Geochemistry and specific features of manganese ore formation in sediments of oceanic bioproductive zones

Processes of authigenic manganese ore formation in sediments of the northern equatorial Pacific are considered on the basis of study of the surface layer (<2 mm) of ferromanganese nodule and four micronodule size fractions from the associated surface sediment (0–7 cm). Inhomogeneity of the nodule composition is shown. The Mn/Fe ratio is maximal in samples taken from the lateral sectors of nodule at the water-sediment interface. Compositional differences of nodules are related to the preferential accumulation of microelements in iron oxyhydroxides (P, Sr, Pb, U, Bi, Th, Y, and REE), manganese hydroxides (Co, Ni, Cu, Zn, Cd, Mo, Tl, W), and lithogenous component trapped during nodule growth (Ga, Rb, Ba, and Cs). The Ce accumulation in the REE composition is maximal in the upper and lower parts of the nodule characterized by the minimal Mn/Fe values. The compositional comparison of manganese micronodules and surface layers of the nodule demonstrated that the micronodule material was subjected to a more intense reworking during the diagenesis of sediments. The micronodules are characterized by higher Mn/Fe and P/Fe ratios but lower Ni/Cu and Co/Ni ratios. The micronodules and nodules do not differ in terms of contents of Ce and Th that are least mobile elements during the diagenesis of elements. Differences in the chemical composition of micronodules and nodules are related not only to the additional input of Mn in the process of diagenesis, but also to the transformation of iron oxyhydroxides after the removal of Mn from the close association with Fe formed in the suspended matter at the stage of sedimentation.     

Geochemistry of trace and minor elements in sediments and manganese micronodules from the Angola Basin

Indicator role of trace elements in sedimentation and ore formation is considered for sediments from Station 2182 in the Angola Basin. It is shown that pelagic sediments were formed from two main sources: biogenic calcium carbonate and lithogenic sediment component compositionally similar to the miopelagic clay. Increase of the Mn/Al ratio, Ce anomaly in the REE composition, Co/Ni and Mo/W ratios, and anomalous accumulation of Tl, Pb, Bi and other microelements indicate that sediments from horizons 15–20 and 30–35 cm contain significant amounts of hydrogenic material as Fe-Mn oxyhydroxides. Manganese micronodules (MN) were extracted from different horizons (10–15, 15–20, and 30–35 cm) and analyzed to study the hydrogenic component. Their development is related to retardation of biogenic and lithogenic sedimentation. The studied manganese micronodules are represented by the hydrogenic-diagenetic formations >100 μm in size with Mn/Fe = 2.0–2.8, Co/Ni = 0.2–0.4, Ce an = 4.2–5.7, and Mo/W = 5.2–7.9. The MN content is too low to affect the major and trace element composition of sediments. The main part of Fe and Mn is confined to fraction <10 μm.     

Isotopic compositions of C,O, Sr,and S and problem of ages of the Katera and Uakit Groups,western Transbaikal region

The age of the Katera Group, which occupies a large area in the western North Muya Range and occurs 100–150 km east of the Uakit Group, is a debatable issue. Based on geological correlations with reference sections of the Baikal Group and Patom Complex, the Katera and Uakit groups were previously considered nearly coeval units and assigned to Late Precambrian (Khomentovskii and Postnikov, 2002; Salop, 1964). This was supported partly by the Sm–Nd model datings (Rytsk et al., 2007, 2009, 2011). Finds of the Paleozoic flora substantiated the revision of age of the Uakit Group and its assignment to the Late Devonian–Early Carboniferous (Gordienko et al., 2010; Minina, 2003, 2012, 2014). We have established that Sr and C isotopic compositions in carbonates of these groups differ drastically, as suggested by their different ages. Sediments of the Nyandoni Formation (Katera Group), which contains carbonates characterized by minimum values of ⁸⁷Sr/⁸⁶Sr = 0.7056 and maximum values of δ¹³C = 4.9‰, were accumulated in the first half of Late Riphean (800–850 Ma ago), whereas the overlying Barguzin Formation (⁸⁷Sr/⁸⁶Sr_min = 0.70715, δ¹³C_max= 10.5‰) was deposited at the end of Late Riphean (700–750 Ma). Judging from the isotope data, the Nerunda Formation (Uakit Group), which contains carbonates with characteristics matching the most rigorous criteria of fitness for the chemostratigraphic correlation (Sr content up to 4390 μg/g, Mn/Sr < 0.1, δ¹⁸O = 23.0 ± 1.8‰), was deposited at the end of Vendian ~550–540 Ma ago). The sequence includes thick typical carbonate horizons with very contrast carbon isotopic compositions: the lower unit has anomalous high δ¹³C values (5.8 ± 1.0‰); the upper unit, by anomalous low δ¹³C values (–5.2 ± 0.5‰]). Their Sr isotopic composition is relatively homogeneous (⁸⁷Sr/⁸⁶Sr = 0.7084 ± 0.0001) that is typical of the Late Vendian ocean. The S isotopic composition of pyrites from the Nyandoni Formation (Katera Group) (δ³⁴S = 14.1 ± 6.8‰) and pyrites from the Mukhtunny Formation (Uakit Group) (δ³⁴S = 0.7 ± 1.4‰) does not contradict the C and Sr isotopic stratigraphic data.     

Geochemistry of Rare Earth Elements in Ferromanganese Micro- and Macronodules from the Pacific Nonproductive Zone

Ferromanganese micro- and macronodules in eupelagic clays at Site 35 of the South Basin were examined in order to check the REE distribution during the ferromanganese ore formation in nonproductive zones of the Pacific Ocean. We studied host sediments and their labile fraction, ferromanganese micronodules (fractions 50–100, 100–250, 250–500, and >500 m) from eupelagic clays (horizons 37–40, 105–110, 165–175, and 189–190 cm), and buried ferromanganese micronodules (horizons 64–68, 158–159, and 165–166 cm). Based on phase analysis data, the anomalous REE enrichment of eupelagic clays from Site 35 is related to the accumulation of rare earth elements in iron hydroxophosphates. The Ce concentration, generally linked to manganese oxyhydroxides, is governed by the oxidation of Mn and Ce in oceanic surficial waters. Micronodules (Mn/Fe = 0.7–1.6) inherit compositional features of the labile fraction of sediments. The Ce, Co, and Th concentrations depend on the micronodule dimension. The enrichment of micronodules in hydrogenic or hydrothermal substance is governed by their dimension and the dominant source of suspended oxyhydroxide material. The study of buried ferromanganese micronodules revealed general regularities in the compositional evolution of oxyhydroxide matrices of ferromanganese micro- and macronodules. The compositional variation of micro- and macronodules, relative to the labile fraction of sediments, in the Pacific nonproductive zone dramatically differs from the pattern in bioproductive zones, where micronodule compositions in larger fractions are similar to those in associated macronodules and labile fractions of the host sediment as a result of the more intense suboxidative diagenesis.     

Geochemistry of the Manganese Ore Process in the Ocean: Evidence from Rare Earth Elements

Processes governing the formation of rare earth elements (REE) composition are considered for ferromanganese deposits (nodules, separate parts of nodules, and micronodules of different fractions) within the Clarion–Clipperton ore province in the Pacific Ocean. It is shown that ferromanganese oxyhydroxide deposits with different chemical compositions can be produced in sediments under similar sedimentation conditions. In areas with high bioproductivity, the size of micronodules has a positive correlation with the Mn content and Mn/Fe and P/Fe ratios and a negative correlation with Fe, P, REE, and Ce anomaly. The behavior of REE in micronodules from sediments within bioproductive zones is related to increase of the influence of diagenetic processes in sediments as a response to the growth of the size of micronodules. Distinctions in the chemical composition of micronodules and nodules are related to their interrelations with associated sediments. Micronodules grow in sediments using hydrogenous ferromanganese oxyhydroxides. As they grow, micronodules are enriched in the labile fraction of sediments reworked during diagenesis. Sources of the material of ferromanganese nodules are governed by their formation at the water bottom interface. Their upper part is formed by direct settling of iron oxyhydroxides from the bottom water, whereas the lower part is accumulated due to diagenetic processes in sediments. Differences of REE compositions in ferromanganese deposits are caused by the reduction of manganese during diagenesis and its separation from iron. Iron oxyhydroxides form a sorption complex due to the sorption of phosphate-ion from bottom and pore waters. The sorption of phosphate-ion results in an additional sorption of REE.     

Geochemistry of the authigenic ferromanganese ore formation in sediments of the Northeast Pacific Basin

Authigenic ferromanganese formations in sediments from two horizons (0–10 and 240–250 cm) located in the low/high bioproductive transitional zone of the Pacific Ocean were studied. In addition to the compositionally different two types of micronodules, crusts and ferromanganese nodules were detected in the surface horizon (0–1 cm). Three size fractions (50–100, 100–250, and 250–500 μm) of manganese micronodules were investigated. In terms of surface morphology, color, and shape, the micronodules are divided into the dull round (MN1) and angular lustrous (MN2) varieties with different mineral and chemical compositions. The dull MN1 are enriched in Mn and depleted in Fe as compared with the lustrous MN2. The Mn/Fe value in the dull MN1 varies from 13 to 14. Asbolane-buserite and birnessite are the major manganese minerals in them. The lustrous MN2 is mainly composed of vernadite with Mn/Fe = 4.3–4.8. Relative to the dull MN1, fraction 50–100 μm of the lustrous MN2 is enriched in Fe (2.6 times), W (1.8), Mo (3.2), Th (2.3), Ce (5.8), and REE (1.2–1.8). Relative to counterparts from the dull MN1, separate fractions of the lustrous MN2 are characterized by a greater compositional difference. For example, increase in the size of micronodules leads to decrease in contents of the following elements: Fe (by 10 rel %), Ce (2 times), W (2.1 times), Mo (2.2 times), and Co (1.5 times). At the same time, one can see increase in contents of other elements: Th and Cu (2.1 times), Ni (1.9 times), and REE (1.2–1.6 times). Differences in the chemical and mineral compositions of MN1 and MN2 fractions can be related to alternation of oxidative and suboxidative conditions in the sediments owing to the input of a labile organic matter, which serves as the major reducer, and the allochthonous genesis of MN2.     

Early Carboniferous intra-oceanic arc and back-arc basin system in the West Junggar,NW China

A series of Lower Carboniferous volcanic rocks occur in the Hatu, Darbut, and Baogutu areas of Xinjiang Province. Secondary ion mass spectrometry (SIMS) zircon U–Pb isotopic data indicate that two samples of these rocks coevally erupted at 324.0 ± 2.8 Ma and 324.9 ± 3.4 Ma. Three detailed profile measurements show that the volcanics include the Hatu basalt, the Baogutu andesite and dacite, and the Darbut andesite. Whole-rock compositions suggest that the Hatu volcanics are tholeiites and have a mid-ocean ridge basalt (MORB)-like signature with a small negative Nb anomaly, suggesting formation in a back-arc basin. Their isotopic compositions (?Nd(t) = +2.2 to +4.0, (⁸⁷Sr/⁸⁶Sr)i = 0.70414 to 0.70517) suggest a mixing origin from depleted to enriched mantle sources. In contrast, the Baogutu and Darbut rocks are andesite and dacite possessing a transitional tholeiite to calc–alkaline character and have E-MORB-like and OIB signatures, with a marked negative Nb anomaly and Th/Yb-enrichment, indicating that they were generated in a subduction zone setting. Isotopically, they display consistently depleted Sr–Nd isotopic compositions [(⁸⁷Sr/⁸⁶Sr)i = 0.70377–0.70469, ?Nd(t) = 1.0–5.2], suggesting that they were derived from a depleted mantle, and that fluid and sediments were involved in their petrogenesis. These features suggest that an early Carboniferous intra-oceanic arc and back-arc basin system generated the studied volcanic units in the West Junggar.     

Geochemistry of ferromanganese nodule–sediment pairs from Central Indian Ocean Basin

Fourteen ferromanganese nodule–sediment pairs from different sedimentary environments such as siliceous ooze (11), calcareous ooze (two) and red clay (one) from Central Indian Ocean Basin (CIOB) were analysed for major, trace and rare earth elements (REE) to understand the possible elemental relationship between them. Nodules from siliceous and calcareous ooze are diagenetic to early diagenetic whereas, nodule from red clay is of hydrogenetic origin. Si, Al and Ba are enriched in the sediments compared to associated nodules; K and Na are almost in the similar range in nodule–sediment pairs and Mn, Fe, Ti, Mg, P, Ni, Cu, Mo, Zn, Co, Pb, Sr, V, Y, Li and REEs are all enriched in nodules compared to associated sediments (siliceous and calcareous). Major portion of Si, Al and K in both nodules and sediments appear to be of terrigenous nature. The elements which are highly enriched in the nodules compared to associated sediments from both siliceous and calcareous ooze are Mo – (307, 273), Ni – (71, 125), Mn – (64, 87), Cu – (43, 80), Co – (23, 75), Pb – (15, 24), Zn – (9, 11) and V – (8, 19) respectively. These high enrichment ratios of elements could be due to effective diagenetic supply of metals from the underlying sediment to the nodule. Enrichment ratios of transition metals and REEs in the nodule to sediment are higher in CIOB compared to Pacific and Atlantic Ocean. Nodule from red clay, exhibit very small enrichment ratio of four with Mn and Ce while, Al, Fe, Ti, Ca, Na, K, Mg, P, Zn, Co, V, Y and REE are all enriched in red clay compared to associated nodule. This is probably due to presence of abundant smectite, fish teeth, micronodules and phillipsite in the red clay. The strong positive correlation (r ? 0.8) of Mn with Ni, Cu, Zn and Mo and a convex pattern of shale-normalized REE pattern with positive Ce-anomaly of siliceous ooze could be due to presence of abundant manganese micronodules. None of the major trace and REE exhibits any type of inter-elemental relationship between nodule and sediment pairs. Therefore, it may not be appropriate to correlate elemental behaviour between these pairs.     

Composition of manganese nodules and manganese carbonates from Loch Fyne,Scotland

Manganese nodules and manganese carbonate concretions occur in the upper 10–15 cm of the Recent sediments of Loch Fyne, Argyllshire in water depths of 180–200 m. The nodules are spherical, a few mm to 3 cm in diameter, and consist of a black, Mn-rich core and a thin, red, Fe-rich rim. The carbonate occurs as irregular concretions, 0.5–8 cm in size, and as a cement in irregular nodule and shell fragment aggregates. It partially replaces some nodule material and clastic silicate inclusions, but does not affect aragonitic and calcitic shell fragments.The nodules are approximately 75% pure oxides and contain 30% Mn and 4% Fe. In the cores, the principal mineral phase is todorokite, with a Mn/Fe ratio of 17. The rim consists of X-ray amorphous Fe and Mn oxides with a Mn/Fe ratio of 0.66. The cores are enriched, relative to Al, in K, Ba, Co, Mo, Ni and Sr while the rims contain more P, Ti, As, Pb, Y and Zn.The manganese carbonate has the composition (Mn_47.7 Ca_45.1 Mg_7.2) CO₃. Apart from Cu, all minor elements are excluded from significant substitution in the carbonate lattice.Manganese nodules and carbonates form diagenetically within the Recent sediments of Loch Fyne. This accounts for the high Mn/Fe ratios in the oxide phases and the abundance of manganese carbonate concretions. Mn concentrations in the interstitial waters of sediment cores are high (ca. 10 ppm) as also, by inference, are the dissolved carbonate concentrations.     

Constraints on the petrogenesis of Martian meteorites from the Rb-Sr and Sm-Nd isotopic systematics of the lherzolitic shergottites ALH77005 and LEW88516

Detailed Rb-Sr and Sm-Nd isotopic analyses have been completed on the lherzolitic shergottites ALH77005 and LEW88516. ALH77005 yields a Rb-Sr age of 185 ± 11 Ma and a Sm-Nd age of 173 ± 6 Ma, whereas the Rb-Sr and Sm-Nd ages of LEW88516 are 183 ± 10 and 166 ± 16 Ma, respectively. The initial Sr isotopic composition of ALH77005 is 0.71026 ± 4, and the initial ε_Nd value is +11.1 ± 0.2. These values are distinct from those of LEW88516, which has an initial Sr isotopic composition of 0.71052 ± 4 and an initial ε_Nd value of +8.2 ± 0.6. Several of the mineral and whole rock leachates lie off the Rb-Sr and Sm-Nd isochrons, indicating that the isotopic systematics of the meteorites have been disturbed. The Sm-Nd isotopic compositions of the leachates appear to be mixtures of primary igneous phosphates and an alteration component with a low ¹⁴³Nd/¹⁴⁴Nd ratio that was probably added to the meteorites on Mars. Tie lines between leachate-residue pairs from LEW88516 mineral fractions and whole rocks have nearly identical slopes that correspond to Rb-Sr ages of 90 ± 1 Ma. This age may record a major shock event that fractionated Rb/Sr from lattice sites located on mineral grain boundaries. On the other hand, the leachates could contain secondary alteration products, and the parallel slopes of the tie lines could be coincidental.Nearly identical mineral modes, compositions, and ages suggest that these meteorites are very closely related. Nevertheless, their initial Sr and Nd isotopic compositions differ outside analytical uncertainty, requiring derivation from unique sources. Assimilation-fractional-crystallization models indicate that these two lherzolitic meteorites can only be related to a common parental magma, if the assimilant has a Sr/Nd ratio near 1 and a radiogenic Sr isotopic composition. Further constraints placed on the evolved component by the geochemical and isotopic systematics of the shergottite meteorite suite suggest that it (a) formed at ∼4.5 Ga, (b) has a high La/Yb ratio, (c) is an oxidant, and (d) is basaltic in composition or is strongly enriched in incompatible elements. The composition and isotopic systematics of the evolved component are unlike any evolved lunar or terrestrial igneous rocks. Its unusual geochemical and isotopic characteristics could reflect hydrous alteration of an evolved Martian crustal component or hydrous metasomatism within the Martian mantle.     

Subduction of Indian continent beneath southern Tibet in the latest Eocene (~ 35 Ma): Insights from the Quguosha gabbros in southern Lhasa block

Geophysical data illustrate that the Indian continental lithosphere has northward subducted beneath the Tibet Plateau, reaching the Bangong–Nujiang suture in central Tibet. However, when the Indian continental lithosphere started to subduct, and whether the Indian continental crust has injected into the mantle beneath southern Lhasa block, are not clear. Here we report new results from the Quguosha gabbros of southern Lhasa block, southern Tibet. LA-ICP-MS zircon U–Pb dating of two samples gives a ca. 35 Ma formation age (i.e., the latest Eocene) for the Quguosha gabbros. The Quguosha gabbro samples are geochemically characterized by variable SiO₂ and MgO contents, strongly negative Nb–Ta–Ti and slightly negative Eu anomalies, and uniform initial ⁸⁷Sr/⁸⁶Sr (0.7056–0.7058) and ε_Nd(t) (− 2.2 to − 3.6). They exhibit Sr–Nd isotopic compositions different from those of the Jurassic–Eocene magmatic rocks with depleted Sr–Nd isotopic characteristics, but somewhat similar to those of Oligocene–Miocene K-rich magmatic rocks with enriched Sr–Nd isotopic characteristics. We therefore propose that an enriched Indian crustal component was added into the lithospheric mantle beneath southern Lhasa by continental subduction at least prior to the latest Eocene (ca. 35 Ma). We interpret the Quguosha mafic magmas to have been generated by partial melting of lithospheric mantle metasomatized by subducted continental sediments, which entered continental subduction channel(s) and then probably accreted or underplated into the overlying mantle during the northward subduction of the Indian continent. Continental subduction likely played a key role in the formation of the Tibetan plateau at an earlier date than previously thought.     

Thorium and uranium isotopes in a manganese nodule from the Peru basin determined by alpha spectrometry and thermal ionization mass spectrometry (TIMS): Are manganese supply and growth related to climate?

Thorium- and uranium isotopes were measured in a diagenetic manganese nodule from the Peru basin applying alpha- and thermal ionization mass spectrometry (TIMS). Alpha-counting of 62 samples was carried out with a depth resolution of 0.4 mm to gain a high-resolution²³⁰Th_excess profile. In addition, 17 samples were measured with TIMS to obtain precise isotope concentrations and isotope ratios. We got values of 0.06–0.59 ppb (²³⁰Th), 0.43–1.40 ppm (²³²Th), 0.09–0.49 ppb (²³⁴U) and 1.66–8.24 ppm (²³⁸U). The uranium activity ratio in the uppermost samples (1–6 mm) and in two further sections in the nodule at 12.5±1.0 mm and 27.3–33.5 mm comes close to the present ocean water value of 1.144±0.004. In two other sections of the nodule, this ratio is significantly higher, probably reflecting incorporation of diagenetic uranium. The upper 25 mm section of the Mn nodule shows a relatively smooth exponential decrease in the²³⁰Th_excess concentration (TIMS). The slope of the best fit yields a growth rate of 110 mm/Ma up to 24.5 mm depth. The section from 25 to 30.3 mm depth shows constant²³⁰Th_excess concentrations probably due to growth rates even faster than those in the top section of the nodule. From 33 to 50 mm depth, the growth rate is approximately 60 mm/Ma. Two layers in the nodule with distinct laminations (11–15 and 28–33 mm depth) probably formed during the transition from isotopic stage 8 to 7 and in stage 5e, respectively. The Mn/Fe ratio shows higher values during interglacials 5 and 7, and lower ones during glacials 4 and 6. A comparison of our data with data from adjacent sediment cores suggests (a) a variable supply of hydrothermal Mn to sediments and Mn nodules of the Peru basin or (b) suboxic conditions at the water sediment interface during periods with lower Mn/Fe ratios.     

Origin of the Dexing Cu-bearing porphyries,SE China: elemental and Sr–Nd–Pb–Hf isotopic constraints

The Dexing porphyry copper deposit, part of the circum-Pacific porphyry copper ore belt, is the largest porphyry copper deposit in China. We present new LA–ICP–MS zircon U–Pb and molybdenite Re–Os dating, bulk-rock elemental and Sr–Nd–Pb isotopic as well as in situ zircon Hf isotopic geochemistry for these ore-bearing porphyries, in an attempt to better constrain their petrogenesis. LA–ICP–MS zircon U–Pb dating shows that the Dexing porphyries were emplaced in the early Middle Jurassic (～171 Ma); molybdenite Re–Os dating indicates that the associated Cu–Mo mineralization was contemporaneous (～171 Ma) with the igneous intrusion. The rocks are mainly high-K calc-alkaline and show adakitic affinities, including high Sr and low Y and Yb contents, high Sr/Y and La/Yb ratios, and high Mg# (higher than pure crustal melts). These porphyries have initial ⁸⁷Sr/⁸⁶Sr ratios of 0.7044?0.7047, ?_Nd(T) values of –1.5 to?+0.6, and ?_Hf(T) (in situ zircon) values of?+2.6 to?+4.6. They show unusually radiogenic Pb isotopic compositions with initial ²⁰⁶Pb/²⁰⁴Pb ratios up to 18.41 and ²⁰⁷Pb/²⁰⁴Pb up to 15.61. These isotopic compositions are distinctly different from either Pacific MORB or Yangtze lower crust but are similar to the subducting sediments in the western Pacific trenches. Detailed elemental and isotopic data suggest that the Dexing porphyries were emplaced in a continental arc setting coupled with westward subduction of the palaeo-Pacific plate. Partial melting involved the subducted slab (mainly the overlying sediments), with generated melts interacting with the lithospheric mantle wedge, thereby forming the investigated high-K calc-alkaline porphyry magmas.     

Geochemical response to varying tectonic settings: an example from southern Sulawesi (Indonesia)

The South arm of Sulawesi was an active continental margin from approximately 60 to 10 Ma, when it collided with the microcontinental fragment of Buton. Pre-collisional samples analyzed for this study are characterized by a geochemical signature typical of arc volcanics: high LILE/HFSE ratios; ⁸⁷Sr/⁸⁶Sr slightly higher than MORB; ¹⁴³Nd/¹⁴⁴Nd ratios similar to MORB. Syn-collisional samples have more enriched isotopic signatures, and are relatively potassium rich. This is interpreted to reflect a larger contribution from subducted sediments, added to the mantle wedge as a silicic melt. Melting of subducted sediments is interpreted to result from a decrease in subduction rate and an increase of temperature in the slab. Magmatism that postdates the collisional event by 10 Ma is characterized by higher Nb/Y ratios than the pre- or syn-collisional samples, and Sr and Nd isotopic signatures intermediate between these two groups. This is likely to reflect melting of a subduction-modified mantle, with a significant contribution from the sub-continental lithospheric mantle. Comparison with post-collisional magmatism from other areas of the world suggests that trace element signatures are similar, but isotopic characteristics are variable. The latter are likely to reflect both the age of the sub-continental lithospheric mantle and the time lag between cessation of subduction and formation of the post-collisional magmas.     

Geochemistry, U-Pb Geochronology and Sr-Nd-Hf Isotopes of the Early Cretaceous Volcanic Rocks in the Northern Da Hinggan Mountains

Whole-rock geochemical, zircon U-Pb geochronological and Sr-Nd-Hf isotopic data are presented for the Early Cretaceous volcanic rocks from the northern Da Hinggan Mountains. The volcanic rocks generally display high SiO2(73.19–77.68 wt%) and Na2O+K2O(6.53–8.98 wt%) contents, with enrichment in Rb, Th, U, Pb and LREE, and depletion in Nb, Ta, P and Ti. Three rhyolite samples, one rhyolite porphyry sample, and one volcanic breccia sample yield weighted mean 206Pb/238 U ages of 135.1±1.2 Ma, 116.5±1.1 Ma, 121.9±1.0 Ma, 118.1±0.9 Ma and 116.9±1.4 Ma, respectively. All these rocks have moderate(87Sr/86Sr)i values of 0.704912 to 0.705896, slightly negative εNd(t) values of –1.4 to –0.1, and positive εHf(t) values of 3.7 to 8. Their zircon Hf and whole-rock Nd isotopic model ages range from 594 to 1024 Ma. These results suggest that the Early Cretaceous volcanic rocks were originated from melting of subducted oceanic crust and associated sediments during the closure of the Mongol-Okhotsk Ocean.     

Formation of the Japan Sea basin: Reassessment from Ar–Ar ages and Nd–Sr isotopic data of basement basalts of the Japan Sea and adjacent regions

Many studies have examined the Japan Sea basalts recovered during Ocean Drilling Program (ODP) Leg127/128. Of these, the ⁴⁰Ar–³⁹Ar dating undertaken is important in constraining the timing of the formation of the Japan Sea; however, the implications of their results do not appear to be fully appreciated by the geological community. In this paper, I reassess the ⁴⁰Ar–³⁹Ar age data of the basalts with reference to Nd–Sr isotopic data. The ⁴⁰Ar–³⁹Ar dating was performed on basalts somewhat enriched in large-ion lithophile elements and recovered from ODP Sites 794, 795 and the lower part of 797, yielding the plateau ages of 21.2–17.7 Ma. These basalts show the Nd–Sr isotopic signature of a moderately depleted mantle source (ε_Nd: 0.6–6.9). In contrast, the basalts from the upper part of Site 797 have yet to be dated due to their low K content, although their Nd isotopic compositions are similar to that of MORB (ε_Nd: 8.4–10.4). By analogy to the secular Nd–Sr isotopic trends reported for Sikhote-Alin and northeast Japan, the age of the upper basalts at Site 797 may be inferred to be younger than the lower basalts, probably around 16 Ma. The Nd–Sr isotopic compositions of the Japan Sea basalts have been interpreted in terms of eastward asthenospheric flow, as have the lavas of the Sikhote-Alin and northeastern Japan. The timing of volcanic activity in the Japan Sea region (i.e., from 21.2 to 14.86 Ma) is consistent with the timing of rotational crustal movements inferred from paleomagnetic studies of the Japanese Islands (i.e., 14.8–4.2 Ma for southwest Japan and 16.5–14.4 Ma for northeast Japan).     

Petrology and Sr–Nd–Hf isotope geochemistry of gabbro xenoliths from the Hyblean Plateau: a MARID reservoir beneath SE Sicily?

In situ trace-element and isotopic (⁸⁷Sr/⁸⁶Sr) data and whole-rock Sr–Nd–Hf data on 12 gabbro xenoliths from the Hyblean Plateau (south-eastern Sicily) illustrate the complex petrogenetic evolution of this lithospheric segment. The gabbros formed by precipitation of plagioclase + clinopyroxene from a HIMU-type alkaline melt, then were cryptically metasomatized by a low-Rb, high-⁸⁷Sr/⁸⁶Sr fluid, and finally infiltrated by an exotic, late Fe–Ti-rich melt with ⁸⁷Sr/⁸⁶Sr ~ 0.7055, carrying high concentrations of Sr, Rb and HFSE. The geochemical and isotopic features of both the metasomatizing fluid and the Fe–Ti-rich melt are compatible with their common derivation by the progressive melting of an amphibole–phlogopite–ilmenite metasomatic domain (MARID-type?) that probably resided within the subcontinental lithospheric mantle. Therefore, both the astenosphere and the lithosphere underneath the Hyblean Plateau contributed to the petrogenesis of the gabbros. Sm–Nd dating yields an age of 253 ± 60 Ma for the cumulitic pile, roughly coinciding with a hydrothermal event recorded by crustal zircons in the area. We suggest that the Hyblean Plateau suffered a thermal event—probably related to lithospheric thinning and upwelling and melting of the asthenosphere—in Permo-Triassic time (the opening of the Ionian Basin?). The induced perturbation in the lithosphere caused consequent melting of some previously metasomatised portions.     

Post-collisional adakitic volcanism in the eastern part of the Sakarya Zone, Turkey: evidence for slab and crustal melting

New geochemical and isotopic data for post-collisional Early Eocene and Late Miocene adakitic rocks from the eastern part of the Sakarya Zone, Turkey, indicate that slab and lower crustal melting, respectively, played key roles in the petrogenesis of these rocks. The Early Eocene Yoncal?k dacite (54.4 Ma) exhibits high Sr/Y and La/Yb ratios, low Y and HREE concentrations, moderate Mg# (44–65), and relatively high εNd and low ISr values, similar to adakites formed by slab melting associated with subduction. Geochemical composition of the Yoncal?k dacite cannot be explained by simple crystal fractionation and/or crustal contamination of andesitic parent magma, but is consistent with the participation of different proportions of melts derived from subducted basalt and sediments. Sr/Y correlates horizontally with Rb/Y, and Pb/Nd correlates vertically with Nd isotopic composition, indicating that Sr and Pb budgets are strongly controlled by melt addition from the subducting slab, whereas positive correlations between Th/Nd and Pb/Nd, and Rb/Y and Nb/Y point to some contribution of sediment melt. In addition to low concentrations of heavy rare earth elements (~2–3 times chondrite), a systematic decrease in their concentrations and Nb/Ta ratios with increasing SiO₂ contents suggests that slab partial melting occurred in the garnet stability field and that these elements were mobilized by fluid flux. These geochemical and isotopic signatures are best explained by slab breakoff and fusion shortly after the initiation of collision. Although the Late Micone Tavda?? rhyolite (8.75 Ma) has some geochemical features identical to adakites, such as high Sr/Y and La/Yb ratios, low Y and HREE concentrations, other requirements, such as sodic andesite and/or dacite with relatively high MgO and Mg# (>50), relatively high Ni and Cr, low K₂O/Na₂O (<0.4), high Sr (>400 ppm), for slab-derived adakites are not provided. It is sodic in composition and shows no traces of fractionation from dacitic parent magma. Low Nd and high Sr isotope ratios suggest derivation by partial fusion of calc-alkaline, juvenile crust with high Sr/Y and La/Yb ratios.     

Petrology of an intrusion-related high-grade migmatite: implications for partial melting of metasedimentary rocks and leucosome-forming processes

Intrusion-related migmatites comprise a substantial part of the high-grade part of the southern Damara orogen, Namibia which is dominated by Al-rich metasedimentary rocks and various granites. Migmatites consist of melanosomes with biotite+sillimanite+garnet+cordierite+hercynite and leucosomes are garnet- and cordierite-bearing. Metamorphic grade throughout the area is in the upper amphibolite to lower granulite facies (5–6 kbar at 730–750 °C). Field evidence, petrographic observations, chemical data and mass balance calculations suggest that intrusion of granitic magmas and concomitant partial melting of metasedimentary units were the main processes for the generation of the migmatites. The intruding melts were significantly modified by magma mixing with in situ partial melts, accumulation of mainly feldspar and contamination with garnet from the wall rocks. However, it is suggested that these melts originally represented disequilibrium melts from a metasedimentary protolith. The occurrence of LILE-, HFSE- and LREE-enriched and -depleted residues within the leucosomes implies that both quartzo-feldspathic and pelitic rocks were subjected to partial melting. Isotope ratios of the leucosomes are rather constant (¹⁴³Nd/¹⁴⁴Nd (500 Ma): 0.511718–0.511754, ε Nd (500 Ma): ?3.54 to ?5.11) and Sr (⁸⁷Sr/⁸⁶Sr (500 Ma): 0.714119–0.714686), the metasedimentary units have rather constant Nd isotope ratios (¹⁴³Nd/¹⁴⁴Nd (500 Ma): 0.511622–0.511789, ε Nd (500 Ma): ?3.70 to ?6.93) but variable Sr isotope ratios Sr (⁸⁷Sr/⁸⁶Sr (500 Ma): 0.713527–0.722268). The most restitic melanosome MEL 4 has a Sr isotopic composition of ⁸⁷Sr/⁸⁶Sr (500 Ma): 0.729380. Oxygen isotopes do not mirror the proposed contamination process, due to the equally high δ¹⁸O contents of metasediments and crustal melts. However, the most LILE-depleted residue MEL 4 shows the lowest δ¹⁸O value (<10). Mass balance calculations suggest high degrees of partial melting (20–40%). It is concluded that partial melting was promoted by heat transfer and release of a fluid phase from the intruding granites. High degrees of partial melting can be reached as long as the available H₂O, derived from the crystallization of the intruding granites, is efficiently recycled within the rock volume. Due to the limited amounts of in situ melting, it seems likely that such regional migmatite terranes are not the sources for large intrusive granite bodies. The high geothermal gradient inferred from the metamorphic conditions was probably caused by exhumation of deep crustal rocks and contemporaneous intrusion of huge masses of granitoid magmas. The Davetsaub area represents an example of migmatites formed at moderate pressures and high temperatures, and illustrates some of the reactions that may modify leucosome compositions. The area provides constraints on melting processes operating in high-grade metasedimentary rocks.     

The Sr isotopic characterization and Pb-Pb age of carbonate rocks from the Satka formation,the Lower Riphean Burzyan Group of the southern Urals

The Rb-Sr and U-Pb systematics are studied in carbonate deposits of the Satka and Suran formations corresponding to middle horizons of the Lower Riphean Burzyan Group in the Taratash and Yamantau anticlinoria, respectively, the southern Urals. The least altered rock samples retaining the ⁸⁷Sr/⁸⁶Sr ratio of sedimentation basin have been selected for analysis using the original method of leaching the secondary carbonate phases and based on strict geochemical criteria of the retentivity (Mn/Sr < 0.2, Fe/Sr < 5 and Mg/Ca < 0.024). The stepwise dissolution in 0.5 N HBr has been used to enrich samples in the primary carbonate phase before the Pb-Pb dating. Three (L-4 to L-6) of seven consecutive carbonate fractions obtained by the step-wise leaching are most enriched in the primary carbonate (in terms of the U-Pb systematics). In the ²⁰⁶Pb/²⁰⁴Pb-²⁰⁷Pb/²⁰⁴Pb diagram, data points of these fractions plot along an isochron determining age of 1550 ± 30 Ma (MSWD = 0.7) for the upper member of the Satka Formation. The initial ⁸⁷Sr/⁸⁶Sr ratio in the least altered limestones of this formation is within the range of 0.70460–0.70480. Generalization of the Sr isotopic data published for the Riphean carbonates from different continents showed that 1650–1350 Ma ago the ⁸⁷Sr/⁸⁶Sr ratio in the world ocean was low, slightly ranging from 0.70456 to 0.70494 and suggesting the prevalent impact of mantle flux.