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[1] The X-ray fluorescence (XRF) core scanner provides bulk-sediment chemistry data measured nondestructively at the split core sediment surface. Although this method is widely accepted, there is little known about the effects of physical properties such as density and water content on XRF core scanner data. Comparison of XRF scanner measurements from the sediment surface and dry powder samples of sediment core GeoB7920 indicates strongly reduced element intensities for the lighter elements Al and Si. We relate the lower element intensities of the measurements taken at the sediment surface to the amount of water in the sample volume analyzed by the XRF core scanner. The heavier elements K, Ca, Ti, and Fe remain relatively unaffected by the variation of any physical property within sediment core GeoB7920. Additionally, we successfully use the elemental intensity of Cl as a proxy for the seawater content in the sample volume analyzed by the XRF core scanner. This enables the establishment of a correction function for the elements Al and Si that corrects for the radiation absorption of the water content in sediment core GeoB7920 off Cape Blanc, NW Africa.

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A multivariate log-ratio calibration (MLC) model for XRF-core-scanning devices is presented, based on a combination of basic XRF-spectrometry theory and principles of compositional data analysis. The performance of the MLC model is evaluated in comparison with other empirical calibration procedures for XRF core scanner data using two data sets acquired with two different XRF core scanners. The quality of calibration models is assessed by calculating the uncertainties associated with predicted concentrations using cross-validation techniques. Results show that (1) the commonly used direct linear calibration (DLC) methods, which are based on the questionable assumption of a unique linear relation between intensities and concentrations and do not acknowledge the compositional nature of the calibration problem, give poor results; (2) the univariate log-ratio calibration (ULC) model, which is consistent with the compositional nature of the calibration problem but does not fully incorporate absorption and enhancement effects on intensities, and permits estimation of "relative" concentrations only, is markedly better, and (3) the MLC algorithm introduced in this contribution, which incorporates measurement uncertainties, accommodates absorption and enhancement effects on intensities, and exploits the covariance between and among intensities and concentrations, is the best by far. The predictive power of the MLC model may be further increased by employing automatic sample selection based on the multivariate geometry of intensity measurements in log-ratio space. The precision attained by MLC in conjunction with automatic sample selection is comparable to that attained by conventional XRF analysis of heterogenous materials under laboratory conditions. A solution to the long-standing problem of XRF core scanner calibration implies that high-resolution records of sediment composition with associated uncertainties can now be routinely established, which should increase the range of quantitative applications of XRF-core-scanning devices and strengthen inferences based on analysis of geochemical proxies.

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A potential human footprint on Western Central African rainforests before the Common Era has become the focus of an ongoing controversy. Between 3,000 y ago and 2,000 y ago, regional pollen sequences indicate a replacement of mature rainforests by a forest-savannah mosaic including pioneer trees. Although some studies suggested an anthropogenic influence on this forest fragmentation, current interpretations based on pollen data attribute the ''rainforest crisis'' to climate change toward a drier, more seasonal climate. A rigorous test of this hypothesis, however, requires climate proxies independent of vegetation changes. Here we resolve this controversy through a continuous 10,500-y record of both vegetation and hydrological changes from Lake Barombi in Southwest Cameroon based on changes in carbon and hydrogen isotope compositions of plant waxes. [Formula: see text]C-inferred vegetation changes confirm a prominent and abrupt appearance of C plants in the Lake Barombi catchment, at 2,600 calendar years before AD 1950 (cal y BP), followed by an equally sudden return to rainforest vegetation at 2,020 cal y BP. [Formula: see text]D values from the same plant wax compounds, however, show no simultaneous hydrological change. Based on the combination of these data with a comprehensive regional archaeological database we provide evidence that humans triggered the rainforest fragmentation 2,600 y ago. Our findings suggest that technological developments, including agricultural practices and iron metallurgy, possibly related to the large-scale Bantu expansion, significantly impacted the ecosystems before the Common Era.

The limited availability of high-resolution continuous archives, insufficient chronological control, and complex hydro-climatic forcing mechanisms lead to many uncertainties in palaeo-hydrological reconstructions for the Western Mediterranean. In this study we present a newly recovered 19.63��m long core from Lake Sidi Ali in the North African Middle Atlas, a transition zone of Atlantic, Western Mediterranean and Saharan air mass trajectories. With a multi-proxy approach based on magnetic susceptibility, carbonate and total organic C content, core-scanning and quantitative XRF, stable isotopes of ostracod shells, charcoal counts, Cedrus pollen abundance, and a first set of diatom data, we reconstruct Western Mediterranean hydro-climatic variability, seasonality and forcing mechanisms during the last 12,000��yr. A robust chronological model based on AMS 14C dated pollen concentrates supports our high-resolution multi-proxy study. Long-term trends reveal low lake levels at the end of the Younger Dryas, during the mid-Holocene interval 6.6 to 5.4��cal ka BP, and during the last 3000 years. In contrast, lake levels are mostly high during the Early and Mid-Holocene. The record also shows sub-millennial- to centennial-scale decreases in Western Mediterranean winter rain at 11.4, 10.3, 9.2, 8.2, 7.2, 6.6, 6.0, 5.4, 5.0, 4.4, 3.5, 2.9, 2.2, 1.9, 1.7, 1.5, 1.0, 0.7, and 0.2��cal ka BP. Early Holocene winter rain minima are in phase with cooling events and millennial-scale meltwater discharges in the sub-polar North Atlantic. Our proxy parameters do not show so far a clear impact of Saharan air masses on Mediterranean hydro-climate in North Africa. However, a significant hydro-climatic shift at the end of the African Humid Period (���5 ka) indicates a change in climate forcing mechanisms. The Late Holocene climate variability in the Middle Atlas features a multi-centennial-scale NAO-type pattern, with Atlantic cooling and Western Mediterranean winter rain maxima generally associated with solar minima

The Holocene sediment record of Lake Tiefer See exhibits striking alternations between well-varved and non-varved intervals. Here, we present a high-resolution multi-proxy record for the past ~6000 years and discuss possible causes for the observed sediment variability. This approach comprises microfacies, geochemical and microfossil analyses and a multiple dating concept including varve counting, tephrochronology and radiocarbon dating. Four periods of predominantly well-varved sediment were identified at 6000–3950, 3100–2850 and 2100–750 cal. a BP and AD 1924–present. Except of sub-recent varve formation, these periods are considered to reflect reduced lake circulation and consequently, stronger anoxic bottom water conditions. In contrast, intercalated intervals of poor varve preservation or even extensively mixed non-varved sediments indicate strengthened lake circulation. Sub-recent varve formation since AD 1924 is, in addition to natural forcing, influenced by enhanced lake productivity due to modern anthropogenic eutrophication. The general increase in periods of intensified lake circulation in Lake Tiefer See since ~4000 cal. a BP presumably is caused by gradual changes in the northern hemisphere orbital forcing, leading to cooler and windier conditions in Central Europe. Superimposed decadal- to centennial-scale variability of the lake circulation regime is likely the result of additional human-induced changes of the catchment vegetation. The coincidence of major non-varved periods at Lake Tiefer See and intervals of bioturbated sediments in the Baltic Sea implies a broader regional significance of our findings.