Mineralogy and geochemistry of clay fractions from different saprolites,Egypt: implications for the source of sedimentary kaolin deposits

The clay fractions of saprolites from granites, basalt, and schists in Egypt were subjected to mineralogical and geochemical investigations to examine the effect of source rock on the composition of the saprolites and the possibilities of these saprolites as a source of the nearby sedimentary kaolin deposits. The clay fractions of the studied saprolites show mineralogical and geochemical variations. Saprolites from the granites consist of kaolinite, while saprolites from the basalts are composed entirely of smectite. Schists-derived saprolites are composed of kaolinite in some cases and of a mixture of kaolinite, illite, and chlorite in the other. Saprolite from the basalt is characterized by relatively higher contents of TiO₂ and Ni compared to the saprolites from granites. Saprolites from granites have higher contents of Ba, Li, Pb, Sr, Th, Y, and Zr compared to those of the saprolites from the basalts and schists. Saprolites from different schists show variations in the distributions of many constituents, such as TiO₂, Cr, Ni, Ba, Y, and Zr. Although chondrite-normalized rare earth elements (REE) patterns are characterized by relative enrichments in the light rare earth elements (LREE) compared to the heavy rare earth elements (HREE) in all saprolites, granitic saprolites show negative Eu anomalies, while saprolite from basalt has no Eu anomaly. REE patterns of the saprolites from schists exhibit slight positive Ce anomalies and slight to moderate negative Eu anomalies. Weathering of saprolites from the basalt and metasediments is classified as the bisiallitization type, while weathering of saprolite from the granite is allitization type. Saprolites from schists vary from the bisiallitization (Aswan and Abu Natash) and allitization (Khaboba) types. Saprolites from the Khaboba schist can be considered the possible source of the Carboniferous kaolin deposits in the Hasber and Khaboba areas of Sinai, based on the similarity in the mineralogy and geochemistry of major, trace, and REE between the saprolites and the deposits. On the other hand, Carboniferous sedimentary kaolin deposits in the Abu Natash area, as well as the Cretaceous kaolin deposits in all areas of Sinai, might have been derived from the nearby schist saprolites, based on the similarity in the mineralogy and geochemistry between the saprolites and the kaolin deposits. Granites from the Arabian-Nubian Shield (ANS) and East Sahara Craton (ESC) are the possible sources of the pisolitic and plastic kaolin deposits in the Kalabsha area (Aswan), as indicated by the similarity in the mineralogy and geochemistry of the granitic saprolites and the kaolin deposits.     

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.     

Precambrian iron formations from the Cauvery Suture Zone,Southern India: Implications for sub-marine hydrothermal origin in Neoarchean and Neoproterozoic convergent margin settings

Thick horizons of iron formations including Banded Iron Formations (BIFs) and Banded Silicate Formations (BSFs) occur as E–W trending bands in the eastern part of Cauvery Suture Zone (CSZ) in the Sothern Granulite Terrane of India. Some of these occur in close association with the Neoarchean-Neoproterozoic suprasubduction zone complexes, where as some others are associated with metamorphosed accretionary sequences including pyroxene granulites and other high grade rocks. The iron formations are highly deformed and metamorphosed under amphibolite to granulite facies conditions and are composed of quartz–magnetite–hematite–goethite–garnet–pyrite together with grunerite and pyroxene. Here we report the geochemical characteristics of twenty representative samples from the iron formations that reveal a widely varying composition with Fe₂O₃^(t) (22–65 wt.% as total iron) total- Fe₂O₃/TiO₂ (205–6532), MnO/TiO₂ (0.25–12.66) and SiO₂ (33–85 wt.%), broadly representing the two types of iron formations. These formations also show very low Al/(Al + Fe + Mn) ratio (0.001–0.01), Al₂O₃ (0.07–0.76 wt.%), Al₂O₃/TiO₂ ratio (2.7–21), MgO (0.01–4.41 wt.%), CaO (0.1–1.24 wt.%), Na₂O (0.01–0.05 wt.%) and K₂O (0.01 wt.%) together with low total REE (3.38–31.63 ppm). The trace and REE elemental distributions show wide variation with high Ni (274 ppm), and Zn contents (up to 87 ppm) when compared to mafic volcanics of the adjoining areas. Tectonic discrimination plots indicate that the iron formations of the Cauvery Suture Zone are of hydrothermal origin. Their chondrite normalized patterns show slight positive Eu anomaly (Eu/Eu* = up to 1.77) and relatively less fractionation of REE with slight LREE enrichment compared to HREE. However, the PAAS (Post Archean Average of Australian Sediments) normalized REE patterns display significant positive Eu anomaly (Eu/Eu* up to 2.32) with well represented negative Ce anomalies (Ce/Ce* = 0.66–1.28). The above results together with petrological characteristics and available geochronology of the associated lithologies suggest that the iron formations can be correlated to Algoma-type. The Fe and Si were largely supplied by medium to high temperature sub-marine hydrothermal systems in Neoarchean and Neoproterozoic convergent margin settings.     

Major, trace element and oxygen isotope study of glass cosmic spherules of chondritic composition: The record of their source material and atmospheric entry heating

New geochemical data on cosmic spherules (187 major element, 76 trace element, and 10 oxygen isotope compositions) and 273 analyses from the literature were used to assess the chemical diversity observed among glass cosmic spherules with chondritic composition. Three chemical groups of glass spherules are identified: normal chondritic spherules, CAT-like spherules (where CAT refers to Ca-Al-Ti-rich spherules), and high Ca-Al spherules. The transition from normal to high Ca-Al spherules occurs through a progressive enrichment in refractory major elements (on average from 2.3 wt.% to 7.0 wt.% for CaO, 2.8 wt.% to 7.2 wt.% for Al₂O₃, and 0.14 wt.% to 0.31 wt.% for TiO₂) and refractory trace elements (from 6.2 μg/g to 19.3 μg/g for Zr and 1.6CI-4.3CI for Rare Earth Elements-REEs) relative to moderately refractory elements (Mg, Si) and volatile elements (Rb, Na, Zn, Pb). Based on a comparison with experimental works from the literature, these chemical groups are thought to record progressive heating and evaporation during atmospheric entry. The evaporative mass losses evaluated for the high Ca-Al group (80-90%) supersede those of the CAT spherules which up to now have been considered as the most heated class of stony cosmic spherules. However, glass cosmic spherules still retain isotopic and elemental evidence of their source and precursor mineralogy. Four out of the 10 normal and high Ca-Al spherules analysed for oxygen isotopes are related to ordinary chondrites (δ¹⁸O = 13.2-17.3‰ and δ¹⁷O = 7.6-9.2‰). They are systematically enriched in Ni and Co (Ni = 24-500 μg/g) with respect to spherules related to carbonaceous chondrites (Ni < 1.2 μg/g, δ¹⁸O = 13.1-28.0‰ and δ¹⁷O = 5.1-14.0‰). REE abundances in cosmic spherules, which are not fractionated according to parent body or atmospheric entry heating, can then be used to unravel the precursor mineralogy. Spherules with flat REE pattern close to unity when normalized to CI are the most abundant in our dataset (54%) and likely derive from homogeneous, fine-grained chondritic precursors. Other REE patterns fall into no more than five categories, a surprising reproducibility in view of the mineralogical heterogeneity of chondritic lithologies at the micrometeorite scale.     

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

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

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

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

The Origin and Tectonic Setting of Precambrian Greywacke of Ribandar‐Chimbel,Goa, India: Petrological and Geochemical Evidence

The Precambrian greywacke of Ribandar‐Chimbel belonging to the Sanvordem Formation of the Goa Group, India, has been studied for petrography and analyzed for major trace elements. The greywacke is characterized by angular to sub‐round grains of quartz, feldspar, biotite, chlorite and clay minerals. The abundance of clay in the matrix seems to have influenced the Al₂O₃ content and the K₂O/Al₂O₃ ratio. The variation diagrams indicate a decreasing trend of TiO₂, Al₂O₃, Fe₂O₃ and MgO; whereas Na₂O and CaO exhibit a scatter which could be a result of the variable presence of feldspar within the sediments. The immobile elements, vanadium (25 to 144 ppm), nickel (up to 107 ppm) and chromium (up to 184 ppm), reflect abundance of clay minerals. The greywacke shows strongly fractionated REE patterns with La_N/Yb_N = 8 to 26 and with higher total REE abundances (up to 245 ppm). The low REE enrichment and depletion in heavier REE with prominent negative Eu anomaly (Eu/Eu*= 0.54 to 0.79) suggest a derivation of the greywacke from an old upper continental crust composed chiefly of felsic components. Petrological evidence and geochemical data suggest that the deposition of the greywacke largely took place in a deep to shallow basin that progressively changed from that of a continental island arc to an active continental setting.     

Genesis of the Nasirabad manganese occurrence,Fars province,Iran: Geochemical evidences

The Nasirabad manganese occurrence is located to the south of the Neyriz in the Fars province. Structurally and lithologically, this occurrence lies in the southwest part of the Zagros Thrust Belt and was deposited as Mn-nodules and interconnected ore-bearing interlayer's with radiolarite cherts in the vicinity of the Neyriz ophiolites. The present work deals with the geology and geochemistry of the Nasirabad manganese occurrence with a discussion of its genesis. High Mn/Fe (average 18.85) and high Ba (average 28,830 ppm) with low Pb (2.0 ppm) and LREE > HREE, La_n/Nd_n (average 4.5), Dy_n/Yb_n (average 1.2) and negative Eu anomaly suggest distal hydrothermal source. The Co/Zn (average 2.2), Ce/La ratio (average 0.67) and trace element discrimination diagrams indicate hydrothermal–hydrogenous processes. Y/Ho ratio (average 24.85) and strong positive correlation coefficient between major oxides and some high field strength elements (HFSE) like; TiO₂ vs Fe₂O₃ (r = 0.98), Al₂O₃ vs Zr (r = 0.97), Al₂O₃ vs Fe₂O₃ (r = 0.98), Zr vs K₂O (r = 0.98), Nb vs TiO₂ (r = 0.92), Th vs Fe₂O₃ (r = 0.76), Th vs MgO (r = 0.86) reveal the presence of volcaniclastics and (or) terrigenous detritals of mafic composition being deposited into the depositional basin. It seems that intermittent interlayering of mafic detrital material derived from volcanic eruption of the Neyriz island arc directly affected the physicochemical conditions of hydrothermal ore precipitation in this basin and consequently the Nasirabad manganese ores represent hydrothermal–hydrogenous geochemical characteristics. The Nasirabad is an example of non-sulphidic, oxic Mn-mineralization. Similar trend between the enrichment and depletion of some bioessential elements (e.g., Mn, As, Ba, Sr, Co, Ce) might have been resulted from selective sequestering of metal ions by microbial processes and hence hydrogenous characteristics may also be the result of biogenetic processes. Moreover the high dilution of distal hydrothermal exhalations by sea water cannot be ruled out.     

Geochemistry of peridotite and granite xenoliths during the early stage of weathering in the Nyos volcanic region (NW Cameroon): Implications for PGE exploration

Peridotite and granite xenoliths, in the early stage of weathering, occur in the Nyos volcanic region (NW Cameroon). Geochemical data shows that peridotites are marked by high concentrations of MgO (42.30 wt.%, with SiO₂/MgO ∼ 1), chromium (2100 ppm), nickel (2100 ppm) and cobalt (104 ppm), as well as by low lanthanide contents (ΣREE: 7.41 ppm). Granites display SiO₂ contents (70–73 wt.%), and are mostly peraluminous (1.40 > A/CNK < 1.6). They are also characterized by low contents in chromium (<24 ppm), nickel (ranging from 6 to 15 ppm) and cobalt (ranging from 3 to 6 ppm). Granites possess high lanthanide contents (ΣREE varying between 248.00 and 463.00 ppm), particularly in light lanthanides (LREE/HREE ratios ranging from 21 to 32). The chondrite-normalized patterns of the studied xenoliths are characterized by: (i) LREE enrichments in both rock types; (ii) negative Eu anomalies ([Eu/Eu*] ranging from 0.45 to 0.64) and weak positive Ce anomalies ([Ce/Ce*] ranging from 1.06 to 1.46) in granites. The weathering process provokes a remobilization of several trace elements notably light lanthanides.The geochemical survey of Platinum-Group Elements (PGE) done in these rocks in the early stage of weathering shows that PGE contents are less than 7 ppb in the peridotites. The highly concentrated elements are ruthenium (6.26 ppb) and platinum (5.53 ppb). The total PGE content is 14.57 ppb. These concentrations normalized with respect to chondrites display a flat spectrum from iridium to platinum. PGE contents in the granites are below detection limit except for two samples (LNY01 and LNY02) whose platinum content is close to 0.23 ppb.     

Petrographical and geochemical investigation of the Triassic marbles associated with Menderes massif metamorphics,Kavaklıdere,Muğla,SW Turkey

Vast marble deposits occur in a cover sequence of the Menderes Massif, SW Turkey. Four major marble deposits are recognized in Mu?la province based on the stratigraphic levels. These are Permo-Carboniferous aged black marbles (1), Triassic aged marbles (2), Upper Cretaceous aged marbles (3), and Paleocene aged pelagic marbles (4). This study deals with Triassic aged marbles of the southern part of the Menderes Massif. The Triassic marbles from SW Turkey consist of two big marble horizons in the Çayboyu (ÇM) and Kestanecik (KM) regions. The characteristic samples are collected from different stratigraphic levels in marble deposits in the ÇM and KM horizons. Mineralogical and major, trace, and rare earth element (REE) analyses of marble, limestone, and schist were conducted on these samples to reveal their petrographical and geochemical characteristics. The ÇM horizon is represented by calcitic marble layers. Nickel, cobalt, manganese, and iron elements filled in fractures, fissures, and intergranular spaces of calcite crystals and these elements give the pinky colour to the marble from the ÇM horizon. KM marbles were deformed, metamorphosed, and recrystallized under greenschist facies P–T conditions. As a result of the metasomatic reaction of magnesium and manganese rich fluids with marbles, dolomite, and manganese, minerals such as rhodochrosite and pyrolusite have crystallized along vein walls and layers in the KM horizon. Dolomitization was determined in KM marbles, whereas ÇM marbles show the character of limestone. MgO, MnO, Fe₂O₃, Ni, and Zn contents of marbles from the KM horizon are higher than those of ÇM marbles due to metasomatic reactions. The Sr content in white coloured marbles ranges between 11.20 ppm and 112.20 ppm and this concentration reaches up to 272.70 ppm due to metasomatic reactions and fluid intake. The REE content of Triassic marbles is independent of the abundance of carbonate and the REE enrichment observed due to syn-metamorphic fluid flow. The significant negative Eu anomaly in REE patterns indicates that the protoliths of Triassic marbles are carbonate rocks of sedimentary origin.     

Rare-earths in size fractions and sedimentary rocks of Pennsylvanian-Permian age from the mid-continent of the U.S.A.

The REE (rare-earth) contents of sixty-three <2 μ fractions of Pennsylvanian and Permian platform sediment from the mid-continent of the U.S.A. vary considerably (ΣREE = 46–439 ppm;La/ Lu = 5.2–15.7; correlation coefficient of REE with La/Lu = 0.89), but the Eu/Sm ratios are nearly constant even in reducing environments that concentrate U (0.16–0.22). There is no correlation of REE content to clay mineralogy.Lower Permian <2 μ fractions from continental to nearshore marine sediment in Oklahoma have higher REE content (244–261 ppm) than marine facies in Kansas (46–140ppm), but <2μ Upper Permian fractions in an evaporite basin have constant but high REE content (288–281 ppm; one = 153—ppm). All Pennsylvanian <2 μ fractions from Oklahoma have high REE content (209–439 ppm), and fractions from Kansas cyclothems have variable REE content (86–438 ppm). REE content in the <2 μ fractions is inherited from the provenance, but is modified by ion exchange during weathering, transportation, or deposition. Exchangable REE tend to be concentrated in clay minerals in basic environments, but removed in acid environments.Sand and gravel-size fractions consist mostly of quartz or chert so their REE content is low (7.9–40.6 ppm) although heavy minerals may contribute a large fraction of the REE content. Unexpectedly, silt-size fractions have REE contents (74–355 ppm) that are usually lower but similar to their <2 μ fractions, and the REE contents do not correlate to clay mineral/quartz ratios. The interpretation of REE content in sedimentary rocks needs to be done cautiously due to the above factors.     

Adakite-like signature of porphyry granitoid stocks in the Meiduk and Parkam porphyry copper deposits,NE of Shahr-e-Babak,Kerman, Iran: Constrains on geochemistry

The Middle Miocene porphyry granitoid stocks of Meiduk and Parkam porphyry copper deposits are intruded in the north-western part of the Dehaj-Sarduiyeh volcano-sedimentary belt in the south-eastern extension of the Urumieh-Dukhtar Magmatic Arc (UDMA) in Iran. The porphyritic to microgranular granitoids are mainly consist of quartz diorite, granodiorite and diorite. The whole rock geochemical analyses of these rocks reveals sub-alkaline, calc-alkaline, meta-peraluminous and I-type characteristics. Their geochemical characteristics such as Al₂O₃ content of 13.51–17.05 wt%, high Sr concentration (mostly >400 ppm), low Yb (an average of 0.74 ppm) and Y (an average of 9.02 ppm) contents, strongly differentiated REE patterns (La/Yb ≥ 20), lack of Eu anomaly (Eu/Eu¹ ≥ 1) are indicative of adakitic signature. Their enrichment in low field strength elements (LFSE) and conspicuous negative anomalies for Nb, Ta and Ti are typical of subduction related magmas. Detailed petrological studies and geochemical data indicated that Meiduk and Parkam porphyry granitoids were derived from amphibole fractionation of hydrous melts at a depth of >40 km in a post-collisional tectonic setting.     

Geology,geochemistry and genesis of the Godar Sabz Mn deposit in the Baft region,Iran

The Godar Sabz Mn deposit is located in the Nain-Baft ophiolitic belt in the northeast margin of the Sanandaj-Sirjan zone, Iran. The Nain-Baft back-arc extensional basin resulted from the subduction of the oceanic crust of Neo-Tethys under the southern margin of the Iranian Plate in the Early Cretaceous and hosts several mineral deposits, including volcanogenic massive sulfide, chromite, and Mn deposits. The mineralization in the Godar Sabz Mn deposit occurred predominantly as stratabound, massive, banded, layered, and lenticular orebodies in radiolarian cherts within Baft ophiolitic complex. The main ore minerals are pyrolusite, braunite, with minor amounts of todorokite. The significant geochemical features of the Godar Sabz ores, such as the high MnO content (21.82–80.65 wt%, average = 64.91 wt%), high Mn/Fe (average = 278), Si/Al ratios (average = 92.6), high Ba contents (average = 4495.6 ppm), the low average contents of Cu (81.8 ppm), Ni (106.2 ppm), Co (29.4 ppm), LREE > HREE, and trace element discrimination diagrams indicate a hydrothermal-exhalative source for mineralization. Chondrite-normalized REE patterns of studied ores have negative Ce and slightly positive Eu anomalies, which are similar to hydrothermal Mn deposits. The REE patterns of Mn ores coincide with basaltic lavas, suggesting that the Mn-mineralization in the Godar Sabz deposit was genetically related to the leaching of basaltic lavas. The Godar Sabz Mn deposit has many similarities with the main characteristics of the hydrothermal exhalative Mn deposits, including tectonic setting, host rock type, the morphology of orebodies, ore textures, mineralogy, and chemical features of ores.     

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

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

Geochemistry and Nd–Sr isotopic studies of Late Mesozoic granitoids in the southeastern Hubei Province, Middle–Lower Yangtze River belt, Eastern China: Petrogenesis and tectonic setting

A geochemical and isotopic study was carried out for the Mesozoic Yangxin, Tieshan and Echeng granitoid batholiths in the southeastern Hubei Province, eastern China, in order to constrain their petrogenesis and tectonic setting. These granitoids dominantly consist of quartz diorite, monzonite and granite. They are characterized by SiO₂ and Na₂O compositions of between 54.6 and 76.6 wt.%, and 2.9 to 5.6 wt.%, respectively, enrichment in light rare earth elements (LREE) and large ion lithophile elements (LILE), and relative depletion in Y (concentrations ranging from 5.17 to 29.3 ppm) and Yb (0.34–2.83 ppm), with the majority of the granitoids being geochemically similar to high-SiO₂ adakites (HSA). Their initial Nd (ε_Nd = − 12.5 to − 6.1) and Sr ((⁸⁷Sr/⁸⁶Sr)_i = 0.7054–0.7085) isotopic compositions, however, distinguish them from adakites produced by partial melting of subducted slab and those produced by partial melting of the lower crust of the Yangtze Craton in the Late Mesozoic. The granitoid batholiths in the southeastern Hubei Province exhibit very low MgO ranging from 0.09 to 2.19 wt.% with an average of 0.96 wt.%, and large variations in negative to positive Eu anomalies (Eu/Eu = 0.22–1.4), especially the Tieshan granites and Yangxin granite porphyry (Eu/Eu = 0.22–0.73). Geochemical and Nd–Sr isotopic data demonstrate that these granitoids originated as partial melts of an enriched mantle source that experienced significant contamination of lower crust materials and fractional crystallization during magma ascent. Late Mesozoic granitoids in the southeastern Hubei Province of the Middle–Lower Yangtze River belt were dominantly emplaced in an extensional tectonic regime, in response to basaltic underplating, which was followed by lithospheric thinning during the early Cretaceous.     

Geochemistry and microprobe investigations of Abu Tartur REE-bearing phosphorite,Western Desert,Egypt

Phosphorites in Egypt occur in the Eastern Desert, the Nile Valley and the Western Desert at Abu Tartur area and present in Duwi Formation as a part of the Middle Eastern to North African phosphogenic province of Late Cretaceous to Paleogene age (Campanian–Maastrichtian). The Maghrabi-Liffiya phosphorite sector is considered as the most important phosphorite deposits in the Abu Tartur area due to its large reserve thickness and high-grade of lower phosphorite bed beside high content of REE. Back scattered electron (BSE) images show framboidal pyrite filling the pores of the phosphatic grains, suggesting diagenetic reducing conditions during phosphorites formation.Electron Probe Micro Analyzer (EPMA) chemical mapping was conducted to examine the variation and distributions of selected elements (P, F, La, Fe, Yb, Si, Ce, W, Eu, S, Ca, Y and Er) within the shark teeth, coprolites and bone fragments. In the teeth W, S, Fe are concentrated along the axis of the teeth, the bone fragments show high concentration of W, Yb, Er and Eu, whereas coprolites are nearly homogenous in composition contains S, Er with some Si as micro-inclusions. Fluorapatite is considered as main phosphate mineral whereas pyrite occurs as pore-filling within the phosphatic grains and cement materials. Maghrabi-Liffiya samples show a wide range in the P₂O₅ content, between 19.8 wt.% and 29.8 wt.% with an average of 24.6 wt.% and shows low U content ranging from 15 ppm to 34 ppm with an average of 22 ppm. The total REE content in nine samples representing the Maghrabi-Liffiya ranges from 519 to 1139 ppm with an average of about 879 ppm. The calculation of LREE (La–Gd) show indeed a marked enrichment relative to the HREE (Tb–Lu) where LREE/HREE ratio attains 8.4 indicating a strong fractionation between the LREE and HREE. Chondrite-normalized REE patterns of the studied phosphorite samples show a negative Eu anomaly.     

Uranium-bearing and barren granites from the Taoshan Complex,Jiangxi Province,South China: Geochemical and petrogenetic discrimination and exploration significance

The Taoshan uranium ore district is one of the most important granite-hosted uranium producers in South China. The Taoshan granitic complex can be petrographically classified into several units of Caijiang, Huangpi, Daguzhai, and Luobuli, but the uranium deposits only occur within the Daguzhai granite unit. LA-ICP-MS zircon U–Pb dating indicates that both the Daguzhai granite and the Huangpi granite were emplaced at 154 ± 2 Ma. U contents (average 19.5 ppm) of the Daguzhai granite are higher than those of the Huangpi granite (average 7.3 ppm). The Daguzhai granite is composed of medium-grained two-mica granite, and the Huangpi granite is composed of medium- to coarse-grained biotite granite. These two granites show obvious differences in major element, trace element and isotopic geochemical characteristics. Compared to the Huangpi granite, the Daguzhai granite has higher A/CNK ratios, higher P₂O₅ contents and lower CaO contents, and is more enriched in Rb, Ba, U, and more depleted in Sr, Eu and Ti. The ε_Nd(t) values of the Daguzhai granite vary from − 12.2 to − 11.0 with two-stage model ages of 1.84 to 1.93 Ga. The ε_Nd(t) values of the Huangpi granite are slightly higher (− 9.7 to − 8.6) and the Nd model ages are younger (1.64 to 1.73 Ga). Comparative studies imply that the Daguzhai granite belongs to typical S-type and might be derived from the partial melting of parametamorphic rocks from metamorphic basement of the Zhoutan Group. In contrast, the Huangpi granite belongs to fractioned I-type, which might be derived from the partial melting of a mixture of ortho- and para-metamorphic rocks of the Zhoutan Group. These different magma sources might explain the different U contents of the two granites. In general, the source factor is an important controlling factor for the genesis of U-bearing granites in South China. U-bearing granites in South China show some common mineralogical and geochemical characteristics, which can be used to guide further exploration of granite-hosted U deposits.     

Geochemistry of black shales from the Lower Cretaceous Paja Formation,Eastern Cordillera,Colombia: Source weathering,provenance, and tectonic setting

The major and trace element characteristics of black shales from the Lower Cretaceous Paja Formation of Colombia are broadly comparable with those of the average upper continental crust. Among the exceptions are marked enrichments in V, Cr, and Ni. These enrichments are associated with high organic carbon contents. CaO and Na₂O are strongly depleted, leading to high values for both the Chemical Index of Alteration (77–96) and the Plagioclase Index of Alteration (86–99), which indicates derivation from a stable, intensely weathered felsic source terrane. The REE abundances and patterns vary considerably but can be divided into three main groups according to their characteristics and stratigraphic position. Four samples from the lower part of the Paja Formation (Group 1) are characterized by LREE-enriched chondrite-normalized patterns (average La_N/Yb_N = 8.41) and significant negative Eu anomalies (average Eu/Eu¹ = 0.63). A second group of five samples (Group 2), also from the lower part, have relatively flat REE patterns (average La_N/Yb_N = 1.84) and only slightly smaller Eu anomalies (average Eu/Eu¹ = 0.69). Six samples from the middle and upper parts (Group 3) have highly fractionated patterns (average La_N/Yb_N = 15.35), resembling those of Group 1, and an identical average Eu/Eu¹ of 0.63. The fractionated REE patterns and significant negative Eu anomalies in Groups 1 and 3 are consistent with derivation from an evolved felsic source. The flatter patterns of Group 2 shale and strongly concave MREE-depleted patterns in two additional shales likely were produced during diagenesis, rather than reflecting more mafic detrital inputs. An analysis of a single sandstone suggests diagenetic modification of the REE, because its REE pattern is identical to that of the upper continental crust except for the presence of a significant positive Eu anomaly (Eu/Eu¹ = 1.15). Felsic provenance for all samples is suggested by the clustering on the Th/Sc–Zr/Sc and Gd_N/Yb_N–Eu/Eu¹ diagrams. Averages of unmodified Groups 1 and 3 REE patterns compare well with cratonic sediments from the Roraima Formation in the Guyana Shield, suggesting derivation from a continental source of similar composition. In comparison with modern sediments, the geochemical parameters (K₂O/Na₂O, La_N/Yb_N, La_N/Sm_N, Eu/Eu¹, La/Sc, La/Y, Ce/Sc) suggest the Paja Formation was deposited at a passive margin. The Paja shales thus represent highly mature sediments recycled from deeply weathered, older, sedimentary/metasedimentary rocks, possibly in the Guyana Shield, though Na-rich volcanic/granitic rocks may have contributed to some extent.     

Metamorphic garnet pyroxenite from the 540-600 m main borehole of the Chinese Continental Scientific Drilling (CCSD) project

Compared to other mafic and ultramafic rocks from the CCSD main borehole as well as from the outcrops, rocks from the 540-600 m section is extraordinary in terms of its geophysical as well as geochemical properties. It consists of > 70% hematite-ilmenite garnet pyroxenite (HI-GPX) and < 30% intercalated rutile garnet pyroxenite (R-GPX). Whole-rock geochemical data show that HI-GPXs have: (1) relatively high V with an average of 606 ppm, but lower Nb and Ta; (2) highest TFeO, Fe₂O₃/FeO ratio, and highly variable but strong positive Eu anomalies with Eu/Eu? up to 2.9; (3) anomalously high V/Sc ratios ranging from 8.39 to 43.23, average 15.03; and (4) high amounts of hematite-ilmenite solid solutions with a very fine intergrowth structure down to nanometer scale. V/Sc ratios in the CCSD garnet pyroxenites are correlated negatively with MgO, but positively with Fe₂O₃/FeO ratios. Both suites of pyroxenites have similar rare earth elements and high field strength elements geochemistry. These features demonstrate that these pyroxenites were formed from metamorphism of high-Fe and/or -Ti gabbroic cumulates. This can account not only for low high field strength elements (HFSE) and rare earth elements (REE) but also low Nb/Ta and Zr/Hf ratios in these rocks. Seemingly negative correlation between Nb/Ta and Zr/Hf in the CCSD metabasites, not significantly affected by UHP metamorphism, is also consistent with the silicate differentiation trend in a basaltic magma chamber.     

Permian bimodal dyke of Tarim Basin, NW China: Geochemical characteristics and tectonic implications

This study reports for the first time the occurrence of bimodal dyke in the Shuigongtuan area of Bachu County, Tarim Basin, NW China. Here, quartz syenite porphyry and diabase dykes occur in direct contact showing bimodal feature. The quartz syenitic porphyry is metaluminous, enriched in K₂O + Na₂O (10–11 wt.%) and total rare earth elements (REE), with low Mg/(Mg + Fe) ratios, high LREE/HREE, and negative Eu anomalies. The chemical characteristics and tectonic discriminative diagrams show that the rocks have geochemical affinity with A-type granites. The diabase dyke shows 45–52 wt.% SiO₂ and Mg/(Mg + Fe) ratio in the range of, with high total REE, high LREE/HREE ratios and lack of Eu anomalies, broadly corresponding to tholeiitic composition. Based on low Y/Nb (as low as 0.4, and less than 1.2), enrichment in LILE and HFSE, and uniform Nb-enrichment patterns in spider diagram for the quartz syenitic porphyry, together with the geochemical patterns of the diabases, this biomodal association is interpreted to be derived from a mantle source and formed under typical within-plate environment. The quartz syenitic porphyry and diabase have Daly gap of 46 wt.%–67 wt.% in SiO₂, which is explained through formation under bimodal rifting. The quartz syenitic dyke probably formed during Early Permian (277 Ma) and has geochemical affinity with the Xiaohaizi syenitic body. We propose that magmas sourced from the mantle intruded into middle–upper crust and were emplaced as dykes, which indicate large-scale extension during the Permian in Tarim Basin. The bimodal dyke has genetic affinity with the huge volume of Permian basalts and igneous rocks (248–292 Ma) that occur in the Tarim Basin. The magmatism manifests the culmination of the major thermal event in the Tarim Basin.