Controls on the distribution of rare earth elements in deep-sea sediments in the North Atlantic Ocean

Deep-sea sediments can contain relatively high concentrations of rare earth elements and yttrium (REY), with a growing interest in their exploitation as an alternative to land-based REY resources. To understand the processes that lead to enrichment of the REY in deep-sea sediments, we have undertaken a detailed geochemical study of sediments recovered from the Atlantic Ocean, on a transect along ~ 24°N that includes the deep Nares Abyssal Plain and the Canary and North America Basins.Total REY concentrations (ΣREY) range from 7.99 to 513 ppm, and total concentrations of the heavy REY (Eu - Lu) range from 0.993 to 56.3 ppm. REY concentrations are highest in slowly accumulating pelagic red clays, especially in samples that contain ferromanganese micronodules. Factor analysis reveals that hydrogenous Fe- and Mn-(oxyhydr)oxides are the primary REY carrier phase in the red clays. In situ analysis of individual micronodules confirms that they have high ΣREY (up to 3620 ppm). REY concentrations are higher in micronodules that have a hydrogenous source, characterised by higher Fe/Mn, compared to micronodules that have a diagenetic source.The ΣREY content of North Atlantic deep-sea sediments is ~ 4 times lower than in Pacific deep-sea sediments. We calculate that the area of seafloor required to extract ~ 10% of the global annual REY demand is ~ 100 km², assuming removal of the upper 1 m of sediment.     

Cycling of calcite and hydrous metal oxides and chemical changes of major element and REE chemistry in monomictic hardwater lake: Impact on sedimentation

The variation of major and rare earth elements and yttrium (REY) in the monomictic hardwater Lake Tiberias during the wet and dry seasons of the hydrological year was studied in two profiles. The average volume and Cl concentration of the known and unknown saline inflows of 1.6 × 10⁷ m³ and 1.2 × 10⁹ mol are derived by closing both balances. This brine corresponds to a mixture of 83% of groundwater from Cretaceous aquifers and 17% of very saline deep brine. Taking cycling of calcite in the hypolimnion into account, the settling rate of authigenic calcite is estimated to be 3.3 mol m⁻² a⁻¹.In the stratified lake of the dry season dissolved inorganic carbon increases by 490 μM at the thermo-/chemocline due to microbial reduction of SO₄²⁻, NO₃⁻, chemical reduction of Fe(III) and MnO₂ colloids, and cycling of calcite in the hypolimnion. REY distribution in the stratified water column is dominantly controlled by coprecipitation with calcite, hydrous ferric oxides and MnO₂ in the epilimnion and cycling of these compounds in the hypolimnion. The positive Ce anomaly in the hypolimnetic water is produced by cycling of MnO₂. The simulation of the increase of REY in the hypolimnion reveals that hydrous ferric and manganese oxides only play a negligible role except Ce. Only about 10% of REY from cycled matter enhance REY in solution. Most of the released REY are adsorbed by particular matter and thus settling on the floor of the lake.Different from Na, U, SO₄²⁻ and SiO₂, the other elements, in particular REY, increase in the mixed water column from the top to the lower third and mostly decrease thereafter toward the bottom in the mixed lake during the wet season. The behavior of REY is caused by some cycling of calcite and pH-dependent re-equilibration of REY bound to hydrous ferric and manganese oxides adsorbed by particular matter.     

Strategic and rare elements in Cretaceous-Cenozoic cobalt-rich ferromanganese crusts from seamounts in the Canary Island Seamount Province (northeastern tropical Atlantic)

Thick ferromanganese (Fe-Mn) crusts from four Cretaceous seamounts (The Paps, Tropic, Echo and Drago) at the southern Canary Island Seamount Province (CISP) in the northeastern tropical Atlantic were recovered along the flanks and summits from 1700 to 3000 m water depths. CISP is composed of > 100 seamounts and submarine hills, is likely the oldest hotspot track in the Atlantic Ocean, and is the most long-lived of known hotspots globally. The Fe-Mn crusts grow on basalt-sedimentary rock substrates below the northeastern tropical Atlantic core of the oxygen minimum zone (OMZ) with a maximum thickness of 250 mm at a water depth of 2400 m. The mineralogical and chemical composition of these Fe-Mn crusts indicate a hydrogenetic origin. The main Mn minerals are vernadite with minor interlayered todorokite and asbolane-buserite. Fe oxides are essentially ferroxyhyte and goethite. The Fe-Mn crusts show high average contents in Fe (23.5 wt%), Mn (16.1 wt%), and trace elements like Co (4700 μg/g), Ni (2800 μg/g), V (2400 μg/g) and Pb (1600 μg/g). Rare earth elements plus yttrium (REY) averages 2800 μg/g with high proportions of Ce (1600 μg/g). Total platinum group elements (PGEs) average 230 ng/g, with average Pt of 182 ng/g. Two main types of growth layers form the crusts: 1) a dense laminae of oxides with high contents in Mn, Co and Ni associated with vernadite and Cu, Ni, and Zn associated with todorokite; 2) botryoidal layers with high contents in Fe, Ti, V and REY associated with goethite. The Fe-Mn crusts from the CISP region show higher contents in Fe, V, Pb and REY but lower Mn, Co, Ni and PGEs contents than Pacific or Indian ocean seamount crusts. The oldest maximum age of initiation of crust growth was at 76 Ma (Campanian, Late Cretaceous). Using a combination of high resolution Co-chronometer and geochemical data along an Electron Probe Micro Analysis (EPMA) transect, four stages in morphology, chemical contents and growth rates can be differentiated in the the Cenozoic crusts since 28 Ma, which we interpret as due to changes in the ventilation of the North Atlantic OMZ and to the increase of Saharian dust inputs. An earliest growth period, characterized by similar contents of Fe and Mn in the interval 27.8–24.45 Ma (late Oligocene-early Miocene) reflects slow precipitation related to a thick OMZ. An intermediate laminated zone with higher contents of Fe, Si and P, high growth rates reaching 4.5 mm/Ma, and precipitation of Fe-Mn oxides during the interval 24.5–16 Ma is related to periods of ventilation of the OMZ by intrusion of deep upwelling currents. Significant increase in Fe contents at ca. 16 Ma correlates with the onset of incursions of Northern Component Waters into the North Atlantic. Finally, since 12 Ma, the very low growth rates (< 0.5 mm/Ma) of the crust are related to a thick North Atlantic OMZ, an increase in Sahara dust input and a stable thermohaline circulation.     

Petrogenesis and W-Mo fertility indicators of the Gaojiabang “satellite” granodiorite porphyry in southern Anhui Province,South China

The Gaojiabang W-Mo mineralized granodiorite porphyry occurs as a “satellite” intrusion on the northern margin of the Qingyang-Jiuhua pluton in southern Anhui Province, South China. The geology, mineral and whole-rock geochemistry of the granodiorite porphyry is I-type and formed from a reduced melt. The Gaojiabang mineralized granodiorite porphyry was derived from the transition zone between the lower crust and upper mantle, and underwent high-degree fractional crystallization during emplacement. There is no obvious genetic relationship between the granodiorite porphyry and the granodiorite pluton of the Qingyang-Jiuhua plutonic complex. The key characteristics of the W-Mo mineralized Gaojiabang granodiorite porphyry include: 1) small volume (<0.5 km³), 2) an abundance of hornblende (>5 vol%), 3) low ∑REE concentrations (145.50–159.46 ppm) accompanying weak negative Eu anomalies (0.85–0.94), 4) high differentiation-indices degree and water contents, and 5) low oxygen fugacity. These criteria can be used to identify potential W-Mo mineralized intrusions in southern Anhui Province, South China.     

3D geological modeling for prediction of subsurface Mo targets in the Luanchuan district,China

Three-dimensional (3D) district-scale geoscience information for the Luanchuan Mo district was integrated for understanding the development of its regional geology and ore-forming processes and for decision-making about potential targets for mineral exploration. The methodology and datasets used were: (1) construction of an initial geological model (25 km × 20 km × 2.5 km) using 1:10,000 scale geological map, nine geological cross-sections and gravity and magnetic data; (2) construction of three large-scale Mo deposits model (5 km × 4 km × 2.5 km) using 1:2000 scale geological and topographic maps, 288 boreholes (total core length of 158,700 m), and 32 1:2000 scale cross-sections; (3) 3D inversion of 1:25,000 scale gravity and magnetic data for identification metallogenic anomaly zones which are associated with Jurassic intrusions; (4) extraction of ore-controlling formation and sequence of the Luanchuan Group using the large-scale 3D models of Mo deposits and results of analysis of lithogeochemical samples from outcrops and borehole cores; (5) identification of ore-forming and ore-controlling faults using the large-scale 3D model of Mo deposits and mineralized Jurassic granite porphyry stocks; (6) boost weights-of-evidence and concentration–volume (C–V) fractal analyses to integrate metallogenic information and to identify and classify potential Mo targets. Four classes of exploration targets were identified using C–V modeling and 3D known orebodies model: the first and second class targets are mainly located in three large magma-skarn type deposit camps, occupying ~ 1.4 km³ with total estimated reserve of ~ 2.3 Mt; the third class targets, which are mainly located in Huangbeiling and Yuku deposit camps comprising concealed magma-skarn type deposits, occupy ~ 2.8 km³ and represent a new target exploration zone in the Luanchuan district; the fourth class targets, which are located in the Huoshenmiao, Majuan, and Daping zones, occupy ~ 15 km³ and represent potential mineral resources with likely similar orebody features as the Yuku deposit.     

Basement configuration of the Jhagadia–Rajpipla profile in the western part of Deccan syneclise,India from travel-time inversion of seismic refraction and wide-angle reflection data

2-D velocity structure up to the basement is derived by travel-time inversion of the first arrival seismic refraction and wide-angle reflection data along the SW–NE trending Jhagadia–Rajpipla profile, located on the western part of Deccan syneclise in the Narmada–Tapti region. The study region is mostly covered by alluvium. Inversion of refraction and wide-angle reflection data reveals four layered velocity structure above the basement. The first two layers with P-wave velocities of 1.95–2.3 km s^?1 and 2.7–3.05 km s^?1 represent the Recent and Quaternary sediments respectively. The thickness of these sediments varies from 0.15 km to 3.4 km. The third layer with a P-wave velocity of 4.8–5.1 km s^?1 corresponds to the Deccan volcanics, whose thickness varies from 0.5 km to 1.0 km. Presence of a low velocity zone (LVZ) below the high velocity volcanic rocks in the study area is inferred from the travel-time ‘skip’ and amplitude decay of the first arrival refraction data and the wide-angle reflection from top of the LVZ present immediately after the first arrival refraction from Deccan Trap layer. The thickness of the low velocity Mesozoic sediments varies from 0.3 km to 1.7 km. The basement with a P-wave velocity of 5.9–6.15 km s^?1 lies at a depth of 4.9 km near Jhagadia and shallows to 1.2 km towards northeast near Rajpipla. The results indicate presence of low velocity Mesozoic sediments hidden below the Deccan Trap layer in the western part of the Deccan syneclise.     

Boron content of Lake Ulubat sediment: A key to interpret the morphological history of NW Anatolia,Turkey

Freshwater Lake Ulubat (c. 1.5 m deep and c. 138 km²) receives sediment from a 10.414 km² area in the seismically active Susurluk Drainage Basin (SDB) of NW Turkey. The B and trace element contents of the lake infill seem to be a link between the fresh landforms of the SDB and the lacustrine sediment. Deposition in Lake Ulubat has been 1.60 cm a⁻¹ for the last 50 a according to radionucleides; however the sedimentation rate over the last millennium was 0.37 cm a⁻¹ based on ¹⁴C dating. The B content of the lacustrine infill displays a slight increase at 0.50 m and a drastic increase at 4 m depth occurring c. 31 a and c. 1070 a ago, respectively. Probably the topmost change corresponds to the start of open mining in the SDB and the second one to the natural trenching of borate ore-deposits. These dates also show indirectly a 1.4 cm a⁻¹ erosion rate during the last millennium as the borate beds were trenched up to 15 m. By extrapolation, it is possible to establish that the formation of some of the present morphological features of the southern Marmara region, especially river incision, began in the late Pleistocene, and developed especially over the last 75 ka.     

Mechanisms controlling acid neutralization and metal mobility within a Ni-rich tailings impoundment

Low-quality pore waters containing high concentrations of dissolved H⁺, SO₄, and metals have been generated in the East Tailings Management Area at Lynn Lake, Manitoba, as a result of sulfide-mineral oxidation. To assess the abundance, distribution, and solid-phase associations of S, Fe, and trace metals, the tailings pore water was analyzed, and investigations of the geochemical and mineralogical characteristics of the tailings solids were completed. The results were used to delineate the mechanisms that control acid neutralization, metal release, and metal attenuation. Migration of the low-pH conditions through the vadose zone is limited by acid-neutralization reactions, resulting in the development of distinct pore-water pH zones at depth; the neutralization reactions involve carbonate (pH ⩾ 5.7), Al-hydroxide (pH ⩾ 4.0), and aluminosilicate solids. As the zone of low-pH pore water expands, the pH will then be primarily controlled by less soluble solids, such as Fe(III) oxyhydroxides (pH < 3.5) and the relatively more recalcitrant aluminosilicates (pH ⩾ 1.3). Precipitation/dissolution reactions involving secondary Fe(III) oxyhydroxides and hydroxysulfates control the concentrations of dissolved Fe(III). Concentrations of dissolved SO₄ are principally controlled by the formation of gypsum and jarosite. Geochemical extractions indicate that the solid-phase concentrations of Ni, Co, and Zn are associated predominantly with reducible and acid-soluble fractions. The concentrations of dissolved trace metals are therefore primarily controlled by adsorption/complexation and (or) co-precipitation/dissolution reactions involving secondary Fe(III) oxyhydroxide and hydroxysulfate minerals. Concentrations of dissolved metals with relatively low mobility, such as Cu, are also controlled by the precipitation of discrete minerals. Because the major proportion of metals is sequestered through adsorption and (or) co-precipitation, the metals are susceptible to remobilization if low-pH or reducing conditions develop within the tailings.     

Shrimp U–Pb zircon geochronology,geochemistry, and Nd–Sr isotopic study of contrasting granites in the Emeishan large igneous province,SW China

The Cida A-type granitic stock (∼ 4 km²) and Ailanghe I-type granite batholith (∼ 100 km²) in the Pan-Xi (Panzhihua-Xichang) area, SW China, are two important examples of granites formed during an episode of magmatism associated with the Permian Emeishan mantle plume activity. This is a classic setting of plume-related, anorogenic magmatism exhibiting the typical association of mantle-derived mafic and alkaline rocks along with silicic units. SHRIMP zircon U–Pb data reveal that the Cida granitic pluton (261 ± 4 Ma) was emplaced shortly before the Ailanghe granites (251 ± 6 Ma). The Cida granitoids display mineralogical and geochemical characteristics of A-type granites including high FeO^⁎/MgO ratios, elevated high-field-strength elements (HFSE) contents and high Ga/Al ratios, which are much higher than those of the Ailanghe granites. All the granitic rocks show significant negative Eu anomalies and demonstrate the characteristic negative anomalies in Ba, Sr, and Ti in the spidergrams. It can be concluded that the Cida granitic rocks are highly fractionated A-type granitoids whereas the Ailanghe granitic rocks belong to highly evolved I-type granites.The Cida granitoids and enclaves have Nd and Sr isotopic initial ratios (ε_Nd(t) = − 0.25 to + 1.35 and (⁸⁷Sr/⁸⁶Sr)_i = 0.7023 to 0.7053) close to those of the associated mafic intrusions and Emeishan basalts, indicating the involvement of a major mantle plume component. The Ailanghe granites exhibit prominent negative Nb and Ta anomalies and weakly positive Pb anomalies in the spidergram and have nonradiogenic ε_Nd(t) ratios (− 6.34 to − 6.26) and high (⁸⁷Sr/⁸⁶Sr)_i values (0.7102 to 0.7111), which indicate a significant contribution from crustal material. These observations combined with geochemical modeling suggest that the Cida A-type granitoids were produced by extensive fractional crystallization from basaltic parental magmas. In contrast, the Ailanghe I-type granites most probably originated by partial melting of the mid-upper crustal, metasedimentary–metavolcanic rocks from the Paleo-Mesoproterozoic Huili group and newly underplated basaltic rocks.In the present study, it is proposed that petrogenetic distinctions between A-type and I-type granites may not be as clear-cut as previously supposed, and that many compositional and genetically different granites of the A- and I-types can be produced in the plume-related setting. Their ultimate nature depends more importantly on the type and proportion of mantle and crustal material involved and melting conditions. Significant melt production and possible underplating and/or intrusion into the lower crust, may play an important role in generating the juvenile mafic lower crust (average 20 km) in the central part of the Emeishan mantle plume.     

Coexistence of the moderately refractory and fertile mantle beneath the eastern Central Asian Orogenic Belt

Relative to the North China Craton, the subcontinental lithospheric mantle (SCLM) beneath the Central Asian Orogenic Belt is little known. Mantle-derived peridotite xenoliths from the Cenozoic basalts in the Xilinhot region, Inner Mongolia, provide samples of the lithospheric mantle beneath the eastern part of the belt. The xenoliths are predominantly lherzolites with minor harzburgites, and can be subdivided into three groups, based on the REE patterns of clinopyroxenes. Group 1 peridotites (LREE-enriched), with low modal Cpx (3–7%), high Mg^# in olivine (> 90.6) and Cr^# in spinel (> 43.8), low whole-rock CaO + Al₂O₃ contents (1.62–3.22 wt.%) and estimated temperatures of 1043–1126 °C, represent moderately refractory SCLM that has experienced carbonatite-related metasomatism. Group 2 peridotites (LREE-depleted), with high modal Cpx (9–13%), low Mg^# in olivine (< 90.6) and Cr^# in spinel (< 20.0), high whole-rock CaO + Al₂O₃ contents (4.93–6.37 wt.%) and estimated temperatures of 814–970 °C, show affinity with Phanerozoic fertile SCLM that has undergone silicate-related metasomatism. Group 3 peridotites (convex-upward REE patterns), show wide ranges of olivine-Mg^# (88.4–90.6), spinel-Cr^# (11.5–47.6), and modal Cpx (3–14%) that overlap Groups 1 and 2. Their spinels have high TiO₂ contents (> 0.41 wt.%), implying involvement of reactions between melt and peridotites. The estimated temperatures of Group 3 (1033–1156 °C) are similar to those of Group 1. We suggest that the pre-existing moderately refractory lithospheric mantle (i.e., Group 1) beneath the eastern part of the Central Asian Orogenic Belt was strongly penetrated by upwelling asthenospheric material, and the cooling of this material produced fertile lithospheric mantle (i.e., Group 2). The present lithospheric mantle of this area consists of interspersed volumes of younger fertile and older more refractory lithosphere, with the fertile type dominating the shallower levels of the mantle.     

Postdated melting of subcontinental lithospheric mantle by the Emeishan mantle plume: Evidence from the Anyi intrusion,Yunnan, SW China

The Anyi intrusion is located in the central zone of Emeishan large igneous province (ELIP), SW China. It outcrops in an area of about 0.65 km² and ~ 1 km thick and dips to the southwest. The Anyi intrusion consists of a lower clinopyroxenite zone, middle gabbro zone, and an upper monzonite–syenite zone. Up to 400 m thick stratiform disseminated Fe–Ti oxide layer with grades of 16–18 wt.% total Fe is hosted in the lower clinopyroxenite zone. Zircon SHRIMP U–Pb age (247 ± 3 Ma) indicates that the Anyi intrusion represents postdated mafic magmatism resulting from the ~ 260 Ma Emeishan mantle plume. Compared with the typical oxide-bearing intrusions (such as Panzhihua and Baima) formed at ~ 260 Ma in the ELIP, the Anyi intrusion is characterized by high alkaline contents and LREE/HREE ratios, extremely low εNd values (− 6.2 to − 7.6) and moderate high (⁸⁷Sr/⁸⁶Sr)_i values (0.7072 to 0.7086). These characteristics of the Anyi intrusion cannot be explained by fractional crystallization or crustal contamination, but may reflect a unique enriched continental lithospheric mantle source (a mantle source mixed between garnet pyroxenite and spinel peridotite). We propose that the postdated mafic magmatism associated with the formation of the Anyi intrusion and its Fe–Ti oxide ore may be the product of melting of a mantle source mixed between garnet pyroxenite and spinel peridotite in the shallow lithosphere caused by conductive heating combined with lithosphere thinning due to plume–lithosphere interaction.     

Carboniferous magmatism and mineralization in the area of the Fuxing Cu deposit,Eastern Tianshan,China: Evidence from zircon U–Pb ages,petrogeochemistry, and Sr–Nd–Hf–O isotopic compositions

The newly discovered Fuxing porphyry Cu deposit is located in the Dananhu–Tousuquan arc, adjacent to the Tuwu–Yandong Cu deposits of Eastern Tianshan, in the southern Central Asian Orogenic Belt. The Fuxing deposit is hosted by volcanic rocks (basalt and dacite) in the Early Carboniferous Qi'eshan Group and Carboniferous felsic intrusions (plagiogranite porphyry, monzogranite, and quartz diorite). New SIMS zircon U–Pb dating indicates that the plagiogranite porphyry and monzogranite emplaced at 332.1 ± 2.2 Ma and 328.4 ± 3.4 Ma, respectively. The basalts are characterized by low SiO₂ contents (47.47–54.90 wt.%), a lack of Eu anomalies, strong depletion of Na, Ta, and Ti elements but positive Sr, U, and Pb anomalies, high Y (20.8–28.2 ppm) and HREE concentrations (Yb = 2.23–3.06 ppm), and relatively low (La/Yb)_N (2.20–3.92) values; the dacite samples have high SiO₂ contents (66.13–76.93 wt.%), clearly negative Eu anomalies, high Mg^# values (36–51), and high Y (41.8–54.9 ppm) and Yb (5.76–8.98 ppm) concentrations. The basalts and dacites exhibit similar signatures as normal arc rocks, and were considered to be derived from partial melting of mantle-wedge peridotite that was previously metasomatized by slab melts. In contrast, the plagiogranite porphyry, monzogranite, and quartz diorite show the same geochemical affinity with modern adakites, which are characterized by high SiO₂ contents (67.55–79.00 wt.%), minor negative to positive Eu anomalies, strong depletion of heavy rare earth elements (Yb = 0.17–1.19 ppm) and Y (1.86–10.1 ppm), positive K, Rb, Sr, and Ba but negative Nb, Ta, Th, and Ti anomalies, and high (La/Yb)_N ratios and Mg^# values. Moreover, these adakitic felsic intrusions display relatively high positive zircon ε_Hf(t) values (+ 11.4 to + 18.3), low ⁸⁷Sr/⁸⁶Sr (0.706080–0.711239), high ¹⁴³Nd/¹⁴⁴Nd (0.512692–0.512922) ratios, and consistent zircon δ¹⁸O values (4.41‰–5.48‰), suggesting that their parental magma were most likely derived from partial melting of the subducted oceanic crust followed by mantle peridotite interaction. Based on the whole-rock geochemical and Sr–Nd–Hf–O isotopic data, as well as detailed petrographic analyses, we further suggest that the Fuxing igneous rocks and associated porphyry Cu mineralization were generated by the northward subduction of the paleo-Tianshan oceanic plate beneath the Dananhu–Tousuquan island arc during the Early Carboniferous.     

Geochemical signatures of uranium oxides in the Lufilian belt: From unconformity-related to syn-metamorphic uranium deposits during the Pan-African orogenic cycle

The Pan-African Lufilian belt (Zambia and Democratic Republic of Congo) is known for its world-class copper and cobalt deposits. In addition, the Lufilian Copperbelt hosts several uranium occurrences concentrated within deformed siliciclastic rocks of the basal Neoproterozoic Katanga Supergroup. We report LA-ICPMS and EMP analyses of the rare earth element (REE) and yttrium (Y) abundances (designated as the REY signatures) of uranium oxides from two uranium mineralizing events of the Lufilian belt previously dated at 652 ± 8 Ma and 530 ± 6 Ma by the U–Pb method on uraninite. Uranium oxides dated at ca. 650 Ma from the External fold-and-thrust belt are characterized by (i) bell shape REE patterns centered on middle REE (MREE), (ii) positive europium (Eu) anomalies and (iii) relatively low Y contents. In contrast, uranium oxides dated at ca. 530 Ma from the Domes region are characterized by (i) REE patterns but with a less pronounced light REE (LREE) fractionation, (ii) negative Eu anomalies and (iii) higher Y contents. Moreover, the External fold-and-thrust belt also contains uranium mineralization dated at ca. 530 Ma having the same characteristics as the ca. 530 Ma uranium oxides from the Domes region (a moderately fractionated REE pattern and a negative Eu anomaly).As REY signatures are known to reflect mineralizing processes, the distinct geochemical signatures of the two uranium oxide generations (ca. 650 Ma and ca. 530 Ma) provide meaningful information about the uranium cycle during the Pan-African orogeny. Compared to the REY signatures of the known worldwide uranium deposit types, the REY signature of uranium oxides dated at ca. 650 Ma of the External fold-and-thrust belt is similar to the REE patterns from unconformity-related U deposits (Athabasca in Canada and Kombolgie in Australia). Uranium oxides of the Domes region and some of the External fold-and-thrust belt display similar characteristics to syn-metamorphic U deposit (Mistamisk in Canada). Accordingly, we propose that the two stages of uranium oxide crystallizations within the Lufilian belt, at ca. 650 and ca. 530 Ma, occurred under distinct physico-chemical conditions. The first stage, at ca. 650 Ma, may be related to late diagenesis hydrothermal processes, at the basement/cover interface, with the circulation of highly saline basinal brines linked to evaporites of the Roan Group. This Pan-African unconformity-related uranium deposit is the youngest of this type described to date. The second stage may be connected to metamorphic fluid circulations, at about 530 Ma, during the Lufilian orogeny in the Domes region and also in the External fold-and-thrust belt.     

Changes in the glacier extent and surface elevation along the Ningchan and Shuiguan river source,eastern Qilian Mountains,China

We investigate the changes at nine glaciers in the Ningchan and Shuiguan river source, eastern Qilian Mountains, between 1972 and 2010. According to analysis of topographic maps and multispectral satellite data, all nine glaciers in the study area have retreated, by a maximum of 250 ± 57.4 m and a minimum of 91 ± 57.4 m. The total glacier area decreased by 1.20 km², corresponding to 9.9% of the glacierized area in 1972. Comparing the two DEMs generated from the topographic maps and Real-Time Kinematic GPS data, the mean glacier thinning rate was 0.64 m yr^− 1 between 1972 and 2010. The most significant thinning generally occurred on the termini. The ice-volume loss was about 106.8 ± 46.7 × 10^− 3 km³ (equal to 90.8 ± 39.7 × 10^− 3 km³ w.e.), which suggested a mean water discharge of 0.1 ± 0.05 m³/s during 1972–2010. Based on analysis of meteorological data, the summer temperature (June–August) tends to increase over a similar time period. The consistency of temperature increase and glacier shrinkage allows us to suggest that air temperature plays an important role in glacier changes in this region.     

Chemical weathering rates in the Alaknanda–Bhagirathi river basins in Himalayas,India

The Alaknanda and Bhagirathi rivers flow through the Higher and Lesser Himalayas and confluence at Devprayag, which represents the origin of the Ganga (or Ganges) river. In the present study, a vast number of temporal and spatial samples of the river waters were collected and analyzed for major cations and anions. In addition, more recent and time series water flow data have been obtained and based on these inputs, a more refined dissolved flux rates have been estimated. The Alaknanda and Bhagirathi rivers show significant variations in chemical compositions during different seasons. Carbonate rock weathering is responsible for more than 70% of the chemical compositions in the river waters. The chemical weathering rates show seasonal variations and are much higher during non-monsoon season. The dissolved flux of Alaknanda river is much higher (1.80 × 10⁶ tons yr^?1) as compared to the Bhagirathi river (0.34 × 10⁶ tons yr^?1). The chemical weathering rates in the basin vary between 85 and 155 tons km^?2 yr^?1, which is significantly higher compared to the global average of ～24 tons km^?2 yr^?1.     

Zircon and molybdenite geochronology and geochemistry of the Kalmakyr porphyry Cu–Au deposit,Almalyk district,Uzbekistan: Implications for mineralization processes

Copper, gold and molybdenum mineralization of the Kalmakyr porphyry deposit in Uzbek Tien Shan occurs as stockworks, veinlets and disseminations in the phyllic and K-silicate alteration zones developed predominantly in a middle to late Carboniferous intrusive complex composed of monzonite and granodiorite porphyry. Zircon U–Pb dating yielded an age of 327.2 ± 5.6 Ma for the ore-hosting monzonite and an age of 313.6 ± 2.8 Ma for the ore-bearing granodiorite porphyry. Re–Os dating of seven molybdenite samples from stockwork and veinlet ores yielded model ages from 313.2 to 306.3 Ma, with two well-constrained isochron ages of 307.6 ± 2.5 Ma (five stockwork ores) and 309.1 ± 2.2 Ma (five stockwork ores and two veinlet ores), respectively. These results indicate that Cu–Au mineralization post-dated the emplacement of the monzonite, started right after the emplacement of the granodiorite porphyry, and lasted for ca. 7 Ma afterward. The geochronological and geochemical data suggest that the Kalmakyr deposit was formed in a late Carboniferous mature magmatic arc setting, probably related to the latest subduction process of the Turkestan Ocean beneath the Middle Tien Shan. The ε_Hf(t) values of zircon grains from the monzonite vary from +11 to +1.7, with an average of +5.1, and those of zircon grains from the granodiorite porphyry range from +5.7 to −1.8, with an average of +2.4. These data indicate that the magma of both monzonite and granodiorite porphyry was derived from partial melting of a thickened lower crust with input of mantle components and variable crustal contamination, and that there was more mantle contribution to the formation of the monzonite than the granodiorite porphyry. The high rhenium concentrations of molybdenite (98–899 ppm) also indicate major mantle contribution of rhenium and by inference ore metals. The relatively high Eu_N/Eu_N¹ values (average 0.68), Ce⁴⁺/Ce³ values (average 890) and Ce/Nd values (average 36.8) for zircon grains from the granodiorite porphyry than those from the monzonite (average Eu_N/Eu_N¹ = 0.33, average Ce⁴⁺/Ce³ = 624, average Ce/Nd = 3.9) suggest that the magma for the syn-mineralization granodiorite porphyry has higher oxygen fugacity than that for the pre-mineralization monzonite. Based on these data, it is proposed that while the monzonite was emplaced, the oxygen fugacity and volatile contents in the magma were relatively low, and ore metals might disperse in the intrusive rock, whereas when the granodiorite porphyry was emplaced, the oxygen fugacity and volatile contents in the magma were increased, favoring copper and gold enrichment in the magmatic fluids. The Kalmakyr deposit formed from a long-lived magmatic-hydrothermal system connected with fertile magmatic sources in relation to the subduction of the Turkestan Ocean beneath the Middle Tien Shan.     

Post-collisional ultrapotassic rocks and mantle xenoliths in the Sailipu volcanic field of Lhasa terrane,south Tibet: Petrological and geochemical constraints on mantle source and geodynamic setting

Post-collisional ultrapotassic magmatic rocks (15.2–18.8 Ma), containing mantle xenoliths, are extensively distributed in the Sailipu volcanic field of the Lhasa terrane in south Tibet. They could be subdivided into high-MgO and low-MgO subgroups based on their petrological and geochemical characteristics. The high-MgO subgroup has olivine-I (Fo_87–92), phlogopite and clinopyroxene as phenocryst phases, while the low-MgO subgroup consists mainly of phlogopite, clinopyroxene and olivine-II (Fo_77–89). These ultrapotassic magmatic rocks have high MgO (4.6–14.5 wt%), Ni (145–346 ppm), Cr (289–610 ppm) contents, and display enrichment in light rare earth element (REE) over heavy REE and enriched large ion lithophile elements (LILE) relative to high field strength elements (HFSE) with strongly negative Nb-Ta-Ti anomalies in primitive mantle-normalized trace element diagrams. They have extremely radiogenic (⁸⁷Sr/⁸⁶Sr)_i (0.7167–0.7274) and unradiogenic (¹⁴³Nd/¹⁴⁴Nd)_i (0.5118–0.5120), high (²⁰⁷Pb/²⁰⁴Pb)_i (15.740–15.816) and (²⁰⁸Pb/²⁰⁴Pb)_i (39.661–39.827) at a given (²⁰⁶Pb/²⁰⁴Pb)_i (18.363–18.790) with high δ¹⁸O values (7.3–9.7‰). Strongly linear correlations between depleted mid-ocean ridge basalt-source mantle (DMM) and the Indian continental crust (HHCS) in Sr-Nd-Pb-O isotopic diagrams indicate that the geochemical features could result from reaction between mantle peridotite and enriched components (fluids and melts) released by the eclogitized Indian continental crust (HHCS) in the mantle wedge. The high-MgO (13.7–14.5 wt%) subgroup displays higher (¹⁴³Nd/¹⁴⁴Nd)_i, lower (⁸⁷Sr/⁸⁶Sr)_i and (²⁰⁶Pb/²⁰⁴Pb)_i ratios and lower δ¹⁸O values compared with the low-MgO (4.6–8.8 wt%) subgroup. High Ni (850–4862 ppm) contents of olivine phenocrysts and high whole-rock SiO₂, NiO, low CaO contents indicate that the low-MgO ultrapotassic magmatic rocks are derived from partial melting of olivine-poor mantle pyroxenite. However, lower Ni concentrations of olivine phenocryst and lower whole-rock SiO₂, NiO, higher CaO contents of the high-MgO ultrapotassic rocks may indicate their peridotite mantle source. This could be attributed to different amounts of silicate-rich components added into the mantle sources of the parental magmas in the mantle wedge caused by the northward subduction of the Indian continental lithosphere. The reaction-formed websterite xenoliths, reported for the first time in this study, are made up of anhedral and interlocking clinopyroxene (45–65 vol%) and orthopyroxene (30–50 vol%) with minor phlogopite (< 3 vol%) and quartz (< 2 vol%) and are suggested to be formed by silicate metasomatism of the mantle peridotite. The harzburgites, another major type of mantle xenolith in south Tibet, have a mineral assemblage of olivine (60–75 vol%), orthopyroxene (20–35 vol%), clinopyroxene (< 3 vol%), phlogopite (< 2 vol%) and spinel (< 2 vol%) and may have experienced subduction-related metasomatism. Combined with two types of ultrapotassic magmas, we propose that compositions of mantle wedge beneath south Tibet may gradually evolve from harzburgite through lherzolite to websterite with strong metasomatism of silicate-rich components in their mantle source region. Partial melting of the enriched mantle sources could be triggered by rollback of Indian continental slab during 25–8 Ma in south Tibet.     

Geology,geochemistry, and geochronology of the Wangjiazhuang porphyry–breccia Cu(–Mo) deposit in the Zouping volcanic basin,eastern North China Block

The Wangjiazhuang porphyry–breccia Cu(–Mo) deposit is located in the Zouping volcanic basin, western Shandong Province. Seven molybdenite samples yield a Re–Os weighted mean age of 127.8 ± 0.7 Ma (2σ), which is identical within error to the zircon weighted mean ²⁰⁶Pb/²³⁸U age of 128.3 ± 1.3 Ma (2σ) determined for quartz monzonite samples. The host rock is characterized by high concentrations of K₂O (4.26–4.53 wt.%), Na₂O (4.97–5.76 wt.%), LILEs and LREEs, and high Mg# (> 40), and low concentrations of HFSEs and HREEs, with K₂O/Na₂O ratios of 0.76–0.88. The quartz monzonite also has high Sr/Y (69.9–112.5) and (La/Yb)_N (22.0–30.0) ratios, similar to adakitic rocks worldwide. Relatively low initial ⁸⁷Sr/⁸⁶Sr ratios (0.70549–0.70556), high ε_Nd(t) values (2.58–3.06), high radiogenic Pb [(²⁰⁶Pb/²⁰⁴Pb)i = 18.3424–18.4606, (²⁰⁷Pb/²⁰⁴Pb)_i = 15.5692–15.5985, (²⁰⁸Pb/²⁰⁴Pb)_i = 38.1714–38.2734] and high zircon ε_Hf(t) values (− 2.1 to + 4.3) indicate that the magma was likely derived from the partial melting of subducted oceanic crust which then reacted with the peridotitic mantle wedge. Both the breccia and porphyry ores have a narrow range of δ³⁴S (− 4.8 to + 2.1‰) and Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.295–18.402, ²⁰⁷Pb/²⁰⁴Pb = 15.551–15.573, and ²⁰⁸Pb/²⁰⁴Pb = 38.215–38.331), suggesting that the ore metals were extracted primarily from the quartz monzonite or similar source. Subduction of the Paleo-Pacific slab during the Early Cretaceous resulted in the formation of the Wangjiazhuang quartz monzonite and associated Cu(–Mo) deposit in western Shandong Province.     

Geochemistry of S,Cu, Ni,Cr and Au-PGE in the garnet amphibolites from the Akom II area in the Archaean Congo Craton,Southern Cameroon

The fresh and weathered garnet amphibolites, from the Akom II area in the Archaean Congo Craton, were investigated to determine the S, Cu, Ni, Cr, and Au-PGE values. The garnet amphibolites are composed of amphibole, plagioclase, garnet, quartz, and accessory apatite, spinel, sericite, pyrite, chalcopyrite and non-identified opaque minerals. The presence of apatite, sericite, and two generations of opaque minerals suggests that they might be affected by hydrothermal alteration. They are characterized by moderate Al₂O₃, Fe₂O₃, CaO, V, Zn, and Co contents with negative Eu- and Ce-anomalies. The sulfur concentrations are variable (380–1710 ppm). According to the sulfur contents, amphibolites can be grouped into two: amphibolites with low contents, ranging between 380 and 520 ppm (av. = 457 ppm); and amphibolites with elevated contents, varying from 1140 to 1710 ppm (av. = 1370 ppm). Amphibolites contain contrast amounts of Cu (∼ 1800 to 5350 ppm) while nickel contents attain 121 ppm. Chromium contents vary from 43 to 194 ppm. Sulfur correlates positively with Cu and Cr, but negatively with Ni and Ni/Cr ratio. The total Au-PGE contents attain 59 ppb.The presence of amphibole and feldspars confirms the low degree of amphibolite weathering. The secondary minerals are constituted of kaolinite, gibbsite, goethite and hematite. Despite the accumulation of some elements, the major and trace element distribution is quite similar to that of fresh amphibolites. Nevertheless, the weathering processes lead to the depletion of several elements such as S (239–902 ppm), Cu (520–2082 ppm), and Ni (20–114 ppm). Chromium and Au-PGE show an opposite trend marked by a slight enrichment in the weathered amphibolites. Amidst the Au-PGE, Pd (60 ppb) and Pt (23 ppb) have elevated contents in the fresh rocks as well as in the weathered materials. The PPGE contents are much higher than IPGE contents in both types of materials. The Pd/Pt, Pd/Rh, Pd/Ru, Pd/Ir, Pd/Os, and Pd/Au values indicate that Pt, Rh, Ru, Ir, Os and Au are more mobile than Pd. Chondrite-normalized base metal patterns confirm the abundance of Pd and the slight enrichment of Au-PGE in weathered rocks. Palladium, Rh and Ir are positively correlated with S. Conversely Pt and Ru are negatively correlated with S and Au is not correlated with S. Despite the high and variable S and Cu contents, the garnet amphibolites possess low Au-PGE and other base metals contents.