Combining sedimentological, trace metal (Mn, Mo) and molecular evidence for reconstructing past water-column redox conditions: The example of meromictic Lake Cadagno (Swiss Alps)

Here, we present sedimentological, trace metal, and molecular evidence for tracking bottom water redox-state conditions during the past 12,500 years in nowadays sulfidic and meromictic Lake Cadagno (Switzerland). A 10.5 m long sediment core from the lake covering the Holocene period was investigated for concentration variations of the trace metals Mn and Mo (XRF core scanning and ICP-MS measurements), and for the presence of anoxygenic phototrophic sulfur bacteria (carotenoid pigment analysis and 16S rDNA real time PCR). Our trace metal analysis documents an oxic-intermediate-sulfidic redox-transition period beginning shortly after the lake formation similar to 12.5 kyr ago. The oxic period is characterized by low sedimentary Mn and Mo concentrations, as well as by the absence of any remnants of anoxygenic phototrophic sulfur bacteria. Enhanced accumulation/preservation of Mn (up to 5.6 wt%) in the sediments indicates an intermediate, Mn-enriched oxygenation state with fluctuating redox conditions during a similar to 2300-year long transition interval between similar to 12.1 and 9.8 kyr BP. We propose that the high Mn concentrations are the result of enhanced Mn2+ leaching from the sediments during reducing conditions and subsequent rapid precipitation of Mn-(oxyhydr) oxide minerals during episodic and short-term water-column mixing events mainly due to flood-induced underflows. At 9800 +/- 130 cal yr BP, a rapid transition to fully sulfidic conditions is indicated by the marked enrichment of Mo in the sediments (up to 490 ppm), accompanied by an abrupt drop in Mn concentrations and the increase of molecular biomarkers that indicate the presence of anoxygenic photosynthetic bacteria in the water column. Persistently high Mo concentrations >80 ppm provide evidence that sulfidic conditions prevailed thereafter until modern times, without any lasting hypolimnetic ventilation and reoxygenation. Hence, Lake Cadagno with its persistently stable chemocline offers a framework to study in great temporal detail over similar to 12 kyr the development of phototrophic sulfur bacteria communities and redox processes in a sulfidic environment, possibly depicting analogous conditions in an ancient ocean. Our study underscores the value of combining sedimentological, geochemical, and microbiological approaches to characterize paleo-environmental and -redox conditions in lacustrine and marine settings.

Influence of catchment quality and altitude on the water and sediment composition of 68 small lakes in Central Europe

68 lakes (63 Swiss, 2 French and 3 Italian) located in an altitudinal range between 334 and 2339m spanning a wide range of land-use have been investigated. The aim of the study was to discuss influences of geographic location, vegetation and land-use in the catchment area on the water and sediment chemistry of small lakes. Detailed quantitative description of land-use, vegetation, and climate in the watershed of all lakes was established. Surface and bottom water samples collected from each lake were analyzed for major ions and nutrients. Correlations were interpreted using linear regression analysis. Chemical parameters of water and sediment reflect the characteristics of the catchment areas. All lakes were alkaline since they were situated on calcareous bedrock. Concentrations of nitrogen and phosphorus strongly increase with increasing agricultural land-use. Na and K, however, are positively correlated with the amount of urbanization within the catchment area. These elements as well as dissolved organic carbon (DOC), Mg, Ca, and alkalinity, increase when the catchment is urbanized or used for agriculture. Total nitrogen and organic carbon in the sediments decrease distinctly if large parts of the catchment consist of bare land. No correlations between sediment composition and maximum water depth or altitude of the lakes were found.¶Striking differences in the water compositions of lakes above and below approximately 700 m of altitude were observed. Concentrations of total nitrogen and nitrate, total phosphorus, DOC, Na, K, Mg, Ca, and alkalinity are distinctly higher in most lakes below 700 m than above, and the pH of the bottom waters of these lakes is generally lower. Estimates of total nitrogen concentrations, even in remote areas, indicate that precipitation is responsible for increased background concentrations. At lower altitudes nitrogen concentrations in lakes is explained by the nitrogen loaded rain from urban areas deposited on the catchment, and with high percentages of agricultural land-use in the watershed.