X-ray Fluorescence Core Scanning Research Articles

XRF core scanning yields reliable semiquantitative data on the elemental composition of highly organic-rich sediments: Evidence from the Füramoos peat bog (Southern Germany)

X-ray fluorescence core scanning (XRF-CS) has become a standard tool in paleoenvironmental studies. Allowing rapid, inexpensive and non-destructive analysis of the elemental composition of sediment cores at high spatial resolution, it is ideally suited for the reconstruction of short-term climatic change. However, its applicability to cores consisting of peat and other highly organic-rich sediments has yet remained poorly explored. We have therefore investigated the application of XRF-CS to two cores consisting of ombrotrophic peat and of fen peat and organic-rich muds of Late Glacial–Holocene and Eemian age, respectively, from a peat bog in Southern Germany using an Avaatech 4th-generation XRF core scanner. The XRF-CS-derived distributions of elements widely used in (paleo)environmental research (i.e., Al, Ca, Fe, K, Mg, Mn, S, Si, and Ti) were systematically compared to the results of inductively coupled plasma optical emission spectrometry analyses. For the Late Glacial–Holocene peat core, XRF-CS yielded reliable semiquantitative data for the majority of the investigated elements (i.e., Ca, Fe, K, Mn, S, Si, and Ti), with R2 ≥ 0.5. XRF-CS of the Eemian fen peat and organic-rich muds yielded reliable data for Al, K, S, and Ti (R2 ≥ 0.5) and, to a lesser extent, for Fe (R2 = 0.46). and Si (R2 = 0.25). This indicates that XRF-CS allows to semiquantitatively reconstruct the distribution of the majority of paleoclimatically relevant elements in peat and other highly organic-rich sediments. Hence, XRF-CS is well suited to complement the analytical toolbox for the paleoenvironmental study of such sediments.

Brief oxygenation events in locally anoxic oceans during the Cambrian solves the animal breathing paradox

Oxygen is a prerequisite for all large and motile animals. It is a puzzling paradox that fossils of benthic animals are often found in black shales with geochemical evidence for deposition in marine environments with anoxic and sulfidic bottom waters. It is debated whether the geochemical proxies are unreliable, affected by diagenesis, or whether the fossils are transported from afar or perhaps were not benthic. Here, we improved the stratigraphic resolution of marine anoxia records 100–1000 fold using core-scanning X-Ray Fluorescence and established a centennial resolution record of oxygen availability at the seafloor in an epicontinental sea that existed ~501–494 million years ago. The study reveals that anoxic bottom-water conditions, often with toxic hydrogen sulfide present, were interrupted by brief oxygenation events of 600–3000 years duration, corresponding to 1–5 mm stratigraphic thickness. Fossil shells occur in some of these oxygenated intervals suggesting that animals invaded when conditions permitted an aerobic life style at the seafloor. Although the fauna evidently comprised opportunistic species adapted to low oxygen environments, these findings reconcile a long-standing debate between paleontologists and geochemists, and shows the potential of ultra-high resolution analyses for reconstructing redox conditions in past oceans.

Quantitative integration of sedimentological core descriptions and petrophysical data using high-resolution XRF core scans

Abstract In light of the huge investments needed to acquire sediment cores and the growing need of energy-providing companies to predict reservoir quality, it is remarkable that the standard workflow in core analysis has not been optimized to extract as much information from cores as possible. The Integrated Core Analysis (ICA) protocol presented in this study provides a statistical framework for multivariate calibration and prediction of a wide range of properties measured in core, based on integration of high-resolution X-ray fluorescence core-scanning (XRF-CS) proxy records with records of sparsely sampled petrophysical data and sedimentological core descriptions. The downscaling of numerical data involves the application of invertible transformations to remove range constraints on data, followed by calibration with Partial Least Squares regression through cross validation. Categorical data (i.e. lithofacies) are downscaled by associating each class with a statistical model based on the XRF-CS data. All data points are reassigned to their most likely class by applying Quadratic Discriminant Analysis. The result of the ICA is a multivariate data set in which all properties are specified at the same high resolution along the core with their prediction uncertainties. Downscaling of all variables to 1-cm vertical resolution permits investigation of the variability among petrophysical properties, geochemical proxies, and lithofacies memberships. Petrographic analysis is fundamental for interpretation of the XRF-CS records (element-mineral affinity) and for understanding the sedimentological controls on predicted petrophysical properties. Application of the ICA protocol to a 32 m thick, heterogeneous, Upper Carboniferous fluvial sandstone interval resulted in a near 30-fold increase of the petrophysical data base, which allowed identification of the main depositional and diagenetic controls on the spatial distribution of reservoir quality. Successful implementation of the novel ICA protocol will greatly increase the economic value of legacy core data in studies that aim to re-use depleted hydrocarbon reservoirs.

An evaluation of methodologies for calibrating Itrax X-ray fluorescence counts with ICP-MS concentration data for discrete sediment samples

Core-scanning X-ray Fluorescence (XRF-CS) is a well-established technique for rapid (<30 s/interval) analysis of sediment core geochemistry at sub-mm resolution with substantially less analytical cost compared to methods that rely on physical sub-sampling. Due to issues inherent in analyzing wet sediment of heterogeneous particle size and composition with irregular surface topography using XRF, XRF-CS results are generally considered semi-quantitative. The result of early efforts to calibrate XRF-CS data with conventional geochemical results (e.g. WD- or ED-XRF, ICP-AES, ICP-MS) showed weak correlations for less abundant or poorly detectable elements, however, more recent methods have been proposed to improve accuracy. These methods include: 1) converting XRF-CS results to dry mass concentration; 2) normalizing XRF-CS data to conservative elements (Si, Ca), total counts/second, or X-ray scatter (CIR); and 3) calibration of data using multivariate analysis of elemental log-ratios (MLC). These approaches are not yet widely employed, and require additional testing on a variety of sediment compositions. Recently developed equipment enables analysis of discrete sediment samples, providing >30 replicate analyses for up to 180 samples in a single XRF-CS run. These replicate measurements allow for rigorous testing of precision and accuracy of XRF-CS data. To determine the ideal method of data transformation to improve XRF-CS calibration to quantitative geochemical concentration, 100 lake sediment-surface samples collected from Harvey Lake, New Brunswick, Canada, were analyzed using Itrax-XRF-CS, and then with ICP-MS analysis after multi-acid digestion. Normalization using the CIR and correction for water content showed strong correlation coefficients (Kendall's τ) for elements with atomic number > 18 and high concentrations in the sediment. Results for lighter elements and those with lower concentrations did not perform well using these calibration methods. The MLC provided the most accurate reproduction of observed ICP-MS trends and strong correlations (R) between predicted and actual geochemical concentrations. Based on these results, CIR-normalized or wet-corrected calibrations are ideal for studies where absolute geochemical values are of lesser importance, and the MLC method is appropriate for studies with large numbers of sediment samples (n > 100), or those where absolute concentrations of elements are of greater importance.

Application of Avaatech X-ray fluorescence core-scanning in Sr/Ca analysis of speleothems

Application of X-ray fluorescence core-scanning (XRF-CS) on both marine and lake sediments has achieved remarkable results. However, its application has not been widely extended to the research on speleothems. In this study, we measure the Sr abundance and the Sr/Ca ratios of three stalagmites (two aragonite stalagmites, one calcite stalagmite) using the state-of-the-art fourth-generation Avaatech high-resolution XRF core scanner. Through comparisons among different scan paths and among different scan resolutions, as well as comparisons with inductively coupled plasma optical emission spectrometer (ICP-OES), Itrax XRF, and Artax XRF results, we confirm that the Avaatech XRF core scanner could precisely, quickly, and non-destructively analyze the high-resolution Sr abundance of speleothems. Furthermore, we combine the stalagmite δ18O records to explore the paleoclimatic significance of the measured stalagmite Sr/Ca.

Is XRF core scanning a viable method for coral palaeoclimate temperature reconstructions?

The use of X-Ray Fluorescence (XRF) Core Scanning for continuous high-resolution analysis of Sr/Ca in corals is investigated here as a new method for analyzing coral material. Corals are valuable archives for generating high resolution palaeoclimate records of sea surface temperatures of the tropical oceans, but traditional methods of analyzing coral geochemistry involve extensive subsampling and wet chemistry techniques to obtain high precision elemental records. More recent developments of micro-beam techniques have limitations in the length of core that can be scanned at any one time. XRF core scanning provides a fast, non-destructive method of analyzing long sections of coral cores whilst maintaining a high sampling resolution. Here we apply this method to two modern corals, from the Sunda Strait, Indonesia and One Tree Island, Great Barrier Reef Australia. We find that results show that XRF core scanning of corals produce Sr/Ca records that capture the annual cycle, particularly from reef sites with a large sea surface temperature range. Coupled density measurements of the coral skeleton also aid in increasing the utility of XRF measurements obtained from coral material, although difficulties remain in reliably reconstructing interannual temperature variability using XRF Sr/Ca determinations. We recommend that XRF can provide a valuable method of quick and non-destructive screening of coral material, prior to more targeted analysis using traditional destructive geochemical analysis.

Trace metal analysis of sediment cores using a novel X-ray fluorescence core scanning method

The trace-metal composition of sediments provides important information on (past) environmental conditions, such as bottom water oxygenation, marine productivity, sediment provenance, and pollution. Whereas major and minor elements are often routinely analyzed using X-Ray Fluorescence (XRF) core scanning, analysis of trace metals with the same method is not yet established as a routine procedure. Here, we used a recently developed state-of-the-art XRF detector with a core scanner (Avaatech) to examine the optimal settings for analyzing a suite of trace metals (V, Cr, Ni, Cu, Zn, Mo, and U). Settings were optimized for fast analyses of sediment cores by extensive testing of primary energy settings, filters, and exposure times on two eastern Mediterranean Sea sapropel layers that archive episodes of past sea-floor anoxia. We reveal the following most advantageous (i.e., optimized for analytical accuracy and time efficiency) settings: (1) V, Cr, Ni at 20 kV with aluminum primary beam filter, (2) Cu, Zn, and U at 30 kV with ‘thick’ (125 μm) palladium primary beam filter, and (3) Mo at 50 kV with copper primary beam filter. For these trace elements, generally, ≥30 s of measurement are required for obtaining reliable data. Synthetic mixtures show that matrix effects, which are inherent to XRF analyses, are of particular importance for V. A correction for these matrix effects on V (e.g., using Compton scattering) may be necessary for samples with a large variability in carbonate content. XRF core-scanning measurements on synthetically, laminated sediments show that trace metals with contrasting atomic weights and related XRF penetration depths (V and Mo) can be determined at sub-mm resolution. We show that intensity results from the new XRF detector can be converted into concentrations using multivariate log-ratio calibration, allowing a fast quantitative prediction of sedimentary trace metal content using XRF core scanning.

X-ray fluorescence scanning of discrete samples – An economical perspective

We measured discrete, powdered, homogenized samples from geochemical reference standards (GRS) and from a loess-paleosol sequence (LPS) with an ITRAX XRF core-scanner. The objective is to highlight cost- and time-efficiency of X-ray fluorescence (XRF) scanning of discrete samples in comparison to conventional XRF. Based on data precision (mainly < 4% mean relative standard deviation) and data reliability (often R2 ≥ 0.9) tests with six different measurement times (1, 5, 10, 30, 60 and 100 s) and two different X-ray tubes (Mo, Cr), reasonable minimal measurement times for thirteen considered elements were assessed. Accordingly, we designed test case scenarios for 10, 30 and 100 s measurement time in comparison to conventional XRF analysis with regard to cost- and time-efficiency.As long as qualitative geochemical data are sufficient for scientific research questions at hand, XRF scanning of discrete samples is proven to be more efficient by factors of 15–23 as to time and by factors of 4.5–51 as to cost when compared with conventional wavelength-dispersive (WD)-XRF analysis commonly applied to discrete samples. This underlines XRF scanning of discrete samples as a versatile, non-destructive qualitative geochemical screening tool with unprecedented time- and cost-efficiency. Such efficiency will foster application of this technique in a broad scientific field including e.g. terrestrial paleoenvironmental reconstructions and/or environmental pollution studies.

The iBox-FC: A new containment vessel for Itrax X-ray fluorescence core-scanning of freeze cores

A combination of Itrax micro-X-ray fluorescence core scanning (μXRF-CS) and freeze coring can facilitate the development of high-resolution (e.g. sub-decadal) paleoclimate records in lacustrine systems where low sedimentation rates and poorly consolidated “colloidal soup” at the sediment/water interface prevents retrieval and Itrax-μXRF-CS analysis of undisturbed cores using conventional gravity corers. The iBox-FC containment vessel described and tested here delays thawing of highly perishable freeze cores for up to two hours, providing adequate time to carry out high-resolution Itrax-μXRF-CS analysis. The iBox-FC is comprised of an open-topped Styrofoam box divided into chambers using high-density polyethylene (HDPE) that are filled with freeze pack gel. When the vessel is frozen, core slabs up to 13 cm long may be positioned into a central chamber and then scanned following normal Itrax-μXRF-CS methodology. To test the reliability of μXRF-CS analysis obtained from frozen sediments, a freeze core recovered from Control Lake, Northwest Territories, Canada, was sub-sectioned and analyzed using μXRF-CS and then subsampled for ICP-MS following near-total acid digestion. Comparison of μXRF-CS and ICP-MS results showed strong correlations (R2 > 0.8) for six of nine elements calibrated, and moderate correlations (R2 > 0.3) for the remaining three. Additive log-ratio transformation of data minimized specimen, matrix and edge effects associated with the high porewater contents of the freeze cores and slight melting of the sediment during analysis. These analytical effects had more impact on the lower concentration elements (As, Zn, Ni, Cu) than the higher concentration elements (Ti, K, Mn, Fe, Ca).

Eastern Mediterranean hydroclimate reconstruction over the last 3600 years based on sedimentary n-alkanes, their carbon and hydrogen isotope composition and XRF data from the Gialova Lagoon, SW Greece

Understanding past hydroclimate variability and related drivers is essential to improve climate forecasting capabilities especially in areas with high climatic sensitivity, such as the Mediterranean. This can be achieved by using a broad spectrum of high resolution, multiple proxy records which can also allow us to assess linkages between regional hydroclimate variability and shifts in the large-scale atmospheric patterns. Here, we present a multiproxy reconstruction of the central-eastern Mediterranean hydroclimate changes over the last 3600 years based on a sediment core from the Gialova Lagoon, a shallow coastal ecosystem in SW Peloponnese, Greece. Our combined dataset consists of the distribution and compound-specific carbon and hydrogen isotope (δ13C and δD) composition of n-alkanes, bulk organic matter properties and X-ray fluorescence (XRF) core scanning data. This approach was complemented with a semi-quantitative analysis of plant remains in the core. The results indicate a high contribution of local aquatic vegetation to organic matter. Large δ13C variations in predominantly aquatic plant-derived mid-chain alkanes (C23-25) mainly reflect changes in the aquatic plant abundance and their carbon source. Our data suggest that higher δ13C23-25 values (up to −19‰) largely correspond to expansion of aquatic vegetation during wet and/or cold periods causing carbon-limiting conditions in the water and assimilation of isotopically-enriched bicarbonate by the plants. The δD records of the individual n-alkanes (C17 to C31) exhibit a nearly identical pattern to each other, which implies that they all reflect changes in the source water isotope composition, driven by hydroclimate variability. In addition, the δD profiles are consistent with the XRF data with both proxies being driven by a common hydroclimate signal. We observe two major shifts from dry and/or warm periods at ca 3600-3000 cal BP and ca 1700-1300 cal BP to wet and/or cold episodes at ca 3000-2700 cal BP and ca 1300-900 cal BP. The period ca 700-200 cal BP is the wettest and/or coldest in our record and coeval with the Little Ice Age. The climatic fluctuation reported in this study can be explained by the relative dominance of high-latitude (e.g. North Atlantic Oscillation during winters) and the low-latitude atmospheric patterns (Intertropical convergence zone, Subtropical High and the effects of Asian monsoons during summers) which suggests an Atlantic-Mediterranean-Monsoon climate link in this area for the late Holocene.

Sedimentary records of coastal storm surges: Evidence of the 1953 North Sea event

The expression of storm events in the geological record is poorly understood; therefore, stratigraphic investigations of known events are needed. The 1953 North Sea storm surge was the largest natural disaster for countries bordering the southern North Sea during the twentieth century. We characterize the spatial distribution of a sand deposit from the 1953 storm surge in a salt marsh at Holkham, Norfolk (UK). Radionuclide measurements, core scanning X-ray fluorescence (Itrax), and particle size analyses, were used to date and characterise the deposit. The deposit occurs at the onset of detectable 137Cs - coeval with the first testing of nuclear weapons in the early 1950s. The sand layer is derived from material eroded from beach and dunes on the seaward side of the salt marsh. After the depositional event, accumulation of finer-grained silt and clay materials resumed. This work has important implications for understanding the responses of salt marshes to powerful storms and provides a near-modern analogue of storm surge events for calibration of extreme wave events in the geological record.

Profiling of inorganic elements in coal seams using laboratory-based core scanning X-ray fluorescence techniques

The major inorganic elements in cores of coal and interbedded non-coal materials, ranging from 0.9 to 1.7 m in length, have been evaluated using energy-dispersive X-ray fluorescence (ED-XRF) measurement at close-spaced (2 mm) intervals in a laboratory-based Itrax core scanner, to evaluate the potential of this type of technology for use in quality assessment of potentially mineable coal seams in exploration and mine geology programs. The ED-XRF measurements from the scanner were calibrated against a suite of independently-analysed coals to provide quantitative data on the percentages of Si, Al, K, Ca, Fe, Ti and S at each individual point. With the exception of (total) S, also used in quality assessment, these values were recalculated as percentages of the relevant oxides, and combined to provide an estimate of the expected ash yield. Profiles were prepared illustrating the variation in the different components through the seam section, plotted alongside optical and X-radiograph images of the scanned core. Samples of selected intervals were analysed by conventional techniques and the ash yield, total sulphur and individual oxide percentages compared to those indicated for the same intervals by the core scan data. Despite difficulties due to precipitated salts and anomalous element concentrations on or near some core surfaces, as well as differences in moisture content between the scanned core and the conventionally-analysed samples, the results of this cross-checking have shown a general level of agreement for the different coal and non-coal materials involved. While the precision is not as high as that from conventional methods, the scan data allow the materials in the cores, including composites representing potentially mineable intervals, to be categorised to an extent that is of significant value for many exploration and mine geology applications.

Storm-generated Holocene and historical floods in the Manawatu River, New Zealand

This paper reports the first reconstruction of storm-generated late Holocene and historical river floods in the North Island of New Zealand. The sedimentary infills of nine palaeochannels were studied in the lower alluvial reaches of the Manawatu River. Floods in these palaeochannels were recorded as a series of sand-rich units set within finer-grained fills. Flood chronologies were constrained using a combination of radiocarbon dating, documentary sources, geochemical markers, and palynological information. Flood units were sedimentologically and geochemically characterised using high resolution ITRAX™ X-Ray Fluorescence (XRF) core scanning and laser diffraction grain-size analysis. The longest palaeoflood record extends back ca.3000 years. The temporal resolution and length of the Manawatu record reflects accommodation space for fluvial deposits, channel dynamics and mobility, and high sediment supply. Floods that occurred in the Manawatu during the mid-1800s at the time of European land clearance and in the first decade of the twentieth century appear to be among the largest recorded in the last 3000 years.

Late Maastrichtian carbon isotope stratigraphy and cyclostratigraphy of the Newfoundland Margin (Site U1403, IODP Leg 342)

Earth’s climate during the Maastrichtian (latest Cretaceous) was punctuated by brief warming and cooling episodes, accompanied by perturbations of the global carbon cycle. Superimposed on a long-term cooling trend, the middle Maastrichtian is characterized by deep-sea warming and relatively high values of stable carbon-isotope ratios, followed by strong climatic variability towards the end of the Cretaceous. A lack of knowledge on the timing of climatic change inhibits our understanding of underlying causal mechanisms. We present an integrated stratigraphy from Integrated Ocean Drilling Program (IODP) Site U1403, providing an expanded deep ocean record from the North Atlantic (Expedition 342, Newfoundland Margin). Distinct sedimentary cyclicity suggests that orbital forcing played a major role in depositional processes, which is confirmed by statistical analyses of high resolution elemental data obtained by X-ray fluorescence (XRF) core scanning. Astronomical calibration reveals that the investigated interval encompasses seven 405-kyr cycles (Ma4051 to Ma4057) and spans the 2.8 Myr directly preceding the Cretaceous/Paleocene (K/Pg) boundary. A high-resolution carbon-isotope record from bulk carbonates allows us to identify global trends in the late Maastrichtian carbon cycle. Low-amplitude variations (up to 0.4‰) in carbon isotopes at Site U1403 match similar scale variability in records from Tethyan and Pacific open-ocean sites. Comparison between Site U1403 and the hemipelagic restricted basin of the Zumaia section (northern Spain), with its own well-established independent cyclostratigraphic framework, is more complex. Whereas the pre-K/Pg oscillations and the negative values of the Mid-Maastrichtian Event (MME) can be readily discerned in both the Zumaia and U1403 records, patterns diverge during a ~ 1 Myr period in the late Maastrichtian (67.8–66.8 Ma), with Site U1403 more reliably reflecting global carbon cycling. Our new carbon isotope record and cyclostratigraphy offer promise for Site U1403 to serve as a future reference section for high-resolution studies of late Maastrichtian paleoclimatic change.

Holocene paleohydrological reconstruction of Lake Strzeszy\u0144skie (western Poland) and its implications for the central European climatic transition zone

Western Poland is located in the central European climatic transition zone, which separates the mild and humid Atlantic climate of Western Europe and the East European continental climate. This region is sensitive to lateral shifts of the European climate zones and is particularly suitable for reconstructing Holocene climate variability. This paper presents detailed analyses of the sedimentary record from Lake Strzeszyńskie since the Late Pleistocene. These include smear-slide and thin-section observations, X-ray fluorescence core scanning, magnetic susceptibility measurements, pollen analyses, and radiocarbon dating. The sediment record reveals three distinct sedimentary units consisting of: (1) an alternation of sand layers and laminated silt and clay deposits accumulated prior to 14,600 cal yr BP; (2) faintly laminated calcareous sediments intercalated with organic matter-rich layers deposited between 14,600 and 10,200 cal yr BP; and (3) massive calcareous mud deposited after 10,200 cal yr BP. The Holocene period is marked by nine phases of organic-rich sedimentation and enhanced Fe deposition, which occurred at ca. 10.1, 9.3, 6.4–6.1, 5.5–5.1, 4.7–4.5, 2.7–2.4, 1.3–1.2, 0.8–0.6, 0.4–0.2 kyr cal BP. These phases are associated with high lake levels and correspond with wet periods recognized in several other records from Poland and central Europe. These phases partly coincide with North Atlantic cold periods, which may suggest that high lake levels are triggered by an ocean-continent linking mechanism.

Astronomical calibration of the Ypresian timescale: implications for seafloor spreading rates and the chaotic behavior of the solar system?

Abstract. To fully understand the global climate dynamics of the warm early Eocene with its reoccurring hyperthermal events, an accurate high-fidelity age model is required. The Ypresian stage (56–47.8 Ma) covers a key interval within the Eocene as it ranges from the warmest marine temperatures in the early Eocene to the long-term cooling trends in the middle Eocene. Despite the recent development of detailed marine isotope records spanning portions of the Ypresian stage, key records to establish a complete astronomically calibrated age model for the Ypresian are still missing. Here we present new high-resolution X-ray fluorescence (XRF) core scanning iron intensity, bulk stable isotope, calcareous nannofossil, and magnetostratigraphic data generated on core material from ODP Sites 1258 (Leg 207, Demerara Rise), 1262, 1263, 1265, and 1267 (Leg 208, Walvis Ridge) recovered in the equatorial and South Atlantic Ocean. By combining new data with published records, a 405 kyr eccentricity cyclostratigraphic framework was established, revealing a 300–400 kyr long condensed interval for magnetochron C22n in the Leg 208 succession. Because the amplitudes are dominated by eccentricity, the XRF data help to identify the most suitable orbital solution for astronomical tuning of the Ypresian. Our new records fit best with the La2010b numerical solution for eccentricity, which was used as a target curve for compiling the Ypresian astronomical timescale (YATS). The consistent positions of the very long eccentricity minima in the geological data and the La2010b solution suggest that the macroscopic feature displaying the chaotic diffusion of the planetary orbits, the transition from libration to circulation in the combination of angles in the precession motion of the orbits of Earth and Mars, occurred ∼ 52 Ma. This adds to the geological evidence for the chaotic behavior of the solar system. Additionally, the new astrochronology and revised magnetostratigraphy provide robust ages and durations for Chrons C21n to C24n (47–54 Ma), revealing a major change in spreading rates in the interval from 51.0 to 52.5 Ma. This major change in spreading rates is synchronous with a global reorganization of the plate–mantle system and the chaotic diffusion of the planetary orbits. The newly provided YATS also includes new absolute ages for biostratigraphic events, magnetic polarity reversals, and early Eocene hyperthermal events. Our new bio- and magnetostratigraphically calibrated stable isotope compilation may act as a reference for further paleoclimate studies of the Ypresian, which is of special interest because of the outgoing warming and increasingly cooling phase. Finally, our approach of integrating the complex comprehensive data sets unearths some challenges and uncertainties but also validates the high potential of chemostratigraphy, magnetostratigraphy, and biostratigraphy in unprecedented detail being most significant for an accurate chronostratigraphy.

A sample carrier for measuring discrete powdered samples with an ITRAX XRF core scanner

The elemental composition of discrete powdered sediment samples can be measured by the energy‐dispersive X‐ray fluorescence (XRF) system that is installed in XRF core scanners. Because an appropriate sample carrier for powdered samples is currently not available, for example, for the ITRAX XRF core scanner, such a carrier is presented in this technical note. The designed sample carrier can hold 30 sample cups with a volume of 0.88 cm3 each. A maximum of 5 sample carriers, that is, 150 samples, can be measured in one run. The sample cups and carriers are optimized for a measurement procedure with a step size of 5 mm and variable count times up to 100 s per sample. With this setting, data are collected from an area of 100 mm2 in the center of the sample thereby ensuring a good representativeness of the signal because potential sample inhomogeneity is accounted for. Because the described sample carrier system allows rapid element analyses of discrete powdered environmental samples with an XRF core scanner, it may in some cases represent a time‐ and cost‐efficient alternative to conventional XRF analyses.

Periodic input of dust over the Eastern Carpathians during the Holocene linked with Saharan desertification and human impact

Abstract. Reconstructions of dust flux have been used to produce valuable global records of changes in atmospheric circulation and aridity. These studies have highlighted the importance of atmospheric dust in marine and terrestrial biogeochemistry and nutrient cycling. By investigating a 10 800-year-long paleoclimate archive from the Eastern Carpathians (Romania) we present the first peat record of changing dust deposition over the Holocene for the Carpathian–Balkan region. Using qualitative (X-ray fluorescence (XRF) core scanning) and quantitative inductively coupled plasma optical emission spectrometer(ICP-OES) measurements of lithogenic (K, Si, Ti) elements, we identify 10 periods of major dust deposition between 9500–9200, 8400–8100, 7720–7250, 6350–5950, 5450–5050, 4130–3770, 3450–2850, 2000–1450, 800–620, and 60 cal yr BP to present. In addition, we used testate amoeba assemblages preserved within the peat to infer local palaeohydroclimatic conditions. Our record highlights several discrepancies between eastern and western European dust depositional records and the impact of highly complex hydrological regimes in the Carpathian region. Since 6100 cal yr BP, we find that the geochemical indicators of dust flux have become uncoupled from the local hydrology. This coincides with the appearance of millennial-scale cycles in the dust input and changes in geochemical composition of dust. We suggest that this is indicative of a shift in dust provenance from local–regional (likely loess-related) to distal (Saharan) sources, which coincide with the end of the African Humid Period and the onset of Saharan desertification.

A 3 million year index for North African humidity/aridity and the implication of potential pan-African Humid periods

Mediterranean sediments are valuable archives of both African monsoon variability and higher-latitude climate processes, and can also be used to provide an environmental context for early human migrations and settlements. However, the long history of Mediterranean palaeoclimate studies largely pre-dates the advent of widespread x-ray fluorescence (XRF) core-scanning, so there are few continuous and high-resolution geochemical records from this key region that extend beyond the last glacial cycle. Here we present XRF core-scanning results for ODP Site 967 (Eastern Mediterranean) that have been fully-calibrated into element concentrations spanning the last 3 million years (My). Comparison with independent geochemical data from conventional XRF highlights disparities for certain element/element ratios, thus suggesting the need for caution when taking ratios of scanning XRF data. Principal component analysis of the calibrated XRF dataset reveals two dominant components: detrital inputs (PC1) and a ‘sapropel’ (≈monsoon run-off) signal (PC2), which we use to establish a new orbitally-tuned chronology. We observe inverse covariation between PC2 and a previously published aeolian dust record from ODP Site 967 (Larrasoaña et al., 2003), and combine these records to produce a composite index of humidity and aridity for the wider North African region over the past 3 My. We propose that by combining run-off and dust signals in a single metric, our index captures the effects of both strengthening/northward migration (increased run-off) and weakening/southward retreat (increased dust) of the North African monsoon. Comparison of the index with published records of Northwest and East African palaeohumidity suggests that it tracks the timing of “Green Sahara Periods” throughout the Plio-Pleistocene, and that at least 30 of these intervals coincided with increased humidity across East Africa. We tentatively suggest that these specific episodes may be termed “pan-African Humid Periods”, as a means to highlight large-scale climate trends and to provide an environmental framework for palaeo-anthropological research.

The application of X-ray fluorescence core scanning in multi-element analyses of a stratified archaeological cave deposit at Wee Jasper, Australia

Archaeological sediments retain elements from natural and anthropogenic inputs for many years, often forming stratified geochemical records of site formation and human use. This study evaluates the validity and potential of an X-ray fluorescence core scanner (XRF-CS) to contribute to the histories of stratified archaeological sites. Geochemical data sets from an archaeological deposit at Wee Jasper in southeast Australia are obtained using two sediment preparation techniques; the results are compared to trends identified through cultural artefacts and several more traditional methods of sediment analysis. Potential anthropogenic and organic element signatures are identified, and the sediment preparation techniques are evaluated. Minimally processed bulk samples provide consistent XRF results that strongly correlate with the trends observed in other proxies; results from unprocessed sediment columns, however, reveal methodological complications with the XRF-CS technique due to topographical and structural inconsistencies in the columns.