Genetic implications of the trace element distribution pattern in the upper knox carbonate rocks,copper ridge district,East Tennessee

The Lower Ordovician, Upper Knox Group rocks (the Kingsport and Mascot formations) in the Copper Ridge district consist predominantly of fine-grained dolostones, medium and coarser grained dolostones, and limestones. Dolomite crystals of medium and coarser grained dolostones show up to eight cathodoluminescent zones of variable width and intensity. Electron microprobe analyses indicate that the zoning is related to variation in Fe/Mn ratios, the brighter luminescent zones corresponding to lower ratios. Superposed on this growth zoning is a compositional zoning characterized by a general increase in Fe from core to rim of individual dolomite crystals.Field and petrographic studies (Churnet, 1979; Churnet et al., 1981) indicate that the fine-grained dolostones formed in supratidal to upper intratidal environments, whereas the precursor lime muds of the limestones as well as of the medium and coarser grained dolostones formed in shallow subtidal to lower intertidal environments. The large areal extent of the dolostones must have required a regionally abundant source of Mg such as marine water. Yet, both limestones and dolostones have low Na and Sr contents suggestive of their formation in solutions more dilute than normal marine water. It is proposed that the fine-grained dolostones formed by aggradation of initially very fine-grained dolostones in presence of fresh water, and that the limestones stabilized and the medium and coarser grained dolostones formed in environments of mixed marine and fresh waters. Considered in the light of ordering of partition coefficients, such a mixing model can account for the observed correlation pattern of trace elements (especially, SMn and SrFe) as well as the Fe distribution in the zoned dolomite crystals. Variation of the partition coefficient of Mn due to fluctuations in the relative proportions of fresh and marine waters in the diagenetic solution may explain the different Fe/Mn ratios observed in the growth zones (luminescence bands) of zoned dolomite crystals.     

Diagenesis of Carbonate and Siderite Deposits of the Lower Riphean Bakal Formation,the Southern Urals: Sr Isotopic Characteristics and Pb-Pb Age

The Rb-Sr and U-Pb systematics were studied for carbonate rocks of the Lower Riphean Bakal Formation of the southern Urals and related siderite ores of the Bakal iron deposit. The least-altered limestones taken at a significant distance from the Bakal ore field satisfy the strict geochemical criteria of retentivity: Mn/Sr < 0.2, Fe/Sr < 0.5, and ⁸⁷Sr/⁸⁶Sr (difference between the measured ⁸⁷Sr/⁸⁶Sr values in secondary and primary carbonate phases) < 0.001. The least-altered carbonate phases were extracted by the stepwise dissolution in 0.5 N HBr. The Pb-Pb date of limestones (1430 ± 30 Ma) defines the age of early diagenesis of carbonate sediments of the Bakal Formation. The ⁸⁷Sr/⁸⁶Sr ratio in the sedimentary environment of the Bakal carbonates (0.70457–0.70481) yields isotopic signature for the Early Riphean seawater. The Pb-Pb age of metasomatic siderites (1010 ± 100 Ma), which formed at the end of the main ore formation stage and did not undergo late epigenesis, corresponds to the final phases of the Grenville tectonogenesis. Siderites of the main ore formation stage are confined to central parts of the thickest carbonate units and have high ratios of ⁸⁷Sr/⁸⁶Sr (0.73482–0.73876) and ²⁰⁸Pb/²⁰⁴Pb (41.4–42.9). Iron-bearing solutions formed during the diagenesis of mainly Lower Riphean clayey rocks and migrated along low-density zones and faults. The solutions discharged at the interformational unconformity between the Bakal and Zigalga formations. At the contact with shales, carbonate rocks and siderites experienced the later epigenetic dolomitization (partial desideritization) caused by the circulation of solutions enriched in radiogenic ⁸⁷Sr and low-radiogenic ²⁰⁶Pb. This dolomitization occurred simultaneously with the Cadomian tectonothermal activation of the region.__________Translated from Litologiya i Poleznye Iskopaemye, No. 3, 2005, pp. 227–249.Original Russian Text Copyright © 2005 by Kuznetsov, Krupenin, Ovchinnikova, Gorokhov, Maslov, Kaurova, Ellmies.     

U-Pb age and Sr isotope signature of cap limestones from the Neoproterozoic Tsagaan Oloom Formation, Dzabkhan River Basin, Western Mongolia

The U-Pb and Pb-Pb methods were used for determining age of cap limestones from the Neoproterozoic Tsagaan Oloom Formation corresponding to the lower part of the sedimentary cover in the Dzabkahn microcontinent of Central Asia. The weighted average age value appeared to be equal to 632 ± 14 Ma (MSWD = 0.11, probability 0.74). This value allows the following assumptions: (1) the lower boundary of the Tsagaan Oloom Formation corresponds to the beginning of the Ediacaran; (2) Dzabkhan tillites are correlative with glacial sediments of the Marinoan Epoch. The low ²³⁸U/²⁰⁴Pb and ²³²Th/²³⁸U ratios observed in initial Pb sources of limestones from the Tsagaan Oloom Formation indicate that the Dzabkhan paleobasin received at its early development stages a bulk of material from eroded upper Riphean juvenile rocks. The ⁸⁷Sr/⁸⁶Sr ratio in fractions of Tsagaan Oloom limestones enriched with primary carbonate material and satisfying geochemical criteria of Rb-Sr systems retentivity (Mn/Sr < 0.20 and Fe/Sr < 1) varies from 0.70676 to 0.70691 and reflects this ratio in the World Ocean approximately 630 Ma ago.     

Permian volcanic rocks from the Apuseni Mountains (Romania): Geochemistry and tectonic constraints

An Early Permian volcanic assemblage is well exposed in the central-western part of the Apuseni Mountains (Romania). The rocks are represented by rhyolites, basalts and subordinate andesites suggesting a bimodal volcanic activity that is intimately associated with a post-orogenic (Variscan) syn-sedimentary intra-basinal continental molasse sequences. The mafic and mafic-intermediate rocks belong to sub-alkaline tholeiitic series were separated in three groups (I–III) showing a high Th and Pb abundances, depletion in Nb, Ta and Sr, and slightly enriched in LREE patterns (La_N/Yb_N = 1.4–4.4). Isotopically, the rocks of Group I have the initial ratios ⁸⁷Sr/⁸⁶Sr_(i) = 0.709351–0.707112, ¹⁴³Nd/¹⁴⁴Nd_(i) = 0.512490–0.512588 and high positive ?_Nd270 values from 3.9 to 5.80; the rocks of Group II present for the initial ratios values ⁸⁷Sr/⁸⁶Sr_(i) = 0.709434–0.710092, ¹⁴³Nd/¹⁴⁴Nd_(i) = 0.512231–0.512210 and for ?_Nd270 the negative values from −1.17 to −1.56; the rocks of Group III display for the initial ratios the values ⁸⁷Sr/⁸⁶Sr_(i) = 0.710751–0.709448, ¹⁴³Nd/¹⁴⁴Nd_(i) = 0.512347–0.512411 and for ?_Nd270 the positive values from 1.64 to 2.35. The rocks resembling continental tholeiites, suggest a mantle origin and were further affected by fractionation and crustal contamination. In addition, the REE geochemistry (1 > Sm_N/Yb_N < 2.5; 0.9 > La_N/Sm_N < 2.5) suggests that these rocks were generated by high percentage partial melting of a metasomatized mantle in the garnet peridotite facies. The felsic rocks are enriched in Cs, Rb Th and U and depleted in Nb, Ta, Sr, Eu, and Ti. The REE fractionation patterns show a strong negative Eu anomaly (Eu/Eu* = 0.23–0.40). The felsic rocks show the initial ratios the values: ⁸⁷Sr/⁸⁶Sr_(i) = 0.704096–0.707805, ¹⁴³Nd/¹⁴⁴Nd_(i) = 0.512012–0.512021 and for ?_Nd270 the negative values from −5.27 to −5.44. They suggest to be generated within the lower crust during the emplacement of mantle-derived magmas that provided necessary heat to crustal partial melting.     

Input of Sr/Sr ratios and Sr geochemical signatures to update knowledge on thermal and mineral waters flow paths in fractured rocks (N-Portugal)

Strontium isotopes and other geochemical signatures are used to determine the relationships between CO₂-rich thermal (Chaves: 76 °C) and mineral (Vilarelho da Raia, Vidago and Pedras Salgadas: 17 °C) waters discharging along one of the major NNE–SSW trending faults in the northern part of mainland Portugal. The regional geology consists of Hercynian granites (syn-tectonic-310 Ma and post-tectonic-290 Ma) intruding Silurian metasediments (quartzites, phyllites and carbonaceous slates). Thermal and mineral waters have ⁸⁷Sr/⁸⁶Sr isotopic ratios between 0.716713 and 0.728035. ⁸⁷Sr/⁸⁶Sr vs. 1/Sr define three end-members (Vilarelho da Raia/Chaves, Vidago and Pedras Salgadas thermal and mineral waters) trending from rainfall composition towards that of the CO₂-rich thermal and mineral waters, indicating different underground flow paths. Local granitic rocks have ⁸⁷Sr/⁸⁶Sr ratios of 0.735697–0.789683. There is no indication that equilibrium was reached between the CO₂-rich thermal and mineral waters and the granitic rocks. The mean ⁸⁷Sr/⁸⁶Sr ratio of the thermal and mineral waters (0.722419) is similar to the Sr isotopic ratios of the plagioclases of the granitic rocks (0.71261–0.72087). The spatial distribution of Sr isotope and geochemical signatures of waters and the host rocks suggests that the thermal and mineral waters circulate in similar but not the same hydrogeological system. Results from this study could be used to evaluate the applicability of this isotope approach in other hydrogeologic investigations.     

Origin and evolution of formation water at the Jujo–Tecominoacán oil reservoir,Gulf of Mexico. Part 2: Isotopic and field-production evidence for fluid connectivity

The chemical and isotopic characterization of formation water from 18 oil production wells, extracted from 5200 to 6100 m b.s.l. at the Jujo–Tecominoacán carbonate reservoir in SE-Mexico, and interpretations of historical production records, were undertaken to determine the origin and hydraulic behavior of deep groundwater systems. The infiltration of surface water during Late Pleistocene to Early Holocene time is suggested by ¹⁴C-concentrations from 2.15 to 31.86 pmC, and by ⁸⁷Sr/⁸⁶Sr-ratios for high-salinity formation water (0.70923–0.70927) that are close to the composition of Holocene to modern seawater. Prior to infiltration, the super-evaporation of seawater reached maximum TDS concentrations of 385 g/L, with lowest δ¹⁸O values characterizing the most hypersaline samples. Minor deviations of formation water and dolomite host rocks from modern and Jurassic ⁸⁷Sr/⁸⁶Sr-seawater composition, respectively, suggest ongoing water–rock interaction, and partial isotopic equilibration between both phases. The abundance of ¹⁴C in all sampled formation water, ⁸⁷Sr/⁸⁶Sr-ratios for high-salinity water close to Holocene – present seawater composition, a water salinity distribution that is independent of historic water-cut, and a total water extraction volume of 2.037 MMm³ (1/83–4/07) excludes a connate, oil-leg origin for the produced water of the Jurassic–Cretaceous mudstone-dolomite sequence. Temporal fluctuations of water chemistry in production intervals, the accelerated migration of water fronts from the reservoir flanks, and isotopic mixing trends between sampled wells confirms the existence of free aquifer water below oil horizons. Vertical and lateral hydraulic mobility has probably been accelerated by petroleum extraction.     

山西襄汾奥陶系岩石学特征及沉积环境分析

山西襄汾地区奥陶系只有下、中统,主要由碳酸盐岩与蒸发岩组成.燧石及陆源碎屑岩少见。同位素资料表明δ13O较低（平均-5.832‰PDB）,δ13C（平均-1.210‰PDB）变化较小,表示古盐度的指数Z多大于120。微量元素表明碳酸盐岩沉积于近陆环境,受大气淡水影响强烈。沉积环境主要是潮上（膏泻湖）、潮间坪、潮下局限海及开阔海。峰峰期后最大的海退结束了本区海相沉积史。     

湖北兴山大峡口剖面二叠系岩石特征及沉积环境分析

湖北兴山大峡口剖面二叠系自下而上可以分为栖霞组、茅口组、吴家坪组和长兴组,总厚度为43372 m。该剖面岩石以石灰岩为主,含少量的白云岩、硅岩和页岩。石灰岩可进一步分为生屑石灰岩、生屑质石灰岩、含生屑石灰岩、泥（粉）晶石灰岩和眼球状石灰岩。眼球状石灰岩主要分布于栖霞组下部和茅口组中下部,为沉积作用和成岩作用的共同产物。白云岩主要是呈斑块状分布的石灰质白云岩,主要分布于长兴组上部,其可能为石灰岩经埋藏白云化作用而形成。硅岩呈结核状、团块状、条带状,为交代成因。根据岩性、古生物化石、沉积构造等相标志分析,划分出了滨岸、碳酸盐岩台地、盆地边缘和盆地等4种沉积环境,其中碳酸盐岩开阔台地内局部出现浅滩环境。沉积演化表明,该地区二叠纪发生了两次较大规模的海进、海退旋回,第1次海侵始于中二叠世栖霞组沉积初期,结束于茅口组沉积末期;第2次海侵始于吴家坪组沉积初期,直至长兴组沉积期末结束。初步分析表明,研究区二叠系具有良好的烃源岩条件和储集条件。     

Types and Origin of Dolostones in Tarim Basin, Northwest China:Petrographic and Geochemical Evidence

In the Tarim Basin of northwestern China hydrocarbon deposits have been discovered in parts of the thick strata of Cambrian dolostones. Based on petrographic study, six types of dolostone have been distinguished: Type-1, pink mud-bearing silty crystalline dolostone (PMSD); Type-2, gypsum- and salt-bearing fine crystalline dolostone (GSFD); Type-3, fine crystalline dolostone with dolomite crystals with cloudy core and clear rim (CCFD); Type-4, deep gray mud-bearing silty crystalline dolostone (GMSD); Type-5, euhedral coarse crystalline dolostone (ECD); and Type-6, xenotopic coarse crystalline dolostone (XCD). Applying petrographic and geochemical methods, the genesis of the dolostones is studied in this paper. Normally, Type-1 dolostone shows U- and Mo-depleted characteristics, reflecting a more oxidized formation environment; High δ18O and the purple color are consistent with formation of Sabkha dolostones on a supratidal flat. Types 2, 3, 4 dolostones show strata formation, similar REE patterns and 87Sr/86Sr ratios with contemporaneous limestones, suggesting a penecontemporaneous origin from seawater. Types 5 and 6 dolostones commonly occur as interbedded rocks, indicating secondary genesis after diagenesis. Type-6 dolostone has the highest order degree (OD) values (average 0.86), the lowest oxygen isotope values and positive Eu anomalies, which are consistent with previously reported hydrothermal dolostones. Differently, Type-5 shows euhedral texture, higher δ18O value, similar REE characteristic and 87Sr/86Sr ratios in comparison with contemporaneous limestones, suggesting that this type might have been dolomitized by down-transferring evaporated seawater during shallow burial stage. Dolostone fluid sources, formation environments and crystallizing dynamics are summarized and possible genetic models for the six types are proposed.     

Formation and preservation of pedogenic carbonates in South India, links with paleo-monsoon and pedological conditions: Clues from Sr isotopes, U-Th series and REEs

The influence of the pedogenic and climatic contexts on the formation and preservation of pedogenic carbonates in a climosequence in the Western Ghats (Karnataka Plateau, South West India) has been studied. Along the climosequence, the current mean annual rainfall (MAR) varies within a 80 km transect from 6000 mm at the edge of the Plateau to 500 mm inland. Pedogenic carbonates occur in the MAR range of 500-1200 mm. In the semi-arid zone (MAR: 500-900 mm), carbonates occur (i) as thick hardpan calcretes on pediment slopes and (ii) as nodular horizons in polygenic black soils (i.e. vertisols). In the sub-humid zone (MAR: 900-1500 mm), pedogenic carbonates are disseminated in the black soil matrices either as loose, irregular and friable nodules of millimetric size or as indurated botryoidal nodules of centimetric to pluricentimetric size. They also occur at the top layers of the saprolite either as disseminated pluricentimetric indurated nodules or carbonate-cemented lumps of centimetric to decimetric size.Chemical and isotopic (⁸⁷Sr/⁸⁶Sr) compositions of the carbonate fraction were determined after leaching with 0.25 N HCl. The corresponding residual fractions containing both primary minerals and authigenic clays were digested separately and analyzed. The trend defined by the ⁸⁷Sr/⁸⁶Sr signatures of both labile carbonate fractions and corresponding residual fractions indicates that a part of the labile carbonate fraction is genetically linked to the local soil composition. Considering the residual fraction of each sample as the most likely lithogenic source of Ca in carbonates, it is estimated that from 24% to 82% (55% on average) of Ca is derived from local bedrock weathering, leading to a consumption of an equivalent proportion of atmospheric CO₂. These values indicate that climatic conditions were humid enough to allow silicate weathering: MAR at the time of carbonate formation likely ranged from 400 to 700 mm, which is 2- to 3-fold less than the current MAR at these locations.The Sr, U and Mg contents and the (²³⁴U/²³⁸U) activity ratio in the labile carbonate fraction help to understand the conditions of carbonate formation. The relatively high concentrations of Sr, U and Mg in black soil carbonates may indicate fast growth and accumulation compared to carbonates in saprolite, possibly due to a better confinement of the pore waters which is supported by their high (²³⁴U/²³⁸U) signatures, and/or to higher content of dissolved carbonates in the pore waters. The occurrence of Ce, Mn and Fe oxides in the cracks of carbonate reflects the existence of relatively humid periods after carbonate formation. The carbonate ages determined by the U-Th method range from 1.33 ± 0.84 kyr to 7.5 ± 2.7 kyr and to a cluster of five ages around 20 kyr, i.e. the Last Glacial Maximum period. The young occurrences are only located in the black soils, which therefore constitute sensitive environments for trapping and retaining atmospheric CO₂ even on short time scales. The maximum age of carbonates depends on their location in the climatic gradient: from about 20 kyr for centimetric nodules at Mule Hole (MAR = 1100 mm/yr) to 200 kyr for the calcrete at Gundlupet (MAR = 700 mm/yr, Durand et al., 2007). The intensity of rainfall during wet periods would indeed control the lifetime of pedogenic carbonates and thus the duration of inorganic carbon storage in soils.     

A geochemical study of some lithified carbonate sediments from the deep-sea

Unconsolidated oozes, partially lithified oozes, recrystallized limestones, dolostones and crystalline aragonite are some of the varieties of carbonate sediment that have been found in the deep-sea; chemical and isotopic analyses of these varieties are presented here. The consolidated oozes and recrystallized limestones are low-Mg calcites and are often associated with basement rock (generally serpentinized peridotite or basalt) detritus. Lithification is suggested to arise from changes in the carbonate-equilibria system of the interstitial waters resulting from chemical degradation of the igneous rocks. When compared to unconsolidated oozes, lithification is seen to be accompanied by loss of Sr and a slight increase in B, Ba, Co, Cr, Ni and Y in most instances. The tuffaceous limestones are also low-Mg calcites, but are characterized by low Sr and relatively high B, Ba, Co, Cr, Cu, Ni, V, Y and Zn concentrations compared to the oozes. Three dolostones are described of very different isotopic and chemical composition, possibly indicating three different pathways of dolomitization. One with much depleted ¹³C and high Ba concentrations is probably derived from waters containing carbon from a fractionated organic source. Another is not greatly different from the consolidated limestones in minor and trace element composition and may be derived from them. The third variety is characterized by low concentrations of Sr, B, Ba, Cu and Y and relatively high concentrations of Pb: Crystalline aragonite is commonly found in many areas associated with serpentinized peridotite. This aragonite is characterized by relatively high concentrations of Sr and Ni; petrographic and isotopic analyses indicate precipitation from cold, carbonate-rich solutions percolating through the peridotite.     

Plio-Pleistocene basanitic and melilititic series of the Bohemian Massif: K-Ar ages,major/trace element and Sr–Nd isotopic data

The Plio-Pleistocene volcanic rocks of the Bohemian Massif comprise a compositional spectrum involving two series: an older basanitic series (6.0–0.8 Ma) and a younger, melilititic series (1.0–0.26 Ma). The former consists of relatively undifferentiated basaltic rocks, slightly silica-undersaturated, with Mg# ranging from 62 to almost primitive mantle-type values of 74. The major and trace element characteristics correspond to those of primitive intra-plate alkaline volcanic rocks from a common sub-lithospheric mantle source (European Asthenospheric Reservoir – EAR) including positive Nb, and negative K and Pb anomalies. ⁸⁷Sr/⁸⁶Sr ratios of 0.7032–0.7034 and ¹⁴³Nd/¹⁴⁴Nd of 0.51285–0.51288 indicate a moderately depleted mantle source as for other mafic rocks of the central European volcanic province with signs of HIMU-like characteristics commonly attributed to recycling of subducted oceanic crust in the upper mantle during the Variscan orogeny. The melilititic series is characterized by higher degrees of silica-undersaturation, and high Mg# of 68–72 values, compatible with primitive-mantle-derived compositions. The high OIB-like Ce/Pb (19–47) and Nb/U (32–53) ratios indicate that assimilation of crustal material was negligible. In both series, concentrations of incompatible elements are mildly elevated and ⁸⁷Sr/⁸⁶Sr ratios (0.7034–0.7036) and ¹⁴³Nd/¹⁴⁴Nd ratios (0.51285–0.51288) overlap. Variations in incompatible element concentrations and isotopic compositions in the basanitic series and melilititic series can be explained by a lower degree of mantle melting for the latter with preferential melting of enriched mantle domains. The Sr and Nd isotopic compositions of both rock series are similar to those of the EAR. Minor differences in geochemical characteristics between the two series may be attributed to: (i) to different settings with respect to crust and lithospheric mantle conditions in (a) Western Bohemia (WB) and (b) Northeastern Bohemia (NEB) and the Northern Moravia and Silesia (NMS) areas, (ii) a modally metasomatized mantle lithosphere in WB in contrast to cryptically metasomatized domains in the NEB and NMS, (iii) different degrees of partial melting with very low degrees in WB but higher degrees in NEB and NMS. The geochemical and isotopic similarity between the Plio-Pleistocene volcanic rocks and those of the late Cretaceous and Cenozoic (79–6 Ma) suggests that their magmas came from compositionally similar mantle sources, that underwent low degrees of melting over an interval of ∼80 Ma. The Oligocene to Miocene basanitic series that accompanied the Plio-Pleistoicene basanitic series in the NMS region indicate that they shared a common mantle source. There is no geochemical evidence for thermal erosion of the lithospheric mantle or significant changes in mantle compositions within the time of a weak thermal perturbation in the asthenospheric mantle. These perturbations were caused by a dispersed mantle plume or passively upwelling asthenosphere in zones of lithospheric thinning.     

New data on Sr-and C-isotopic chemostratigraphy of the Upper Riphean type section (Southern Urals)

New data on Sr-and C-isotopic systematics of carbonate rocks from the Upper Riphean stratotype (Karatau Group of the southern Urals) are obtained for several southwestern sections of the Bashkirian meganticlinorium, which have not been studied before. The results obtained supplement the Sr-and C-isotopic information for the group upper horizons thus detailing chemostratigraphic characterization of the entire succession. Limestone and dolostone samples used to analyze the Sr isotope composition satisfy strict geochemical criteria of the isotopic system retentivity and have been subjected to preliminary treatment in ammonium acetate to remove secondary carbonate phases. Data on 255 samples of carbonate rocks (171 studied for the first time) show that δ¹³C value varies in the Karatau Group succession from ?2.8 to +5.9 ‰ V-PDB with several in-phase excursions from the general trend in all the sections studied in the area 90 × 130 km. The δ¹³C variation trend demarcates several levels in the carbonate succession of the Karatau Group suitable for objectives of regional stratigraphy and for C-isotope chemostratigraphic subdivision of the Upper Riphean. The results of Sr isotopic analysis of 121 samples (51 unstudied before) from the Karatau Group imply that rocks in its lower part (the Katav Formation and basal horizon of the Inzer Formation) experienced considerable secondary alterations, while limestones and dolostones of the overlying interval of the group are frequently unaltered. In the “best” samples satisfying geochemical criteria of the isotopic system retentivity, the ⁸⁷Sr/⁸⁶Sr initial ratio increases from 0.70521–0.70532 in the lower Inzer deposits to 0.70611 in the upper Min’yar carbonates, decreasing to <0.70600 near the top of the latter. Above the regional hiatus separating the Min’yar and Uk formation, this ratio grows from 0.70533 to 0.70605–0.70609 in the limestone succession of the last formation.     

Iron isotopes in natural carbonate minerals determined by MC-ICP-MS with a Fe-Fe double spike

We have developed a method for iron isotope analysis by multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) using a ⁵⁸Fe-⁵⁴Fe double spike. A 20 min analysis produces mass-bias-corrected iron isotope data with an external reproducibility of ±0.05 (2 SD) on δ⁵⁶Fe, which represents a decrease in analysis time compared to sample-standard bracketing techniques. The estimation of external reproducibility is based on replicate analysis of the ETH hematite in-house standard. The double spike method has two advantages. First, matrix effects during MC-ICP-MS analysis are decreased with tests showing that accurate iron isotope data can, in some cases, be obtained even when matrix levels exceed iron concentration (Na/Fe, Mg/Fe, and Ca/Fe up to 5, 2, and 0.1, respectively). Because chemical separation reduces matrix/Fe to levels more than three orders of magnitude lower than this, measured Fe isotope compositions are unlikely to be compromised by matrix effects. Second, it is possible to spike samples before chemical purification, which enables any isotopic fractionation effect because of incomplete recovery of iron from a sample to be accounted for. This may be important where obtaining quantitative iron yields from samples is difficult, such as the extraction of dissolved iron from water samples. Fe isotope data on a set of standard reference materials (igneous rocks, ferromanganese nodules, sedimentary rocks, and ores) are presented, which are in agreement with previously published data considering analytical uncertainties. Mantle-derived standard rock samples that are the source of iron for surficial, (bio)geochemical cycling yield a mean δ⁵⁶Fe of 0.041 ± 0.11‰ (n = 8; 2 SD) with reference to IRMM-14. Hydrothermal and metamorphic calcium carbonate rocks with a relatively low iron content (100-4000 ppm) have δ⁵⁶Fe = −1.25 to −0.07‰. Structural Fe(II) in hydrothermal calcites has δ⁵⁶Fe = −1.25 to −0.27‰. The light iron in this range of carbonate minerals may reflect the iron isotope composition of the hydrothermal fluids from which the carbonate precipitated, or the presence of Fe(III) and/or organic material in the hydrothermal fluids during calcite precipitation.     

A first approach to study the mobility and behavior of lead in hypersaline salt marsh sediments: Diffusive and advective fluxes,geochemical partitioning and Pb isotopes

A geochemical study of interstitial water and solid phase sediment using bulk concentration and geochemical partitioning was undertaken in vertical sediment profiles to trace diagenetic processes of lead (Pb) in hypersaline salt marsh sediments. In addition, we measured the stable isotopic composition of Pb in order to distinguish its input sources. Concentrations of Pb increased from low or background values in the bottommost layer (< 60 cm depth), followed by fluctuations in the middle layer (20–60 cm) and peak values in the subsurface layer (3–5 cm). Pb associated to reactive fractions (e.g. OM, Fe–Mn oxyhydroxides and carbonates) accounted for 60% of that initially deposited. Stable Pb isotope data (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁷Pb/²⁰⁸Pb) suggested that most of the Pb in the upper sediments (1.204 ± 0.002 and 2.469 ± 0.007) is still derived from the leaded gasoline combustion (1.201 ± 0.006 and 2.475 ± 0.005). Profile of dissolved Pb was related to those for ammonium, phosphates and dissolve Fe and Mn, which reveals the influence of the diagenetic reactions on the Pb behavior. OM, Fe–Mn oxyhydroxides and the sulfide minerals play a significant role for mobilizing and trapping the Pb. Metal mobilization was calculated considering an advective–diffusive system. The advective process constitutes the dominant mechanism of Pb mobilization. A low diffusive outflux with respect to the Pb mobilization rate suggested that most of the released Pb is retained in the sediments. Authigenic oxides precipitated at the oxic–suboxic layers (0–4 cm depth) and authigenic sulfide minerals formed Pb in the anoxic layers (7–20 cm depth) constituting the main scavengers for Pb that is diagenetically released. This retention has significant environmental implications because it reduces the availability and toxicity of Pb to biota, including humans.     

阿姆河盆地卡洛夫-牛津阶碳酸盐岩储层地球化学特征和成岩流体分析

卡洛夫-牛津阶碳酸盐岩为土库曼斯坦阿姆河盆地主力天然气产层,以储层岩石学分析为基础,结合Fe、Sr、Mn微量元素和C、O、Sr同位素及流体包裹体地球化学特征,分析了储层成因和成岩流体性质,得出以下几点认识:(1)由厚壳蛤壳体测定的87Sr/86Sr比值在全球锶同位素地层曲线上可标定的年龄为157.2Ma,储层发育层位属于卡洛夫-牛津阶;(2)卡洛夫-牛津阶为一持续海侵-海退旋回,持续海侵期是礁、滩相储层形成期,而持续海退期为致密盖层发育期;(3)较高的Fe和Sr及较低的Mn含量,以及伴随成岩强度加大δ13C变化不大而δ18O向负值方向偏移的演化趋势,证明成岩作用发生在缺乏大陆淡水影响和以温度为主控因素的还原性封闭系统中;(4)综合同位素地球化学与流体包裹体和镜质体反射率特征,可确定洛夫-牛津阶碳酸盐岩仍处在中成岩阶段;(5)礁、滩相灰岩的溶蚀、埋藏白云化和充填缝、洞的方解石是不同成岩阶段的水-岩反应产物,成岩流体主要来自于深部富Sr的地层热卤水。     

Diagenetic processes on metals in hypersaline mudflat sediments from a subtropical saltmarsh (SE Gulf of California): Postdepositional mobility and geochemical fractions

To understand the biogeochemical cycles of trace metals (Cd, Cu, Fe, Mn, Ni and Zn) in a hypersaline subtropical marsh, geochemical studies of both interstitial and solid phases were conducted on sediment cores from Chiricahueto marsh, SE Gulf of California. The sequential extraction procedure proposed by Tessier was used to estimate the percentages of the metals present in each geochemical phase of the sediment. Metal concentrations in the solid phase were found to be enriched in the upper layers and mainly associated with reactive fractions such as organic matter, Fe–Mn oxyhydroxides and carbonates (46–74% of Ni, Mn and Cd, and 11–19% of Cu and Zn). Principal factor analysis (PFA) and Spearman correlation analysis revealed a strong positive association of metals and their reactive phases with OC (the diagenetic component), and a negative or non-association with the mud content, Al, Fe and Li (the lithogenic component). Diagenetically released metals are mainly mobilized within hypersaline sediments by buoyancy transport (>90% of total flux) in response to an extreme salinity gradient by input of fresh groundwater (3–6 psu cm⁻¹). The molecular diffusion due to the gradient of metals in porewater (maximum and higher levels at 5–7 and below 20 cm depth, respectively) is significantly less important to the advective transport. Most of the metals mobilized by diffusion–advection processes are re-precipitated in the sediments by authigenic minerals, only <10% of most metals are extruded out to the overlying water column. Authigenic accumulation rates were estimated as 1.42–7.09 mg m⁻² a⁻¹ for Cd; 58.8–378 for Cu; 6922–17,985 for Fe; 38.2–345 for Mn; 20.8–263 for Ni; and 282–2956 mg m⁻² a⁻¹ for Zn. The Mn–Fe oxyhydroxides (40–85% of reactive metals) in the upper oxic–suboxic layers (<5 cm below surface) and sulfide minerals (75–97%) in anoxic sediment layers (7–18 cm) constitute the main scavengers for metals.     

Sr isotope chemostratigraphy of Upper Jurassic carbonate rocks in the Demerdzhi Plateau (Crimean Mountains)

The first Sr chemostratigraphic data are obtained for the Upper Jurassic carbonate sections in the Demerdzhi Plateau of the Crimean Mountains. The oncoid, microbial, and organogenic-detrital limestone varieties representing shallow-water marine microfacies of the carbonate platform served as material for these studies. The limestone samples for reconstructing the isotopic parameters of depositional environments were selected using geochemical criteria (Mn/Sr < 0.2, Fe/Sr < 1.6, Mg/Ca < 0.024) and subjected to the preliminary treatment in a 1 N ammonium acetate solution. The ⁸⁷Sr/⁸⁶Sr value in the least altered samples increases up the section from 0.70701 to 0.70710. The obtained ⁸⁷Sr/⁸⁶Sr values are correlated with the Sr isotope properties of belemnite rostrae characterizing the Pectinatites scitulus-Pavlovia rotunda ammonite zone in the zonal scale of the Boreal realm, Hyponoticeras hybonotum-M. ponti/B. peroni Zone in the zonal scale of the Tethyan realm, and lower part of the Dorsoplanites panderi Zone in the zonal scale for the transitional domain of the East European Platform. The Sr chemostratigraphic correlation indicates the early Tithonian age of sediments developed in the eastern part of the Demerdzhi Plateau and restricts the upper boundary of the limestone section redeposited within carbonate breccia of Mount Severnaya Demerdzhi to the terminal early Tithonian. The Sr isotope data are used for calculating the sedimentation rates for limestones. They are estimated to be at least 0.23 m/1000 years, which is an anomalously high value for pre-Quaternary carbonate platforms.     

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.     

Formation and evolution of carbonate chimneys at the Lost City Hydrothermal Field

The Lost City Hydrothermal Field at 30°N, near the Mid-Atlantic Ridge, is an off-axis, moderate temperature, high-pH (9-10.8), serpentinite-hosted vent system. The field is hosted on ∼1.5 Ma crust, near the summit of the Atlantis Massif. Within the field, actively venting carbonate chimneys tower up to 60 m above the seafloor, making them the tallest vent structures known. The chemistry of the chimneys and vent fluids is controlled by serpentinization reactions between seawater and underlying peridotite. Mixing of <40-91 °C calcium-rich vent fluids with seawater results in the precipitation of variable mixtures of aragonite, calcite, and brucite. The resultant deposits range from tall, graceful pinnacles to fragile flanges and delicate precipitates that grow outward from fissures in the bedrock. In this study, mineralogy, petrographic analyses, major and trace element concentrations, and Sr isotopic compositions are used to propose a model for the growth and chemical evolution of carbonate chimneys in a serpentinite-hosted environment. Our results show that nascent chimneys are characterized by a porous, interlacing network of aragonite, and brucite minerals that form extremely fragile structures. The chemistry of these young deposits is characterized by ∼10 wt% Ca and up to 27 wt% Mg, extremely low trace metal concentrations, and ⁸⁷Sr/⁸⁶Sr isotope ratios near 0.70760. During aging of the chimneys, progressive reactions with seawater result in the dissolution of brucite, the conversion of aragonite to calcite, and infilling of pore spaces with calcite. The oldest chimneys are dominated by calcite, with bulk rock values of up to 36 wt% Ca and <1 wt% Mg. These older structures contain higher concentrations of trace metals (e.g., Mn and Ti), and have Sr isotope ratios near seawater values (0.70908). Exposed ultramafic rocks are prevalent along the Mid-Atlantic, Arctic, and Indian Ocean ridge networks and it is likely that other Lost City-type systems exist.