Investigation of the fate of nitrogen in Palaeozoic shales of the Central European Basin

Nitrogen geochemistry of Upper Carboniferous shales from the Central European Basin (CEB) was investigated by elemental analysis, stable isotope mass spectrometry and non-isothermal pyrolysis. Total N-contents of Namurian shales from four deep wells (4400–7000 m) in NE Germany ranged between 520 and 2680 ppm. Up to 90% of this nitrogen occurs as ammonium in minerals with δ¹⁵N values between + 1‰ and + 3.5‰. Low nitrogen contents (down to 460 ppm) and high δ¹⁵N values (up to + 5.6‰) in one well in the basin centre suggest a large-scale release of nitrogen associated with isotopic fractionation. Pyrolytic liberation of N₂ from pelagic Namurian A shales of NW and NE Germany occurred at significantly lower temperatures than from paralic Namurian B shales and terrestrial Westphalian samples. On-line isotope analysis of N₂ liberated between 400 and 1200 °C indicates the presence of precursor pools with different thermal stability and nitrogen isotopic composition.     

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.     

Zr-rich accessory minerals (titanite, perrierite, zirconolite, baddeleyite) record strong oxidation associated with magma mixing in the south Peruvian potassic province

The Oroscocha Quaternary volcano, in the Inner Arc Domain of the Andean Cordillera (southern Peru), emitted peraluminous rhyolites and trachydacites that entrained decimetric to millimetric lamprophyric blobs. These latter show kersantite modal compositions (equal proportion of groundmass plagioclase and K-feldspar) and potassic bulk-rock compositions (1<K₂O/Na₂O<2; 6.7–7.2 wt.% CaO). Kersantite blobs have shapes and microstructures consistent with an origin from a mixing process between mafic potassic melts and rhyolitic melts. Both melts did exchange their phenocrysts during the mixing process. In addition to index minerals of lamprophyres (Ba–Ti–phlogopite, F-rich apatite, andesine and Ca-rich sanidine), the groundmass of kersantite blobs displays essenite-rich diopside (up to 22 mol%), Ti-poor magnetite microlites, Ti-poor hematite microlites and a series of Ca–Ti–Zr- and REE-rich accessory minerals that have never been reported from lamprophyres. Titanite [up to 5.3 wt.% ZrO₂ and 5.2 wt.% (Y₂O₃ + REE₂O₃)] and Zr- and Ca-rich perrierite (up to 7.2 wt.% ZrO₂ and 10.8 wt.% CaO) predate LREE- and iron-rich zirconolite and Fe-, Ti-, Hf-, Nb- and Ce-rich baddeleyite (up to 5.3 wt.% Fe₂O₃, 3.2 wt.% TiO₂, 1.5 wt.% HfO₂, 1.2 wt.% Nb₂O₅, 0.25 wt.% CeO₂) in the crystallization order of the groundmass. Isomorphic substitutions suggest iron to occur as Fe³⁺ in all the accessory phases. This feature, the essenitic substitution in the clinopyroxene and the occurrence of hematite microlites, all indicate a drastic increase of the oxygen fugacity (from FMQ − 1 to FMQ + 5 log units) well above the HM synthetic buffer within a narrow temperature range (1100–1000 °C). Such a late-magmatic oxidation is ascribed to assimilation of water from the felsic melts during magma mixing, followed by rapid degassing and water dissociation during eruption of host felsic lavas. Thus, magma mixing involving felsic melt end-members provides a mechanism for mafic potassic melts to be oxidized beyond the HM synthetic buffer curve.     

11 Å tobermorite from cement bypass dust and waste container glass: A feasibility study

A novel one-step hydrothermal synthesis of 11 Å tobermorite, a cation exchanger, from a unique combination of waste materials is reported. 11 Å tobermorite was prepared from stoicheiometric quantities of cement bypass dust and waste container glass at 100 °C in water. The product also comprised 10 wt.% calcite and trace quartz as residual parent phases from the cement bypass dust. In a batch sorption study at 20 °C the uptakes of Cd²⁺ and Pb²⁺ by the waste-derived tobermorite product were found to be 171 mg g^− 1 and 467 mg g^− 1, respectively, and in both cases the removal process could be described using a simple pseudo-second-order rate model (k₂ = 2.30 × 10^− 5 g mg^− 1 min^− 1 and 5.09 × 10^− 5 g mg^− 1 min^− 1, respectively). The sorption characteristics of the 11 Å tobermorite are compared with those of other waste-derived sorbents and potential applications are discussed.     

Petrology and CHIME geochronology of Pan-African high K and Sr/Y granitoids in the Nkambe area, Cameroon

The Central African Belt in the Nkambe area, northwestern Cameroon represents a collisional zone between the Saharan metacraton and the Congo craton during the Pan-African orogeny, and exposes a variety of granitoids including foliated and massive biotite monzogranites in syn- and post-kinematic settings. Foliated and massive biotite monzogranites have almost identical high-K calc-alkaline compositions, with 73–67 wt.% SiO₂, 17–13 wt.% Al₂O₃, 2.1–0.9 wt.% CaO, 4.4–2.7 wt.% Na₂O and 6.3–4.4 wt.% K₂O. High concentrations of Rb (264–96 ppm), Sr (976–117 ppm), Ba (3680–490 ppm) and Zr (494–99 ppm), with low concentrations of Y (mostly< 20 ppm with a range 54–6) and Nb (up to 24 ppm) suggest that the monzogranites intruded in collisional and post-collisional settings. The Sr/Y ratio ranges from 25 to 89. K, Rb and Ba resided in a single major phase such as K-feldspar in the source. Garnet was present in the source and remained as restite at the site of magma generation. This high K₂O and Sr/Y granitic magma was generated by partial melting of a granitic protolith under high-pressure and H₂O undersaturated conditions where garnet coexists with K-feldspar, albitic plagioclase. CHIME (chemical Th–U-total Pb isochron method) dating of zircon yields ages of 569 ± 12–558 ± 24 Ma for the foliated biotite monzogranite and 533 ± 12–524 ± 28 Ma for the massive biotite monzogranite indicating that the collision forming the Central African Belt continued in to Ediacaran (ca 560 Ma).     

Late Paleozoic underplating in North Xinjiang: Evidence from shoshonites and adakites

Shoshonitic series volcanic rocks (SSVR) and adakites are widely distributed in the Permian terrestrial volcanic strata of the Yishijilike–Awulale range of west Tianshan, north Xinjiang, China. Isotopic dating yields Permian ages of 280–250 Ma. The SSVR include absarokite, shoshonite and banakite which are characterized by enrichment of alkalis, particularly in K, combined with lower Ti, higher Al (A/NKC = 0.70–0.99, metaluminous) and Fe₂O₃ > FeO. The SSVR that are rich in LILE with high REE contents and Eu/Eu range from 0.59 to 1.30. They are rich in LREE ((La/Yb)_N 2.15–11.97) and depleted in Nb, Ta and Ti (TNT negative anomalies). The adakites are metaluminous to weakly peraluminous (A/NKC = 0.85-1.16) and belong to the high-SiO₂ type of adakite (HSA, SiO₂ = 62%–71%). They are characterized by lower ΣREE with strong LREE enrichment ((La/Yb)_N 13–35). Pronounced positive Eu anomalies (Eu/Eu = 1.02–1.27), very low Yb contents and distinct TNT-negative anomalies are evident. The SSVR have ε_Nd(t) (+ 1.28 to + 4.92) and (⁸⁷Sr/⁸⁶Sr)_i (0.7041–0.7057) that are similar to adakites in the regions which are characterized by ε_Nd(t) = 0.95 to + 5.69 and (⁸⁷Sr/⁸⁶Sr)_i = 0.7050–0.7053. Trace element, REE and Sr/Nd isotopic compositions suggest that both SSVR and adakites possess similar source regions associated with underplated mantle-derived basaltic materials. Lithosphere extension driven by magmatic underplating was responsible for the generation of both the SSVR and adakites. This magmatism serves as a petrological indicator of underplating during the Permian. Obviously thickened crust (62–52 km), a complex Moho discontinuity, high heat flow (~ 100 mw·m^− 2), widespread contemporary alkali-rich granites, basic dike swarms (K–Ar ages of 187–271 Ma, Ar–Ar ages of 174–270 Ma and Rb–Sr ages of 255 ± 28 Ma; ε_Nd(t) + 1.84 to + 10.1; (⁸⁷Sr/⁸⁶Sr)_i 0.7035 and 0.7065), and basic granulites (SHRIMP U–Pb age of 268–279 ± 5.6 Ma) provide additional evidences for the underplating event in this area during Permian.     

Upper crustal abundances of trace elements: A revision and update

We report new estimates of abundances of rarely analyzed elements (As, B, Be, Bi, Cd, Ge, In, Mo, Sb, Sn, Te, Tl, W) in the upper continental crust based on precise ICP-MS analyses of well-characterized upper crustal samples (shales, pelites, loess, graywackes, granitoids and their composites) from Australia, China, Europe, New Zealand and North American. Obtaining a better understanding of the upper crustal abundance and associated uncertainties of these elements is important in placing better constraints on bulk crust composition and, from that, whole Earth models of element cycling and crust generation. We also present revised abundance estimates of some more commonly analyzed trace elements (Li, Cr, Ni, and Tm) that vary by > 20% compared to previous estimates. The new estimates are mainly based on significant (r² > 0.6) inter-element correlations observed in clastic sediments and sedimentary rocks, which yield upper continental crust elemental ratios that are used in conjunction with well-determined abundances for certain key elements to place constraints on the concentrations of the rarely analyzed elements. Using the well-established upper crustal abundances of La (31 ppm), Th (10.5 ppm), Al₂O₃ (15.40%), K₂O (2.80%) and Fe₂O₃ (5.92%), these ratios lead to revised upper crustal abundances of B = 47 ppm, Bi = 0.23 ppm, Cr = 73 ppm, Li = 41 ppm, Ni = 34 ppm, Sb = 0.075, Te = 0.027 ppm, Tl = 0.53 ppm and W = 1.4 ppm. No significant correlations exist between Mo and Cd and other elements in the clastic sediments and sedimentary rocks, probably due to their enrichment in organic carbon. We thus calculate abundances of these elements by assuming the upper continental crust consists of 65% granitoid rocks plus 35% clastic sedimentary rocks. The validity of this approach is supported by the similarity of SiO₂, Al₂O₃, La and Th abundances calculated in this way with their upper crustal abundances given in Rudnick and Gao [Rudnick, R., Gao, S., 2003. Composition of the continental crust. In: Rudnick, R.L. (Ed.), The Crust. In: Holland, H.D., Turekian, K.K. (Eds.), Treatise on Geochemistry, vol. 3. Elsevier–Pergamon, Oxford, pp. 1–64.]. The upper crustal abundances thus obtained are Mo = 0.6 ppm and Cd = 0.06 ppm. Our data also suggest a  20% increase of the Tm, Yb and Lu abundances reported in Rudnick and Gao [Rudnick, R., Gao, S., 2003. Composition of the continental crust. In: Rudnick, R.L. (Ed.), The Crust. In: Holland, H.D., Turekian, K.K. (Eds.), Treatise on Geochemistry, vol. 3. Elsevier–Pergamon, Oxford, pp. 1–64.].     

Geology and geochemistry of the adjacent Changkeng gold and Fuwang silver deposits, Guangdong Province, South China

The Changkeng Au and Fuwang Ag deposits represent an economically significant and distinct member of the Au–Ag deposit association in China. The two deposits are immediately adjacent, but the Au and Ag orebodies separated from each other. Ores in the Au deposit, located at the upper stratigraphic section and in the southern parts of the orefield, contain low Ag contents (< 11 ppm); the Ag orebodies, in the lower stratigraphic section, are Au-poor (< 0.2 ppm). Changkeng is hosted in brecciated cherts and jasperoidal quartz and is characterized by disseminated ore minerals. Fuwang, hosted in the Lower Carboniferous Zimenqiao group bioclastic limestone, has vein and veinlet mineralization associated with alteration comprised of quartz, carbonate, sericite, and sulfides. Homogenization temperatures of fluid inclusions from quartz veinlets in the Changkeng and Fuwang deposits are in the range of 210 ± 80 °C and 230 ± 50 °C, respectively. Salinities of fluid inclusions from the two deposits range from 1.6 to 7.3 wt.% and 1.6 to 2.6 wt.% equiv. NaCl, respectively. The δD_H2O, δ¹⁸O_H2O, δ¹³C_CO2 and ³He/⁴He values of the fluid inclusions from the Changkeng deposit range from − 80‰ to − 30‰, − 7.8‰ to − 3.0‰, − 16.6‰ to − 17.0‰ and 0.0100 to 0.0054 Ra, respectively. The δD_H2O, δ¹⁸O_H2O, δ¹³C_CO2 and ³He/⁴He values of fluid inclusions from the Fuwang deposit range from − 59‰ to − 45‰, − 0.9‰ to 4.1‰, − 6.7‰ to − 0.6‰ and 0.5930 to 0.8357 Ra, respectively. The δD_H2O, δ¹⁸O_H2O, δ¹³C_CO2 and ³He/⁴He values of the fluid inclusions suggest the ore fluids of the Changkeng Au-ore come from the meteoric water and the ore fluids of the Fuwang Ag-ore are derived from mixing of magmatic water and meteoric water. The two deposits also show different Pb-isotopic signatures. The Changkeng deposit has Pb isotope ratios (²⁰⁶Pb/²⁰⁴Pb: 18.580 to 19.251, ²⁰⁷Pb/²⁰⁴Pb: 15.672 to 15.801, ²⁰⁸Pb/²⁰⁴Pb: 38.700 to 39.104) similar to those (²⁰⁶Pb/²⁰⁴Pb: 18.578 to 19.433, ²⁰⁷Pb/²⁰⁴Pb: 15.640 to 15.775, ²⁰⁸Pb/²⁰⁴Pb: 38.925 to 39.920) of its host rocks and different from those (²⁰⁶Pb/²⁰⁴Pb: 18.820 to 18.891, ²⁰⁷Pb/²⁰⁴Pb: 15.848 to 15.914, ²⁰⁸Pb/²⁰⁴Pb: 39.579 to 39.786) of the Fuwang deposit. The different signatures indicate different sources of ore-forming material. Rb–Sr isochron age (68 ± 6 Ma) and ⁴⁰Ar–³⁹Ar age (64.3 ± 0.1 Ma) of the ore-related quartz veins from the Ag deposit indicate that the Fuwang deposit formed during the Cenozoic Himalayan tectonomagmatic event. Crosscutting relationships suggests that Au-ore predates Ag-ore. The adjacent Changkeng and Fuwang deposits could, however, represent a single evolved hydrothermal system. The ore fluids initially deposited Au in the brecciated siliceous rocks, and then mixing with the magmatic water resulted in Ag deposition within fracture zones in the limestone. The deposits are alternatively the product of the superposition of two different geological events. Age evidence for the Fuwang deposit, together with the Xiqiaoshan Tertiary volcanic-hosted Ag deposit in the same area, indicates that the Pacific Coastal Volcanic Belt in the South China Fold Belt has greater potential for Himalayan precious metal mineralization than previous realized.     

Hydrochemistry and isotope compositions of groundwater from the Shihongtan sandstone-hosted uranium deposit, Xinjiang, NW China

Groundwaters and surface water in the Shihongtan sandstone-hosted U ore district, Xinjiang, NW China, were sampled and analyzed for their major-, and trace element concentrations and oxygen, hydrogen, boron and strontium isotope compositions in order to assess the possible origins of the waters and water–rock interactions that occurred in the deep aquifer system. The waters in the study district have been grouped into three hydrochemical facies: Facies 1, potable spring-water, is a pH neutral (7.0), Na–Ca–HCO₃ type water with low total dissolved solids (TDS; 0.2 g/l, fresh) and has δ¹⁸O of − 8.3‰, δD of − 48.2‰,δ¹¹B of 1.5‰, and ⁸⁷Sr/⁸⁶Sr of 0.70627. Facies 2 groundwaters are mildly acidic to mildly alkaline (pH of 6.5–8.0, mean 7.3), Na–Ca–Mg–Cl–SO₄ type waters with moderate TDS (8.2 g/l–17.2 g/l, mean 9.3 g/l, brackish) and haveδ¹⁸O values in the − 5.8‰ to − 9.3‰ range (mean − 8.1‰), δD values in the − 20.8‰ to − 85.5‰ range (mean − 47.0‰),δ¹¹B values in the + 9.5‰ to + 39.1‰ range (mean + 17.1‰), and ⁸⁷Sr/⁸⁶Sr values in the 0.70595 to 0.70975 range (mean 0.70826). Facies 3, Aiting Lake water, is a mildly alkaline (pH = 7.4), Na–Ca–Mg–Cl–SO₄ type water with the highest TDS (249.1 g/l, brine) and has δ¹⁸O of − 2.8‰, δD of − 45.8‰,δ¹¹B of 21.2‰, and ⁸⁷Sr/⁸⁶Sr of 0.70840. The waters from the study district show a systematic increase in major, trace element and TDS concentrations and δ¹¹B values along the pathway of groundwater migration which can only be interpreted in terms of water–rock interaction at depth and strong surface evaporation. The hydrochemical and isotopic data presented here confirm that the groundwaters in the Shihongtan ore district are the combined result of migration, water–rock interaction and mixing of meteoric water with connate waters contained in sediments.     

Continuity of the North Qilian and North Qinling orogenic belts, Central Orogenic System of China: Evidence from newly discovered Paleozoic adakitic rocks

Adakitic intrusive rocks of  430–450 Ma were discovered in the North Qilian orogenic belt, the western section of the Central Orogenic System (COS) in China. These adakitic rocks were lower crust melts rather than slab melts as indicated by their crustal Ce/Pb, Nb/U, Ti/Eu, and Nd/Sm ratios and radiogenically enriched (⁸⁷Sr/⁸⁶Sr)_i of 0.7053–0.7066 and ε_Nd(t) of − 0.9 to − 1.7. While they are all characterized by low Yb (< 1.1 ppm) and Y (< 11.5 ppm) abundances with high Sr/Y (> 65) and (La/Yb)_N (> 13.7) ratios, these adakitic rocks are classified into the low-MgO–Ni–Cr and high-MgO–Ni–Cr groups. The low-MgO samples were derived from partial melting of thickened lower crust, whereas the high-MgO samples were melts from delaminated lower crust, which subsequently interacted with mantle peridotite upon ascent. Adakitic rocks from the adjacent North Qinling orogenic belt also originated from thickened lower crust at  430 Ma. In addition, the North Qilian and North Qinling orogenic belts both consist of lithological assemblages varying from subduction-accretionary complexes at south to central arc assemblages, which include adakitic rocks, then to backarc phases at north. Such a sequence reflects northward subduction of the Qilian and Qinling oceans. In these two orogenic belts, the occurrence of adakitic rocks of common origin and ages together with the similarities in tectonic configurations and lithological assemblages are considered to be the evidence for the continuity between eastern Qilian and western Qinling, forming a > 1000 km Early Paleozoic orogenic belt. In such a tectonic configuration, the Qilian and Qinling oceans that subducted from south possibly represent parts of the large “Proto-Tethyan Ocean”. This inference is supported by the coexistence of Early Paleozoic coral and trilobite specimens from Asia, America and Australia in the North Qilian orogenic belt. Post-400 Ma volcanic rocks occur in the North Qinling orogenic belt but are absent in the North Qilian orogenic belt, indicating that these two orogenic belts underwent distinct evolution history after the closure of the Proto-Tethyan Ocean ( 420 Ma).     

Comparison of methods for the estimation of pyrite oxidation rate in a waste rock pile at Mine Doyon site, Quebec, Canada

Several methods were evaluated and compared for the estimation of pyrite oxidation rates (POR) in waste rock at Mine Doyon, Quebec, Canada. Methods based on data collected in situ, such as the interpretation of temperature and oxygen concentration profiles (TOP) measured in the waste rock pile and pyrite mass balance (PMB) on solid phase samples were compared with the oxygen consumption measurements (OCM) in closed chamber in the laboratory. A 1-D analytical solution to a gas and heat transport equation used temperature and oxygen profiles (TOP) measured in the pile for the preliminary POR estimates at a site close to the slope of the pile (Site 6) and in the core of the pile (Site 7). Resulting POR values were 1.1 × 10^− 9 mol(O₂) kg^− 1 s^− 1 and 1.0 × 10^− 10 mol(O₂) kg^− 1 s^− 1 for the slope site and the core site, respectively. Oxidation rates based on pyrite mass balance (PMB) calculations for solid samples were 2.21 × 10^− 9 mol(O₂) kg^− 1 s^− 1 and 2.03 × 10^− 9 mol(O₂) kg^− 1 s^− 1, respectively, for the same slope and core sites, but the difference between sites was within the error margin. The OCM measurements in the laboratory on fresh waste rock samples yielded higher POR values than field methods, with average oxidation rate of 6.7 × 10^− 8 mol(O₂) kg^− 1 s^− 1. However, the OCM results on weathered and decomposed material from the rock stockpile (average oxidation rate 3.4 × 10^− 9 mol(O₂) kg^− 1 s^− 1) were consistent with results from the field-based estimates. When POR values based on fresh material are excluded, the remaining POR values for all methods range from 1.0 × 10^− 10 to 3.4 × 10^− 9 mol(O₂) kg^− 1 s^− 1. The lowest estimated value (1.0 × 10^− 10 mol(O₂) kg^− 1 s^− 1) was based on TOP estimates in the interior of the pile where oxygen transport was limited by diffusion from the surface. These results suggest that small-scale OCM laboratory experiments may provide relatively representative values of POR in the zones of waste rock piles in which oxygen transport is not dominated by diffusion.     

Combined Sr isotope and trace element analysis of melt inclusions at sub-ng levels using micro-milling, TIMS and ICPMS

This paper describes a technique, which allows precise and accurate Sr isotope measurement combined with trace element analysis of individual melt inclusions, of sample sizes  1 ng of Sr. The technique involves sampling by micro-milling, chemical dissolution, micro Sr column chemistry, TIMS, and ICPMS analyses. A 10% aliquot of each sample solution is used for trace element analysis by double focusing magnetic sector field ICPMS, while Sr is chemically separated from the remaining 90% and used for ⁸⁷Sr/⁸⁶Sr determinations by TIMS.During the development of the technique outlined above, we documented in detail the potential sources of blank contributions and their magnitude. The average size and Sr isotope composition of our laboratory total procedural blank during this study was 5.4 pg ± 0.3 pg Sr (n = 21) with an ⁸⁷Sr/⁸⁶Sr of 0.7111 ± 0.0002 (2SE, n = 3). The total procedural Rb blank was 1.9 ± 0.7 pg (n = 21). The total procedural blank was found to have minimal effect (< 150 ppm shift) on the ⁸⁷Sr/⁸⁶Sr of sample material containing down to  250 pg Sr. Applying a blank correction allows ‘in house’ standards of this size to be corrected back to within 175 ppm of their accepted values. By applying blank corrections we can confidently measure the Sr isotope composition on sample sizes down to  25 pg Sr to an accuracy better than 400 ppm.The utility of the technique is illustrated by application to a suite of melt inclusions from NW Iceland and their host olivines. It is shown that the effect of a small amount of entrainment of the host olivine during sampling of 50 μm melt inclusions has a negligible effect on the measured Sr isotope and trace element composition. Furthermore, where melt inclusions are < 50 μm it is possible to obtain Sr isotope and trace element data on multiple melt inclusions hosted in a single olivine. This provides similar information to that of the single melt inclusions.     

Distribution of copper, zinc, lead and cadmium concentrations in stream sediments from the Mapocho River in Santiago, Chile

The Mapocho river, which crosses downtown Santiago, is one of the most important rivers in contact with a population of about six million inhabitants. Anthropogenic activities, industrialization, farming activities, transport, urbanization, animal and human excretions, domestic wastes and copper mining have affected the river, contaminating it and its sediments with heavy metals. Concentration and distribution of Cu, Zn, Pb and Cd were studied with the purpose of determining their bioavailability and their relation with the characteristics of the sediments. Freshly deposited seasonal sediments were collected from 0–8 cm depths from 6 locations (S₁ to S₆) along the 30-km long channel length, in the four seasons of year on the following dates: May 2001 (D₁, autumn); August 2001 (D₂, winter); October 2001 (D₃, spring) and January 2002 (D₄, summer). The dried samples were sifted to obtain the < 63-μm sediment fraction, since it has been shown that large amounts of heavy metals are bound in the fine-grained fraction of the sediment. Cu and Zn were analyzed by atomic absorption spectrophotometry and Pb and Cd by square wave anodic stripping voltammetry. The highest concentrations of Cu (2850 μg g^− 1) were found in the northern part of the river (S₁, average D₁–D₄), near the mountains and a copper mine, and then decreased downstream to 209 μg g^− 1 (S₆). Total Zn showed an irregular variation, with higher values at S₁ (1290 μg g^− 1) and high values in some winter sampling (1384 μg g^− 1 S₄, S₅–D₂). Pb showed different trends, increasing from S₁ to S₆ (17 to 61 μg g^− 1), with the highest values in the summer samples (83 μg g^− 1, S₄–S₆, D₄), and total Cd increased slightly from mean values of 0.2 and 0.5 μg g^− 1. Partition into five fractions was made using Tessier's analytical sequential extraction technique; the residue was treated with aqua regia for recovery studies, although this step is not part of the Tessier procedure. The results show that Cu, Zn and Pb in the sediments were dependent on the sampling places along the river, and variation in two years was low (D₁–D₄). The highest values of total organic matter, carbonate and conductivity were found in S₆, which has the smallest size particles, while at S₁ the sediments were predominantly sand and contain larger amounts of silica. Cu associated with carbonate decreased gradually from 58% (1771 μg g^− 1, S₁) to 16% (32 μg g^− 1, S₆); Cu bonded to reducible fraction was almost constant (33% to 37%), and Cu associated with oxidizable fraction increased from 7% (S₁) to 34% (S₆), but copper content was lower (214 to 68 μg g^− 1). Zn had a similar fractionation profile. However, Pb bound to oxidizable fraction did not show significant percent variation along the river (20% to 19%), but the amount bounded was 4 to 12 μg g^− 1. The residual fraction increased from 24% to 41% (5 to 25 μg g^− 1, S₁ to S₆). The distribution of Cd in the sediment was almost independent of the sampling stations and was bound to carbonate, reducible and residual fraction in similar proportion. Cu and Zn at S₁ were mainly bound to carbonates and reducible phases with 91% and 73% (2779 and 965 μg g^− 1, respectively), and with a change in the pH and/or the redox potential of the sediment–water system, these contaminants could easily enter the food chain. In S₆ the amount of Cu and Zn in these phases was 50% and 53% (100 to 313 μg g^− 1, respectively).     

Mercury mobilization by oxidative dissolution of cinnabar (α-HgS) and metacinnabar (β-HgS)

Cinnabar (α-HgS) and metacinnabar (β-HgS) dissolved at environmentally significant rates in oxygenated slurry experiments simulating a low-flow fluvial system. Based on SO₄²⁻ production, cinnabar dissolution rates were 2.64 to 6.16 μmol (SO₄²⁻) m^− 2 day^− 1, and metacinnabar dissolution rates were 1.20 to 1.90 μmol (SO₄²⁻) m^− 2 day^− 1. Monodentate-bound thiosulfate (S₂O₃²⁻) was identified as an oxidation product on the HgS surface by ATR-IR spectroscopy based on strong infrared absorption bands in the 1140–1145 cm^− 1 and 1006–1014 cm^− 1 regions. The presence of sulfide oxidation intermediates on the HgS surface indicates that SO₄²⁻ concentration underestimates α-HgS and β-HgS dissolution in this setting. Mercury release rates during dissolution were more than two orders of magnitude less than SO₄²⁻ production, but were significant: 0.47 mg (Hg) m^− 2 y^− 1 from cinnabar [6.45 nmol (Hg) m^− 2 day^− 1], and 0.17 mg (Hg) m^− 2 y^− 1 from metacinnabar [2.29 nmol (Hg) m^− 2 day^− 1]. The Hg mobilized during α-HgS and β-HgS dissolution is sufficient to form natural Au–Hg amalgam in downstream placer settings. The proportion of mercury that is not remobilized during α-HgS and β-HgS dissolution likely adsorbs to the dissolving mercuric sulfide. Adsorption of Hg²⁺ to cinnabar was detected in situ by anodic stripping voltammetry using a cinnabar-modified carbon paste electrode following accumulation of Hg²⁺ on the electrode at open circuit potential.     

Geochemical signature of porphyries in the Baogutu porphyry copper belt, western Junggar, NW China

The Baogutu porphyry copper belt lies in the Darbut transitional island arc of the western Junggar, in the western section of the Central Asian Orogenic Belt in NW China. Our new petrographic results for the ore-bearing porphyry stocks in the Baogutu porphyry copper belt recognize them as diorite porphyry stocks rather than the granodiorite porphyry stocks as previously identified. The copper mineralization is hosted in the diorite, diorite porphyries and related breccias of the diorite porphyry stocks.Geochemical data indicate that the ore-bearing porphyries have a predominantly intermediate composition with a transitional character from tholeiite to calc-alkaline, and are enriched in large ion lithophile elements (LILE) and depleted in high field strength elements (HFSE) with a clear negative Nb anomaly. REE patterns show distinct enrichments in LREE relative to HREE. The rocks also exhibit high initial εNd(t) (+ 2.7 to + 6.3) ratios and low initial ⁸⁷Sr/⁸⁶Sr values (0.70359–0.70397). Many samples are chemically similar to adakites (e. g. Yb < 1.9 ppm, Y < 18 ppm, Sr/Yb > 20, ⁸⁷Sr/⁸⁶Sr < 0.7045). These data are consistent with a transitional island arc from immature arc to mature arc and suggest that the ore-bearing porphyry system was derived from the partial melting of multiple sources including oceanic crust and a subduction-modified mantle wedge, with melts undergoing significant crystal fractionation during convergence between the paleo-Junggar ocean and the Darbut arc.     

An early Paleoproterozoic high-K intrusive complex in southwestern Tarim Block, NW China: Age, geochemistry, and tectonic implications

Systematic geochronologic, geochemical, and Nd isotopic analyses were carried out for an early Paleoproterozoic high-K intrusive complex exposed in southwestern Tarim, NW China. The results provide a better understanding of the Paleoproterozoic tectonic evolution of the Tarim Block. Zircon U–Pb age dating indicates two Paleoproterozoic magmatic episodes occurring at ca. 2.41 Ga and ca. 2.34 Ga respectively, which were followed by a ca. 1.9 Ga metamorphic event. The 2.41 Ga granodiorite–adamellite suite shares characteristics of late to post-orogenic metaluminous A-type granites in its high alkalinity (Na₂O + K₂O = 7.6–9.3%), total REE (410–788 ppm), Zr (370–660 ppm), and Y (21.7–58.4 ppm) contents. εNd(t) values for the suite range from − 3.22 to − 4.71 and accordingly the Nd modal ages (T_2DM) vary between 3.05 Ga and 3.17 Ga. Based on geochemical data, the 2.34 Ga suite can be subdivided into two sub-suites, namely A-type and S-type. However, both types have comparable Nd isotope compositions (εNd(t) ≈ − 0.41 to − 2.08) and similar narrow T_2DM ranges (2.76–2.91 Ga).Geochemical and Nd isotopic data for the high-K intrusive complex, in conjunction with the regional geological setting, suggest that both the 2.41 Ga suite and the 2.34 Ga A-type sub-suite might have been produced by partial melting of the Archean mafic crust in a continental rift environment. The S-type sub-suite is thought to have formed by partial melting of felsic pelites and/or metagreywackes recycled from Archean crust (TTG?). Gabbro enclaves with positive εNd(t) value (2.15) have been found to be intermingling within the 2.34 Ga suite; ca. 2.34–2.36 Ga gabbroic dykes and adamellites have previously been documented in eastern Tarim. These observations indicate that the high-K intrusions may reflect the emergence of depleted mantle upwelling beneath the Tarim Block at that time. We suggest a three-stages model for the Precambrian crustal evolution in the Tarim Block: (1) the formation of proto-crust (TTG) by ca. 2.5 Ga, (2) episodes of felsic magmatism possibly occurring in continental rift environments at ca. 2.41 Ga and ca. 2.34–2.36 Ga, and (3) ca. 1.9 Ga metamorphism that may represent the solidification of the Precambrian basement of the Tarim Block.     

Which water formed Australian sediment-hosted precious and potch opal?

The means and timing of the formation of Australian sediment-hosted precious opal remain a subject of continuing debate. In this study, the question of which water formed the opal is addressed by examination of rare earth element data for opals and host rocks. The available data, mainly for Lightning Ridge, NSW, suggest a positive Eu anomaly, relative to the neighbouring Sm and Dy, occurs in opals whereas no such anomaly was found for the weathered Cretaceous sediments hosting the opal. Such anomalies may be inherited from the source rock with a similar positive Eu anomaly or generated in situ by severe reduction. There is no indication of major reduction processes during the opal formation that could have led to such a Eu anomaly so this is likely inherited from a source rock. As the opal host rocks did not show this anomaly, the source rocks must be external to the opal fields. Calcite cements within rocks hosting the aquifers of the Eromanga and Surat basins of the Great Artesian Basin have been reported to have a positive Eu anomaly, which strongly suggests that opal was formed by upwelling Great Artesian Basin artesian waters. This work has also highlighted variations in trace-element concentrations in opals, which indicate significant variation in the source water composition during opal formation or different water sources were involved. Either of these is indicative of the source for the opal with its trace elements derived from external sources. These conclusions have significant implications to considerations of how opal formed, and hence, for the exploration for other deposits and to the chemistry and timing that led to the formation of opal.     

On the possibility of a kinetic fractionation of nitrogen stable isotopes during natural diamond growth

In a diamond from New South Wales (Australia), cubic and octahedral growth sectors, as identified by cathodoluminescence (CL), show slight differences in N-contents of 29 and 42 ppm respectively but no significant differences in either δ¹³C, δ¹⁵N and nitrogen aggregation state with values at +1.96‰, +19.4‰, and 25% Type IaAB aggregation, respectively.Two gem cubes from the Orapa kimberlite (Botswana) were studied by CL revealing a nonfaceted cubic growth. Accordingly, nine other gem cubes were combusted and yielded δ¹³C-values from -5.33‰ to -6.63‰, δ¹⁵N from -1.0‰ to -5.5‰, and nitrogen contents from 914 to 1168 ppm, with nitrogen aggregation state being only Type IaA (zero % B). The gem cubes show striking similarities to fibrous/coated diamonds, not only in both δ¹³C ranges (less than 3‰ from -5 to -8‰), but also in the high levels of nitrogen (≈ 1000 ppm), suggesting that the two diamond types are related. Additionally, no δ¹⁵N variation was detected between the cube and octahedral growth sectors of the Australian diamond, in the cube sectors of the nine gem cubes from Botswana, nor in fibrous/coated diamonds previously studied. These analyses contrast with an earlier study on a synthetic diamond, which reported a strong kinetic fractionation of N-isotopes of about 40‰ between cube and octahedral growth. The present evidence, therefore, suggests that kinetic fractionation of N-isotopes does not operate during natural diamond formation.     

Adsorption of NO, SO2 and light hydrocarbons on activated Greek brown coals

Twenty-eight samples of peat, peaty lignites and lignites (of both matrix and xylite-rich lithotypes) and subbituminous coals have been physically activated by pyrolysis. The results show that the surface area of the activated coal samples increases substantially and the higher the carbon content of the samples the higher the surface area.The adsorption capacity of the activated coals for NO, SO₂, C₃H₆ and a mixture of light hydrocarbons (CH₄, C₂H₆, C₃H₈ and C₄H₁₀) at various temperatures was measured on selected samples. The result shows a positive correlation between the surface area and the gas adsorption. In contrast, the gas adsorption is inversely correlated with the temperature. The maximum recorded adsorption values are: NO = 8.22 × 10^− 5 mol/g at 35 °C; SO₂ = 38.65 × 10^− 5 mol/g at 60 °C; C₃H₆ = 38.9 × 10^− 5 mol/g at 35 °C; and light hydrocarbons = 19.24 × 10^− 5 mol/g at 35 °C. Adsorption of C₃H₆ cannot be correlated with either NO or SO₂. However, there is a significant positive correlation between NO and SO₂ adsorptions. The long chain hydrocarbons are preferentially adsorbed on activated lignites as compared to the short chain hydrocarbons.The results also suggest a positive correlation between surface area and the content of telohuminite maceral sub-group above the level of 45%.     

Rare earth element geochemistry of the Woxi W–Sb–Au deposit, Hunan Province, South China

The Woxi W–Sb–Au deposit in Hunan, South China, is hosted by Proterozoic metasedimentary rocks, a turbiditic sequence of slightly metamorphosed (greenschist facies), gray-green and purplish red graywacke, siltstone, sandy slate, and slate. The mineralization occurs predominantly (> 70%) as stratabound/stratiform ore layers and subordinately as stringer stockworks. The former consists of rhythmically interbedded, banded to finely laminated stibnite, scheelite, quartz, pyrite and silty clays, whereas the latter occurs immediately beneath the stratabound ore layers and is characterized by numerous quartz + pyrite + gold + scheelite stringer veins or veinlets that are typically either subparallel or subvertical to the overlying stratabound ore layers. The deposit has been the subject of continued debate in regard to its genesis. Rare earth element geochemistry is used here to support a sedimentary exhalative (sedex) origin for the Woxi deposit. The REE signatures of the metasedimentary rocks and associated ores from the Woxi W–Sb–Au deposit remained unchanged during post-depositional processes and were mainly controlled by their provenance. The original ore-forming hydrothermal fluids, as demonstrated by fluid inclusions in quartz from the banded ores, are characterized by variable total REE concentrations (3.5 to 136 ppm), marked LREE enrichment (La_N/Yb_N = 28–248, ∑LREE/∑HREE = 16 to 34) and no significant Eu-anomalies (Eu/Eu = 0.83 to 1.18). They were most probably derived from evolved seawater that circulated in the clastic sediment pile and subsequently erupted on the seafloor. The bulk banded ores are enriched in HREE (La_N/Yb_N = 4.6–11.4, ∑LREE/∑HREE = 3 to 14) and slightly depleted in Eu (Eu/Eu = 0.63 to 1.14) relative to their parent fluids. This is interpreted as indicating the influence of seawater rather than a crystallographic control on REE content of the ores. Within a single ore layer, the degree of HREE enrichment tends to increase upward while the total REE concentrations decrease, reflecting greater influence and dilution of seawater. There is a broad similarity in chondrite-normalized REE patterns and the amount of REE fractionation of the banded ores in this study and exhalites from other sedex-type polymetallic ore deposits, suggesting a similar genesis for these deposits. This conclusion is in agreement with geologic evidence supporting a syngenetic (sedex) model for the Woxi deposit.