Spatial geochemistry of a Carboniferous platform-margin-to-basin transect: Balancing environmental and diagenetic factors

Conventional (one-dimensional) chemostratigraphy of marine carbonates assesses the chemical archive of individual stratigraphic sections and their correlation in space and time. Whereas this approach has shown to be of value when linking isobathymetric domains, usually characterised by similar facies, more caution is needed when correlations are extended across different physiographic settings and hence different facies belts. Here, the spatial geochemical record of Pennsylvanian platform-margin-to-basin transects across a bathymetric range of about 800 m is documented and discussed in a process-oriented context. Particularly, the presence of layered palaeo-water masses and their potential control on slope facies distribution and geochemical properties requires attention. Whereas Carboniferous thermo- and/or chemo-clines most likely affected depth-related slope facies zonation, it was facies change and hence, variances in porosity–permeability properties, that controlled differential early burial diagenetic alteration. Specifically, the lower-slope related breccia facies is characterised by higher volumes of early burial carbonate cements. This implies that these sediments entered the shallow-burial domain with a considerable open pore space and gave way to an increased rock:fluid ratio. Whereas the δ¹³C record is invariant with bathymetry, the more diagenesis-sensitive δ¹⁸O proxy, records pronounced shifts observed across major facies boundaries. From this it is concluded that although the primary controlling factor of slope facies distribution with depth is probably palaeoceanographic in nature, it is differential rock:fluid ratios that control the first-order, spatial shifts in δ¹⁸O composition. These findings show that one-dimensional chemostratigraphy will severely underestimate the complexity of three-dimensional (bathymetric) data sets across platform margins. This is of relevance for the interpretation of the geochemical archive of fossil carbonate platforms in general.     

Upwelling signals in radiocarbon from early 20th-century Peruvian bay scallop (Argopecten purpuratus) shells

We quantified Δ¹⁴C, δ¹⁸O, and δ¹³C cycles along ontogeny within four bay scallop (Argopecten purpuratus) shells collected from Callao Bay, Salaverry, and Sechura Bay, Peru following the 1907–1908 non-El Niño years and the 1925–1926 El Niño. Δ¹⁴C and δ¹³C generally covary; Δ¹⁴C and δ¹⁸O vary inversely. Simultaneous decreases in Δ¹⁴C and increases in δ¹⁸O in non-El Niño shells are followed by constant Δ¹⁴C and gradually decreasing δ¹⁸O, which we interpret as evidence for discrete marine upwelling events followed by warming of the initially cold upwelled water. Upwelling changes from El Niño events are detectable with difficulty in mollusk shell Δ¹⁴C.     

The biogenic origin of needle fibre calcite

Needle fibre calcite is one of the most ubiquitous habits of calcite in vadose environments (caves deposits, soil pores, etc.). Its origin, either through inorganic, indirect or direct biological processes, has long been debated. In this study, investigations at 11 sites in Europe, Africa and Central America support arguments for its biogenic origin. The wide range of needle morphologies is the result of a gradual evolution of the simplest type, a rod. This rod is the elementary brick which, by aggregation and welding, builds more complex needles. The absence of cross‐welded needles implies that they are welded in a mould, or under a longitudinal and unidirectional constraint, before being released inside the soil pores. The difference between the lengthening of the needles and the c axis can be explained by the existence of needles observed under a scanning electron microscope in organic sleeves, which can act as a mould during rod growth. Complex morphologies with epitaxial outgrowths on straight rods cannot have grown entirely inside organic microtubes; they must result from soil diagenesis after the release of straight rods in a soil‐free medium. Whisker crystals are interpreted as the result of growth and coalescence of euhedral crystals on a rod. Rhomb chains are considered to be the consequence of successive epitaxial growth steps on a needle during variations in growth conditions. Isotopic signatures for needle fibre calcite vary from ?16·63‰ to +1·10‰ and from ?8·63‰ to ?2·25‰ for δ¹³C and δ¹⁸O, respectively. The absence of high δ¹⁸O values for needle fibre calcite precludes a purely physicochemical origin (evaporative) for this particular habit of calcite. As epitaxial growth cannot precipitate in the same conditions as initial needles, needle fibre calcite stable isotopic signatures should be used with caution as a proxy for palaeoenvironmental reconstructions. In addition, it is suggested that the term needle fibre calcite should be kept for the original biogenic form. The other habit should be referred to as epitaxial forms of needle fibre calcite.     

Carbon-isotope records of the Early Jurassic (Toarcian) oceanic anoxic event from the Valdorbia (Umbria–Marche Apennines) and Monte Mangart (Julian Alps) sections: palaeoceanographic and stratigraphic implications

The Toarcian oceanic anoxic event ( ca 183 Ma) coincides with a global perturbation marked by enhanced organic carbon burial and a general decrease in calcium carbonate production, probably triggered by changes in the composition of marine plankton and elevated carbon dioxide levels in the atmosphere. This study is based on high-resolution sampling of two stratigraphic successions, located in Valdorbia (Umbria–Marche Apennines) and Monte Mangart (Julian Alps), Italy, which represent expressions of the Toarcian oceanic anoxic event in deep-water pelagic sediments. These successions are characterized by the occurrence of black shales showing relatively low total organic carbon concentrations (compared with coeval strata in Northern Europe), generally < 2%, and low hydrogen indices. On this basis, they are similar to other Toarcian black shales described from the Tethyan region. The positive and negative carbon-isotope records from the two localities permit a high-resolution correlation such that ammonite biostratigraphy information from Valdorbia can be transferred to those parts of the Monte Mangart section that lack these fossils. Spectral analyses of δ¹³C_org values and of CaCO₃ percentages from the sedimentary records of both the Valdorbia and Monte Mangart sections reveal a strong cyclic pattern, best interpreted as an eccentricity signal which hence implies a duration of ca 500 kyr for the negative carbon-isotope excursion. Based on the carbon-isotope curves obtained, the high-resolution correlation between the Italian successions and a section in Yorkshire (Northern Europe) confirms the supposition that the apparent mismatch between the dating of the Toarcian oceanic anoxic event in the Boreal and Tethyan realms is an artefact of biostratigraphy.     

Geochronological framework and Pb, Sr isotope geochemistry of the Qingchengzi Pb–Zn–Ag–Au orefield, Northeastern China

The Qingchengzi orefield in northeastern China, is a concentration of several Pb–Zn, Ag, and Au ore deposits. A combination of geochronological and Pb, Sr isotopic investigations was conducted. Zircon SHRIMP U–Pb ages of 225.3 ± 1.8 Ma and 184.5 ± 1.6 Ma were obtained for the Xinling and Yaojiagou granites, respectively. By step-dissolution Rb–Sr dating, ages of 221 ± 12 Ma and 138.7 ± 4.1 Ma were obtained for the sphalerite of the Zhenzigou Zn–Pb deposit and pyrargyrite of the Ag ore in the Gaojiabaozi Ag deposit, respectively. Pb isotopic ratios of the Ag ore at Gaojiabaozi (²⁰⁶Pb/²⁰⁴Pb = 18.38 to 18.53) are higher than those of the Pb–Zn ores (²⁰⁶Pb/²⁰⁴Pb = 17.66 to 17.96; Chen et al. [Chen, J.F., Yu, G., Xue, C.J., Qian, H., He, J.F., Xing, Z., Zhang, X., 2005. Pb isotope geochemistry of lead, zinc, gold and silver deposit clustered region, Liaodong rift zone, northeastern China. Science in China Series D 48, 467–476.]). Triassic granites show low Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb = 17.12 to 17.41, ²⁰⁷Pb/²⁰⁴Pb = 15.47 to 15.54, ²⁰⁸Pb/²⁰⁴Pb = 37.51 to 37.89) and metamorphic rocks of the Liaohe Group have high ratios (²⁰⁶Pb/²⁰⁴Pb = 18.20 to 24.28 and 18.32 to 20.06, ²⁰⁷Pb/²⁰⁴Pb = 15.69 to 16.44 and 15.66 to 15.98, ²⁰⁸Pb/²⁰⁴Pb = 37.29 to 38.61 and 38.69 to 40.00 for the marble of the Dashiqiao Formation and schist of the Gaixian Formation, respectively).Magmatic activities at Qingchengzi and in adjacent regions took place in three stages, and each contained several magmatic pulses: ca. 220 to 225 Ma and 211 to 216 Ma in the Triassic; 179 to 185 Ma, 163 to 168 Ma, 155 Ma and 149 Ma in the Jurassic, as well as ca. 140 to 130 Ma in the Early Cretaceous. The Triassic magmatism was part of the Triassic magmatic belt along the northern margin of the North China Craton produced in a post-collisional extensional setting, and granites in it formed by crustal melting induced by mantle magma. The Jurassic and Early Cretaceous magmatism was related to the lithospheric delamination in eastern China. The Triassic is the most important metallogenic stage at Qingchengzi. The Pb–Zn deposits, the Pb–Zn–Ag ore at Gaojiabaozi, and the gold deposits were all formed in this stage. They are temporally and spatially associated with the Triassic magmatic activity. Mineralization is very weak in the Jurassic. Ag ore at Gaojiabaozi was formed in the Early Cretaceous, which is suggested by the young Rb–Sr isochron age, field relations, and significantly different Pb isotopic ratios between the Pb–Zn–Ag and Ag ores. Pb isotopic compositions of the Pb–Zn ores suggest binary mixing for the source of the deposits. The magmatic end-member is the Triassic granites and the other metamorphic rocks of the Liaohe Group. Slightly different proportions of the two end-members, or an involvement of materials from hidden Cretaceous granites with slightly different Pb isotopic ratios, is postulated to interpret the difference of Pb isotopic compositions between the Pb–Zn–(Ag) and Ag ores. Sr isotopic ratios support this conclusion. At the western part of the Qingchengzi orefield, hydrothermal fluid driven by the heat provided by the now exposed Triassic granites deposited ore-forming materials in the low and middle horizons of the marbles of the Dashiqiao Formation near the intrusions to form mesothermal Zn–Pb deposits. In the eastern part, hydrothermal fluids associated with deep, hidden Triassic intrusions moved upward along a regional fault over a long distance and then deposited the ore-forming materials to form epithermal Au and Pb–Zn–Ag ores. Young magmatic activities are all represented by dykes across the entire orefield, suggesting that the corresponding main intrusion bodies are situated in the deep part of the crust. Among these, only intrusions with age of ca. 140 Ma might have released sufficient amounts of fluid to be responsible for the formation of the Ag ore at Gaojiabaozi.Our age results support previous conclusions that sphalerite can provide a reliable Rb–Sr age as long as the fluid inclusion phase is effectively separated from the “sulfide” phase. Our work suggests that the separation can be achieved by a step-resolution technique. Moreover, we suggest that pyrargyrite is a promising mineral for Rb–Sr isochron dating.     

青海玉树东莫扎抓铅锌矿床地质特征及碳氢氧同位素地球化学研究

东莫扎抓铅锌矿床位于青藏高原羌塘地体东北缘,是"三江"北段铅锌铜银多金属成矿带中的典型代表,对该矿床地质特征和成因类型的研究有助于理解区域铅锌铜银多金属成矿规律,对区域找矿具有重要意义.笔者通过详细的矿区地质考察、系统的矿石光薄片显微镜下鉴定和矿石中方解石的碳、氢、氧同位素分析测试,概述了东莫扎抓铅锌矿床的地质特征和成矿流体的碳、氢、氧同位素组成特征.东莫扎抓铅锌矿床矿体呈似层状展布,产状严格受到矿区逆冲断层的控制,赋矿围岩为上三叠统结扎群波里拉组灰岩和下一中二叠统开心岭群尕迪考组灰岩,发育强白云石化和弱硅化,矿物组合简单,主要为闪锌矿+方铅矿+黄铁矿+白云石+方解石+重晶石,矿石结构以皮壳状、草莓状等胶状结构和他形粒状结构为主,矿石构造为浸染状、角砾状、团块状和脉状.矿石中方解石的δ~(13)C_(V-PDB)值、δ~(18)O_(V-SMOW)值分别为δD_(V-SMOW)值分别为-1.8‰～+3.3‰、+6.1‰～+24.6‰和-137‰～-53‰,计算得到成矿流体的δ~(18)O_(流体)值为-0.5‰～+13.8‰.研究结果表明,东莫扎抓铅锌矿床的成矿流体主要来自盆地封存热卤水和大气降水,金属物质可能由区域流体在长距离迁移过程中通过与碳酸盐岩地层相互作用,以及淋滤含矿地层底部的火山岩而得来,成矿过程中伴随着碳酸盐岩的溶解作用,可能存在有机质的参与.据此,笔者将东莫扎抓矿床归为发育在碰撞造山带中受逆冲推覆断裂构造控制的类MVT铅锌矿床,并初步建立了东莫扎抓铅锌矿床的构造控矿模型.     

The spatial distribution of sedimentary compounds and their environmental implications in surface sediments of Lake Khar Nuur (Mongolian Altai)

Lake sediments are valuable natural archives to reconstruct paleoclimate and paleoenvironmental changes which consist of inorganic and organic sediment compounds of allochthonous origin from the catchment and of autochthonous production in the lake. However, for robust paleo-reconstructions it is important to develop a better understanding about sedimentation processes, the origin of inorganic and organic sediment compounds and their distribution within the lake. In this context, modern process studies provide important insights, although environmental and anthropological changes can affect the spatial distribution of sediment compounds through time. Therefore, in this study the spatial distribution of grain size and geochemical proxies in 52 surface sediment samples from Lake Khar Nuur, a small high-altitude lake in the Mongolian Altai with a small and anthropogenically used hydrological catchment, is investigated. The results show a distinct sediment focussing in the two deep basins of the lake, which therefore act as accumulation zones. In those accumulation zones, total organic carbon (TOC), total nitrogen (N) and their isotopic composition (δ¹³C_TOC, δ¹⁵N) as well as n-alkanes indicate that organic sediment compounds are a mixture of both allochthonous and autochthonous origin. While the recent catchment vegetation consists of grasses/herbs and the shrub Betula nana (L.) with distinct differences in their n-alkane homologue patterns, those differences are not reflected in the sediment surface samples which rather indicates that grass-derived n-alkanes become preferentially incorporated in the lake. Extensive anthropogenic activity such as grazing and housing in the southern part of the catchment causes soil erosion which is well reflected by high TOC, N and sulphur (S) contents and ¹⁵N depleted δ¹⁵N values at the central southern shore, i.e. increased allochthonous sediment input by anthropogenically-induced soil erosion. Overall, the surface sediments of Lake Khar Nuur origin from allochthonous and autochthonous sources and are focussed in the accumulation zones of the lake, while their distribution is both environmentally and anthropogenically driven.     

Subarctic catchment water storage and carbon cycling – Leading the way for future studies using integrated datasets at Pallas,Finland

Subarctic ecohydrological processes are changing rapidly, but detailed and integrated ecohydrological investigations are not as widespread as necessary. We introduce an integrated research catchment site (Pallas) for atmosphere, ecosystems, and ecohydrology studies in subarctic conditions in Finland that can be used for a new set of comparative catchment investigations. The Pallas site provides unique observational data and high-intensity field measurement datasets over long periods. The infrastructure for atmosphere- to landscape-scale research in ecosystem processes in a subarctic landscape has recently been complemented with detailed ecohydrological measurements. We identify three dominant processes in subarctic ecohydrology: (a) strong seasonality drives ecohydrological regimes, (b) limited dynamic storage causes rapid stream response to water inputs (snowmelt and intensive storms), and (c) hydrological state of the system regulates catchment-scale dissolved carbon dynamics and greenhouse (GHG) fluxes. Surface water and groundwater interactions play an important role in regulating catchment-scale carbon balances and ecosystem respiration within subarctic peatlands, particularly their spatial variability in the landscape. Based on our observations from Pallas, we highlight key research gaps in subarctic ecohydrology and propose several ways forward. We also demonstrate that the Pallas catchment meets the need for sustaining and pushing the boundaries of critical long-term integrated ecohydrological research in high-latitude environments.     

High spatial-resolution monitoring to investigate nitrate export and its drivers in a mesoscale river catchment along an anthropogenic land-cover gradient

Nitrate monitoring is commonly conducted with low-spatial resolution, only at the outlet or at a small number of selected locations. As a result, the information about spatial variations in nitrate export and its drivers is scarce. In this study, we present results of high-spatial resolution monitoring conducted between 2012 and 2017 in 65 sub-catchments in an Alpine mesoscale river catchment characterized by a land-use gradient. We combined stable isotope techniques with Bayesian mixing models and geostatistical methods to investigate nitrate export and its main drivers, namely, microbial N turnover processes, land use and hydrological conditions. In the investigated sub-catchments, mean values of NO₃⁻ concentrations and its isotope signatures (δ¹⁵N_NO3 and δ¹⁸O_NO3) varied from 2.6 to 26.7 mg L⁻¹, from −1.3‰ to 13.1‰, and from −0.4‰ to 10.1‰, respectively. In this study, land use was an important driver for nitrate export. Very strong and strong positive correlations were found between percentages of agricultural land cover and δ¹⁵N_NO3, and NO₃⁻ concentration, respectively. Mean proportional contributions of NO₃⁻ sources varied spatially and seasonally, and followed land-use patterns. The mean contribution of manure and sewage was much higher in the catchments characterized by a high percentage of agricultural and urban land cover comparing to forested sub-catchments. Specific NO₃⁻ loads were strongly correlated with specific discharge and moderately correlated with NO₃⁻ concentrations. The nitrate isotope and concentration analysis results suggest that nitrate from external sources is stored and accumulated in soil storage pools. Nitrification of reduced nitrogen species in those pools plays the most important role for the N-dynamics in the Erlauf river catchment. Consequently, nitrification of reduced N sources was the main nitrate source except for a number of sub-catchments dominated by agricultural land use. In the Erlauf catchment, denitrification plays only a minor role in controlling NO₃⁻ export on a regional scale.     

Storage-discharge characteristics of an active rock glacier catchment in the Innere Ölgrube,Austrian Alps

The active rock glacier “Innere Ölgrube” and its catchment area (Ötztal Alps, Austria) are assessed using various hydro(geo)logical tools to provide a thorough catchment characterization and to quantify temporal variations in recharge and discharge components. During the period from June 2014 to July 2018, an average contribution derived from snowmelt, ice melt and rainfall of 35.8%, 27.6% and 36.6%, respectively, is modelled for the catchment using a rainfall-runoff model. Discharge components of the rock glacier springs are distinguished using isotopic data as well as other natural and artificial tracer data, when considering the potential sources rainfall, snowmelt, ice melt and longer stored groundwater. Seasonal as well as diurnal variations in runoff are quantified and the importance of shallow groundwater within this rock glacier-influenced catchment is emphasized. Water derived from ice melt is suggested to be provided mainly by melting of two small cirque glaciers within the catchment and subordinately by melting of permafrost ice of the rock glacier. The active rock glacier is characterized by a layered internal structure with an unfrozen base layer responsible for groundwater storage and retarded runoff, a main permafrost body contributing little to the discharge (at the moment) by permafrost thaw and an active layer responsible for fast lateral flow on top of the permafrost body. Snowmelt contributes at least 1/3rd of the annual recharge. During droughts, meltwater derived from two cirque glaciers provides runoff with diurnal runoff variations; however, this discharge pattern will change as these cirque glaciers will ultimately disappear in the future. The storage-discharge characteristics of the investigated active rock glacier catchment are an example of a shallow groundwater aquifer in alpine catchments that ought to be considered when analysing (future) river runoff characteristics in alpine catchments as these provide retarded runoff during periods with little or no recharge.