Quantifying calcium carbonate and organic carbon content in marine sediments from XRF-scanning spectra with a machine learning approach.

Geochemical variations of sedimentary records contain vital information for understanding paleoenvironment and paleoclimate. However, to obtain quantitative data in the laboratory is laborious, which ultimately restricts the temporal and spatial resolution. Quantification based on fast-acquisition and high-resolution provides a potential solution but is restricted to qualitative X-ray fluorescence (XRF) core scanning data. Here, we apply machine learning (ML) to advance the quantification progress and target calcium carbonate (CaCO3) and total organic carbon (TOC) for quantification to test the potential of such an XRF-ML approach. Raw XRF spectra are used as input data instead of software-based extraction of elemental intensities to avoid bias and increase information. Our dataset comprises Pacific and Southern Ocean marine sediment cores from high- to mid-latitudes to extend the applicability of quantification models from a site-specific to a multi-regional scale. ML-built models are carefully evaluated with a training set, a test set and a case study. The acquired ML-models provide better results with R2 of 0.96 for CaCO3 and 0.78 for TOC than conventional methods. In our case study, the ML-performance for TOC is comparably lower but still provides potential for future optimization. Altogether, this study allows to conveniently generate high-resolution bulk chemistry records without losing accuracy.

Elevated dust depositions in West Asia linked to ocean-atmosphere shifts during North Atlantic cold events.

Rapid North Atlantic cooling events during the last deglaciation caused atmospheric reorganizations on global and regional scales. Their impact on Asian climate has been investigated for monsoonal domains, but remains largely unknown in westerly wind-dominated semiarid regions. Here we generate a dust record from southeastern Iran spanning the period 19 to 7 cal. ka B.P. We find a direct link between frequent occurrences of dust plumes originating from the Arabian Peninsula and North Africa and rapid southward shifts of the westerlies associated with changes of the winter stationary waves during Heinrich Stadial 1, the Younger Dryas, the Preboreal Oscillation, and the 8.2-ka event. Dust input rises and falls abruptly at the transitions into and out of these cooling events, which we attribute to changes in the ocean circulation strength that are modulated by the North Atlantic winter sea-ice cover. Our findings reveal that waxing and waning of North American ice sheets have a stronger influence than those of European ice sheets on the winter climate over West Asia.

Human and climate global-scale imprint on sediment transfer during the Holocene.

Accelerated soil erosion has become a pervasive feature on landscapes around the world and is recognized to have substantial implications for land productivity, downstream water quality, and biogeochemical cycles. However, the scarcity of global syntheses that consider long-term processes has limited our understanding of the timing, the amplitude, and the extent of soil erosion over millennial time scales. As such, we lack the ability to make predictions about the responses of soil erosion to long-term climate and land cover changes. Here, we reconstruct sedimentation rates for 632 lakes based on chronologies constrained by 3,980 calibrated 14C ages to assess the relative changes in lake-watershed erosion rates over the last 12,000 y. Estimated soil erosion dynamics were then complemented with land cover reconstructions inferred from 43,669 pollen samples and with climate time series from the Max Planck Institute Earth System Model. Our results show that a significant portion of the Earth surface shifted to human-driven soil erosion rate already 4,000 y ago. In particular, inferred soil erosion rates increased in 35% of the watersheds, and most of these sites showed a decrease in the proportion of arboreal pollen, which would be expected with land clearance. Further analysis revealed that land cover change was the main driver of inferred soil erosion in 70% of all studied watersheds. This study suggests that soil erosion has been altering terrestrial and aquatic ecosystems for millennia, leading to carbon (C) losses that could have ultimately induced feedbacks on the climate system.

Urban point sources of nutrients were the leading cause for the historical spread of hypoxia across European lakes.

Enhanced phosphorus (P) export from land into streams and lakes is a primary factor driving the expansion of deep-water hypoxia in lakes during the Anthropocene. However, the interplay of regional scale environmental stressors and the lack of long-term instrumental data often impede analyses attempting to associate changes in land cover with downstream aquatic responses. Herein, we performed a synthesis of data that link paleolimnological reconstructions of lake bottom-water oxygenation to changes in land cover/use and climate over the past 300 years to evaluate whether the spread of hypoxia in European lakes was primarily associated with enhanced P exports from growing urbanization, intensified agriculture, or climatic change. We showed that hypoxia started spreading in European lakes around CE 1850 and was greatly accelerated after CE 1900. Socioeconomic changes in Europe beginning in CE 1850 resulted in widespread urbanization, as well as a larger and more intensively cultivated surface area. However, our analysis of temporal trends demonstrated that the onset and intensification of lacustrine hypoxia were more strongly related to the growth of urban areas than to changes in agricultural areas and the application of fertilizers. These results suggest that anthropogenically triggered hypoxia in European lakes was primarily caused by enhanced P discharges from urban point sources. To date, there have been no signs of sustained recovery of bottom-water oxygenation in lakes following the enactment of European water legislation in the 1970s to 1980s, and the subsequent decrease in domestic P consumption.

Global spread of hypoxia in freshwater ecosystems during the last three centuries is caused by rising local human pressure.

The spread of hypoxia is a threat to aquatic ecosystem functions and services as well as to biodiversity. However, sparse long-term monitoring of lake ecosystems has prevented reconstruction of global hypoxia dynamics while inhibiting investigations into its causes and assessing the resilience capacity of these systems. This study compiles the onset and duration of hypoxia recorded in sediments of 365 lakes worldwide since AD 1700, showing that lacustrine hypoxia started spreading before AD 1900, 70 years prior to hypoxia in coastal zones. This study also shows that the increase of human activities and nutrient release is leading to hypoxia onset. No correlations were found with changes in precipitation or temperature. There is no evidence for a post-1980s return to well-oxygenated lacustrine conditions in industrialized countries despite the implementation of restoration programs. The apparent establishment of stable hypoxic conditions prior to AD 1900 highlights the challenges of a growing nutrient demand, accompanied by increasing global nutrient emissions of our industrialized societies, and climate change.

Universally applicable model for the quantitative determination of lake sediment composition using fourier transform infrared spectroscopy.

Fourier transform infrared spectroscopy (FTIRS) can provide detailed information on organic and minerogenic constituents of sediment records. Based on a large number of sediment samples of varying age (0-340,000 yrs) and from very diverse lake settings in Antarctica, Argentina, Canada, Macedonia/Albania, Siberia, and Sweden, we have developed universally applicable calibration models for the quantitative determination of biogenic silica (BSi; n = 816), total inorganic carbon (TIC; n = 879), and total organic carbon (TOC; n = 3164) using FTIRS. These models are based on the differential absorbance of infrared radiation at specific wavelengths with varying concentrations of individual parameters, due to molecular vibrations associated with each parameter. The calibration models have low prediction errors and the predicted values are highly correlated with conventionally measured values (R = 0.94-0.99). Robustness tests indicate the accuracy of the newly developed FTIRS calibration models is similar to that of conventional geochemical analyses. Consequently FTIRS offers a useful and rapid alternative to conventional analyses for the quantitative determination of BSi, TIC, and TOC. The rapidity, cost-effectiveness, and small sample size required enables FTIRS determination of geochemical properties to be undertaken at higher resolutions than would otherwise be possible with the same resource allocation, thus providing crucial sedimentological information for climatic and environmental reconstructions.

Effects of land-use change on deposition and composition of organic matter in Frickenhauser See, northern Bavaria, Germany.

Characterization of bulk organic matter (OM) from lacustrine sediments of Frickenhauser See (northern Bavaria, Germany) reveals considerable variation during the last two millennia. Atomic C/N ratios and total organic carbon (TOC) content are positively correlated with arboreal pollen percentages which are used as an indicator of land-use intensity. Despite possible alterations of OM during early diagenesis, differences between three major lithological units are large enough to be interpreted as human impact on the sedimentation of OM in the lake. Sediments deposited prior to deforestation in the catchment area (unit C) are characterized by mean C/N ratios of 14.5, indicating a mixed composition of organic matter derived from lacustrine and terrestrial sources (forest litter). During a period of intensive soil erosion (ca. 1000 AD until 1870 AD; unit B), low C/N ratios of around 7.7 suggest that the relative proportion of forest litter decreased in favour of the lacustrine component and soil OM. Terrestrial plant detritus is only transported into the lake through numerous turbidite events. Deforestation and agriculture also coincide with a decreasing TOC content from an average value of 10.7% to 1.5%. This decrease is explained through a dilution effect due to the high input of minerogenic matter. Stable carbon isotopes indicate eutrophication of the lake due to the mobilization of nutrients through soil erosion. Starting around 1870 AD, organic-rich sapropelic sediments are deposited (unit A). A decline of turbidite events and increased wind shelter from trees due to reduced land-use intensity led to meromictic conditions. Consequently, negative excursions in the delta13C isotope record at the onset of unit A probably reflect methanogenesis under permanently anoxic conditions.