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.

Gotland Deep (Baltic Sea) independent age model based on Palaeomagnetic Secular Variation (PSV) and lead (Pb) deposition profiles

Dating of sediment cores from the Baltic Sea has proven to be difficult due to uncertainties surrounding the 14C reservoir age and a scarcity of macrofossils suitable for dating. Here we present the results of multiple dating methods carried out on cores in the Gotland Deep area of the Baltic Sea. Particular emphasis is placed on the Littorina stage (8 ka ago to the present) of the Baltic Sea and possible changes in the 14C reservoir age of our dated samples. Three geochronological methods are used. Firstly, palaeomagnetic secular variations (PSV) are reconstructed, whereby ages are transferred to PSV features through comparison with varved lake sediment based PSV records. Secondly, lead (Pb) content and stable isotope analysis are used to identify past peaks in anthropogenic atmospheric Pb pollution. Lastly, 14C determinations were carried out on benthic foraminifera (Elphidium spec.) samples from the brackish Littorina stage of the Baltic Sea. Determinations carried out on smaller samples (as low as 4 µg C) employed an experimental, state-of-the-art method involving the direct measurement of CO2 from samples by a gas ion source without the need for a graphitisation step - the first time this method has been performed on foraminifera in an applied study. The PSV chronology, based on the uppermost Littorina stage sediments, produced ten age constraints between 6.29 and 1.29 cal ka BP, and the Pb depositional analysis produced two age constraints associated with the Medieval pollution peak. Analysis of PSV data shows that adequate directional data can be derived from both the present Littorina saline phase muds and Baltic Ice Lake stage varved glacial sediments. Ferrimagnetic iron sulphides, most likely authigenic greigite (Fe3S4), present in the intermediate Ancylus Lake freshwater stage sediments acquire a gyroremanent magnetisation during static alternating field (AF) demagnetisation, preventing the identification of a primary natural remanent magnetisation for these sediments. An inferred marine reservoir age offset (deltaR) is calculated by comparing the foraminifera 14C determinations to a PSV & Pb age model. This deltaR is found to trend towards younger values upwards in the core, possibly due to a gradual change in hydrographic conditions brought about by a reduction in marine water exchange from the open sea due to continued isostatic rebound.

Pliocene stable oxygen and carbon isotope record of benthic foraminifera from ODP Site 138-846 in the eastern equatorial Pacific

Oxygen and carbon isotope ratios were measured in benthic foraminifers from the entire Pliocene and latest Miocene sections of Site 846, a 180-m section, at a sampling interval of 10 cm. This provides a temporal resolution of about 2500 yr. The documented continuity of the record is excellent. Using the time scale that was developed on the basis of orbital tuning of GRAPE density records, we observed a fairly constant phase relationship between delta18O and variations in the obliquity of Earth's rotational axis. A new numbering scheme for Pliocene isotope stages is proposed. This high-resolution delta18O record clarifies several interesting aspects of late Neogene climatic evolution, including a "glacial" event that may have caused the final Messinian desiccation of the Mediterranean Sea; one or more "interglacial" events that might have caused refilling of the Mediterranean; a well-resolved couplet of glacial events at about the age of the Sidujfall Subchron; interglacial extremes in the early part of the Gauss that could have resulted from either significant deglaciation on Antarctica or from warming of deep water; and a gradual ramp of increasingly extreme "glacial" events, starting at about the Kaena Subchron and culminating with delta18O stage 100 in the earliest Matuyama.

Physical properties, pore water geochemistry, 210Pb-dating of sediment cores GeoB16426-1, GeoB16427-1, GeoB16429-1

We present differential bathymetry and sediment core data from the Japan Trench, sampled after the 2011 Tohoku-Oki (offshore Japan) earthquake to document that prominent bathymetric and structural changes along the trench axis relate to a large (~27.7 km**2) slump in the trench. Transient geochemical signals in the slump deposit and analysis of diffusive re-equilibration of disturbed SO4**2- profiles over time constrain the triggering of the slump to the 2011 earthquake. We propose a causal link between earthquake slip to the trench and rotational slumping above a subducting horst structure. We conclude that the earthquake-triggered slump is a leading agent for accretion of trench sediments into the forearc and hypothesize that forward growth of the prism and seaward advance of the deformation front by more than 2 km can occur, episodically, during a single-event, large mega-thrust earthquake.

Geochemistry and mineralogy of ultramafic rocks from conical seamount

The Mariana arc-trench system, the easternmost of a series of backarc basins and intervening remnant arcs that form the eastern edge of the Philippine Sea Plate, is a well-known example of an intraoceanic convergence zone. Its evolution has been studied by numerous investigators over nearly two decades (e.g., Kang, 1971; Uyeda and Kanamori, 1979; LaTraille and Hussong, 1980; Fryer and Hussong, 1981; Mrosowski et al., 1982; Hussong and Uyeda, 1981; Bloomer and Hawkins, 1983; Karig and Ranken, 1983; McCabe and Uyeda, 1983; Hsui and Youngquist, 1985; Fryer and Fryer, 1987; Johnson and Fryer, 1988; Johnson and Fryer, 1989; Johnson et al., 1991). The Mariana forearc has undergone extensive vertical uplift and subsidence in response to seamount collision, to tensional and rotational fracturing associated with adjustments to plate subduction, and to changes in the configuration of the arc (Hussong and Uyeda, 1981; Fryer et al., 1985). Serpentine seamounts, up to 2500 m high and 30 km in diameter, occur in a broad zone along the outer-arc high (Fryer et al., 1985; Fryer and Fryer, 1987). These seamounts may be horsts of serpentinized ultramafic rocks or may have been formed by the extrusion of serpentine muds. Conical Seamount, one of these serpentine seamounts, is located within this broad zone of forearc seamounts, about 80 km from the trench axis, at about 19°30'N. The seamount is approximately 20 km in diameter and rises 1500 m above the surrounding seafloor. Alvin submersible, R/V Sonne bottom photography, seismic reflection, and SeaMARC II studies indicate that the surface of this seamount is composed of unconsolidated serpentine muds that contain clasts of serpentinized ultramafic and metamorphosed mafic rocks, and authigenic carbonate and silicate minerals (Saboda et al., 1987; Haggerty, 1987; Fryer et al., 1990; Saboda, 1991). During Leg 125, three sites were drilled (two flank sites and one summit site) on Conical Seamount to investigate the origin and evolution of the seamount. Site 778 (19°29.93'N, 146°39.94'E) is located in the midflank region of the southern quadrant of Conical Seamount at a depth of 3913.7 meters below sea level (mbsl) (Fig. 2). This site is located in the center of a major region of serpentine flows (Fryer et al., 1985, 1990). Site 779 (19°30.75'N, 146°41.75'E), about 3.5 km northeast of Site 778, is located approximately in the midflank region of the southeast quadrant of Conical Seamount, at a depth of 3947.2 mbsl. This area is mantled by a pelagic sediment cover, overlying exposures of unconsolidated serpentine muds that contain serpentinized clasts of mafic and ultramafic rocks (Fryer et al., 1985, 1990). Site 780 (19°32.5'N, 146°39.2'E) is located on the western side of Conical Seamount near the summit, at a depth of 3083.4 mbsl. This area is only partly sediment covered and lies near active venting fields where chimney structures are forming (Fryer et al., 1990).

Paleomagnetic and rock magnetic characterization of ODP Leg 210 cores

We conducted an integrated paleomagnetic and rock magnetic study on cores recovered from Ocean Drilling Program Sites 1276 and 1277 of the Newfoundland Basin. Stable components of magnetization are determined from Cretaceous-aged sedimentary and basement cores after detailed thermal and alternating-field demagnetization. Results from a series of rock magnetic measurements corroborate the demagnetization behavior and show that titanomagnetites are the main magnetic carrier. In view of the normal polarity of magnetization and radiometric dates for the sills at Site 1276 (~98 and ~105 Ma, both within the Cretaceous Normal Superchron) and for a gabbro intrusion in peridotite at Site 1277 (~126 Ma, Chron M1), our results suggest that the primary magnetization of the Cretaceous rocks is likely retained in these rocks. The overall magnetic inclination of lithologic Unit 2 in Hole 1277A between 143 and 180 meters below seafloor is 38°, implying significant (~35° counterclockwise, viewed to the north) rotation of the basement around a horizontal axis parallel to the rift axis (010°). The paleomagnetic rotational estimates should help refine models for the tectonic evolution of the basement. The mean inclinations for Sites 1276 and 1277 rocks imply paleolatitudes of 30.3° ± 5.1° and 22.9° ± 12.0°, respectively, with the latter presumably influenced by tectonic rotation. These values are consistent with those inferred from the mid-Cretaceous reference poles for North America, suggesting that the inclination determinations are reliable and consistent with a drill site on a location in the North America plate since at least the mid-Cretaceous. The combined paleolatitude results from Leg 210 sites indicate that the Newfoundland Basin was some 1800 km south of its current position in the mid-Cretaceous. Assuming a constant rate of motion, the paleolatitude data would suggest a rate of 12.1 mm/yr for the interval from ~130 Ma (Site 1276 age) to present, and 19.6 mm/yr for the interval from 126 Ma (Site 1277 age) to recent. The paleolatitude and rotational data from this study are consistent with the possibility that Site 1276 may have passed over the Canary and Madeira hotspots that formed the Newfoundland Seamounts in the mid-Cretaceous.

Magnetic properties of ODP Site 191-1179 sediments

As reported by Shipboard Scientific Party (2001b, doi:10.2973/odp.proc.ir.191.104.2001) in the Site 1179 chapter of the Initial Reports volume, Leg 191 Site 1179 is located on abyssal seafloor northwest of Shatsky Rise, ~1650 km east of Japan. This part of the Pacific plate was formed during the Early Cretaceous, as shown by northeast-trending M-series magnetic lineations that become younger toward the northwest (Larson and Chase, 1972, doi:10.1130/0016-7606(1972)83[3627:LMEOTW]2.0.CO;2; Sager et al., 1988, doi:10.1029/JB093iB10p11753; Nakanishi et al., 1989, doi:10.1029/1999JB900002). The site is situated on magnetic Anomaly M8 (Nakanishi et al., 1999, doi:10.1029/1999JB900002), corresponding to an age of ~129 Ma and the Hauterivian stage of the Early Cretaceous (Gradstein et al., 1994, doi:10.1029/94JB01889; 1995). The sediments recovered at Site 1179 are split into four lithostratigraphic units based on composition and color (Shipboard Scientific Party, 2001b, doi:10.2973/odp.proc.ir.191.104.2001). Unit I (0-221.52 meters below seafloor [mbsf]) is a dominantly olive-gray clay- and radiolarian-bearing diatom ooze. Unit II (221.52-246.0 mbsf) is a yellowish brown to light brown clay-rich and diatom-bearing radiolarian ooze. Unit III (246.0-283.53 mbsf) is composed of brown pelagic clay. Unit IV (283.53-377.15 mbsf) is composed of chert and some porcellanite; any softer sediments present were washed out of the core barrel by the fluid circulating during the coring process.