Sedimentology on 19 cores from the South China Sea

Based on the study of 10 sediment cores and 40 core-top samples from the South China Sea (SCS) we obtained proxy records of past changes in East Asian monsoon climate on millennial to bidecadal time scales over the last 220,000 years. Climate proxies such as global sea level, estimates of paleotemperature, salinity, and nutrients in surface water, ventilation of deep water, paleowind strength, freshwater lids, fluvial and/or eolian sediment supply, and sediment winnowing on the sea floor were derived from planktonic and benthic stable-isotope records, the distribution of siliciclastic grain sizes, planktonic foraminifera species, and the UK37 biomarker index. Four cores were AMS-14C-dated. Two different regimes of monsoon circulation dominated the SCS over the last two glacial cycles, being linked to the minima and maxima of Northern Hemisphere solar insolation. (1) Glacial stages led to a stable estuarine circulation and a strong O2-minimum layer via a closure of the Borneo sea strait. Strong northeast monsoon and cool surface water occurred during winter, in part fed by an inflow from the north tip of Luzon. In contrast, summer temperatures were as high as during interglacials, hence the seasonality was strong. Low wetness in subtropical South China was opposed to large river input from the emerged Sunda shelf, serving as glacial refuge for tropical forest. (2) Interglacials were marked by a strong inflow of warm water via the Borneo sea strait, intense upwelling southeast of Vietnam and continental wetness in China during summer, weaker northeast monsoon and high sea-surface temperatures during winter, i.e. low seasonality. On top of the long-term variations we found millennial- to centennial-scale cold and dry, warm and humid spells during the Holocene, glacial Terminations I and II, and Stage 3. The spells were coeval with published variations in the Indian monsoon and probably, with the cold Heinrich and warm Dansgaard-Oeschger events recorded in Greenland ice cores, thus suggesting global climatic teleconnections. Holocene oscillations in the runoff from South China centered around periodicities of 775 years, ascribed to subharmonics of the 1500-year cycle in oceanic thermohaline circulation. 102/84-year cycles are tentatively assigned to the Gleissberg period of solar activity. Phase relationships among various monsoon proxies near the onset of Termination IA suggest that summer-monsoon rains and fluvial runoff from South China had already intensified right after the last glacial maximum (LGM) insolation minimum, coeval with the start of Antarctic ice melt, prior to the d18O signals of global sea-level rise. Vice versa, the strength of winter-monsoon winds decreased in short centennial steps only 3000-4000 years later, along with the melt of glacial ice sheets in the Northern Hemisphere.

A new low temperature synthesis route of fraipontite (Zn,Al)3(Si,Al)2O5(OH)4

A low temperature synthesis method based on the decomposition of urea at 90°C in water has been developed to synthesise fraipontite. This material is characterised by a basal reflection 001 at 7.44 Å. The trioctahedral nature of the fraipontite is shown by the presence of a 06l band around 1.54 Å, while a minor band around 1.51 Å indicates some cation ordering between Zn and Al resulting in Al-rich areas with a more dioctahedral nature. TEM and IR indicate that no separate kaolinite phase is present. An increase in the Al content however, did result in the formation of some SiO2 in the form of quartz. Minor impurities of carbonate salts were observed during the synthesis caused by to the formation of CO32- during the decomposition of urea.

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.