Estimation of the normal boiling point of organic compounds via group contributions

The normal boiling point is a fundamental thermo-physical property, which is important in describing the transition between the vapor and liquid phases. Reliable method which can predict it is of great importance, especially for compounds where there are no experimental data available. In this work, an improved group contribution method, which is second order method, for determination of the normal boiling point of organic compounds based on the Joback functional first order groups with some changes and added some other functional groups was developed by using experimental data for 632 organic components. It could distinguish most of structural isomerism and stereoisomerism, which including the structural, cis- and trans- isomers of organic compounds. First and second order contributions for hydrocarbons and hydrocarbon derivatives containing carbon, hydrogen, oxygen, nitrogen, sulfur, fluorine, chlorine and bromine atoms, are given. The fminsearch mathematical approach from MATLAB software is used in this study to select an optimal collection of functional groups (65 functional groups) and subsequently to develop the model. This is a direct search method that uses the simplex search method of Lagarias et al. The results of the new method are compared to the several currently used methods and are shown to be far more accurate and reliable. The average absolute deviation of normal boiling point predictions for 632 organic compounds is 4.4350 K; and the average absolute relative deviation is 1.1047 %, which is of adequate accuracy for many practical applications.

Sea surface temperature estimation of the South Tasman Rise

The Subtropical Front (STF) marking the northern boundary of the Southern Ocean has a steep gradient in sea surface temperature (SST) of approximately 4°C over 0.5° of latitude. Presently, in the region south of Tasmania, the STF lies nominally at 47°S in the summer and 45°S in the winter. We present here SST reconstructions in a latitudinal transect of cores across the South Tasman Rise, southeast of Australia, during the late Quaternary. SST reconstructions are based on two paleotemperature proxies, alkenones and faunal assemblages, which are used to assess past changes in SST in spring and summer. The north-south alignment in core locations allows reconstruction of movement of the STF over the last 100 ka. Surface water temperatures during the last glaciation in this region were ~4°C colder than today. Additional temperature changes greater in magnitude than 4°C seen in individual cores can be attributed to changes in the water mass overlying the core site caused by the movement of the front across that location. During the penultimate interglacial, SST was ~2°C warmer and the STF was largely positioned south of 47°S. Movement of the STF to the north occurred during cool climate periods such as the last marine isotope stages 3 and 4. In the last glaciation, the front was at its farthest north position, becoming pinned against the Tasmanian landmass. It moved south by 4° latitude to 47°S in summer during the deglaciation but remained north of 45°S in spring throughout the early deglaciation. After 11 ka B.P. inferred invigoration of the East Australia Current appears to have pushed the STF seasonally south of the East Tasman Plateau, until after 6 ka B.P. when it achieved its present configuration.

Temperature and CO2 estimation for the Middle Eocene section of ODP Hole 189-1172A

The long-term warmth of the Eocene (~56 to 34 million years ago) is commonly associated with elevated partial pressure of atmospheric carbon dioxide (pCO2). However, a direct relationship between the two has not been established for short-term climate perturbations. We reconstructed changes in both pCO2 and temperature over an episode of transient global warming called the Middle Eocene Climatic Optimum (MECO; ~40 million years ago). Organic molecular paleothermometry indicates a warming of southwest Pacific sea surface temperatures (SSTs) by 3° to 6°C. Reconstructions of pCO2 indicate a concomitant increase by a factor of 2 to 3. The marked consistency between SST and pCO2 trends during the MECO suggests that elevated pCO2 played a major role in global warming during the MECO.

Estimation of sea surface temperature from sediment core PS1768-8

The quantitative diatom analysis of 218 surface sediment samples recovered in the Atlantic and western Indian sector of the Southern Ocean is used to define a base of reference data for paleotemperature estimations from diatom assemblages using the Imbrie and Kipp transfer function method. The criteria which justify the exclusion of samples and species out of the raw data set in order to define a reference database are outlined and discussed. Sensitivity tests with eight data sets were achieved evaluating the effects of overall dominance of single species, different methods of species abundance ranking, and no-analog conditions (e.g., Eucampia Antarctica) on the estimated paleotemperatures. The defined transfer functions were applied on a sediment core from the northern Antarctic zone. Overall dominance of Fragilariopsis kerguelensis in the diatom assemblages resulted in a close affinity between paleotemperature curve and relative abundance pattern of this species downcore. Logarithmic conversion of counting data applied with other ranking methods in order to compensate the dominance of F. kerguelensis revealed the best statistical results. A reliable diatom transfer function for future paleotemperature estimations is presented.

Sea surface temperature estimation of sediment core 86014-12PC51

A recently developed technique for determining past sea surface temperatures (SST), based on an analysis of the unsaturation ratio of long chain C37 methyl alkenones produced by Prymnesiophyceae phytoplankton (U37 k' ), has been applied to an upper Quaternary sediment core from the equatorial Atlantic. U37 k' temperature estimates were compared to those obtained from delta18O of the planktonic foraminifer Globigerinoides sacculifer and of planktonic foraminiferal assemblages for the last glacial cycle. The alkenone method showed 1.8°C cooling at the last glacial maximum, about 1/2 to 1/3 of the decrease shown by the isotopic method (6.3°C) and foraminiferal modern analogue technique estimates for the warm season (3.8°C). Warm season foraminiferal assemblage estimates based on transfer functions are out of phase with the other estimates, showing a 1.4°C drop at the last glacial maximum with an additional 0.9°C drop in the deglaciation. Increased alkenone abundances, total organic carbon percentage and foraminiferal accumulation rates in the last glaciation indicate an increase in productivity of as much as 4 times over present day. These changes are thought to be due to increased upwelling caused by enhanced winds during the glaciation. If U37 k' estimates are correct, as much as 50-70% (up to 4.5°C) of estimated delta18O and modern analogue temperature changes in the last glaciation may have been due to changes in thermocline depth, whereas transfer functions seem more strongly influenced by seasonality changes. This indicates these estimates may be influenced as strongly by other factors as they are by SST, which in the equatorial Atlantic was only reduced slightly in the last glaciation.