X-ray Fluorescence Core Scanning Research Articles

Application of a back propagation neural network model based on genetic algorithm to in situ analysis of marine sediment cores by X-ray fluorescence core scanner

The use of core scanners to perform X-ray fluorescence (XRF) spectroscopic analysis can only obtain the intensities of the target elements, which is not conducive for application in marine geology research. In this paper, using a core scanner, in situ measurements were performed on 15 components: Al2O3, SiO2, K2O, CaO, TiO2, MnO, Fe2O3, V, Cr, Zn, Rb, Sr, Y, Zr, and Ba. We explored the feasibility of reducing the effect of interstitial water by normalizing the original intensity using the intensity of Ca and the ratio of coherent to incoherent and attempted to introduce a genetic algorithm-back propagation neural network model and use its nonlinear fitting capability to correct the matrix effect. The prediction precision of this method was 0.6–15.4%. The proposed method is suitable for the rapid analysis of major and minor components in marine sediment core samples, while taking full advantage of the high-resolution of the XRF core scanner.

Challenges in Interpreting Geochemical Data: An Appraisal of Analytical Techniques Applied to a Karstic Lake Sediment Record

The paleoclimatic and paleoenvironmental changes inferred from shifts in lake sediment geochemistry require reliable, efficient and cost-effective methods of analysis. The available geochemical techniques, however, suggest that different analytical approaches can influence data interpretation. X-ray fluorescence core scanner analyses (XRF-CS), field portable X-ray fluorescence (FPXRF) and inductively coupled plasma optical emission spectrometry (ICP-OES) were concurrently applied to provide a multi-method geochemical appraisal of a 6000-year-long karstic sediment record (Lake Ighiel, Romania). The comparison between techniques was based on a set of elements that are widely employed in environmental reconstructions (Ti, K, Fe, Ca). Descriptive and statistical approaches were used to assess the advantages and disadvantages of each method and assess their optimal use in karstic environments. Our data display similar downcore patterns, with strong to moderate correlations between the datasets. The discrepancies observed between method-specific downcore multi element behaviour are related to the preparation steps and sampling. To best capture the complexity of past environmental changes in karstic settings, a combination of quantitative and qualitative geochemical methods would be the most appropriate approach to reliable data acquisition and subsequent paleoenvironmental interpretation of lake sediment data.

Application of XRF core scanning in varved lake sediments: A case study on Lake Xinluhai in the southeastern margin of Qinghai-Tibetan Plateau

湖泊年纹层以其精确到年乃至季节尺度的高分辨率优势, 成为研究古气候环境变化的重要载体. X射线荧光(XRF)岩芯扫描由于其有分辨率高、分析快速等特点, 在湖泊年纹层研究中发挥了重要的作用. 本文以青藏高原东南缘新路海年纹层为研究对象, 采用X射线荧光(XRF)岩芯扫描, 对新路海湖泊纹层计年、纹层形成机理及古气候重建进行了研究. 结果表明: 利用X射线图像明暗层、Rad峰值、Zr和Fe元素峰值标记法获得的年代序列基本一致, 并且与独立的放射性测年(²¹⁰Pb/¹³⁷Cs)结果吻合, 证实了上述各种纹层计年方法的可行性和可靠性. 新路海年纹层层偶是由粗颗粒碎屑层和细颗粒碎屑层交互组成的, 较厚且Zr和Si元素高的粗颗粒层形成于春、夏季, 而较薄且Fe元素含量高的细颗粒层形成于秋、冬季. 纹层的厚度能够指示西南季风降水量的大小, 近100年以来新路海纹层厚度反映的西南季风演化, 与利用昆明地区历史文献重建的湿度记录(干旱/洪水指数)、树轮δ¹⁸O重建的尼泊尔喜马拉雅地区的季风降水基本一致. 近100年来新路海的纹层厚度具有7~8、4~5和2年的周期, 表明新路海纹层厚度记录的近100年的西南季风演化可能与厄尔尼诺—南方涛动、太平洋年代际振荡、印度洋偶极子和准两年周期震荡有关.;Varved lake sediment has become one of the important archives for paleoclimate and paleoenvironment studies due to its high-resolution at annual to seasonal timescale. X-ray fluorescence (XRF) core scanning plays an important role in the studies on varved lake sediments due to its high resolution and rapid analysis. In this paper, XRF core scanning was used to study the chronology and formation mechanism of varved lake sediments from Lake Xinluhai in the southeastern margin of the Qinghai-Tibetan Plateau, and the paleoclimate reconstruction based on varve thickness. The results show that varve counting produced using X-radiography, Rad peak, Zr and Fe peak method are essentially consistent with that using the independent radioactive dating (²¹⁰Pb/¹³⁷Cs), which confirms the feasibility and reliability of the above varve counting methods. The annual laminae in Lake Xinluhai were composed of coarse and fine clastic layers. The thick coarse layer with high Zr and Si contents was formed in spring and summer, while the thin fine layer with high Fe content was formed in autumn and winter. The varve thickness can be used to indicate the precipitation intensity of the Southwest Summer Monsoon. The evolution of Southwest Summer Monsoon reflected by the varve thickness in the past 100 years was basically consistent with that of monsoon precipitation reconstructed by humidity (drought/flood index) of Kunming, snow accumulation data from Dasuopu Glacier and the δ¹⁸O of tree ring in the Himalayan region of Nepal. In the past 100 years, the varve thickness of Lake Xinluhai had periodicities of 7-8, 4-5 and 2 years, which may be related with El Niño-Southern Oscillation, Pacific Decadal Oscillation, Indian Ocean dipole and Quasi-biennial Oscillation.

Late Glacial and Early Holocene lacustrine sedimentation history of the northern Mologa-Sheksna Lowland derived from Lake Beloye sediments (NW Russia)

Few detailed case studies have been devoted so far to the Late Pleistocene palaeogeography of the northern Mologa-Sheksna Lowland (MSL), compared to adjacent regions covering the Valdai glaciation marginal zone. Lake Beloye (Russia, Vologda region, Babaevo district) bottom sediments were studied using ground penetrating radar (GPR) and subsequently were cored in order to build a palaeoclimatic reconstruction for the northern MSL, because lacustrine deposits are considered to be valuable and representative palaeoarchive of the area. Chronology of regional palaeoclimatic and palaeohydrological changes from the Bølling — Allerød warming to the Early Holocene was traced on the basis of inorganic and organic geochemistry, mineralogical proxies, grain-size, magnetic susceptibility, accelerator mass spectrometry radiocarbon dating and optical microanalysis. During the Late Glacial and the Pleistocene/Holocene transition in the northern MSL interstadial climatic conditions were determined at ~ 14.0 cal. ka BP (Bølling, stage GI-1e of the GICC05 timescale) and ~ 13.0 cal. ka BP (Allerød, stages GI-1c3 — GI-1a). A pronounced cold period associated with Younger Dryas (stage GS- 1) was registered in the multiproxy record at 12.8–11.7 cal. ka BP. High-resolution x-ray fluorescence (XRF) core scanning helped to reveal short-term “cold” events at ~ 13.7, ~ 13.1 and ~11.5 cal. ka BP, which were associated with Older Dryas (stage GI-1d), Gerzensee-Killarney oscillation (stage GI-1b) and Preboreal oscillation respectively, and “warm” episodes at ~ 13.2 and ~ 11.8 cal. ka BP, which presumably correspond to the end of the stage GI-1c1 and Greenlandian Stage/Age respectively. Ultimate interglacial (Holocene) climate onset within the MSL was attributed to ~ 11,7 cal. ka BP, which is marked by the sharp rise of total organic carbon content in the sediments and lithological changes to muddy fraction. Numerous water level oscillations occurred in the large proglacial lakeduring the last glacial termination, ending with Its final drainage in the northern MSL by ~ 10.9 cal. ka BP. The reconstructed palaeoclimatic dynamics is in overall agreements with the global reconstructions for the North Atlantic and Fennoscandia regions.

Holocene climate dynamics on the European scale: Insights from a coastal archaeological record from the temperate Bay of Biscay (SW France)

The main drivers of Europe's climate during the Holocene result from the coupling and interplay of external and internal radiative processes with the shifting patterns of many dynamic components (e.g. glaciers, ocean currents, wind fields, vegetation cover). Those driving forces were expressed across a range of geographical scales, from local to global, in a diverse set of records forming a patchwork of evidence as to the fundamental pacing effect of climate on past ecosystems. Various sedimentary deposits resulting from those complex forcing contexts bear climatic signatures that it is not always easy to disentangle especially with respect to local factors.The present paper focuses on a coastal archaeological site on the Medoc peninsula (the Lède du Gurp site in south-western France) that records Holocene palaeoenvironmental changes, decoded here century after century and integrated with ongoing events on a pan-North-Atlantic scale. Based on updated geoarchaeological approaches, thanks to new applications of proxies, especially X-ray fluorescence (XRF) core scanning methods for this article, continuous sedimentary records have been analysed in order to reconstruct a regional framework for past ecosystem events, including events potentially related to human activity. Our work identifies signals on various scales in the record under study, with both long- and short-term trends and local and global imprints, but all closely bound up with proximal North Atlantic Ocean dynamics. It highlights how western European environments (and so populations) were dependent upon the linearity of climate evolution at the key Northgrippian/Meghalayan transition.

Corascope: Software assisted XRF scan merging

Due to the physical constraints of X-ray Fluorescence (XRF) scanners, all but the shortest sedimentary cores are typically scanned in a piecewise fashion. Pieces are either extracted a section at a time (e.g. Russian peat corer) or are cut and sectioned after extraction (e.g. piston and gravity cores). The XRF core scanner generates an optical line-scan image, an X-ray radiograph, and a table of downcore variations in elemental composition. The subsequent processes of digitally joining the individual section scans so that they correspond to the original core is typically done in an ad-hoc manner with little visual feedback. Manual manipulation of composition tables while maintaining proper alignment with the optical scans is error prone and slow. As a result, image data are typically either discarded or used as a rough reference. This means a potentially valuable data source is normally lost. Corascope is a first-pass data reconstruction tool for the Itrax XRF scanner that aims to streamline data merging before doing any analysis. Immediate visual feedback is provided during the cropping and merging of core sections; it automatically preserves optical and elemental data alignment. It further provides a statistically-guided set of tools for adjusting overlapping core sections. These allow users to go from several overlapped cores to one merged virtual core. This virtual core then provides a reconstruction of the sedimentary record as one continuous piece. In line with the goal of being a first-pass tool, Corascope leaves all data values unperturbed and merged core data are returned in the same format as generated by the Itrax XRF scanner. This ensures that preexisting analysis software and laboratory procedures can continue to work on preprocessed data.

Comparison and Calibration of Elemental Measurements in Sediments Using X-Ray Fluorescence Core Scanning with ICP Methods: A Case Study of the South China Sea Deep Basin

Comparison and Calibration of Elemental Measurements in Sediments Using X-Ray Fluorescence Core Scanning with ICP Methods: A Case Study of the South China Sea Deep Basin

Deciphering Co‐Seismic Sedimentary Processes in the Mediterranean Sea Using Elemental, Organic Carbon, and Isotopic Data

AbstractIdentification of catastrophic events recorded as resedimented deep marine deposits can be challenging because of multiple possible triggering mechanisms. This study investigates seismo‐turbidites (STs) deposited in the Ionian Sea as a consequence of major historical earthquakes related to the Calabrian Arc subduction system. Taking advantage of the available sedimentological reconstructions, we focused our analysis on high‐resolution X‐ray fluorescence core scanner (XRF‐CS), organic carbon and isotopic data to define geochemical signatures characterizing the ST units. The relationships between geochemical and sedimentological proxies were statistically tested using Pearson correlation and principal component analysis (PCA). Up to ∼78% of the total variance in the data set can be reduced to three principal components which identified four elemental ratio groups associated to the degree of terrestrial/coastal influence in each major depositional unit (i.e., pelagic, ST sandy stacked units, homogenites, tsunamite‐seiche laminites, and tsunamite backwash). The sample score results were evaluated together with organic carbon data in order to assess geochemical variability throughout the composite turbidite structure in different basins settings. The basal parts of the ST contain coarse‐grained sediment stacks whose sources can be traced back and sedimentary processes (surficial sediment erosion/massive slope failures) can be defined using geochemical data. The topmost parts of the STs exhibit a mixed compositional character suggesting basin‐wide processes such as seiche oscillations and tsunami wave erosion/backwashing. The application of selected XRF‐CS based elemental ratios as proxies in paleoseismological studies can help reconstruct the seismic history of a continental margin.

Investigation of Adequate Calibration Methods for X-ray Fluorescence Core Scanning Element Count Data: A Case Study of a Marine Sediment Piston Core from the Gulf of Alaska

X-ray fluorescence (XRF) core scanner elemental count data are useful for high-resolution paleoceanographic studies. However, because several factors, such as changes in physical core properties, significantly affect element count intensities, the appropriate calibration of the count data is required. Besides, the existing approaches for calibration were not widely employed and require rigorous testing based on sediment variety. In this study, we analyzed high-resolution element intensity (cps) using a wet muddy marine sediment piston core that was collected from the northeast Gulf of Alaska and tested several approaches with ratio and log-ratio methods, and the reliability was evaluated by comparison with the concentrations that were measured by WD-XRF and an elemental analyzer. The results show that the lighter elements (Ti and K) exhibited a significantly weak relationship between raw counts measured by ITRAX and concentrations that were measured by the WD-XRF, indicating that some factors artificially influence ITRAX intensity data. The Cl intensity that is expressed as the water content in marine sediment increased significantly in the upper 202 cm by 42% and the top 25 cm by 73% as compared to the down-core (below 202 cm), which deviates the X-ray scattering and element-counts. The calibration of raw data through coherent/incoherent X-ray scattering ratio (CIR) and additive- and centered-log ratio reduces the offsets. The calibration by CIR performed best for Sr, Fe, Mn, Ti, Ca, K, and Br (0.56 < R2 < 0.91), and the correlation with concentration significantly increased for Ti and K of 100% and 56%, respectively. Therefore, the study suggests that the correction of raw counts through CIR is an effective approach for wet marine sediment when core physical properties have greater variability.

Climate-driven fluxes of organic-bound uranium to an alpine lake over the Holocene

Uranium (U) isotopic signatures and concentration in sediments are widely used as paleo-redox proxies, as the behavior of U is often controlled by bottom water oxygenation. Here, we investigated the processes controlling U accumulation in the sediments of Lake Nègre (Mediterranean Alps, South-East France) over the past 9200 years. Exceptionally high natural U concentrations (350–1250 μg·g−1) allowed the measurement of U along with other elements by high-resolution X-Ray Fluorescence core-scanning. Weathering and erosion proxies (Ti content, Zr/Al and K/Ti ratios) indicate that sedimentary inputs were controlled by Holocene climatic variations. After a period of low erosion during the Holocene Climatic Optimum, a major regime shift was recorded at 4.2 kyr BP when terrigenous fluxes consistently increased until present with high sensitivity to centennial-scale climatic events. Sedimentary organic matter (OM) inputs were dominated by terrigenous OM from the catchment soils until 2.4 kyr BP, as attested by carbon to nitrogen (C/N) and bromine to organic carbon (Br/TOC) ratios. From 2.4 kyr BP to present, lake primary production and soils equally contributed to sedimentary OM. Uranium fluxes to the sediments were well correlated to terrigenous OM fluxes from 7 kyr BP to present, showing that U supply to the lake was controlled by U scavenging in the soils of the watershed followed by transport of U bound to detrital organic particles. Higher U/OM ratios before 7 kyr BP likely reflect the development of the upstream wetland. The fluctuations of U sedimentary inputs appear to be independent of bottom water oxygenation, as estimated from constant Fe/Mn ratios and δ238U isotopic signatures, and rather controlled by the production, erosion and sedimentation of terrigenous OM. This finding confirms that the use of U (and potentially other metals with high affinity to OM) concentrations alone should be used with caution for paleo-redox reconstructions.

X-ray fluorescence core scanning, magnetic signatures, and organic geochemistry analyses of Ryukyu Trench sediments: turbidites and hemipelagites

The southwestern Ryukyu Trench represents the ultimate sink of sediments shed from Taiwan into the Philippine Sea, which are mainly transported to the trench by turbidity currents via submarine canyons. Here, we present trench turbidites intercalated with hemipelagites in a gravity pilot core and a piston core acquired on the Ryukyu Trench floor at 6147 m water depth. We performed X-ray fluorescence core scans (ITRAX profiles), magnetic measurements, and organic geochemistry analyses to discriminate turbidites from hemipelagites. We identified 36 turbidites (0.9–4.2 cm thick) based on visual core descriptions and Ca/Fe ratios in the ITRAX profiles. Three of these turbidites show magnetic signatures indicating the presence of pyrrhotite and peaks in the magnetic susceptibility profile, suggesting that Taiwan-sourced sediments are transported to the Ryukyu Trench by long-runout turbidity currents. Pyrrhotite is also present in hemipelagites of the upper part of the retrieved cores, indicating a dominant sediment source in Taiwan over the last several thousand years. Ca/Fe and Zr/Rb ratios in the ITRAX profiles mark distal turbidites (about 1–3 cm thick), and Zr/Rb peaks mainly reflect grain size changes. Detailed analyses of a representative turbidite show good correlation between Ca/Fe and Zr/Rb peaks with upward-coarsening and upward-fining trends that delimit the turbidite. Sedimentary organic matter in hemipelagites is characterized by higher total organic carbon and total nitrogen contents and higher δ13C values than that in turbidites. Our multi-proxy approach employing high-resolution XRF core scans to differentiate turbidites from hemipelagites contributes to establishing a comprehensive view of modern trench sedimentation from Taiwan to the southwestern Ryukyu Trench.

The impact of cyclical, multi-decadal to centennial climate variability on arsenic sequestration in lacustrine sediments

Examining paleoclimate-driven changes of elemental contaminants, such as Arsenic (As), increases the understanding of the mobility and fate of elements under a warming climate scenario. To characterize the variability in As sequestration in the sediments of a freshwater system in response to decadal- to centennial-scale climate oscillations, a freeze-core (CON01) was recovered from Control Lake, Northwest Territories. Radiocarbon dating of 13 bulk-organic samples provided temporal reference to core depth. Sediment geochemistry was determined using Itrax X-ray fluorescence core-scanning (Itrax-XRF). Elemental concentrations were measured on a sub-set of samples using ICP-MS after multi-acid (MA) digestion to assess the accuracy of Itrax-XRF results through a multivariate log-ratio (MLC) calibration. Comparison of Itrax-XRF to ICP-MS using the MLC in ItraXelerate software show Pearson's R2 values >0.75, with the exception of As (R2 = 0.44). MLC-calibrated Itrax-XRF elemental data were centered log-ratio (CLR) transformed to eliminate issues related to data closure. During the ca. 3300-yr sedimentary record, moderate-strength negative correlations between AsCLR and KCLR (Spearman's ρ = −0.38, p-value < 0.001, n = 785), and AsCLR and TiCLR, (Spearman's ρ = −0.52, p-value < 0.001, n = 785) suggest that As is primarily sequestered in sediments during intervals of warmer temperatures and higher productivity. Proxies for sediment particle size (TiCLR, KCLR) and As concentration (AsCLR) were examined for response to quasi-periodic climate oscillations using spectral analysis. Significant periodicities were observed with approximately 4–13, 30–60, 90–120, and 160–280 yr periods in TiCLR, KCLR, and AsCLR records. These frequencies are interpreted as corresponding to the North Atlantic Oscillation and/or 8–14-yr Schwabe sunspot cycles, 30–60-yr Pacific Decadal Oscillation, and centennial-scale solar cycles (e.g., 90-yr Gleissberg cycle; 205-yr Suess cycle). Coeval occurrence of these periodicities revealed through wavelet analysis of Control Lake geochemistry data suggests that these climate cycles only impact Control Lake when they occur concurrently.

Suitability of calibrated X-ray fluorescence core scanning for environmental geochemical characterisation of heterogeneous sediment cores

Multi-element analysis of discrete samples via X-Ray fluorescence or inductively coupled plasma spectrometry is commonly used to characterise the composition of solid geo-materials for environmental geochemical characterisation. Conventional geochemical analysis of individual samples is time consuming and costly, which often results in low-resolution sampling with the danger of missing crucial information. X-ray fluorescence Core Scanning (XCS) provides an alternative method to obtain elemental information, which can be potentially used quantitatively when combined with the Multivariate Log-ratio Calibration (MLC) approach. The suitability of the XCS-MLC method was tested for environmental geochemical characterisation on four terrestrial Holocene-Pleistocene sediment cores that have a variable lithology (clay, sand, peat, with variable calcareous content), were stored at ambient room conditions and scanned post sampling. Element contents based on XCS-MLC and conventional geochemical analysis proved to be comparable (R2 > 0.5) for Al, Ca, Cr, Fe, K, Sr, Mn, Ni, Pb, Rb, S, Si, Ti, Zn, Zr, and also for Br as proxy for organic matter. For As, Cu and Ba the correlations were less satisfactory (R2 < 0.4) partially due to the low concentration ranges present in these sediments. For some samples aberrant high values for Ca, Fe, S, and Zn were introduced by application of the MLC method due to extrapolation outside the MLC-calibrated range. Similar to the conventional element analyses the XCS-MLC approach has the ability to retrieve quantitative element contents and enable the calculation of mineral phases such as calcium carbonate and reactive iron species. Both conventional and XCS-MLC methods reproduced the average contents per sediment layer and mostly their ranges. Nevertheless, local features such as diagenetic enrichments were not always evident from the discrete samples. Thus, a better understanding of the spatial heterogeneity in geochemical and mineralogical contents within the sediment layers was obtained with the additional XCS-MLC data. Our study shows that also cores stored under unfavourable conditions can be reliably re-analysed with XCS to generate high resolution records.

Application of Corrected Methods for High-Resolution XRF Core Scanning Elements in Lake Sediments

Contemporary studies emphasize theoretical and analytical aspects of monitoring water quality within lacustrine settings. The X-ray fluorescence (XRF) core scanner provides the most rapid, non-destructive high-resolution elemental measurements for unprocessed sediments. However, the analytical precision of measured elemental composition may be offset due to water content and inhomogeneities in the physical properties of the sediment. A range of calibration approaches developed specifically for converting XRF scanning intensities to element fractions has been made available. Here, two lake sediment-cores retrieved from southwest China were used to evaluate the performance of various calibration methods. In particular, the influence of sediment properties on XRF scanning intensities was assessed by redundancy analyses (RDA) and the generalized additive model (GAM). The results demonstrate that for fine-grained sediments, the impact of grain size results in only minor deviations in the XRF scanning intensities. Water content of the lake sediment was shown to be the most important factor influencing the XRF scanning intensities, especially for light elements (e.g., Al to Fe). Significant decreases in XRF scanning intensities may occur when sediment water content is greater than 47%. We recommend testing the element fractions obtained via conventional techniques throughout the core and applying the multivariate log-ratio calibration for high-resolution XRF scanning elements within lake sediments.

Evaluating Zr/Rb Ratio From XRF Scanning as an Indicator of Grain‐Size Variations of Glaciomarine Sediments in the Southern Ocean

AbstractThe ln(Zr/Rb) count ratio derived from X‐ray fluorescence (XRF) core scanning holds potential as a high‐resolution tracer for grain‐size variations of glaciomarine sediments, and hence current strength. To evaluate this approach, we conducted high‐resolution grain‐size measurements, together with Rb and Zr measurements by XRF core scanning and inductively coupled plasma‐mass spectrometry (ICP‐MS), on a series of sediment cores from different regions of the Southern Ocean. Downcore changes of the ln(Zr/Rb) count ratio from XRF core scanning are consistent with Zr/Rb concentration ratios derived from ICP‐MS analyses, even though Rb and Zr counts deviate significantly from concentrations due to specimen and matrix effects. The ln(Zr/Rb) count ratio displays discrepancies with the bulk mean grain‐size, but correlates well with the mean grain‐size of the sediment fractions that do not include unsorted sand delivered by ice‐rafting. These observations are supported by evidence from a grain‐size separation experiment, which indicates that Zr and Rb are concentrated in different grain‐size fractions. Consistent with its lack of sensitivity to coarse grain‐size fractions derived from ice‐rafting, the ln(Zr/Rb) ratio records similar trends to the sortable silt percent (SS%) and sortable silt mean () grain‐size. Universal gradients exist in plots of SS% versus ln(Zr/Rb), and versus ln(Zr/Rb), such that the ln(Zr/Rb) ratio provides a convenient way to estimate the magnitude of changes in SS% and . Overall, our results support the use of the ln(Zr/Rb) ratio as an indicator of bottom current strength in cases where the sediment is current‐sorted.

Reconstruction of palaeoenvironmental variability based on an inter-comparison of four lacustrine archives on the Peloponnese (Greece) for the last 5000 years

Abstract. A high quantity of well-dated, high-resolution, continuous geoarchives is needed to connect palaeoenvironmental reconstructions with socio-environmental and cultural transformations in a geographically heterogeneous region such as southern Greece. However, detailed and continuous palaeoclimatic and palaeoenvironmental archives from the NE Peloponnese are still sparse. Here, we present two new palaeolake archives of Pheneos and Kaisari covering the last 10 500 and 6500 years, respectively. For the last 5000 years, we compare them with sediment records from adjacent Lake Stymphalia and the Asea valley by applying the same set of sedimentological, geochemical, and statistical analyses to all four lacustrine archives. Continuous geochemical X-ray fluorescence (XRF) core scanning records provide evidence for hydrological variations and environmental changes since the Early Helladic period (5050 BP), the beginning of the Bronze Age in Greece. We hereby focus on different spatial scales to estimate the validity range of the proxy signals. Ten elements were selected (Al, Si, K, Ca, Ti, Mn, Fe, Rb, Sr, Zr) for a principal component analysis. The clr(Ca∕Ti) was chosen as the most meaningful proxy, reflecting varying input of carbonaceous vs. clastic input, which may be linked to changes in the hydrological conditions. Our results show phases when permanent lake water bodies existed (ca. 5000–3600 cal BP) as well as phases with periodic desiccation of the lakes during younger times. While Pheneos and Kaisari show a drying trend during the transition phase from the Late Helladic period to the Proto-Geometric period (ca. 3200–2800 cal BP), Stymphalia and Asea show a rather short dry peak around 3200 cal BP followed by a wetter phase. Although all our geoarchives show evidence for drier phases, their timing and duration display considerable site-to-site differences which may be explained by site-specific responses in individual ecosystems. Age uncertainties, however, may likewise explain some deviations, as the dating is based on bulk sediment samples including potential unknown reservoir effects. The high regional geographical diversity within the Peloponnese combined with the dating challenges in the limestone-rich area and the variation in our data testify that any hypothetical mono-causal connection between palaeoenvironmental changes in a single geoarchive and contemporaneous societal transformations across the Peloponnese would be an oversimplification.

Archive data on climate changes and seismic events in glacial clays of Lake Kucherla (Altai region, Russia)

Core samples taken from the bottom sediments of the glacial Lake Kucherla (Gorny Altai, Russia) clearly show annual layers represented by glacial clays. In our study, age-depth modeling is based the varve chronology and Cs-137, Pb-210 and C-14 isotope data. Our model is a highly accurate and reliable demonstration of the annual sedimentation history within the past 1400 years. The time series of geochemical indicators of climate change were obtained by synchrotron radiation micro X-ray fluorescence (SR- μ XRF) core scanning. Instrumental meteorological observations from 1940 to 2016 were used to construct transfer functions for the average annual temperatures and atmospheric precipitation amounts. A geochemical trace of a catastrophic seismic event, the Mongolian earthquake of 1761, was found in the cross-section of the bottom sediments.

Multivariate Statistical and Multiproxy Constraints on Earthquake-Triggered Sediment Remobilization Processes in the Central Japan Trench.

Understanding the impact of earthquakes on subaqueous environments is key for submarine paleoseismological investigations seeking to provide long‐term records of past earthquakes. For this purpose, event deposits (e.g., turbidites) are, among others, identified and stratigraphically correlated over broad areas to test for synchronous occurrence of gravity flows. Hence, detailed spatiotemporal petrographic and geochemical fingerprints of such deposits are required to advance the knowledge about sediment source and the underlying remobilization processes induced by past earthquakes. In this study, we develop for the first time in paleoseismology a multivariate statistical approach using X‐ray fluorescence core scanning, magnetic susceptibility, and wet bulk density data that allow to test, confirm, and enhance the previous visual and lithostratigraphic correlation across two isolated basins in the central Japan Trench. The statistical correlation is further confirmed by petrographic heavy grain analysis of the turbidites and additionally combined with our novel erosion model based on previously reported bulk organic carbon 14C dates. We find surficial sediment remobilization, a process whereby strong seismic shaking remobilizes the uppermost few centimeters of surficial slope sediment, to be a predominant remobilization process, which partly initiates deeper sediment remobilization downslope during strong earthquakes at the Japan Trench. These findings shed new light on source‐to‐sink transport processes in hadal trenches during earthquakes and help to assess the completeness of the turbidite paleoseismic record. Our results further suggest that shallow‐buried tephra on the slope might significantly influence sediment remobilization and the geochemical and petrographic fingerprints of the resulting event deposits.

Natural and anthropogenic sources of lead, zinc, and nickel in sediments of Lake Izabal, Guatemala

Sediments in Lake Izabal, Guatemala, contain substantial lead (Pb), zinc (Zn), and nickel (Ni). The lack of historical data for heavy metal concentrations in the sediments makes it difficult to determine the sources or evaluate whether inputs of metals to the lake have changed through time. We measured the relative abundances and concentrations of Pb, Zn, and Ni by X-Ray Fluorescence core scanning and by Inductively Coupled Plasma Optical Emission Spectrometry in three sediment cores to explore stratigraphic distributions of metals in the lake deposits. High amounts of Pb and Zn in the core taken near the Polochic Delta suggest that galena and sphalerite mining increased Pb and Zn delivery to Lake Izabal between ~1945 and 1965 CE. An up-core Ni increase in the core taken near a different mine on the north shore of Lake Izabal suggests that recent nickel mining operations led to an increase in Ni concentrations in the local sediments, but amounts in the other cores indicate that Ni is not widely distributed throughout the lake. Sediment cores from Lake Izabal are reliable recorders of heavy metal input to the lake, and were measured to establish background metal levels, which would otherwise be unavailable. Concentrations of Pb, Zn, and Ni in older, pre-20th-century Lake Izabal sediments reflect input from natural erosion of bedrock. Our results provide previously unavailable estimates of background metal concentrations in Lake Izabal before the onset of mining. These results are necessary for future monitoring related to mining contamination of the lake ecosystem.

Lacustrine cyclicity in the early Eocene Green River Formation, Uinta Basin, Utah: Evidence from X-ray fluorescence core scanning

ABSTRACTThe Green River Formation preserves an extraordinary archive of terrestrial paleoclimate during the Early Eocene Climatic Optimum (EECO; ∼ 53–50 Ma), expressing multiple scales of sedimentary cyclicity previously interpreted to reflect annual to Milankovitch-scale forcing. Here we utilize X-ray fluorescence (XRF) core scanning and micro X-ray fluorescence (micro-XRF) scanning in combination with radioisotopic age data to evaluate a rock core record of laminated oil shale and carbonate mudstone from Utah's Uinta Basin, with the parallel objectives of elucidating the paleo-environmental significance of the sedimentary rhythms, testing a range of forcing hypotheses, and evaluating potential linkages between high- and low-frequency forcing. This new assessment reveals that the ∼ 100-μm-scale laminae—the most fundamental rhythm of the Green River Formation—are most strongly expressed by variations in abundance of iron and sulfur. We propose that these variations reflect changes in redox state, consistent with annual stratification of the lake. In contrast to previous studies, no support was found for ENSO or sunspot cycles. However, millimeter- to centimeter-scale rhythms—temporally constrained to the decadal to centennial scale—are strongly expressed as alternations in the abundance of silicate- versus carbonate-associated elements (e.g., Al and Si vs. Ca), suggesting changes in precipitation and sediment delivery to the paleo-lake. Variations also occur at the meter scale, defining an approximate 4 m cycle interpreted to reflect precession. We also identify punctuated intervals, associated principally with one phase of the proposed precession cycle, where Si disconnects from the silicate input. We propose an alternative authigenic or biogenic Si source for these intervals, which reflects periods of enhanced productivity. This result reveals how long-term astronomical forcings can influence short-term processes, yielding insight into decadal- to millennial-scale terrestrial climate change in the Eocene greenhouse earth.