Physicochemical and biological influences on sedimentary‐fabric formation in a salinity and oxygen‐restricted semi‐enclosed sea: Gotland Deep,Baltic Sea

Two ca 8000 year long sediment cores from the Gotland Deep, the central sub‐basin of the Baltic Sea, were studied by means of digital images, X‐radiographs and scanning electron microscopy–energy‐dispersive X‐ray mineralogical analysis to gain understanding of the physicochemical and biological influences on sedimentary‐fabric formation in modern and ancient seas with a high flux of organic carbon, and associated oxygen stress and depauperate ichnofauna. Four lithofacies were recognized: (i) sharply laminated mud; (ii) biodeformed mud; (iii) burrow‐mottled mud; and (iv) sedimentation‐event bed. The sharply laminated and burrow‐mottled facies dominate the cores as alternating long intervals, whereas the biodeformed and sedimentation‐event facies occur as thin interbeds within the sharply laminated intervals. The sharply laminated mud comprises alternating diatom‐rich and lithic laminae, with occasional Mn‐carbonate laminae. Lamination discontinuity horizons within the laminites, where the regular lamination is overlain sharply by gently inclined lamination, challenge the traditional view of mud accumulation by settling from suspension, but indicate localized accumulation by particle‐trapping microbial mats and, potentially, by the rapid lateral accretion of mud from bedload transport. The biodeformed interbeds record brief (few years to few decades) oxic–dysoxic conditions that punctuated the anoxic background conditions and permitted sediment‐surface grazing and feeding by a very immature benthic community restricted to the surface mixed tier. The likely biodeformers were meiofauna and nectobenthic pioneers passively imported with currents. The sedimentation‐event interbeds are distal mud turbidites deposited from turbidity currents probably triggered by severe storms on the adjacent coastal areas. The turbidite preservation was favoured by the anoxic background conditions. The long burrow‐mottled intervals are characterized by intensely bioturbated fabrics with discrete Planolites, rare Arenicolites/Polykladichnus and very rare Lockeia trace fossils, as well as bivalve biodeformational structures which represent shallowly penetrating endobenthic feeding and grazing strategies and permanent dwellings. These burrowed intervals represent longer periods (several years to few centuries) of oxic–dysoxic conditions that permitted maturation in the benthos by means of larval settling of opportunistic worm‐like macrofauna and bivalves, resulting in the development of a transition tier. These observations imply more dynamic and oxic depositional conditions in Gotland Deep than previously thought. Comparison to previous zoobenthic studies in the area allowed discussion of the benthic dynamics, and the identification of probable biodeforming and trace‐producing species. Implications for current biofacies and trace‐fossil models are discussed.     

Quantitative micro‐X‐ray fluorescence scanning spectroscopy of wet sediment based on the X‐ray absorption and emission theories: Its application to freshwater lake sedimentary sequences

Micro‐X‐ray fluorescence scanning spectroscopy of marine and lake sedimentary sequences can provide detailed palaeoenvironmental records through element intensity proxy data. However, problems with the effects of interstitial pore water on the micro‐X‐ray fluorescence intensities have been pointed out. This is because the X‐ray fluorescence intensities are measured directly at the surfaces of split wet sediment core samples. This study developed a new method for correcting X‐ray fluorescence data to compensate for the effects of pore water using a scanning X‐ray analytical microscope. This involved simultaneous use of micro‐X‐ray fluorescence scanning spectroscopy and an X‐ray transmission detector. To evaluate the interstitial pore water content from the X‐ray transmission intensities, a fine‐grained sediment core retrieved from Lake Baikal (VER99‐G12) was used to prepare resin‐embedded samples with smooth surfaces and uniform thickness. Simple linear regression between the linear absorption coefficients of the samples and their porosity, based on the Lambert–Beer law, enabled calculation of the interstitial pore spaces and their resin content with high reproducibility. The X‐ray fluorescence intensities of resin‐embedded samples were reduced compared with those of dry sediment samples because of: (i) the X‐ray fluorescence absorption of resin within sediment; and (ii) the sediment dilution effects by resin. An improved micro‐X‐ray fluorescence correction equation based on X‐ray fluorescence emission theory considers the instrument's sensitivity to each element, which provides a reasonable explanation of these two effects. The resin‐corrected X‐ray fluorescence intensity was then successfully converted to elemental concentrations using simple linear regression between the data from micro‐X‐ray fluorescence scanning spectroscopy and from the conventional analyzer. In particular, the calculated concentration of SiO₂ over the depth of the core, reflecting diatom/biogenic silica concentration, was significantly changed by the calibrations, from a progressively decreasing trend to an increasing trend towards the top of the core.     

Molar-tooth Carbonate Sequences and Sr Isotopes in the Neoproterozoic for Stratigraphic Correlation： Research in the JUin-Liaoning-Xuzhou-Huaiyang Area of the Sino-Korean Plate and Its Correlation with the Yangtze Plate

Based on a study of Neoproterozoic carbonates in the Jilin-Liaoning-Xuzhou-Huaiyang area, especially its cyclic sequence stratigraphy and Sr isotopes, two maximum sea flooding events (at 820 Ma and 835 Ma) have been identified. The resulting isochronous stratigraphic correlation proves that these Precambrian strata were connected between the Qingbaikou and the Nanhuan systems with a time range from 750 Ma to 850 Ma. The disappearance of microsparite carbonate and coming of a glacial stage offer important evidence for worldwide stratigraphic correlation and open a window for further correlation of the stratigraphic successions across the Sino-Korean and Yangtze Plates. A new correlation scheme is therefore provided based on our work.     

Formation of magnesium‐smectite during lacustrine carbonates early diagenesis: Study case of the volcanic crater lake Dziani Dzaha (Mayotte – Indian Ocean)

The volcanic crater lake of Dziani Dzaha in Mayotte is studied to constrain the geochemical settings and the diagenetic processes at the origin of Mg‐phyllosilicates associated with carbonate rocks. The Dziani Dzaha is characterized by intense primary productivity, volcanic gases bubbling in three locations and a volcanic catchment of phonolitic/alkaline composition. The lake water has an alkalinity of ca 0·2 mol l^?1 and pH values of ca 9·3. Cores of the lake sediments reaching up to one metre in length were collected and studied by means of carbon–hydrogen–nitrogen elemental analyzer, X‐ray fluorescence spectrometry and X‐ray powder diffraction. In surface sediments, the content of total organic carbon reaches up to 20 weight %. The mineral content consists of aragonite and hydromagnesite with minor amounts of alkaline feldspar and clinopyroxene from the volcanic catchment. Below 30 cm depth, X‐ray diffraction analyses of the <2 μm clay fraction indicate the presence of a saponite‐like mineral, a Mg‐rich smectite. The saponite‐like mineral accumulates at depth to reach up to ca 30 weight %, concurrent with a decrease of the contents of hydromagnesite and organic matter. Thermodynamic considerations and mineral assemblages suggest that the evolution of the sediment composition resulted from early diagenetic reactions. The formation of the saponite‐like mineral instead of Al‐free Mg‐silicates resulted from high aluminum availability, which is favoured in restricted lacustrine environments hosted in alkaline volcanic terrains commonly emplaced during early stages of continental rifting. Supersaturation of the lake water relative to saponite is especially due to high pH values, themselves derived from high primary productivity. This suggests that a genetic link may exist between saponite and the development of organic‐rich carbonate rocks, which may be fuelled by the input of CO₂‐rich volcanic gases. This provides novel insights into the composition and formation of saponite‐rich deposits under a specific geodynamic context such as the Cretaceous South Atlantic carbonate reservoirs.     

Geochemical Characterization of Bolivian Formative Earthen Architecture by Wavelength‐Dispersive X‐ray Fluorescence

In this study, we employ wavelength‐dispersive X‐ray fluorescence (WDXRF) to characterize construction materials from Formative civic architecture (1000 B.C.E.–C.E. 400), ethnographic mudbricks, and off‐site controls from the Taraco Peninsula, Bolivia. The preparation of earthen construction materials for civic buildings can shed light on aspects of community development such as labor organization, resource management, and architectural technologies. We apply geochemical results to reconstructing how public buildings were made as communities moved toward socio‐political complexity in this region. However, there are few geochemical studies in the Andes, and little prior scientific analysis of earthen architecture. We therefore tested the efficacy of WDXRF for this region, and developed control materials. Our archaeological samples were selected from two Formative villages, Chiripa and Kala Uyuni. In this study, we performed WDXRF analyses on 63 archaeological and control samples including archaeological floors, walling, plasters, and mortars, as well as contemporary ethnographic walling and topsoils. Elemental signatures for 28 elements clearly distinguished the archaeological flooring, walling, plaster, and mortars from ethnographic and off‐site controls. More subtle variations were detected that distinguish study sites and the different material types. Laboratory‐calibrated multi‐element XRF effectively supports efforts to reconstruct the pathways to social complexity in the Titicaca Basin.     

Is X‐ray core scanning non‐destructive? Assessing the implications for optically stimulated luminescence (OSL) dating of sediments

Optically stimulated luminescence (OSL) dating is widely used to date clastic deposits, including those collected by coring. X‐ray scanning of cores has become popular because of the rapidly acquired, high‐resolution information it gives about optical, radiographic and elemental variations. Additionally, X‐ray scanning is widely viewed as a non‐destructive method. However, such instruments use an intense X‐ray beam that irradiates the split core to enable both X‐radiographic and X‐ray fluorescence (XRF) analysis. This irradiation will influence the optically stimulated luminescence signal in the sediments. This study determines the radiation dose delivered to sediments in a core during an X‐ray scan, and assesses the implications for studies wishing to combine X‐ray scanning and OSL dating. Copyright © 2009 John Wiley & Sons, Ltd.     

Identification of Uranyl Minerals Using Oxygen K‐Edge X‐Ray Absorption Spectroscopy

Although most of the world's uranium exists as pitchblende or uraninite, this mineral can be weathered to a great variety of secondary uranium minerals, most containing the uranyl cation. Anthropogenic uranium compounds can also react in the environment, leading to spatial–chemical alterations that could be useful for nuclear forensics analyses. Soft X‐ray absorption spectroscopy (XAS) has the advantages of being non‐destructive, element‐specific and sensitive to electronic and physical structure. The soft X‐ray probe can also be focused to a spot size on the order of tens of nanometres, providing chemical information with high spatial resolution. However, before XAS can be applied at high spatial resolution, it is necessary to find spectroscopic signatures for a variety of uranium compounds in the soft X‐ray spectral region. To that end, we collected the near edge X‐ray absorption fine structure (NEXAFS) spectra of a variety of common uranyl‐bearing minerals, including uranyl carbonates, oxyhydroxides, phosphates and silicates. We find that uranyl compounds can be distinguished by class (carbonate, oxyhydroxide, phosphate or silicate) based on their oxygen K‐edge absorption spectra. This work establishes a database of reference spectra for future spatially resolved analyses. We proceed to show scanning X‐ray transmission microscopy (STXM) data from a schoepite particle in the presence of an unknown contaminant.     

Generation of a realistic 3D sand assembly using X‐ray micro‐computed tomography and spherical harmonic‐based principal component analysis

Three‐dimensional particle morphology is a significant problem in the discrete element modeling of granular sand. The major technical challenge is generating a realistic 3D sand assembly that is composed of a large number of random‐shaped particles containing essential morphological features of natural sands. Based on X‐ray micro‐computed tomography data collected from a series of image processing techniques, we used the spherical harmonics (SH) analysis to represent and reconstruct the multi‐scale features of real 3D particle morphologies. The SH analysis was extended to some highly complex particles with sharp corners and surface cavities. We then proposed a statistical approach for the generation of realistic particle assembly of a given type of sand based on the principle component analysis (PCA). The PCA aims to identify the major pattern of the coefficient matrix, which is made up of the SH coefficients of all the particles involved in the analysis. This approach takes into account the particle size effect on the variation of particle morphology, which is observed from the available results of micro‐computed tomography and QICPIC analyses of sand particle morphology. Using the aforementioned approach, two virtual sand samples were generated, whose statistics of morphological parameters were compared with those measured from real sand particles. The comparison shows that the proposed approach is capable of generating a realistic sand assembly that retains the major morphological features of the mother sand. Copyright © 2016 John Wiley & Sons, Ltd.     

P–T–t estimation of deformation in low‐grade quartz‐feldspar‐bearing rocks using thermodynamic modelling and 40Ar/39Ar dating techniques: example of the Plan‐de‐Phasy shear zone unit (Briançonnais Zone,Western Alps)

Pressure–Temperature–time (P–T–t) estimates of the syn‐kinematic strain at the peak‐pressure conditions reached during shallow underthrusting of the Briançonnais Zone in the Alpine subduction zone was made by thermodynamic modelling and ⁴⁰Ar/³⁹Ar dating in the Plan‐de‐Phasy unit (SE of the Pelvoux Massif, Western Alps). The dated phengite minerals crystallized syn‐kinematically in a shear zone indicating top‐to‐the‐N motion. By combining X‐ray mapping with multi‐equilibrium calculations, we estimate the phengite crystallization conditions at 270 ± 50 °C and 8.1 ± 2 kbar at an age of 45.9 ± 1.1 Ma. Combining this P–T–t estimate with data from the literature allows us to constrain the timing and geometry of Alpine continental subduction. We propose that the Briançonnais units were scalped on top of the slab during ongoing continental subduction and exhumed continuously until collision.     

Production of mud‐grade carbonates by marine fish: Crystalline products and their sedimentary significance

Recent work has established that marine teleost (bony) fish represent a prolific source of mud grade, mainly high‐Mg calcite, carbonate sediment by means of primary precipitation within the intestine. Previously documented crystalline products display a diverse array of morphologies, many unique in shallow tropical marine settings, and have a wide range of magnesium contents (from 18 to 39 mol% MgCO₃). This study utilizes scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray diffraction and liquid ion chromatography to provide a more extensive and expansive morphological, mineralogical and chemical characterization of the crystalline forms produced by a wider range of piscine functional groups (covering 21 different fish species common in The Bahamas). Several crystal morphologies not previously described in fish‐derived carbonates are documented, and chemical composition is found to be more variable than previously reported: in addition to high‐Mg calcites with >18 mol% MgCO₃, high‐Mg calcites with lower MgCO₃ contents and low‐Mg calcites are identified. From the expanded species range, MgCO₃ content in fish‐derived carbonates ranges from ca 0˙5 to > 40 mol%, and particle length is in the range 0˙1 to >50 μm (typically <2 μm for individual crystals). Amorphous Mg‐carbonates (with detectable CaCO₃ of <2 mol%) are also found to varying extent in the precipitates of many species. Dominant mineralogy and MgCO₃ content varies with producing species and crystal morphology (itself a species‐dependent variable). Given the very small grain size and often high MgCO₃ contents of these carbonates, interesting questions arise about their preservation potential. Thus, the extent to which carbonates produced by different species may follow different post‐excretion preservation pathways is considered.     

Platinum‐Group Element Results for Two Cobalt‐Rich Seamount Crust Ultra‐Fine Reference Materials: MCPt‐1and MCPt‐2

Two Co‐rich seamount crust reference materials, MCPt‐1 and MCPt‐2, were prepared using ultra‐fine particle size milling technique and characterised for the platinum‐group elements (PGEs). The raw material for these two reference materials was collected separately from the Magellan seamounts of the western Pacific Ocean and the seamounts of the central Pacific Ocean by Russian and Chinese scientists. First, they were ground by ball mill to a ?200 mesh powder, then further processed by ultra‐fine jet mill and well‐mixed. The particle size distributions of the samples were tested by a laser particle analyser; the average particle size was 1.8 and 1.5 μm (equal to about 2000 mesh) respectively. The homogeneity of six major and minor elements in these two materials was tested at the milligram level of sampling mass by high‐precision wavelength dispersive X‐ray fluorescence (XRF) spectrometry and at the microgram level of sampling mass by electron probe microanalyser. The homogeneity of more than forty trace elements, including Pt, was tested at the microgram level of sampling mass by LA‐ICP‐MS. Except for Rh, all PGEs were determined by isotope dilution‐ICP‐MS. Platinum in MCPt‐1 and MCPt‐2 was characterised as certified values, whereas the other five PGEs in MCPt‐1 and MCPt‐2 were reported as reference values. In addition, the information values of sixty‐two major, minor and trace elements were obtained by XRF, ICP‐AES and ICP‐MS. The minimum sampling mass for the determination of PGEs was 1 g, while the minimum sampling mass for the determination of the other elements was 2–5 mg.     

Multidirectional,synchronously‐triggered seismo‐turbidites and debrites revealed by X‐ray computed tomography (CT)

On 21 April 2007, a M_w 6·2 earthquake struck Aysén fjord (Chilean Patagonia) and caused onshore and offshore mass movements which triggered tsunamis and density flows in the fjord. To better understand the facies successions in, and the intercalation of, the density‐flow deposits, a study was made of the 2007 deposits in 22 short sediment cores taken in the inner Aysén fjord. By combining grain‐size analysis with X‐ray computed tomography scanning, it was possible to demonstrate that the encountered facies correspond to classical divisions of debrites and turbidites. The single‐event deposits consist of a succession of several sub‐deposits deposited under different flow directions and can be interpreted as stacked turbidites. Orientations of: (i) folds; (ii) imbricated mud clasts; (iii) backsets and foresets of climbing ripples; and (iv) asymmetrical convolute lamination were used to determine relative flow directions at the location of the cores. By assigning the basal flow of the stacked debrites and turbidites to the closest principal mass flow, the absolute flow directions of the sub‐deposits were determined which, in combination with multibeam basin‐floor morphology, allowed reconstruction of the 2007 density‐flow successions in Aysén fjord. Furthermore, alternating flow directions provide evidence for a seiche induced by the density flows. It was concluded that X‐ray computed tomography scans provide crucial information for reconstructing palaeoflows and can be a useful tool in marine and lacustrine sedimentology and palaeoseismology. The multidirectionality of sub‐deposits in turbidites is, next to differences in mineralogy, a new criterion to identify stacked turbidites. These multidirectional, stacked turbidites are an indication of simultaneous triggering of density flows and can therefore, in most cases, be attributed to earthquakes, ruling out other triggers, such as floods, storms or other sediment failures.     

A comparison of grain‐size analysis methods for sand‐dominated fluvial sediments

Grain‐size distribution is a fundamental tool for interpreting sedimentary units within depositional systems. The techniques assessed in this study are commonly used to determine grain‐size distributions for sand‐dominated sediments. However, the degree of consistency and differences in interpretation when using a combination of grain‐size methods have not yet been assessed systematically for sand‐dominated fluvial sediments. Results obtained from laser diffraction, X‐ray attenuation and scanning electron microscopy grain‐size analysis techniques were compared with those obtained from the traditional sieve/hydrometer method. Scanning electron microscopy was shown to provide an inaccurate quantitative analysis of grain‐size distributions because of difficulties in obtaining representative samples for examination. The X‐ray attenuation method is unsuitable for sand‐dominated sediments because of its upper size range of only 300 μm. The consistently strong correlation between the laser diffraction results and the sieve/hydrometer results shows that these methods are comparable for sand‐dominated fluvial sediments. Provided that sample preparation is consistent, the latter two methods can be used together within a study of such sediments while maintaining a high degree of accuracy. These results indicate that data for sand‐dominated fluvial sediments gained from the long‐established sieve/hydrometer method can be compared with confidence to those obtained by modern studies using laser diffraction techniques.     

Granular element method for three‐dimensional discrete element calculations

This paper endows the recently‐proposed granular element method (GEM) with the ability to perform 3D discrete element calculations. By using non‐uniform rational B‐Splines to accurately represent complex grain geometries, we proposed an alternative approach to clustering‐based and polyhedra‐based discrete element methods whereby the need for complicated and ad hoc approaches to construct 3D grain geometries is entirely bypassed. We demonstrate the ability of GEM in capturing arbitrary‐shaped 3D grains with great ease, flexibility, and without excessive geometric information. Furthermore, the applicability of GEM is enhanced by its tight integration with existing non‐uniform rational B‐Splines modeling tools and ability to provide a seamless transition from binary images of real grain shapes (e.g., from 3D X‐ray CT) to modeling and discrete mechanics computations.Copyright © 2013 John Wiley & Sons, Ltd.     

Graphitization of organic matter and fluid‐deposited graphite in Palaeoproterozoic (Birimian) black shales of the Kaya‐Goren greenstone belt (Burkina Faso,West Africa)

Palaeoproterozoic black shales form an essential part of the Birimian volcanosedimentary belt in Burkina Faso, West Africa. The mean R_max values and the atomic H/C values of the bulk carbonaceous matter (BCM), together with rock structures and mineral assemblages, indicate that these carbon‐rich rocks were metamorphosed to sub‐greenschist and low‐grade greenschist facies. X‐ray diffraction reveals that the (002) ‘graphite’ peak width in half maximum (FWHM) ranges from 0.43 to 0.71 °2θ in sub‐greenschist facies and from 0.27 to 0.41 °2θ in greenschist facies rocks, but the d(002) values in both groups of rocks are approximately the same (～3.35 Å). The BCM of individual samples is composed of particles with very variable shape, reflectance and Raman spectra. Type I particles that predominate in sub‐greenschist facies are fine‐grained, irregular or elongate bodies 1 to 3 μm in size. Their maximum reflectance (R_max) ranges between 2.5% and 8.2%, and Raman parameters R1 and R2 range from 0.5 to 1.4 and 0.5 to 0.8, respectively. Type II particles are lath‐shaped, up to 40 μm large bodies, commonly arranged parallel to white mica flakes. The number of these particles increases from sub‐greenschist to greenschist facies. Maximum reflectance varies between 6% and 11.2% and R1 and R2 Raman parameters range from 0.05 to 0.7 and from 0.1 to 0.5, respectively. Type III particles occur in hydrothermally altered and sheared rocks; these are nodular aggregates composed of grains up to 10 μm in size. This type of particles has very high reflectance (R_max = 11–15%) and its Raman spectra indicate a very high degree of structural ordering corresponding to well‐ordered graphite. Type I particles represent original organic matter in the metasediments. Type II particles are believed to have been formed either in situ by solid‐state transformation of Type I particles or by crystallization from metamorphic fluids. Gradual graphitization of the Type I organic particles and the growth of lath‐shaped Type II particles from a fluid phase is assumed to have taken place under the peak metamorphic conditions associated with the burial of Birimian sediments during thrust tectonism, progressive tectonic accretion and crustal thickening during the D1 event of the Eburnean orogeny. The growth of equant, high‐reflectance postkinematic nodular aggregates of Type III particles is ascribed to the reduction of CO₂‐rich fluids during a hydrothermal event associated with Late Eburnean D2 exhumation and strike–slip movements. Type I carbonaceous particles were only slightly affected by high‐temperature, low‐pressure contact metamorphism during intrusion of Late Eburnean magmatic bodies, whereas formation of Type II or III particles was not recorded in contact‐metamorphosed rocks at all.     

Three dimensional simulation of fluid flow in X‐ray CT images of porous media

A numerical scheme is developed in order to simulate fluid flow in three dimensional (3‐D) microstructures. The governing equations for steady incompressible flow are solved using the semi‐implicit method for pressure‐linked equations (SIMPLE) finite difference scheme within a non‐staggered grid system that represents the 3‐D microstructure. This system allows solving the governing equations using only one computational cell. The numerical scheme is verified through simulating fluid flow in idealized 3‐D microstructures with known closed form solutions for permeability. The numerical factors affecting the solution in terms of convergence and accuracy are also discussed. These factors include the resolution of the analysed microstructure and the truncation criterion. Fluid flow in 2‐D X‐ray computed tomography (CT) images of real porous media microstructure is also simulated using this numerical model. These real microstructures include field cores of asphalt mixes, laboratory linear kneading compactor (LKC) specimens, and laboratory Superpave gyratory compactor (SGC) specimens. The numerical results for the permeability of the real microstructures are compared with the results from closed form solutions. Copyright © 2004 John Wiley & Sons, Ltd.     

The effects of surface weathering on the geochemical analysis of archaeological lithic samples using non‐destructive polarized energy dispersive XRF

The purpose of this paper is to show the effects of lithic artifact surface weathering on whole rock non‐destructive polarized energy dispersive X‐ray fluorescence (P‐ED‐XRF) major and trace element determinations. Chemical results for a weathered and subsequently mechanically ground subset of New Hampshire Ossipee archaeological flakes, cataloged as hornfels, show that both groups of elements are variably affected by weathering. A graphic approach is developed and proposed to highlight the role and importance of immobile elements. A case is made and an analytical method is proposed for the routine use of P‐ED‐XRF spectrometers to determine the chemical makeup of lithic artifacts and therefore provide a data set compatible with existing geochemical databases and literature. The use of specific variation diagrams is adopted to portray the weathering trend. Internationally approved geochemical rock type diagrams are used to correct the rock type previously assigned to Ossipee artifacts and in turn narrow down potential quarry sources. © 2011 Wiley Periodicals, Inc.     

Geochemistry,Petrography and Spectroscopy of Organic Matter of Clay‐Associated Kerogen of Ypresian Series: Gafsa‐Metlaoui Phosphatic Basin,Tunisia

This work presents geochemical characterization of isolated kerogen out of clay fraction using petrography studies, infrared absorption and solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy, with N‐alkane distributions of saturated hydrocarbon. Mineralogical study of clay mineral associations was carried out using X‐ray diffraction (XRD), on Ypresian phosphatic series from Gafsa‐Metlaoui basin, Tunisia. The XRD data indicate that smectite, palygorskite and sepiolite are the prevalent clay minerals in the selected samples. In this clay mineral association, the N‐alkane (m/z = 57) distribution indicates that the marine organic matter is plankton and bacterial in origin. The kerogens observed on transmitted light microscopy, however, appear to be totally amorphous organic matter, without any appearance of biological form. The orange gel‐like amorphous organic matter with distinct edges and homogenous texture is consistent with a high degree of aliphaticity. This material has relatively intense CH₂ and CH₃ infrared bands in ¹³C NMR peaks. This aliphatic character is related to bacterial origin. Brown amorphous organic matter with diffuse edges has a lower aliphatic character than the previous kerogen, deduced from relatively low CH₂ and CH₃ infrared and ¹³C NMR band intensities.     

Quantitative WD‐XRF calibration for small ceramic samples and their source material

A wavelength‐dispersive X‐ray fluorescence (WD‐XRF) calibration is developed for small powdered samples (300mg) with the purpose of analyzing ceramic artifacts that might be available only in limited quantity. This is compared to a conventional calibration using a larger sample mass (2g). The comparison of elemental intensities obtained in both calibrations shows that the decrease in analyzed sample mass results in a linear decrease in measured intensity for the analyzed elements. This indicates that the small‐ and large‐sample calibrations are comparable. Moreover, the elemental contents of four ceramic sherds and two potential clay sources fall well within the range of the certified reference materials that are the basis of the calibration curves. The advantage with the analytical method presented here is that it is rapid and requires only a small amount of sample that can easily be re‐used for further analyses. This method has great potential in ceramic provenance studies. © 2011 Wiley Periodicals, Inc.     

Effects of Coal Rank and High Organic Sulfur on the Structure and Optical Properties of Coal-based Graphene Quantum Dots

Coal‐based graphene quantum dots (GQDs) were successfully produced via a one‐step chemical synthesis from six different coal ranks, from which two superhigh organic sulfur (SHOS) coals were selected as natural S‐doped carbon sources for the preparation of S‐doped GQDs. The effects of coal properties on coal‐based GQDs were analyzed by means of high‐resolution transmission electron microscopy (HRTEM), X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, X‐ray photoelectron spectroscopy (XPS), ultraviolet‐visible (UV‐Vis) absorption spectroscopy, and fluorescence emission spectra. It was shown that all coal samples can be used to prepare GQDs, which emit blue‐green and blue fluorescence under ultraviolet light. Anthracite‐based GQDs have a hexagonal crystal structure without defects, the largest size, and densely arranged carbon rings in their lamellae; the high‐rank bituminous coal‐based GQDs are relatively reduced in size, with their hexagonal crystal structure being only faintly visible; the low‐rank bituminous coal‐based GQDs are the smallest, with sparse lattice fringes and visible internal defects. As the metamorphism of raw coals increases, the yield decreases and the fluorescence quantum yield (QY) initially increases and then decreases. Additionally, the surface of GQDs that were prepared using high‐rank SHOS coal (high‐rank bituminous coal) preserves rich sulfur content even after strong oxidation, which effectively adjusts the bandgap and improves the fluorescence QY. Thus, high‐rank bituminous coal with SHOS content can be used as a natural S‐doped carbon source to prepare S‐doped GQDs, extending the clean utilization of low‐grade coal.