Computer simulation methods to study interfacial tensions : from the Ising model to colloidal crystals

In condensed matter systems, the interfacial tension plays a central role for a multitude of phenomena. It is the driving force for nucleation processes, determines the shape and structure of crystalline structures and is important for industrial applications. Despite its importance, the interfacial tension is hard to determine in experiments and also in computer simulations. While for liquid-vapor interfacial tensions there exist sophisticated simulation methods to compute the interfacial tension, current methods for solid-liquid interfaces produce unsatisfactory results.rnrnAs a first approach to this topic, the influence of the interfacial tension on nuclei is studied within the three-dimensional Ising model. This model is well suited because despite its simplicity, one can learn much about nucleation of crystalline nuclei. Below the so-called roughening temperature, nuclei in the Ising model are not spherical anymore but become cubic because of the anisotropy of the interfacial tension. This is similar to crystalline nuclei, which are in general not spherical but more like a convex polyhedron with flat facets on the surface. In this context, the problem of distinguishing between the two bulk phases in the vicinity of the diffuse droplet surface is addressed. A new definition is found which correctly determines the volume of a droplet in a given configuration if compared to the volume predicted by simple macroscopic assumptions.rnrnTo compute the interfacial tension of solid-liquid interfaces, a new Monte Carlo method called ensemble switch method'' is presented which allows to compute the interfacial tension of liquid-vapor interfaces as well as solid-liquid interfaces with great accuracy. In the past, the dependence of the interfacial tension on the finite size and shape of the simulation box has often been neglected although there is a nontrivial dependence on the box dimensions. As a consequence, one needs to systematically increase the box size and extrapolate to infinite volume in order to accurately predict the interfacial tension. Therefore, a thorough finite-size scaling analysis is established in this thesis. Logarithmic corrections to the finite-size scaling are motivated and identified, which are of leading order and therefore must not be neglected. The astounding feature of these logarithmic corrections is that they do not depend at all on the model under consideration. Using the ensemble switch method, the validity of a finite-size scaling ansatz containing the aforementioned logarithmic corrections is carefully tested and confirmed. Combining the finite-size scaling theory with the ensemble switch method, the interfacial tension of several model systems, ranging from the Ising model to colloidal systems, is computed with great accuracy.

Bacterial GDGTs in Holocene sediments and catchment soils of a high Alpine lake: application of the MBT/CBT-paleothermometer

A novel proxy for continental mean annual air temperature (MAAT) and soil pH, the MBT/CBT-paleothermometer, is based on the temperature (T) and pH-dependent distribution of specific bacterial membrane lipids (branched glycerol dialkyl glycerol tetraethers – GDGTs) in soil organic matter. Here, we tested the applicability of the MBT/CBT-paleothermometer to sediments from Lake Cadagno, a high Alpine lake in southern Switzerland with a small catchment of 2.4 km2. We analysed the distribution of bacterial GDGTs in catchment soils and in a radiocarbon-dated sediment core from the centre of the lake, covering the past 11 000 yr. The distribution of bacterial GDGTs in the catchment soils is very similar to that in the lake's surface sediments, indicating a common origin of the lipids. Consequently, their transfer from the soils into the sediment record seems undisturbed, probably without any significant alteration of their distribution through in situ production in the lake itself or early diagenesis of branched GDGTs. The MBT/CBT-inferred MAAT estimates from soils and surface sediments are in good agreement with instrumental values for the Lake Cadagno region (~0.5 °C). Moreover, downcore MBT/CBT-derived MAAT estimates match in timing and magnitude other proxy-based T reconstructions from nearby locations for the last two millennia. Major climate anomalies recorded by the MBT/CBT-paleothermometer are, for instance, the Little Ice Age (~14th to 19th century) and the Medieval Warm Period (MWP, ~9th to 14th century). Together, our observations indicate the quantitative applicability of the MBT/CBT-paleothermometer to Lake Cadagno sediments. In addition to the MWP, our lacustrine paleo T record indicates Holocene warm phases at about 3, 5, 7 and 11 kyr before present, which agrees in timing with other records from both the Alps and the sub-polar North-East Atlantic Ocean. The good temporal match of the warm periods determined for the central Alpine region with north-west European winter precipitation strength implies a strong and far-reaching influence of the North Atlantic Oscillation on continental European T variations during the Holocene.

Development of record-breaking statistics for climatological time-series analysis

The number of record-breaking events expected to occur in a strictly stationary time-series depends only on the number of values in the time-series, regardless of distribution. This holds whether the events are record-breaking highs or lows and whether we count from past to present or present to past. However, these symmetries are broken in distinct ways by trends in the mean and variance. We define indices that capture this information and use them to detect weak trends from multiple time-series. Here, we use these methods to answer the following questions: (1) Is there a variability trend among globally distributed surface temperature time-series? We find a significant decreasing variability over the past century for the Global Historical Climatology Network (GHCN). This corresponds to about a 10% change in the standard deviation of inter-annual monthly mean temperature distributions. (2) How are record-breaking high and low surface temperatures in the United States affected by time period? We investigate the United States Historical Climatology Network (USHCN) and find that the ratio of record-breaking highs to lows in 2006 increases as the time-series extend further into the past. When we consider the ratio as it evolves with respect to a fixed start year, we find it is strongly correlated with the ensemble mean. We also compare the ratios for USHCN and GHCN (minus USHCN stations). We find the ratios grow monotonically in the GHCN data set, but not in the USHCN data set. (3) Do we detect either mean or variance trends in annual precipitation within the United States? We find that the total annual and monthly precipitation in the United States (USHCN) has increased over the past century. Evidence for a trend in variance is inconclusive.

Temperature and precipitation signal in two Alpine ice cores over the period 1961-2001

Water stable isotope ratios and net snow accumulation in ice cores are commonly interpreted as temperature or precipitation proxies. However, only in a few cases has a direct calibration with instrumental data been attempted. In this study we took advantage of the dense network of observations in the European Alpine region to rigorously test the relationship of the annual and seasonal resolved proxy data from two highly resolved ice cores with local temperature and precipitation. We focused on the time period 1961–2001 with the highest amount and quality of meteorological data and the minimal uncertainty in ice core dating (±1 year). The two ice cores were retrieved from the Fiescherhorn glacier (northern Alps, 3900 m a.s.l.), and Grenzgletscher (southern Alps, 4200 m a.s.l.). A parallel core from the Fiescherhorn glacier allowed assessing the reproducibility of the ice core proxy data. Due to the orographic barrier, the two flanks of the Alpine chain are affected by distinct patterns of precipitation. The different location of the two glaciers therefore offers a unique opportunity to test whether such a specific setting is reflected in the proxy data. On a seasonal scale a high fraction of δ18O variability was explained by the seasonal cycle of temperature (~60% for the ice cores, ~70% for the nearby stations of the Global Network of Isotopes in Precipitation – GNIP). When the seasonality is removed, the correlations decrease for all sites, indicating that factors other than temperature such as changing moisture sources and/or precipitation regimes affect the isotopic signal on this timescale. Post-depositional phenomena may additionally modify the ice core data. On an annual scale, the δ18O/temperature relationship was significant at the Fiescherhorn, whereas for Grenzgletscher this was the case only when weighting the temperature with precipitation. In both cases the fraction of interannual temperature variability explained was ~20%, comparable to the values obtained from the GNIP stations data. Consistently with previous studies, we found an altitude effect for the δ18O of −0.17‰/100 m for an extended elevation range combining data of the two ice core sites and four GNIP stations. Significant correlations between net accumulation and precipitation were observed for Grenzgletscher during the entire period of investigation, whereas for Fiescherhorn this was the case only for the less recent period (1961–1977). Local phenomena, probably related to wind, seem to partly disturb the Fiescherhorn accumulation record. Spatial correlation analysis shows the two glaciers to be influenced by different precipitation regimes, with the Grenzgletscher reflecting the characteristic precipitation regime south of the Alps and the Fiescherhorn accumulation showing a pattern more closely linked to northern Alpine stations.

Hochwasser-«Katastrophen» in Basel vom 13. bis 21. Jahrhundert Rekonstruktion, Deutung und Lerneffekte

Magnitudes of peak discharges of 43 non-instrumentally measured Rhine river floods at Basel were reconstructed. The methodology is based on a range of different historic sources, containing flood information (including traditional urban inundation reference points from flood reports of medieval and early modern period chroniclers as well as 19th century journalists, flood marks, paintings and drawings, town maps, longitudinal and cross profiles etc.). These traditional pre-instrumental “flood information systems” still existed in the 19th century, when in 1808 the first instrumental hydrological measurements started. They thus could be calibrated with instrumental measurements in the 19th century overlapping period. The result is a 743 year long quantified Rhine river flood series. Floods of both periods (pre-instrumental as well as instrumental) can thus be directly compared for the very first time. The long-range consequences of rivers Kander and Aare deviations in 1714 and 1878 are reflected in a distinct change of magnitudes of peak discharges in Basel. A clear flood “disaster gap” appears in the 20th century. The lack of any extreme floods for such a long time is completely unique during the 743-year period of analysis. This result will influence the statistical assessment of once-in-a-century events, which might be of great interest for insurance campanies.

Water stable oxygen isotope records from six Antarctic ice core sites for the present and last interglacial periods

We compare the present and last interglacial periods as recorded in Antarctic water stable isotope records now available at various temporal resolutions from six East Antarctic ice cores: Vostok, Taylor Dome, EPICA Dome C (EDC), EPICA Dronning Maud Land (EDML), Dome Fuji and the recent TALDICE ice core from Talos Dome. We first review the different modern site characteristics in terms of ice flow, meteorological conditions, precipitation intermittency and moisture origin, as depicted by meteorological data, atmospheric reanalyses and Lagrangian moisture source diagnostics. These different factors can indeed alter the relationships between temperature and water stable isotopes. Using five records with sufficient resolution on the EDC3 age scale, common features are quantified through principal component analyses. Consistent with instrumental records and atmospheric model results, the ice core data depict rather coherent and homogenous patterns in East Antarctica during the last two interglacials. Across the East Antarctic plateau, regional differences, with respect to the common East Antarctic signal, appear to have similar patterns during the current and last interglacials. We identify two abrupt shifts in isotopic records during the glacial inception at TALDICE and EDML, likely caused by regional sea ice expansion. These regional differences are discussed in terms of moisture origin and in terms of past changes in local elevation histories, which are compared to ice sheet model results. Our results suggest that elevation changes may contribute significantly to inter-site differences. These elevation changes may be underestimated by current ice sheet models

Organic temperature proxies in the subpolat region around Iceland

Subpolar regions are key areas to study natural climate variability, due to their high sensitivity to rapid environmental changes, particularly through sea surface temperature (SST) variations. Here, we have tested three independent organic temperature proxies (UK'37, TEX86 and LDI) on their potential applicability for SST reconstruction in the subpolar region around Iceland. UK'37, TEX86 and TEXL86 temperature estimates from suspended particulate matter showed a substantial discrepancy with instrumental data, while long chain alkyl diols were below detection limit in most of the stations. In the northern Iceland Basin, sedimenting particles revealed a seasonality in lipid fluxes i.e. high fluxes of alkenones and GDGTs were measured during late spring-summer, and high fluxes of long chain alkyl diols during late summer. The flux-weighted average temperature estimates had a significant negative (ca. 2.3°C for UK'37) and positive (up to 5°C for TEX86) offset with satellite-derived SSTs and temperature estimates derived from the underlying surface sediment. UK'37 temperature estimates from surface sediments around Iceland correlate well with summer mean sea surface temperatures, while TEX86 derived temperatures correspond with both annual and winter mean 0-200 m temperatures, suggesting a subsurface temperature signal. Anomalous LDI-SST values in surface sediments, and low mass flux of 1,13- and 1,15-diols compared to 1,14-diols, suggest that Proboscia diatoms are the major sources of long chain alkyl diols in this area rather than eustigmatophyte algae, and therefore the LDI cannot be applied in this region.

Annual average Sr/Ca measurements from Porites lutea coral at Ha'afera Island, Tonga

In the South Pacific Convergence Zone (SPCZ), the variability in a sub-seasonally resolved microatoll Porites colony Sr/Ca record from Tonga and a previously published high-resolution record from Fiji are strongly influenced by sea surface temperature (SST) over the calibration period from 1981 to 2004 (R^2 = 0.67 - 0.68). However, the Sr/Ca-derived SST correlation to instrumental SST decreases back in time. The lower frequency secular trend (~1°C) and decadal-scale (~2 - 3°C) modes in Sr/Ca-derived SST are almost two times larger than that observed in instrumental SST. The coral Sr/Ca records suggest that local effects on SST generate larger amplitude variability than gridded SST products indicate. Reconstructed d18O of seawater (d18Osw) at these sites correlate with instrumental sea surface salinity (SSS; r = 0.64 - 0.67) but not local precipitation (r = -0.10 to - 0.22) demonstrating that the advection and mixing of different salinity water masses may be the predominant control on d18Osw in this region. The Sr/Ca records indicate SST warming over the last 100 years and appears to be related to the expansion of the western Pacific warm pool (WPWP) including an increasing rate of expansion in the last ~20 years. The reconstructed d18Osw over the last 100 years also shows surface water freshening across the SPCZ. The warming and freshening of the surface ocean in our study area suggests that the SPCZ has been shifting (expanding) southeast, possibly related to the southward shift and intensification of the South Pacific gyre over the last 50 years in response to strengthened westerly winds.

Foraminifer faunas in the Tagus Prodelta

Pluri-annual proxy records of marine sediment cores from the Tagus Prodelta off Lisbon, Portugal, have been generated to gain insight into the climatic and hydrographic changes in the area during the twentieth century. The study includes benthic and planktonic foraminiferal faunas and the stable isotopic composition of one benthic (Uvigerina celtica) and two planktonic (Globigerina bulloides and Globorotalia inflata) foraminiferal species. Sea bottom and surface water temperatures were estimated based on the d18O values of these species and compared with instrumental data. The foraminiferal fauna and the isotope-based temperature record indicate increasing temperatures throughout the last century. The immigration of a new species, Saidovina karreriana, to the area around 100 years ago indicates changes in the trophic conditions and water mass properties, which are probably at least partly due to anthropogenic pollution.

Triennial skeletal stable oxygen isotope ratios of Diploria labyrinthiformis

The reconstruction of the climatic history during the past several hundred years requires a sufficient geographical coverage of combined climate proxy series. Especially in order to identify causal connections between the atmosphere and the ocean, inclusion of marine records into composite climate time series is of fundamental importance. We present two skeletal delta18O chronologies of coral skeletons of Diploria labyrinthiformis from Bermuda fore-reef sites covering periods in the nineteenth and twentieth centuries and compare them with instrumental temperature data. Both time series are demonstrated to display sea-surface temperature (SST) variability on inter-annual to decadal time scales. On the basis of a specific modern delta18O vs instrumental SST calibration we reconstruct a time series of SST anomalies between AD 1350 and 1630 covering periods during the Little Ice Age. The application of the coral delta18O vs temperature relationship leads to estimates of past SST variability which are comparable to the magnitude of modern variations. Parallel to delta18O chronologies we present time series of skeletal bulk density. Coral delta18O and skeletal density reveal a strong similarity during Little Ice Age, confirming the reliability of both proxy climate indicators. The past coral records, presented in this study, share features with a previously published climate proxy record from Bermuda and a composite time series of reconstructed Northern Hemisphere summer temperatures. The coral proxy data presented here represent a valuable contribution to elucidate northern Atlantic subtropical climate variation during the past several centuries.

(Table 1) Age determination of North Atlantic sediment cores

Four cores raised from the eastern Norwegian Sea and adjacent Norwegian fjords at sites influenced by Atlantic water have been investigated. Oxygen isotope analyses in benthic and planktonic foraminifera are used as a proxy for the paleotemperature development spanning the last 800 years. The cores have been dated using a combination of 210Pb and radiocarbon dates yielding time resolutions of 2-5 years for the last century and 9-25 years beyond this. The proxy records have been compared with instrumental time series covering the last 100 years in order to validate the oxygen isotope measurements as a proxy for paleotemperature. The comparison shows that the paleotemperature variability derived from the oxygen isotope analyses is generally similar to the amplitudes and trends seen in the instrumental time series. In particular, a cooling around 1905-1925 followed by a warming until 1955 is evident in all proxy records as well as in the instrumental time series. Beyond the last century the proxy records show two periods from ~1225-1450 and ~1650-1905(25) when temperatures were 1.3-1.6°C lower than present separated by a period of temperatures periodically comparable to present. The last 80 years represent the modern warming and appear to be the warmest period of the last 800 years. We find that that the ocean temperature variability is comparable to terrestrial reconstructions from the region implying a strong link in the ocean-atmosphere climate system. This suggests that the climate variability in this region beyond the period covered by instrumental time series was also associated with changes in the thermohaline circulation.

Grande sonate pastorale : pour la harpe ; avec une flu te oblige e /

For harp with flute obbligato.

Danses pour harpe chromatique ou harpe à pédales, ou piano, avec accompagnement d'orchestre d'instruments à cordes /

Pl. no.: D. & F. 6429 (score), D. & F. 7578 (part).

No 1, 2, 3 of Haydn's grand symphonies : composed for Mr Salomon's concerts /

1. C major (M.97) -- 2. D major (M.93) -- 3. G major (M.94)

Der kleine Rosengarten : Volkslieder /

Also issued with instrumental settings by Fritz Jöde.