Absence of oxygen isotope fractionation/exchange of (hemi-) cellulose derived sugars during litter decomposition

Aiming at developing a novel tool for palaeoclimate research, we recently proposed a new method for determining the oxygen isotope composition of monosaccharides (Zech, M., Glaser, B., 2009. Compound-specific δ¹⁸O analyses of neutral sugars in soils using GC-Py-IRMS: problems, possible solutions and a first application. Rapid Communications in Mass Spectrometry 23, 3522-3532). In order to answer the question whether isotope fractionation and oxygen exchange reactions during litter decomposition affect the climatically controlled δ¹⁸O values of plant derived sugars, such as for instance xylose and arabinose from hemicelluloses, we studied the compound specific δ¹⁸O values of five different litter species having been decomposed in a field litterbag experiment for 27 months.While δ¹⁸O values of bulk organic matter yielded a systematic ¹⁸O depletion of 3.3‰ (pine) to 4.6‰ (spruce) accompanying total cellulose decomposition of 51% (beech) to 86% (ash), δ¹⁸O values of individual sugars show no significant trend with time. In addition to the observed absence of isotope fractionation during decomposition, we also rule out ¹⁸O exchange reactions affecting the δ¹⁸O signature of sugar molecules during diagenetic processes as well as during analytical procedure based on experimental findings and on theoretical biochemical mechanistic considerations. We conclude that our new method may become an analytical tool that elegantly overcomes extraction, purity and hygroscopicity problems of previous ¹⁸O cellulose methods. It furthermore has the potential to be applied to a wide range of climate archives such as tree rings, lacustrine sediments and loess palaeosol sequences.     

<Superscript>10</Superscript>Be surface exposure dating of the last deglaciation in the Aare Valley,Switzerland

The combined Rhone and Aare Glaciers presumably reached their last glacial maximum (LGM) extent on the Swiss Plateau prior to 24 ka. Two well-preserved, less extensive moraine stades, the Gurten and Bern Stade, document the last deglaciation of the Aare Valley, yet age constraints are very scarce. In order to establish a more robust chronology for the glacial/deglacial history of the Aare Valley, we applied ¹⁰Be surface exposure dating on eleven boulders from the Gurten and Bern Stade. Several exposure ages are of Holocene age and likely document post-depositional processes, including boulder toppling and quarrying. The remaining exposure ages, however yield oldest ages of 20.7 ± 2.2 ka for the Gurten Stade and 19.0 ± 2.0 ka for the Bern Stade. Our results are in good agreement with published chronologies from other sites in the Alps.     

Petrography,Sr-isotope geochemistry and geochronology of the Nxau Nxau kimberlites,north-west Botswana

The Nxau Nxau kimberlites in northwest Botswana belong to the Xaudum kimberlite province that also includes the Sikereti, Kaudom and Gura kimberlite clusters in north-east Namibia. The Nxau Nxau kimberlites lie on the southernmost extension of the Congo Craton, which incorporates part of the Damara Orogenic Belt on its margin. The Xaudum kimberlite province is geographically isolated from other known clusters but occurs within the limits of the NW-SE oriented, Karoo-aged Okavango Dyke Swarm and near NE-SW faults interpreted as the early stages of the East African Rift System. Petrographic, geochronological and isotopic studies were undertaken to characterise the nature of these kimberlites and the timing of their emplacement. The Nxau Nxau kimberlites exhibit groundmass textures, mineral phases and Sr-isotope compositions (⁸⁷Sr/⁸⁶Sr_i of 0.7036 ± 0.0002; 2σ) that are characteristic of archetypal (Group I) kimberlites. U-Pb perovskite, ⁴⁰Ar/³⁹Ar phlogopite and Rb-Sr phlogopite ages indicate that the kimberlites were emplaced in the Cretaceous, with perovskite from four samples yielding a preferred weighted average U-Pb age of 84 ± 4 Ma (2σ). This age is typical of many kimberlites in southern Africa, indicating that the Xaudum occurrences form part of this widespread Late Cretaceous kimberlite magmatic province. This time marks a significant period of tectonic stress reorganisation that could have provided the trigger for kimberlite magmatism. In this regard, the Nxau Nxau kimberlites may form part of a NE-SW oriented trend such as the Lucapa corridor, with implications for further undiscovered kimberlites along this corridor.

     

Experimental partitioning of halogens and other trace elements between olivine, pyroxenes, amphibole and aqueous fluid at 2 GPa and 900–1,300 °C

We present new partition coefficients for various trace elements including Cl between olivine, pyroxenes, amphibole and coexisting chlorine-bearing aqueous fluid in a series of high-pressure experiments at 2 GPa between 900 and 1,300 °C in natural and synthetic systems. Diamond aggregates were added to the experimental capsule set-up in order to separate the fluid from the solid residue and enable in situ analysis of the quenched solute by LA–ICP–MS. The chlorine and fluorine contents in mantle minerals were measured by electron microprobe, and the nature of OH defects was investigated by infrared spectroscopy. Furthermore, a fluorine-rich olivine from one selected sample was investigated by TEM. Results reveal average Cl concentrations in olivine and pyroxenes around 20 ppm and up to 900 ppm F in olivine, making olivine an important repository of halogens in the mantle. Chlorine is always incompatible with Cl partition coefficients D _Cl ^{olivine/fluid} varying between 10^?5 and 10^?3, whereas D _Cl ^{orthopyroxene/fluid} and D _Cl ^{clinopyroxene/fluid} are ~10^?4 and D _Cl ^{amphibole/fluid} is ~5 × 10^?3. Furthermore, partitioning results for incompatible trace element show that compatibilities of trace elements are generally ordered as D ^amph/fluid ≈ D ^cpx/fluid > D ^opx/fluid > D ^ol/fluid but that D ^{mineral/fluid} for Li and P is very similar for all observed silicate phases. Infrared spectra of olivine synthesized in a F-free Ti-bearing system show absorption bands at 3,525 and ~3,570 cm^?1. In F ± TiO₂-bearing systems, additional absorption bands appear at ~3,535, ~3,595, 3,640 and 3,670 cm^?1. Absorption bands at ~3,530 and ~3,570 cm^?1, previously assigned to humite-like point defects, profit from low synthesis temperatures and the presence of F. The presence of planar defects could not be proved by TEM investigations, but dislocations in the olivine lattice were observed and are suggested to be an important site for halogen incorporation in olivine.     

The Sabzevar blueschists of the North-Central Iranian micro-continent as remnants of the Neotethys-related oceanic crust subduction

The Sabzevar ophiolites mark the Neotethys suture in east-north-central Iran. The Sabzevar metamorphic rocks, as part of the Cretaceous Sabzevar ophiolitic complex, consist of blueschist, amphibolite and greenschist. The Sabzevar blueschists contain sodic amphibole, epidote, phengite, calcite ± omphacite ± quartz. The epidote amphibolite is composed of sodic-calcic amphibole, epidote, albite, phengite, quartz ± omphacite, ilmenite and titanite. The greenschist contains chlorite, plagioclase and pyrite, as main minerals. Thermobarometry of a blueschist yields a pressure of 13–15.5 kbar at temperatures of 420–500 °C. Peak metamorphic temperature/depth ratios were low (~12 °C/km), consistent with metamorphism in a subduction zone. The presence of epidote in the blueschist shows that the rocks were metamorphosed entirely within the epidote stability field. Amphibole schist samples experienced pressures of 5–7 kbar and temperatures between 450 and 550 °C. The presence of chlorite, actinolite, biotite and titanite indicate greenschist facies metamorphism. Chlorite, albite and biotite replacing garnet or glaucophane suggests temperatures of >300 °C for greenschist facies. The formation of high-pressure metamorphic rocks is related to north-east-dipping subduction of the Neotethys oceanic crust and subsequent closure during lower Eocene between the Central Iranian Micro-continent and Eurasia (North Iran).     

A late Pleistocene glacial chronology from the Kitschi-Kurumdu Valley,Tien Shan (Kyrgyzstan), based on 10Be surface exposure dating

Surface exposure dating has become a helpful tool for establishing numeric glacial chronologies, particularly in arid high-mountain regions where radiocarbon dating is challenging due to limited availability of organic material. This study presents 13 new ¹⁰Be surface exposure ages from the Kitschi-Kurumdu Valley in the At Bashi Range, Tien Shan. Three moraines were dated to ~ 15, 21 and > 56 ka, respectively, and corroborate previous findings that glacial extents in the Tien Shan during Marine Oxygen Isotope Stage (MIS) 2 were limited compared to MIS 4. This likely documents increasingly arid conditions in Central Asia during the last glacial cycle. Morphological evidence in the Kitschi-Kurumdu Valley and a detailed review of existing numeric glacial chronologies from the Tien Shan indicate that remnants of the penultimate glaciation (MIS 6) are preserved, whereas evidence for MIS 5 glacier advances remains equivocal. Reviewed and recalculated exposure ages from the Pamir mountains, on the other hand, reveal extensive MIS 5 glacial extents that may indicate increased monsoonal precipitation. The preservation of MIS 3 moraines in the Tien Shan and the southern Pamir does not require any monsoonal influence and can be explained alternatively with increased precipitation via the westerlies.     

Chrysophyte cysts as paleolimnological indicators of environmental change due to cottage development and acidic deposition in the Muskoka-Haliburton region, Ontario, Canada

Chrysophyte cysts preserved in recent and pre-industrial lake sediment samples from 54 Muskoka-Haliburton (Ontario) lakes were used in a paleolimnological study to determine the impact of acidic precipitation and cottage development on water quality. A total of 246 cyst morphotypes were identified. Ecological preferences of cyst morphotypes were determined using multivariate statistical analysis, cluster analysis, and species-environment correlations. Recent cyst assemblages were related to water chemistry and lake morphometric variables using Redundancy Analysis (RDA). The distribution of morphotypes was related to a gradient of acid neutralising capacity (ANC), expressed through the association of variables related to buffering (i.e. longitude, watershed area, and ionic concentration) with the first axis (₁ = 0.29). Cyst assemblages were also defined, to a lesser extent (₂ = 0.06), by a trophic status gradient, created through the combination of total nitrogen (TN), total phosphorus (TP), volume-weighted cottage density, and lake depth variables. The identification of lakewater pH and trophic status as important determinants of cyst assemblage structure allowed for the reconstruction of acidification and eutrophication related water chemistry changes using fossil cyst assemblages. The reconstruction of pre-industrial (pre-1850) water quality conditions with fossil cyst assemblages indicated that pH significantly decreased in 24.1% of the study lakes and increased in 16.7% of the lakes. Increases in pH in more alkaline drainage basins are attributed to alkalinity generation processes induced by acidic precipitation as has been shown in other studies. Total phosphorus (TP) concentrations significantly declined in 12.9% of the lakes and increased in 16.6% of lakes. Increases in [TP] were linked to cottage development. Decreases in trophic status may be due to landuse changes, the result of the acidification occurring in the area, or warmer and drier climates. A comparison of chrysophyte cyst and diatom water quality inferences show similar trends in pH changes. There is a good agreement between diatom and chrysophyte bioindicators with respect to [TP] changes in oligotrophic lakes (< 10 g/L); however, diatom inferences suggest that lakes with current [TP] values greater than 10 g/L have decreased in trophic status over time, while chrysophyte reconstructions suggest that these same lakes have become more productive systems.     

Die tertiäre und quartäre Entwicklung im Bereich der Kufrah-Oasen (Zentrale Sahara) unter besonderer Berücksichtigung aktualistischer Vorgänge

Zusammenfassung Im Verlauf der Oberkreide und des Tertiärs bestand im Bereich der Kufrah-Oasen eine Einebnungstendenz, die mit der Bildung einer Peneplain ihre Vollendung fand. Die Umlagerungsprodukte, nur wenige Meter mächtige Sande und Feinkiese, wurden während einer warmfeuchten Klimaperiode lateritisiert und anschließend unter semiariden Bedingungen zur Eisenkruste I verhärtet. Auf den geringfügig höher gelegenen Iateritfreien Erosionsflächen kam es zur Ausbildung einer Silikatkruste. Ein Wechsel zu feuchterem Klima und eventuelle schwache epirogenetische Hebungen des Gebietes bewirkten eine teilweise Erosion der Silikat- und der Eisenkruste sowie der Sedimente der Nubischen Serie. Dabei entstanden teils brecciöse, teils fanglomeratartige Sedimente, die sowohl auf der Eisenkruste I als auch auf dem mesozoischen Untergrund abgelagert wurden. Erneute Klimaveränderungen führten jetzt zur Laterisierung und Verhärtung der vorliegenden maximal 10–12 m mächtigen Sedimente und zur Entstehung der Eisenkruste II.Eine Tiefenerosion setzte ein, die die bestehende Peneplain in Insel- und Tafelberge auflöste. Eine kurzzeitige Unterbrechung der Erosion im Altquartär begünstigte die Sedimentation von Kiesen und von Grobschutt auf einem ca. 50 m unterhalb der ehemaligen Peneplain gelegenen Niveau. Der Grobschutt wurde ebenfalls lateritisiert zur Eisenkruste III.Eine Analyse des fossilen aquatischen Systems zeigt ein stark verzweigtes Flußsystem, das das gesamte Gebiet der Kufrah-Oasen von SW nach NE entwässerte. Die Erosionsprodukte wurden zum größten Teil abtransportiert. Daher sind nur geringmächtige fluviatile Sedimente erhalten.Mit dem Ende des Pleistozän wurde die aquatische Erosionstätigkeit durch Wechsel von feuchtem zu trockenem Klima mit wenigen Ausnahmen beendet. Es kam zur Ablagerung feinklastischer limnischer Sedimente in lokalen Depressionen, denen äolische Sande zwischengeschaltet wurden. In dieser Übergangsphase bildeten sich Schwemmfächer am Fuße von Schichtstufen und Inselbergen, wobei zum Teil bereits existierende Sanddünen überlagert wurden. Es vollzog sich alternierend ein Wechsel von feuchtem zu trockenem Klima. Der Beginn einer ariden Klimaentwicklung kann in die Zeit um 6000 B. P. gesetzt werden.Die meteorologischen Daten der Station Kufrah seit 1933 zeigen nur noch eine äolische Aktivität als Wechselwirkung von Erosion und Sedimentation an. Reliktflächen sind die Hammada- und Serirflächen; überwiegend Sedimentation findet in der Ausbildung von Dünen und Sandtennen statt. Die Sandtennen sind in multimodale ebene und bimodale undulierende Tennen zu unterteilen. Die Bimodalität ist eine Funktion des selektiven Abtransportes mittlerer Korngrößen und deren Anreicherung als Sanddünen oder Sandanwehungen. Die undulierenden Sandtennen sind daher eine Weiterentwicklung ebener Sandtennen. Dünen existieren in Form von Seif- und Barchandünen oder als eine Kombination aus beiden.Die aktualistischen Vorgänge des vollariden Gebietes der Kufrah-Oasen zeigen eine Tendenz zum erneuten Reliefausgleich durch Deflation und Korrasion exponierter Areale und Sedimentation in Depressionen.

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During the Upper Cretaceous and Tertiary time a tendency of relief deplaning existed in the Kufrah-Oasis area which was completed by the development of a peneplain. The eroded material, sands and gravels of a thickness of only a few meters became lateritic during a period of warm and moist and was hardened to ironcrust I during a semiarid climat. On the slightly higher erosional planes without laterite a silicacrust was developed. A change to a more humid climat and possibly slight epirogenic lifting of the territory brought about an in part erosion of the silicacrust, the ironcrust I and the mesozoic rocks. Thereby breccious and fanglomeratic sediments were deposited and after laterization and hardening the ironcrust LI was formed. An indeep erosion began and disolved the existing peneplain into mesas and inselbergs. A short interruption in the erosional activity during Early Quarternary favoured the sedimentation of coarse grained material which was laterized to ironcrust III. An analysis of the fossil aquatic system shows an extensively branched river system which drained the whole territory of the Kufrah area from SW to NE. The eroded material was flushed away to a great extent, so that only some very thin beds of fluvial sediments still exist. At the close of the Pleistocene the aquatic erosional activity ended by a change from humid to arid climate. Only fine clastic limnic sediments were deposited in some local depressions often alternating with aeolian sands. In this transition period alluvial fans developed on the foot of mesas, in some locations sedimentated on top of already existing-sanddunes. The begin of an arid desert climat can be put at approximately 6 000 years before present.The data of the Kufrah meteorological station since 1933 show the possibility of only aeolic activity in form of mutual erosion and sedimentation. The relic planes are the hammada and serir planes. Sedimentation is responsible for the creation of dunes and sandflats. The sandflats can be differenciated into multimodal even flats and bimodal gently undulating flats. The bimodality is a function of the selective removal of sand grains with distinctive diameters and their accumulation as dunes or sand drifts. The undulating sandflats therefore are a further development of the even sandflats. Dunes exist in form of seifdunes or barchan dunes or as combinations of both types.The actualistic events in the fully arid area of the Kufrah-Oasis again show a tendency towards levelling out of the relief by deflation and corrasion of exposed areas and sedimentation in depressions.

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Résumé Au cours du Crétacé supérieur et du Tertiaire, dans la région des Oasis de Koufra eut lieu un aplanissement dont la phase finale a abouti à une pénéplaine. Les produits du remaniement, des sables et des graviers de faible puissance, ont été látéritisés pendant une période chaude et humide indurés sous un climat semi-aride en croute ferrugineuse I. Sur les surfaces d'érosion plus élevées sans latérite se développait une croûte siliceuse. Le changement vers un climat plus humide et de faibles soulèvements tectoniques provoquèrent une érosion partielle des croûtes ferrugineuses et siliceuses et des sédiments de la série nubienne. Par ce remaniement se formaient des brèches et des fanglomérats qui se sont sédimentées aussi bien sur la croûte ferrugineuse I que sur le substratum méozoique. Un nouveau changement de climat provoqua la latéritisation et le durcissement des sédiment bréchiques et fanglomératiques la formation de la croûte ferrugineuse II.A la limite Tertiaire/Quaternaire commenca une érosion intense qui façonna la pénéplaine existente en inselbergs et tafelbergs. Une interruption brève de l'érosion au Quaternaire inférieur favorisa la sédimentation de graviers et blocs à un niveau d'à peu près 50 m inférieur à l'ancienne pénéplaine. Les graviers et les blocs ont été latéritisés ensemble pour former la croûte ferrugineuse III.Une anlyse du système hydrographique du Pleistocéne montre que toute la région des oasis de Koufra était drainée vers le Nord, période durant laquelle aucune sédimentation n'a eu lieu. A la fin du Pleitocène le climat changea une nouvelle fois pour devenir plus sec et l'érosion fluviatile se termina. Dans la phase de transition se déposèrent, au pied des corniches et des inselbergs, des éventails alluviaux en alternance avec le sable éolien. Le changement à un climat plus aride peut être daté à peu près 6000 B. P.Les données météorologiques de la station de Koufra, depuis 1933, ne permettent qu'une activité éolienne soit comme sédimentation soit comme érosion. Les surfaces »Hammada« et »Serir« sont des surfaces d'érosion résiduelles. La sédimentation se manifeste sous la forme de dunes et de plaines de sable. Les dunes existent sous forme de barchanes et de seifs; les plaines de sable sont à subdiviser du point de vue de la granulométrie en aires multimodales et en aires ondulées bimodales. La bimodalité est und fonction du transport sélectif des grains moyens.Le processus exogène récent dans la région des oasis de Koufra montre la tendance à un nouvel aplainissement effectué par une déflation et corrasion des terrains en relief et une sédimentation dans les dépressions.

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Gekürzte Dissertation D 77.     

Salt-marsh foraminifera in Ho Bugt,western Denmark,and their use as sea-level indicators

Twenty-seven surface samples were collected from the Kjelst Enge salt marsh in Ho Bugt, Jutland, to investigate the potential use of salt-marsh foraminifera as sea-level indicators in Holocene intertidal deposits. Previous work from many coastlines around the world has shown that the vertical distribution of salt-marsh foraminifera is strongly controlled by the duration of tidal flooding (or height relative to tide level). Concentrations of foraminifera in Kjelst Enge salt marsh are low, especially in the high marsh, but a strong correlation was found between relative abundances of foraminiferal species and tidal elevation for 16 samples containing more than 30 specimens per 5 cc of sediment (r² = 0.80, root mean square error = 0.16 m). Sediment pH also has a strong influence on the distribution of the foraminifera, but salinity appears to be insignificant.