Biogenic and abiogenic low-Mg calcite (bLMC and aLMC): Evaluation of seawater-REE composition,water masses and carbonate diagenesis

The ΣREE and shale-normalized (PAAS) REE_SN values of modern brachiopods (biogenic low-Mg calcite: bLMC) represented by several species from high- to low latitudes, from shallow- to deep waters and from warm- and cold-water environments, define three distinct average ‘seawater’ trends. The warm- and cold-water brachiopods define two indistinguishable (p < 0.050) groups that mimic open-ocean seawater REE chemistry, exhibiting the typical LREE enrichment with a slightly positive to negative Ce anomaly followed by an otherwise invariant series. Other recent brachiopods from an essentially siliciclastic seabed environment are distinct in both ΣREE and REE_SN trends from the previous two populations, showing a slight enrichment in the MREEs and an increasing trend in the HREEs. Other groups of modern brachiopods are characterized by elevated REE_SN trends relative to the ‘normal’ groups as well as by complexity of the series trends. The most characteristic feature is the decrease in the HREEs in these brachiopods from areas of unusual productivity (i.e., such as upwelling currents, fluvial input and aerosol dust deposition). Preserved brachiopods from the Eocene and Silurian exhibit REE_SN trends and Ce anomalies similar to that of the ‘open-ocean’ modern brachiopods, although, their enriched ΣREE concentrations suggest precipitation of bLMC influenced by extrinsic environmental conditions.Preservation of the bLMC was tested by comparing the ΣREE and REE_SN trends of preserved Eocene brachiopods to those of Oligocene brachiopods that were altered in an open diagenetic system in the presence of phreatic meteoric-water. The altered bLMC is enriched by approximately one order of magnitude in both ΣREE and REE_SN trends relative to that in bLMC of their preserved counterparts. Similarly, the ΣREE and REE_SN of preserved Silurian brachiopod bLMC were compared to those of their enclosing altered lime mudstone, which exhibits features of partly closed system, phreatic meteoric-water diagenesis. Despite these differences in the diagenetic alteration systems and processes, the ΣREEs and REE_SN trends of the bLMC of altered brachiopods and of originally mixed mineralogy lime mudstones (now diagenetic low-Mg calcite) are enriched by about one order of magnitude relative to those observed in the coeval and preserved bLMC.In contrast to the changes in ΣREE and REE_SN of carbonates exposed to phreatic meteoric-water diagenesis, are the REE compositions of late burial calcite cements precipitated in diagenetically open systems from burial fluids. The ΣREE and REE_SN trends of the burial cements mimic those of their host lime mudstone, with all showing slight LREE enrichment and slight HREE depletion, exhibiting a ‘chevron’ pattern of the REE_SN trends. The overall enrichment or depletion of the cement REE_SN trends relative to that of their respective host rock material reflects not only the openness of the diagenetic system, but also strong differences in the elemental and REE compositions of the burial fluids. Evaluation of the (Ce/Ce*)_SN and La = (Pr/Pr*)_SN anomalies suggests precipitation of the burial calcite cements essentially in equilibrium with their source fluids.     

Geochemical behaviour of some heavy metals of the Grot flotation tailing, Southeast Serbia

Grot tailing dump has the highest altitude of all tailing dumps in the Republic of Serbia. About 5.5 million tons of hydrocycloned sand was deposited in the tailing dump. This material was formed by flotation processing of ore from the Blagodat ore field. Vegetation was not developed in any part of the tailing. Minerals determined by X-ray diffraction analyses of representative samples form the tailing are quartz, clay minerals, calcite, feldspars, hematite, siderite, pyrite, sphalerite, galena and chalcopyrite. No regularities were noticed in their quantitative distribution. Statistical analysis of chemical fluctuations of lead, zinc, copper, arsenic and manganese concentrations showed that those with the highest concentrations are usually found on the central plateau. Lead displays the largest concentration range in the whole tailing. Maximal concentrations are found on the central and minimal in the south-western plateau. Zinc concentrations are up to 5,000 mg/kg, except in the central plateau where they reach extreme several times higher values. Copper concentrations are increased in the central plateau. In other parts of the tailing, concentrations are uniform and several times lower. Arsenic concentrations are mostly uniform, with the exception of extreme values in the north-western parts of the central plateau. Manganese shows uniform concentrations, somewhat increased on the south-eastern plateau. Chemical heterogeneity of the tailing material was influenced by the chronological discontinuity of the deposition and resedimentation. Resedimentation was the main cause of the fluctuation in the concentrations of the most mentioned heavy metals.     

Tidal amplification and along‐strike process variability in a mixed‐energy paralic system prograding onto a low accommodation shelf,Edgeøya,Svalbard

The study describes the depositional development and sediment partitioning in a prograding paralic Triassic succession. The deposits are associated with the advance of large prism‐scale clinoforms across a shallower platform area. Approaching the platform, the limited accommodation and associated relative higher rates of deposition generated straighter clinoforms with lower foreset angles. The vertical restriction across the platform is interpreted to have amplified the tidal signature. Sediment was redistributed from the coast into increasingly sandy delta‐front deposits, compared to offshore equivalents. The deposits comprise extensive compound dune fields of amalgamated and increasingly clean sandbodies up‐section. Rapid deposition of significant amounts of sand led to differential subsidence and growth‐faulting in the delta front, with downthrown fault blocks further amplifying the tidal energy through funnelling. A mixed‐energy environment created along‐strike variability along the delta front with sedimentation governing process‐regime. Areas of lower sedimentation were reworked by wave and storm‐action, whereas high sedimentation rates preserved fluvially dominated mouth bars. A major transgression, however, favoured tidally dominated deposits also in these areas, attributed to increasing rugosity of the coastline. Formation of an extensive subaqueous platform between the coast and delta front dampened incoming wave energy, and tidally dominated deposits dominate the near‐shore successions. Meanwhile formation of wave‐built sand‐bars atop the platform attest to continued wave influence. The strong tidal regime led to the development of a heterolithic near‐shore tidally dominated channel system, and sandier fluvial channels up‐river. The highly meandering tidal channels incising the subaqueous platform form kilometre wide successions of inclined heterolithic stratification. The fluvially dominated channels which govern deposition on the delta plain are narrower and slightly less deep, straighter, generally symmetric and filled with cleaner sands. This study provides important insight into tidal amplification and sand redistribution during shallowing on a wide shelf, along with along‐strike process‐regime variability resulting from variations in sediment influx.     

Architecture of growth basins in a tidally influenced,prodelta to delta-front setting: The Triassic succession of Kvalpynten,East Svalbard

World-class examples of fault-controlled growth basins with associated syn-kinematic sedimentary fill are developed in Upper Triassic prodelta to delta-front deposits exposed at Kvalpynten, SW Edgeøya in East Svalbard. They are interpreted to have interacted with north-westerly progradation of a regional delta system. The syn-kinematic successions consist of 4 to 5 coarsening-upward units spanning from offshore mudstones to subtidal heterolithic bars and compound tidal dunes, which were blanketed by regional, post-kinematic sandstone sheets deposited as laterally continuous, subaqueous tidal dune fields. The rate of growth faulting is reflected in the distribution of accommodation, which governs sedimentary architecture and stacking patterns within the coarsening-upward units. Fully compartmentalized basins (12, 200–800 m wide and c. 150 m high grabens and half grabens) are characterized by syn-kinematic sedimentary infill. These grabens and half-grabens are separated by 60–150 m high horsts composed of pro-delta to distal delta-front mudstones. Grabens host tabular tidal dunes (sandwaves), whereas half-grabens bound by listric faults (mainly south-dipping) consist of wedge-shaped, rotated strata with erosive boundaries proximal to the uplifted fault block crests. Heterolithic tidal bars (sand ridges) occur in narrow half-grabens, showing migration oblique to the faults, up the dipslope. Structureless sandstone wedges and localized subaqueous slumps that formed in response to collapse of the block crests were only documented in half-grabens. Late-kinematic deposition during the final stages of faulting occurred in partly compartmentalized basins, filled with variably thick sets of continuous sandstone belts (compound tidal dunes).     

Petrological, organic geochemical and geochemical characteristics of coal from the Soko mine, Serbia

A petrological, organic geochemical and geochemical study was performed on coal samples from the Soko Mine, Soko Banja basin, Serbia. Ten coal and two carbonaceous clay samples were collected from fresh, working faces in the underground brown coal mine from different parts of the main coal seam. The Lower Miocene, low-rank coal of the Soko Mine is a typical humic coal with huminite concentrations of up to 76.2 vol.%, liptinite less than 14 vol.% and inertinite less than 11 vol.%. Ulminite is the most abundant maceral with variable amounts of densinite and clay minerals. Sporinite and resinite are the most common macerals of the liptinite group. Inertodetrinite is the most abundant maceral of the inertinite group. The mineral-bituminous groundmass identified in some coal samples, and carbonaceous marly clay, indicate sub-aquatic origin and strong bacterial decomposition. The mean random huminite reflectance (ulminite B) for the main coal seam is 0.40 ± 0.05% Rr, which is typical for an immature to early mature stage of organic matter.The extract yields from the coal of the Soko Banja basin ranges from 9413 to 14,096 ppm, in which alkanes constituted 1.0–20.1%, aromatics 1.3–14.7%, asphaltenes 28.1–76.2% and resins 20.2–43.5%. The saturated hydrocarbon fractions included n-C₁₅ to n-C₃₂, with an odd carbon number that predominate in almost all the samples. The contents of n-C₂₇ and n-C₂₉ alkanes are extremely high in some samples, as a contribution of epicuticular waxes from higher plants. Acyclic isoprenoid hydrocarbons are minor constituents in the aliphatic fraction, and the pristane/phytane (Pr/Ph) ratio varies between 0.56 and 3.13, which implies anaerobic to oxic conditions during sedimentation. The most abundant diterpanes were abietane, dehydroabietane and 16α(H)-phyllocladane. In samples from the upper part of the coal seam, diterpanes are the dominant constituents of the alkane fraction. Polycyclic alkanes of the triterpane type are important constituents of alkane fractions. The occurrence of ββ- and αβ-type hopanes from C₂₇ to C₃₁, but without C₂₈, is typical for the Soko Banja coals.The major and trace elements in the coal were analysed using X-ray fluorescence (XRF), and inductively coupled plasma-mass spectrometry (ICP-MS). In comparison with world lignites, using the geometric mean value, the coal from the Soko Banja Basin has a high content of strontium (306.953 mg/kg). Higher values than the world lignites were obtained for Mo (3.614 mg/kg), Ni (8.119 mg/kg), Se (0.884 mg/kg), U (2.642 mg/kg) and W (0.148 mg/kg). Correlation analysis shows inorganic affinity for almost all the major and trace elements, except for S, which has an organic affinity.     

<Emphasis Type="Italic">Pleurozium schreberi</Emphasis> of the Tatra mountains (Poland) used as a bioindicational system for observing long range atmospheric transport of chemical elements

Concentrations of the elements Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, V and Zn were measured in the moss Pleurozium schreberi from the Tatra National Park, one of the most protected regions in Poland. The moss samples were collected at different elevations between 860 and 2220 m a.s.l. P. schreberi was used as bioindicator for long range transported atmospheric pollution investigating the hypothesis that elevation influences the concentrations of elements in this moss. Principal component and classification analysis (PCCA) distinguished between mosses from the highest and the lowest elevations and mosses from West/East oriented valleys. P. schreberi from the highest elevations contained the highest concentrations of Cd, Cu, Cr, Fe, Mn, Pb, V and Zn. P. schreberi from the lowest elevation contained the highest concentration of K. P. schreberi from West/East oriented valleys contained the highest concentrations of Ni and Co. P. schreberi from the Tatra National Park, one of the most protected areas in Poland, receives metals originating from long distance aerial transport.     

Sub-annual moraine formation at an active temperate Icelandic glacier

This paper presents detailed geomorphological and sedimentological investigations of small recessional moraines at Fjallsjökull, an active temperate outlet of Öræfajökull, southeast Iceland. The moraines are characterized by striking sawtooth or hairpin planforms, which are locally superimposed, giving rise to a complex spatial pattern. We recognize two distinct populations of moraines, namely a group of relatively prominent moraine ridges (mean height ~1.2 m) and a group of comparatively low-relief moraines (mean height ~0.4 m). These two groups often occur in sets/systems, comprising one pronounced outer ridge and several inset smaller moraines. Using a representative subsample of the moraines, we establish that they form by either (i) submarginal deformation and squeezing of subglacial till or (ii) pushing of extruded tills. Locally, proglacial (glaciofluvial) sediments are also incorporated within the moraines during pushing. For the first time, to our knowledge, we demonstrate categorically that these moraines formed sub-annually using repeat uncrewed aerial vehicle (UAV) imagery. We present a conceptual model for sub-annual moraine formation at Fjallsjökull that proposes the sawtooth moraine sequence comprises (i) sets of small squeeze moraines formed during melt-driven squeeze events and (ii) larger push moraines formed during winter re-advances. We suggest the development of this process-form regime is linked to a combination of elevated temperatures, high surface meltwater fluxes to the bed and emerging basal topography (a depositional overdeepening). These factors result in highly saturated subglacial sediments and high porewater pressures, which induces submarginal deformation and ice-marginal squeezing during the melt season. Strong glacier recession during the summer, driven by elevated temperatures, allows several squeeze moraines to be emplaced. This process-form regime may be characteristic of active temperate glaciers receding into overdeepenings during phases of elevated temperatures, especially where their englacial drainage systems allow efficient transfer of surface meltwater to the glacier bed near the snout margin. © 2020 The Authors. Earth Surface Processes and Landforms published by John Wiley & Sons Ltd     

Sedimentation History of Neogene Lacustrine Sediments of Suseocka Bela Stena Based on Geochemical Parameters (Valjevo-Mionica Basin, Serbia)

Sediments of the western part of the Valjevo-Mionica basin (Serbia) were examined both geochemically and mineralogically to explain, on the basis of their sedimentological characteristics, the causes of changes in their qualitative and quantitative composition. A total of 62 samples obtained from the drillhole at depths up to 400 m was investigated. Using correlation of the obtained data, six geochemical zones were defined, two of which being specially distinguished by their mineralogical, geochemical and sedimentological characteristics. The first one, upper zone A, consists of banded marlstones interbedded with clay and oil shales and is characterized by presence of analcite and searlesite. These minerals and very high contents of Na2O indicate sedimentation in alkaline conditions with increased salinity in arid climate. That provided pronounced water stratification, as well as higher bioproductivity in the basin and sedimentary organic matter preservation. Therefore, the zone A sediments are characterized by high organic matter contents of the type which provides good potential for production of liquid hydrocarbons. Another specific zone, zone F, contains sediments with very high MgO, K2O and Li concentrations. Their geochemical correlation, as well as almost complete absence of illite in this zone, indicates the presence of interstratified clay mineral type illite-saponite (lithium-bearing Mg-smectite).     

Hydrothermally induced diagenesis: Evidence from shallow marine-deltaic sediments,Wilhelmøya,Svalbard

Sedimentary basins containing igneous intrusions within sedimentary reservoir units represent an important risk in petroleum exploration. The Upper Triassic to Lower Jurassic sediments at Wilhelm?ya(Svalbard) contains reservoir heterogeneity as a result of sill emplacement and represent a unique case study to better understand the effect of magmatic intrusions on the general burial diagenesis of siliciclastic sediments. Sills develop contact metamorphic aureoles by conduction as presented in many earlier studies. However, there is significant impact of localized hydrothermal circulation systems affecting reservoir sediments at considerable distance from the sill intrusions. Dolerite sill intrusions in the studied area are of limited vertical extent(～12 m thick), but created localized hydrothermal convection cells affecting sediments at considerable distance(more than five times the thickness of the sill)from the intrusions. We present evidence that the sedimentary sequence can be divided into two units:(1) the bulk poorly lithified sediment with a maximum burial temperature much lower than 60-70 ℃,and(2) thinner intervals outside the contact zone that have experienced hydrothermal temperatures(around 140 ℃). The main diagenetic alteration associated with normal burial diagenesis is minor mechanical plastic deformation of ductile grains such as mica. Mineral grain contacts show no evidence of pressure dissolution and the vitrinite reflectance suggests a maximum temperature of ～40 ℃. Contrary to this, part of the sediment, preferentially along calcite cemented flow baffles, show evidence of hydrothermal alteration. These hydrothermally altered sediment sections are characterized by recrystallized carbonate cemented intervals. Further, the hydrothermal solutions have resulted in localized sericitization(illitization) of feldspars, albitization of both K-feldspar and plagioclase and the formation of fibrous illite nucleated on kaolinite. These observations suggest hydrothermal alteration at T 120-140 ℃ at distances considerably further away than expected from sill heat dissipation by conduction only, which commonly affect sediments about twice the thickness of the sill intrusion. We propose that carbonate-cemented sections acted as flow baffles already during the hydrothermal fluid mobility and controlled the migration pathways of the buoyant hot fluids. Significant hydrothermally induced diagenetic alterations affecting the porosity and hence reservoir quality was not noted in the noncarbonate-cemented reservoir intervals.