Redox-sensitive metals in recent lake sediments proxyindicators of deep-water oxygen and climate conditions
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1 Research Collection Doctoral Thesis Redox-sensitive metals in recent lake sediments proxyindicators of deep-water oxygen and climate conditions Author(s): Schaller, Tobias Lukas Publication Date: 1996 Permanent Link: Rights / License: In Copyright - Non-Commercial Use Permitted This page was generated automatically upon download from the ETH Zurich Research Collection. For more information please consult the Terms of use. ETH Library
2 Diss. ETH No Redox-Sensitive Metals in Recent Lake Sediments Proxy-Indicators of Deep-Water Oxygen Conditions and Climate A dissertation submitted to the SWISS FEDERAL INSTITUTE OF TECHNOLOGY for the degree of DOCTOR OF NATURAL SCIENCES presented by TOBIAS LUKAS SCHALLER dipl. Kultur-Ing. ETH-Zurich born, April 11, 1963 Citizen of Tentlingen FR accepted on the recommendation of Prof. Dr. Bernhard Wehrli, examiner Dr. Michael Sturm, co-examiner Prof. Dr. Helmut Weissert, co-examiner Zurich 1996
3 Summary It was the goal of this thesis to test whether concentration patterns of redox-sensitive metals in lake sediments can be used as a record of past climate conditions. The connecting link between climate and metals are deep-water oxygen conditions. However, the link is indirect. Furthermore, the benthic oxygen balance is influenced to a great extend by eutrophication. Metal concentrations may be affected by geochemical processes, independent of oxygen. A major part of this work was considered with the evaluation of metal concentration pattern which are proxy-indicators of deep-water oxygen conditions. In a first attempt, the lateral distributions of Mn concentrations in the sediments of Baldeggersee and Zugersee under varying oxygen conditions were determined. The comparison of Mn distribution patterns with the deep-water oxygen situation provides strong evidence for a geochemicalfocusing effect, driven by the redox cycle of manganese. Oxygen conditions essential for this process to occur are anoxic sediments in contact with an oxic water-column. The increase of manganese concentrations with water-depth is directly proportional sediment surface area as a function of water-depth. to the increase of This result indicates that geochemical-focusing of manganese in lake sediments is a promising proxy indicator for the reconstruction of oxygen conditions during deposition.
4 11 Summary In the same sediment samples from Baldeggersee, the two-dimensional distribution of Fe, V, Cr, As and Mo was determined. The horizontal distribution pattern of iron indicates a correlation of concentrations with water-depth. Benthic redox-gradients trigger iron transport towards the deepest site (geochemical-focusing) and loss of iron from the shallower parts through the outflow. The internal Fe cycle is at maximum, when an anoxic sediment surface is in contact with oxic deep-water. Fe cycling in the lake is inhibited when oxygen penetration into the sediment is large. Vanadium and arsenic can be used as tracers for the internal Fe cycle. Their distribution patterns are highly correlated with Fe. In case of a stable oxycline in the deep-water Mo is enriched in the sediment and correlates with Mn. Similar to Mn, the horizontal distribution pattern of Fe, V, As and the correlation of Fe and Mn with trace-metals can be used as a record of deep-water oxygen conditions during deposition. Concentration profiles of Mg, K, La, Fe, Mn, V, Cr, As and Mo were determined in a freeze core, taken in 1993 at the deepest site of Baldeggersee. The freeze core technique allowed an exact dating of the sediment samples and an annual resolution of the profiles. Long term oxygen conditions are recorded by trends of metal profiles. Fe, As and Mn enrichments trace the onset of anoxia at the deepest site of the lake. Increased average Mo concentrations correlate with the appearance of oxygen depletion in the water-column. A comparison of oxygen time series with metal profiles between 1950 and 1990 revealed, that Mn reacts sensitively to strong seasonal variations of oxygen conditions. High values of Cr/Mg, Mo and Cr/V indicate periods of stable anoxic conditions. A comparison of benthic oxygen conditions with eutrophication trends and time series of the climatic parameters wind and temperature suggests, that the beginning of anoxia at the deepest site of Baldeggersee at the end of the last century was climatically induced. Only at the time of highest phosphorus loading, the climate signal was masked by eutrophication. The signal of both climate and eutrophication is recorded by metal concentration pattern. However with metal pattern alone, it is not possible to separate the signals. A promising solution of the problem would be to combine the information from redox-sensitive metals with geochemical indicators of nutrient loading.
5 Zusammenfassung Das Ziel der vorliegenden Arbeit war es zu untersuchen, ob sich Konzentrationsmuster redox-sensitiver Metalle in Seesedimenten zur Rekonstruktion vergangener Klimabedingungen eignen. Klima und Metalle sind iiber Sauerstoffbedingungen im Tiefenwasser indirekt miteinander verkniipft. Allerdings wird die Sauerstoffbilanz des Tiefenwassers auch von den Nahrstoffbedingungen stark beeinflusst. Auch konnen viele geo chemische Prozesse unabhangig von den jeweiligen Sauerstoffbedingungen das Verhalten von Metallen bestimmen Ein Grossteil dieser Arbeit umfasst daher die Evaluation von Konzentrationsmustern, die eine Folge spezifischer Sauerstoffbedingungen im Tiefenwasser sind. In einem ersten Ansatz wurden zweidimensionale Konzentrationsverteilungen von Mangan in unter verschiedenen Sauerstoffbedingungen abgelagerten Sedimenten des Baldegger- und Zugersees bestimmt. Der Vergleich zwischen den Konzentrationsverteilungen und den Sauerstoff bedingungen im Tiefenwasser zeigte, dass unter bestimmten Voraussetzungen eine geochemische Fokussierung stattfindet. Diese Art der Fokussierung ist eine Konsequenz des Redoxkreislauf von Mangan. Sie findet statt, wenn ein anoxisches Sediment mit einer oxischen Wassersaule in Kontakt steht. Die Konzentrationszunahme von Mangan mit der Wasser tiefe ist direkt proportional zur Zunahme der Sedimentoberflache als Funktion der Wassertiefe. Diese Resultate zeigen, dass die geochemische Fokussierung von Mangan ein potentieller bedingungen im Tiefenwasser ist. Indikator fiir Sauerstoff
6 IV Zusammenfassung In denselben Sedimentproben vom Baldeggersee wurden auch die Konzentrationen von Eisen, Vanadium, Chrom, Arsen und Molybdan bestimmt. Analog zu Mangan sind Eisenkonzentrationen unter bestimmten Voraussetzungen proportional zur Wassertiefe. Redox-Gradienten im Tiefenwasser fiihren zu einem Eisenverlust im Sediment in Zonen niedriger Wassertiefe und verursachen einen Transport von der Flachwasserzone zu tieferen Stellen. Der Eisenkreislauf im See ist am ausgepragtesten, wenn ein anoxisches Sediment von einer oxischen Wassersaule uberlagert wird. Wenn Sauerstoff ins Sediment eindringen kann, wird der Kreislauf unterbunden. Die Spurenmetalle Vanadium, Arsen und Chrom konnen als Indikatoren fiir den Eisenkreislauf dienen. Die horizontale Konzentrationsverteilung von Eisen in Kombination mit den Korrelationen zwischen Eisen und den Spurenmetallen V, Cr und As sind vielversprechende Indikatoren fiir Rekonstruktionen der Sauerstoffbedingungen in einem See. In einem Gefrierkern, der der tiefsten Stelle des Baldeggersee entnommen wurde, wurden hochaufgeloste Konzentrationsprofile der Metalle Mg, K, La, Fe, Mn, V, Cr, As und Mo bestimmt. Die Gefriertechnik ermoglichte eine exakte Datierung der Sedimentproben. Fe-, Mn- und As-anreicherungen erwiesen sich als potentielle Indikatoren fiir den Beginn anoxischer Verhaltnisse an der tiefsten Stelle. Hohe Moanreicherungen korrelieren mit dem Auftreten anoxischer Bedingungen in grossen Bereichen des Tiefenwassers. Ein Vergleich mittlerer Sauerstoffkonzentrationen im Hypolimnion mit Metallprofilen im Zeitraum 1950 bis 1990 zeigt, dass grosse saisonale Schwankungen der Sauerstoffkonzentrationen zu Mn-anreicherungen im Sediment fiihren. Perioden mit stabilen anoxischen Bedingungen fiihren zu hohen Werten der Parameter Cr/Mg, Cr/Vund Mo. Ein Vergleich zwischen Sauerstoffbedingungen, dem Trend der Nahrstoffbedingungen und Temperatur-, bzw. Winddaten lasst vermuten, dass der Zeitpunkt des Auftretens anoxischer Bedingungen im Tiefenwasser des Baldeggersees klimatisch bedingt war. Metallkonzentrationen registrieren die Signale von Klima und Eutrophierung. Hohe Nahrstoffzufuhr kann das Klimasignal im Sediment verwischen. Eine Trennung der Signale konnte durch eine Kombination von redox-sensitiven Metallen mit geochemischen Indikatoren fiir Nahrstoffbelastung erfolgen.
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