewhere. A combination of micro-scale methods such as those used in this study are shown to be essential for accurately deciphering geological information contained within petrogenetic indicator minerals.

Tectonic-fluid evolution of an ultra-deep carbonate reservoir in the southern Halahatang Oilfield area, Tarim Basin, NW China

Several giant oilfileds have been discovered during recent exploration in the Ordovician carbonates in zone between the Awati and Manjiaer depressions, Tarim Basin, China. These oilfields are deeply buried (>7000 m), and most productive wells are found adjacent to fault zones, suggesting faults may play a crucial role in reservoir development. Here, we use petrographic, microanalytical and geochemical techniques on different stages of void-filling calcite cements to decipher the tectonic-fluid evolution history. Vugs are generally occluded by V1 and V2 calcite cements, which precipitated from marine and burial diagenetic fluids. Two major episodes of fluid invasion are evident in each set of fractures from Middle Ordovician strike-slip faults (F1) to Late Devonian to the Permian strike-slip faults (F2). The sub-horizontal fracture-filling F1 calcite cements show the involvement of near-surface marine to marine-evolved brines, given that δ18Ocarb, restored δ18Ow values and rare earth element and yttrium (REY) profiles of F1-1 calcite cements are comparable to Ordovician seawater. The F1-2 calcite cements are characterized by negative δ18Ocarb, positive restored δ18Ow, and apparent Ce positive anomalies. The sub-vertical fracture-filling ferroan F2-1 calcite cements with fluorescence show the highest restored T(Δ47) (up to 125 °C), high restored δ18Ow values (up to +7.0‰ VSMOW), and an enrichment in MREE, which is consistent with an origin from hot hydrocarbon-bearing basinal brines. The subsequent F2-2 calcite cements may have precipitated during the Late Permian from mixing of basinal brines and deeply circulated meteoric water, as suggested by significantly negative δ18Ocarb values, cooler restored T(Δ47), negative restored δ18Ow values (down to −5.9‰ VSMOW), and flat REY patterns. The 87Sr/86Sr ratios of calcite cements are similar to coeval seawater. This study highlights the importance of fault-related fluid circulation in the development of a hydrocarbon reservoir, and may be applicable to other deep carbonate-hosted reservoirs.

Occupational exposure to rare earth elements: Assessment of external and internal exposure

Our study investigated occupational exposure to rare earth elements (REEs) in a major REE processing plant from North China by assessing both external exposure and internal exposure in the workers. An exposure group, including 50 workers in the processing plant, and a control group, including 50 workers from a liquor factory located 150 km away from the exposure group, were recruited in the study. Portable air sampler was employed to accurately measure individual exposure to the external environment, and the data demonstrating significantly higher contamination in the REE processing plant compared with the control group (i.e., 87.5 versus 0.49 μg/m3 of ΣREEs). Blood concentrations were also significantly higher in the exposure group (3.47 versus 2.24 μg/L of ΣREEs). However, the compositional profiles of REEs resembled between the exposure and control group in blood or air particles, indicating the influence of mining/processing activities on the surrounding regions. External exposure in the occupational environment appeared to significantly influence internal REE exposure in the REE processing workers. Some other sociodemographic and occupational factors, including the residence time and the type of work, could also influence occupational exposure to selected REEs. Our data clearly demonstrated the highly elevated REE contamination in both working environment and human bodies compared with the control subjects, raising the critical need for better assessing the health risks from occupational REE exposure and efficient management for occupational hazards.

Laurentide Ice Sheet extent over the last 130 thousand years traced by the Pb isotope signature of weathering inputs to the Labrador Sea

Understanding the history of continental ice-sheet growth on North America, and in particular that of the Laurentide Ice Sheet (LIS), is important for palaeoclimate and sea-level reconstructions. Information on ice-sheet extent pre-dating the Last Glacial Maximum (LGM) is heavily reliant, though, on the outputs of numerical models underpinned by scant geological data. Important aspects of LIS history that remain unresolved include the timing of its collapse during Termination 2, the first time that it expanded significantly during the Last Glacial Cycle, and whether its volume was significantly reduced during marine isotope stage (MIS) 3. To address these issues and more, we present authigenic iron-manganese (Fe–Mn) oxyhydroxide-derived high-resolution records of Pb isotope data and associated rare earth element profiles for samples spanning the past ∼130 kyr from northwest North Atlantic Labrador Sea, IODP Site U1302/3. We use these new data to track chemical weathering intensity and solute flux to the Labrador Sea associated with LIS extent on the adjacent highly radiogenic (high Pb isotope composition) North American Superior Province (SP) craton since the Penultimate Glacial Maximum (PGM). Our new records show that relatively high (radiogenic) values characterise warm marine isotope stages (MIS) 5, 3 and 1 and the lowest (most unradiogenic) values occurred during cold stages MIS 6, 4 and 2. The radiogenic Pb isotope excursion associated with Termination 2 is short-lived relative to the one documented for Termination 1, suggesting that LIS retreat during the PGM was relatively fast compared to the LGM and that its collapse during the last interglacial occurred ∼125 ka. Highly radiogenic inputs to the Labrador Sea during MIS 5d-a, ∼116–71 ka, most likely reflect a spin-up in Labrador Current vigour, incipient glaciation and renewed glacial erosion of high grounds of the eastern SP craton by localised wet-based ice-caps. A large decrease in Pb isotope values towards unradiogenic LGM-like compositions between ∼75–65 ka across the MIS 5/4 transition likely reflects a slow-down in Labrador Current vigour, an increase in subaerial deposition of aeolian dust and a significant advance of the LIS across Hudson Bay caused a strong reduction or even abandonment of Pb sourcing from the SP. The relatively radiogenic Pb isotope composition of bottom-waters bathing our study site during MIS 3, 57–29 ka, is unlikely to support a recently proposed major reduction in LIS extent for this time. Instead, we argue these values are better explained by southern Greenland Ice Sheet retreat, increased chemical weathering of the Ketelidian Mobile Belt and subsequent Pb runoff from Greenland.

Potential ecological risk assessment of rare earth elements in sediments cores from the Oualidia lagoon, Morocco

ABSTRACT This study’s objective was to evaluate the depth profiles of rare earth elements (REEs) in two Pb-210 dated sediments cores retrieved from the Oualidia lagoon, reconstruct their anthropogenic history, and assess their potential ecological risk. The sediment cores analysis was carried out using instrumental neutron activation analysis. Other physical-chemical parameters (bulk, organic matter, grain size) were also measured. The results indicated that the highest values were recorded in the topmost layers of the sediment cores and depleted with depth. The historical records of REEs revealed an exponential increase in their concentrations from the 50s. The enrichment factor, geo-accumulation index, and contamination factor calculated for each sediment core layer have exhibited important concentrations of Gd, Sm, and Eu, suggesting an anthropogenic origin of detected elements. Based on ecological risk >40 and the risk index >220, Gd, Eu, and Sm pose a high risk on the study area, while the other elements present moderate and mild risk. The obtained results revealed an increasing tendency of REEs accumulation into the Oualidia lagoon and suggested that a new source is feeding the lagoon sediments by these elements. These findings provided a clear picture of REEs evolution between 1903 and 2014 and baseline information on the historical deposition of these elements in the Oualidia lagoon.

Heritage Stone 8. Formation of Pinolitic Magnesite at Quartz Creek, British Columbia, Canada: Inferences from Preliminary Petrographic, Geochemical and Geochronological Studies

Rocks in the Late Proterozoic Horsethief Creek Group at Quartz Creek in British Columbia display rare ‘pinolitic’ textures resembling those described in some sparry magnesite deposits elsewhere in the world. Elongated white magnesite crystals up to 30 cm long occur in a contrasting, dark, fine-grained matrix of dolomite, chlorite, organic material, clay minerals and pyrite. The rocks are aesthetically appealing for use in sculpture and as dimension stone. The term ‘pinolite’ is derived from the superficial similarities between these unusual textures and pinecones. Petrographic examination indicates that these textures formed when metasomatic fluids replaced primary sedimentary dolomite with magnesite. Fluids moved along fractures and bedding planes with repeated fracturing yielding magnesite crystals oriented in opposite directions on either side of annealed fractures, and broken magnesite crystals adjacent to later fractures. Magnesite contains dolomite microinclusions and has elevated Ca contents that are consistent with its formation by replacement of dolomite. Low concentrations of Cr, Ni, Co, Ti, Sr, and Ba in magnesite also imply formation in a metasomatic rather than a sedimentary environment. The rare earth element (REE) concentrations in the Quartz Creek magnesite are higher than those in most evaporitic magnesite and REE patterns lack the Ce and Eu anomalies that characterize carbonate rocks from sedimentary environments. Enrichment in light REE relative to heavy REE, and the similarities between dolomite, chlorite, and magnesite REE profiles, imply that metasomatic fluids modified the original sedimentary geochemical signature of the dolostones during formation of the pinolite rocks. A Late Ordovician to Early Silurian U–Pb age (433 ± 12 Ma), for titanite in the black matrix surrounding the sparry magnesite is younger than the local host rocks, and also younger than the Mesoproterozoic to Middle Cambrian stratigraphic ages of the host rocks for nearby magnesite deposits. The ca. 433 Ma titanite overlaps the ages for numerous fault-associated diatremes and volcaniclastic deposits in the area. Possibly the igneous activity furnished heat for, and/or was the source for, metasomatic fluids that produced the pinolite deposits.

Application of molybdenum and thallium isotopes as indicators of paleoredox conditions and genesis of hyper-enriched black shale deposits, Peel River, Yukon, Canada

ABSTRACT Hyper-enriched black shale (HEBS) deposits in northern Yukon, consist of thin (<10 cm), laterally extensive (tens of thousands of km2) stratiform sulfide mineralization layer(s) that are hyper-enriched in Ni, Mo, Zn, platinum group elements, Re, and Au. The genesis of HEBS deposits and the ambient paleoenvironment in which they formed are the subject of vigorous debate. Non-traditional stable isotopes, particularly molybdenum and thallium, are robust paleoredox indicators and we have employed these isotope systems in this study of Yukon HEBS. Systematic sampling and Mo and Tl isotopic analysis of a continuous 200 m stratigraphic section through the Yukon HEBS mineralization and footwall and hanging-wall strata at the Peel River north and south bank showings (spaced five km apart) give δ98Mo –1.24 to –0.53‰ and –8.1 to –5.2 ε-units for the mineralization and –0.70 to 0.60‰ and –6.5 to –2.0 ε-units for the unmineralized strata. These values preclude a hydrothermal origin and strongly suggest that redox processes were responsible for the Yukon HEBS mineralization. The isotopic compositions, together with rare earth element (REE) systematics (REE profile, Y positive anomalies, Ce negative anomalies, and Y/Ho values) and other bulk geochemical redox indicators (Mo, V, Re/Mo, Ni/Co, U/Th, and V/Cr) indicate that the Peel River HEBS mineralization formed because of metal scavenging from seawater in a quiescent, euxinic basinal paleoenvironment.

High Arctic Large Igneous Province Alkaline Rocks in Canada: Evidence for Multiple Mantle Components

Abstract The Cretaceous High Arctic Large Igneous Province (HALIP) in Canada, although dominated by tholeiites (135–90 Ma), contains two main groups of alkaline igneous rocks. The older alkaline rocks (∼96 Ma) scatter around major fault and basement structures. They are represented by the newly defined Fulmar Suite alkaline basalt dykes and sills, and include Hassel Formation volcanic rocks. The younger alkaline group is represented by the Wootton Intrusive Complex (92·2–92·7 Ma), and the Audhild Bay Suite (83–73 Ma), both emplaced near the northern coast of Ellesmere Island. Fulmar Suite rocks resemble EM-type ocean island basalts (OIB) and most show limited crustal contamination. The Fulmar Suite shows increases of P2O5 at near-constant Ba–K–Zr–Ti that are nearly orthogonal to predicted fractionation- or melting-related variations, which we interpret as the result of melting composite mantle sources containing a regionally widespread apatite-bearing enriched component (P1). Low-P2O5 Fulmar Suite variants overlap compositionally with enriched HALIP tholeiites, and fall on common garnet lherzolite trace element melting trajectories, suggesting variable degrees of melting of a geochemically similar source. High-P2O5 Hassel Formation basalts are unusual among Fulmar rocks, because they are strongly contaminated with depleted lower crust; and because they involve a high-P2O5–Ba–Eu mantle component (P2), similar to that seen in alkali basalt dykes from Greenland. The P2 component may have contained Ba–Eu-rich hawthorneite and/or carbonate minerals as well as apatite, and may typify parts of the Greenlandic sub-continental lithospheric mantle (SCLM). Mafic alkaline Audhild Bay Suite (ABS) rocks are volcanic and hypabyssal basanites, alkaline basalts and trachy-andesites, and resemble HIMU ocean island basalts in having high Nb, low Zr/Nb and low 87Sr/86Sri. These mafic alkaline rocks are associated with felsic alkaline lavas and syenitic intrusions, but crustally derived rhyodacites and rhyolites also exist. The Wootton Intrusive Complex (WIC) contains geochemically similar plutonic rocks (alkali gabbros, diorites and anatectic granites), and may represent a more deeply eroded, slightly older equivalent of the ABS. Low-P2O5 ABS and WIC alkaline mafic rocks have flat heavy rare earth element (HREE) profiles suggesting shallow mantle melting; whereas High-P2O5 variants have steep HREE profiles indicating deeper separation from garnet-bearing residues. Some High-P2O5 mafic ABS rocks seem to contain the P1 and P2 components identified in Fulmar–Hassel rocks, whereas other samples trend towards possible High-P2O5 + Zr (PZr) and High-P2O5 + K2O (PK) components. We argue that the strongly alkaline northern Ellesmere Island magmas sampled mineralogically heterogeneous veins or metasomes in Greenlandic-type SCLM, which contained trace phases such as apatite, carbonates, hawthorneite, zircon, mica or richterite. The geographically more widespread apatite-bearing component (P1) could have formed part of a heterogeneous plume or upwelling mantle current that also generated HALIP tholeiites when melted more extensively, but may also have resided in the SCLM as relics of older events. Rare HALIP alkaline rocks with high K–Rb–U–Th fall on mixing paths implying strong local contamination from either Sverdrup Basin sedimentary rocks or granitic upper crust. However, the scarcity of potassic alkaline HALIP facies, together with the other trace element and isotopic signatures, provides little support for a ubiquitous fossil sedimentary subduction-zone component in the HALIP mantle source.