Global spread of anoxia in aquatic ecosystems has become a major issue that may potentially worsen due to global warming. The reconstruction of long-term hypolimnetic anoxia records can be challenging due to lack of valid and easily measurable proxies. The sedimentary Mn/Fe ratio measured by X-ray fluorescence (XRF) is often used as a proxy for past lake redox conditions. Yet the interpretation of this ratio can be problematic when Fe and Mn accumulation is not solely redox driven. We used the varved sediments of Lake Moossee (Switzerland) to examine the partitioning of Fe and Mn in seven fractions by sequential extraction under various oxygen conditions over the last 15,000 years. We combined this data with XRF scans and an independent diagnostic proxy for anoxia given by a hyperspectral imaging (HSI)-inferred record of bacteriopheophytin, to validate the use of the XRF-Mn/Fe ratio as redox proxy. In the 15,000-year long record, Fe was bound to humins and amorphous, crystalline, sulfide and residual forms. Mn was mainly present in carbonate and amorphous forms. Higher erosion, prolonged anoxia, diagenesis and humic matter input affected Fe and Mn accumulation. Under holomixis the XRF-Mn/Fe ratio successfully reflected lake redox conditions. Periods with higher detrital Fe input obscured the applicability of the ratio. During phases of permanent anoxia, intensified early diagenetic processes trapped Mn in the sediments in carbonate, crystalline oxide and humic forms. Our study shows that the single use of the XRF-Mn/Fe ratio is often not conclusive for inferring past lake redox conditions. The application of the XRF-Mn/Fe as a proxy for anoxia requires taking into account the individual lake characteristics and changes in lake environmental conditions, which affect the accumulation of Fe and Mn in the sediments.
Hyperspectral imaging (HSI) in situ core scanning has emerged as a valuable and novel tool for rapid and non-destructive biogeochemical analysis of lake sediment cores. Variations in sediment composition can be assessed directly from fresh sediment surfaces at ultra-high-resolution (40–300 μm measurement resolution) based on spectral profiles of light reflected from sediments in visible, near infrared, and short-wave infrared wavelengths (400–2500 nm). Here, we review recent methodological developments in this new and growing field of research, as well as applications of this technique for paleoclimate and paleoenvironmental studies. Hyperspectral imaging of sediment cores has been demonstrated to effectively track variations in sedimentary pigments, organic matter, grain size, minerogenic components, and other sedimentary features. These biogeochemical variables record information about past climatic conditions, paleoproductivity, past hypolimnetic anoxia, aeolian input, volcanic eruptions, earthquake and flood frequencies, and other variables of environmental relevance. HSI has been applied to study seasonal and inter-annual environmental variability as recorded in individual varves (annually laminated sediments) or to study sedimentary records covering long glacial–interglacial time-scales (>10,000 years).
Cyanobacteria are ubiquitous aquatic organisms with a remarkable evolutionary history reaching as far as 1.9 Ga. They play a vital role in ecosystems yet also raise concerns due to their association with harmful algal blooms. Understanding the historical patterns and drivers behind these blooms is crucial for effective ecosystem management. Lake-sediment cores are valuable natural environmental archives, recording the histories of such blooms. Among others, phycocyanin, a pigment specific to cyanobacteria, emerges as a promising biomarker for reconstructing past cyanobacterial bloom events. However, due to the physicochemical properties of phycocyanin, there is no validated method available to extract and measure this pigment from complex sediment matrix. This study explores the applicability of hyperspectral imaging (HSI), a non-destructive technique, as a novel approach for high resolution in-situ detection and quantification of phycocyanin in lake sediments. Our experiments show that phycocyanin can be detected by HSI with an absorption trough at 620 nm (relative absorption band depth, RABD620). We established a semi-quantitative calibration of the spectral index RABD620 by conducting spiking experiments with phycocyanin standard (known phycocyanin mass) on organic-rich and mineral-rich sediments of varying water contents. We also assessed potential interference from chlorophyll a, another photosynthetic pigment, ensuring the reliability of hyperspectral phycocyanin measurements. Our findings demonstrate a significant correlation (R2 ranging from 0.37 to 0.997) between the RABD620 index and associated phycocyanin amounts in organic-rich and minerogenic sediments. This indicates the potential of the spectral index to directly measure in-situ biomarker concentrations on split sediment cores. Although confounding factors such as water and chlorophyll a content can influence the spectral signal, this method offers a rapid and non-destructive approach for studying historical cyanobacterial blooms in sedimentary records. This opens promising grounds for various applications, including ecosystem-health assessment and environmental change monitoring.
Discerning ecosystem change and food web dynamics underlying anthropogenic eutrophication and the introduction of non-native species is necessary for ensuring the long-term sustainability of fisheries and lake biodiversity. Previous studies of eutrophication in Lake Victoria, eastern Africa, have focused on the loss of endemic fish biodiversity over the past several decades, but changes in the plankton communities over this same time remain unclear. To fill this gap, we examined sediment cores from a eutrophic embayment, Mwanza Gulf, to determine the timing and magnitude of changes in the phytoplankton and zooplankton assemblages over the past century. Biogeochemical proxies indicate nutrient enrichment began around ~ 1920 CE and led to rapid increases in primary production, and our analysis of photosynthetic pigments revealed three zones: pre-eutrophication (prior to 1920 CE), onset of eutrophication with increases in all pigments (1920–1990 CE), and sustained eutrophication with cyanobacterial dominance (1990 CE–present). Cladoceran remains indicate an abrupt decline in biomass in ~ 1960 CE, in response to the cumulative effects of eutrophication and lake-level rise, preceding the collapse of haplochromine cichlids in the 1980s. Alona and Chydorus, typically benthic littoral taxa, have remained at relatively low abundances since the 1960s, whereas the abundance of Bosmina, typically a planktonic taxon, increased in the 1990s concurrently with the biomass recovery of haplochromine cichlid fishes. Overall, our results demonstrate substantial changes over the past century in the biomass structure and taxonomic composition of Mwanza Gulf phytoplankton and zooplankton communities, providing a historical food web perspective that can help understand the recent changes and inform future resource management decisions in the Lake Victoria ecosystem.