Pollen records of 11 profiles from Wendland in northern Germany

1) Ingesamt 11 Profile aus sechs Mooren und Seen im Gebiet des Hannoverschen Wendlandes wurden pollenanalytisch untersucht. Die Ablagerungen umfassen den Zeitraum vom Beginn der Älteren Tundrenzeit bis zur Gegenwart. 2) Die Waldgeschichte des Hannoverschen Wendlandes weist teils Merkmale der atlantisch geprägten Gebiete Nordwestdeutschlands, teils solche des kontinental beeinflußten nordostdeutschen Raumes auf und nimmt damit eine Zwischenstellung ein. 3) Die Kiefer wandert zu Beginn der Allerödzeit ein, d.h. später als im mecklenburgisch-märkischen Gebiet und im mitteldeutschen Trockengebiet. Im Verlauf der Allerödzeit bildeten sich hier wie dort lichte Kiefern-Birken-Wälder aus. 4) In der Jüngeren Tundrenzeit fand zunächst nur eine geringe Auflichtung der Wälder statt, und die Kiefer überwog weiterhin. Erst im späteren Verlauf dieser stadialen Phase breitete sich die Birke aus und verdrängte die Kiefer. Der späte Rückgang der Kiefer stellt eine Parallele zu der Entwicklung in Südostmecklenburg und in der Altmark dar. Die Abgrenzung dieser Phasen in der Jüngeren Tundrenzeit ist durch eine 14C-Datierung gesichert. 5) Noch im Atlantikum ähneln die Diagramme aus dem Gartower Talsandgebiet im Osten des Wendlandes in ihren hohen Kiefernanteilen denen der Sandergebiete in Brandenburg. Die Diagramme aus dem Moränengebiet des westlichen Wendlandes schließen dagegen mehr an die der östlichen Lüneburger Heide und des Hamburger Gebietes an. Dieser Unterschied wird auf edaphische Unterschiede zurückgeführt. 6) Seit dem frühen Subboreal glich auch die Vegetation des Gartower Gebietes mehr den buchenarmen Waldgesellschaften auf sauren Sandböden, wie sie im atlantischen Westen vorkommen. Die Kiefern sind fast ganz aus dem Waldbild verschwunden, wobei der rasche Rückgang zu Beginn des Subboreals sicher zu einem wesentlichen Teil vom Menschen beeinflusst worden ist. Die anschließende kiefernarme Zeit dauerte im gesamten Wendland bis zum Beginn der Kieferaufforstungen in der Neuzeit. 7) In allen untersuchten Diagrammen ist etwa seit dem Subboreal eine Besiedlung nachzuweisen. Diese muß im Osten des Wendlandes intensiver gewesen sein als im Westen. Es lassen sich Phasen geringer und intensiver Besiedlung nachweisen. 8) Seit Beginn des Subboreals ist das Waldbild schon so stark vom Menschen beeinflusst, dass die Ausbreitungsgeschichte der Laubwaldarten nicht ohne Berücksichtigung der Siedlungsphasen diskutiert werden kann. Besonders im Westen bestand eine ausgedehnte Lindenphase, die durch eine Siedlungszeit (Bronzezeit) beendet wurde. Beim folgenden Rückgang der Siedlungsintensität breitet sich bevorzugt die Hainbuche aus, die dann bei der nächsten Besiedlungsphase (Eisenzeit) zurückging. Erst danach erfolgte die maximale Rotbuchenausbreitung, die nur im Westteil des Wendlandes bedeutende Ausmaße zeigte, während im Ostteil rot- und hainbuchenreiche Eichenwälder entstanden. 9) Seit Beginn der mittelalterlichen Besiedlung ist dann der Eingriff des Menschen so stark gewesen, dass die edaphisch bedingten Unterschiede zwischen Moränen- und Sandergebieten im Pollenspektrum verwischt wurden. Sowohl die buchenreichen Wälder des westlichen als auch die buchenarmen Wälder des mittleren und des östlichen Teilgebietes müssen zu fast reinen Eichenwäldern geworden sein. 10) Calluna-Heiden sind im östlichen Wendland schon in vorgeschichtlicher Zeit nachzuweisen. Im Mittelalter und in der Neuzeit treten sie im gesamten Wendland auf. Etwa im 18. und 19. Jahrhundert war die Ausdehnung der Heideflächen am größten. Erst danach wurden sie im Zuge der Kiefernaufforstungen bis auf geringe Reste verdrängt. 11) Während in der spätglazialen Vegetation Juniperus auftritt, ist der Wacholder sowohl in vorgeschichtlicher als auch in geschichtlicher Zeit - im Gegensatz zur Lüneburger Heide - wohl niemals ein Bestandteil der anthropogenen Calluna-Heiden gewesen.

Pollen profile from sediment core Höllerer See

(expanded by Eberhard Grüger, Göttingen) The site "Höllerer See" is a lake in the northern foreland of the Alps, about 30 km north of the city of Salzburg/Austria, situated in the south-western part of Oberösterreich/Austria. A 2 m long piston core from this locality, consisting entirely of calcareous gyttja, was studied by pollen analysis. The three lowermost samples (1.98, 1.95 and 1.92 m) were deposited during the Preboreal when Pinus and Betula were still the dominating forest trees. High pollen values of thermophilous woody species (mainly Corylus and Quercus, but also Ulmus, Tilia, Fraxinus) prove the Boreal age of the next younger sample (1.91 m). The following two pollen spectra attest that Alnus (1.89 m) and - later (1.88 m) - Fagus had become important members of the local (Alnus) and the regional (Fagus) vegetation. From this level up to the top of the profile these two tree taxa contribute - together with Betula - always 50 to 80 % to the arboreal pollen sum. The upper 1.89 m of sediment of the Höllerer See core evidently date from the Subboreal and the Subatlantic. As Preboreal sediment was stated at the base of the profile it must be concluded that most of the Boreal and the Atlantic is - for whatever reason - not represented by sediment in this core. As no radiocarbon dates are available age estimates of the distinguished pollen zones can be achieved only by correlating major changes of the former vegetation with historical events which probably influenced the then contemporary vegetation. The pollen grains of the Triticum and Hordeum type found in samples of zone 2.1 might indicate the growing of cereals in the region during the Late Bronze Age. The first pollen grains of Secale date from the boundary Hallstatt/Latène Age (zone 2.2). The cereal curves become continuous in Bavarian times (Bajuwarenzeit, Middle Ages, zone 3.3). The Plantago laceolata curve, continuous since 1.7 m depth (zone 2.1), points to animal breeding since the Early Subatlantic (Hallstattzeit). This curve reaches its absolute maximum in Roman time (zone 3.1). Roman time forest clearance caused a drastic decrease of tree pollen curves (start of zone 3.1). Values of anthropogenic indicators as high as in zone 3.1 are found again - after a distinct decrease in zone 3.2 - not till the Bavarians settled in the region (6th century). Maximal Fagus values and the simultaneous total lack of anthropogenic indicators mark the Migration Period (zone 3.2). The Younger Subatlantic (zone 4) is characterized by a decrease of deciduous forests due to medieval forest clearance. At the same time the conifers Pinus and Picea gained in importance. The lake was probably used for retting hemp in Medieval times. The distinction of the pollen grains of Cannabis and Humulus might not be certain in all cases. It is known that hemp as well as hop was cultivated in the study area. Markers were added to the samples at the beginning of pollen preparation (13500 Lycopodium spores, sample volume 0.5 cm**3) and counted together with the pollen grains. Therefore pollen concentrations can be calculated: Concentration = C * F / V (with C = number of grains of a particular pollen type, V = volume of the untreated pollen sample, F = marker added/marker counted). F ranges from 39 to 1688. Factors that large are not suited to produce reliably interpretable pollen concentrations. Consequently no use was made of the pollen concentrations in this thesis, although a concentration diagram is added.

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes : (Part 10) The infrared and Raman characteristics of phthalocyanine in heteroleptic bis(phthalocyaninato) rare earth complexes with decreased molecular symmetry

The infrared (IR) spectroscopic data for a series of eleven heteroleptic bis(phthalocyaninato) rare earth complexes MIII(Pc)[Pc(α-OC5H11)4] (M = Sm–Lu, Y) [H2Pc = unsubstituted phthalocyanine, H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected with 2 cm−1 resolution. Raman spectroscopic properties in the range of 500–1800 cm−1 for these double-decker molecules have also been comparatively studied using laser excitation sources emitting at 632.8 and 785 nm. Both the IR and Raman spectra for M(Pc)[Pc(α-OC5H11)4] are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues due to the decreased molecular symmetry of these double-decker compounds, namely C4. For this series, the IR Pc√− marker band appears as an intense absorption at 1309–1317 cm−1, attributed to the pyrrole stretching. With laser excitation at 632.8 nm, Raman vibrations derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. In contrast, when excited with laser radiation of 785 nm, the ring radial vibrations of isoindole moieties and dihedral plane deformations between 500 and 1000 cm−1 for M(Pc)[Pc(α-OC5H11)4] intensify to become the strongest scatterings. Both techniques reveal that the frequencies of pyrrole stretching, isoindole breathing, isoindole stretchings, aza stretchings and coupling of pyrrole and aza stretchings depend on the rare earth ionic size, shifting to higher energy along with the lanthanide contraction due to the increased ring-ring interaction across the series. The assignments of the vibrational bands for these compounds have been made and discussed in relation to other unsubstituted and substituted bis(phthalocyaninato) rare earth analogues, such as M(Pc)2 and M(OOPc)2 [H2OOPc = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine].

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes: Part 14. The infrared and Raman characteristics of phthalocyanine in “pinwheel-like” homoleptic bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato] rare earth(III) double-decker complexes

The infrared (IR) spectroscopic data and Raman spectroscopic properties for a series of 13 “pinwheel-like” homoleptic bis(phthalocyaninato) rare earth complexes M[Pc(α-OC5H11)4]2 [M = Y and Pr–Lu except Pm; H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected and comparatively studied. Both the IR and Raman spectra for M[Pc(α-OC5H11)4]2 are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues, namely M(Pc)2 and M[Pc(OC8H17)8]2, but resemble (for IR) or are a bit more complicated (for Raman) than those of heteroleptic counterparts M(Pc)[Pc(α-OC5H11)4], revealing the decreased molecular symmetry of these double-decker compounds, namely S8. Except for the obvious splitting of the isoindole breathing band at 1110–1123 cm−1, the IR spectra of M[Pc(α-OC5H11)4]2 are quite similar to those of corresponding M(Pc)[Pc(α-OC5H11)4] and therefore are similarly assigned. With laser excitation at 633 nm, Raman bands derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. The IR spectra reveal that the frequencies of pyrrole stretching and pyrrole stretching coupled with the symmetrical CH bending of –CH3 groups are sensitive to the rare earth ionic size, while the Raman technique shows that the bands due to the isoindole stretchings and the coupled pyrrole and aza stretchings are similarly affected. Nevertheless, the phthalocyanine monoanion radical Pc′− IR marker band of bis(phthalocyaninato) complexes involving the same rare earth ion is found to shift to lower energy in the order M(Pc)2 > M(Pc)[Pc(α-OC5H11)4] > M[Pc(α-OC5H11)4]2, revealing the weakened π–π interaction between the two phthalocyanine rings in the same order.

Raman spectroscopic characteristics of phthalocyanine and naphthalocyanine in sandwich-type phthalocyaninato and porphyrinato rare earth complexes Part 5. – Raman spectroscopic characteristics of naphthalocyanine in mixed [tetrakis(4-tert-butylphenyl)porphyrinato]-(naphthalocyaninato) rare earth double-deckers

Raman spectra were recorded in the range 400–1800 cm−1 for a series of 15 mixed \[tetrakis(4-tert-butylphenyl)porphyrinato](2,3-naphthalocyaninato) rare earth double-deckers M(TBPP)(Nc) (M = Y; La–Lu except Pm) using laser excitation at 632.8 and 785 nm. Comparisons with bis(naphthalocyaninato) rare earth counterparts reveal that the vibrations of the metallonaphthalocyanine M(Nc) fragment dominate the Raman features of M(TBPP)(Nc). When excited with radiation of 632.8 nm, the most intense vibration appears at about 1595 cm−1, due to the naphthalene stretching. These complexes exhibit the marker Raman band for Nc•− as a medium-intense band in the range 1496–1507 cm−1, attributed to the coupling of pyrrole and aza stretching, while the marker Raman band of Nc2− in intermediate-valence Ce(TBPP)(Nc) appears as a strong band at 1493 cm−1 and is due to the isoindole stretchings. By contrast, when excited with radiation of 785 nm that is in close resonance with the main Q absorption band of the naphthalocyanine ligand, the ring radial vibrations at ca 680 and 735 cm−1 for MIII(TBPP)(Nc) are selectively intensified and are the most intense bands. For the cerium double-decker, the most intense vibration also acting as the marker Raman band of Nc2− appears at 1497 cm−1 with contributions from both pyrrole CC and aza CN stretches. The same vibrational modes show weak to medium intensity scattering at 1506–1509 cm−1 for MIII(TBPP)(Nc) and this is the marker Raman band of Nc•− when thus excited. The scatterings due to the Nc breathings, ring radial vibration, aza group stretchings, naphthalene stretchings, benzoisoindole stretchings and the coupling of pyrrole CC and aza CN stretchings in MIII(TBPP)(Nc) are all slightly blue shifted along with the decrease in rare earth ionic radius, confirming the effects of increased ring–ring interactions on the Raman characteristics of naphthalocyanine in the mixed ring double-deckers.