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.

Subdivisions of the sediment column, carbon and calcium carbonate at DSDP Hole 64-480

We analyzed 580 integrated scrape-samples from HPC Site 480 for organic and carbonate carbon. Once precise dating is available, these will provide a high-resolution framework for understanding late Quaternary Oceanographic and climatic fluctuations in this region. Organic carbon ranges mostly within a narrow band of 1.8 to 3.5% C. Calcium carbonate varies from undetectable to over 20%, with an average of only about 5%. Source of carbonate are mostly benthic and planktonic foraminifers, although some sections are dominated by diagenetic carbonate, shelly hash, or nannofossils. Detrital sources are low in carbonate. We divided the sequence into 17 calcium carbonate (CC) zones to separate pulses, low and median values. The CC-Zones show various second-order patterns of cyclicity, asymmetry, and events. Laminated zones have lowest uniform values, but a perfect correlation between carbonate content and homogeneous or laminated facies was not found. Maximum values tend to be located near the transition of these two sediment types, showing that accumulation of carbonate is favored during times of breakdown of stable Oceanographic conditions.

Miocene to Pleistocene sedimentation at ODP Site 133-823

More than 2000 turbidite, debris-flow, and slump deposits recovered at Site 823 record the history of the Queensland Trough since the middle Miocene and provide new insights about turbidites, debris flow, and slump deposits (herein termed gravity deposits). Changes in the composition and nature of gravity deposits through time can be related to tectonic movements, fluctuations in eustatic sea level, and sedimentological factors. The Queensland Trough is a long, relatively narrow, structural depression that formed as a result of Cretaceous to Tertiary rifting of the northeastern Australia continental margin. Thus, tectonics established the geometry of this marginal basin, and its steep slopes set the stage for repeated slope failures. Seismic data indicate that renewed faulting, subsidence, and associated tectonic tilting occurred during the early late Miocene (continuing into the early Pliocene), resulting in unstable slopes that were prone to slope failures and to generation of gravity deposits. Tectonic subsidence, together with a second-order eustatic highstand, resulted in platform drowning during the late Miocene. The composition of turbidites reflects their origin and provides insights about the nature of sedimentation on adjacent shelf areas. During relative highstands and times of platform drowning, planktonic foraminifers were reworked from slopes and/or drowned shelves and were redeposited in turbidites. During relative lowstands, quartz and other terrigenous sediment was shed into the basin. Quartzose turbidites and clay-rich hemipelagic muds also can record increased supply of terrigenous sediment from mainland Australia. Limestone fragments were eroded from carbonate platforms until the drowned platforms were buried under hemipelagic sediments following the late Miocene drowning event. Bioclastic grains and neritic foraminifers were reworked from neritic shelves during relative lowstands. During the late Pliocene (2.6 Ma), the increased abundance of bioclasts and quartz in turbidites signaled the shallowing and rejuvenation of the northeastern Australia continental shelf. However, a one-for-one relationship cannot be recognized between eustatic sea-level fluctuations and any single sedimentologic parameter. Perhaps, tectonism and sedimentological factors along the Queensland Trough played an equally important role in generating gravity deposits. Turbidites and other gravity deposits (such as those at Site 823) do not necessarily represent submarine fan deposits, particularly if they are composed of hemipelagic sediments reworked from drowned platforms and slopes. When shelves are drowned and terrigenous sediment is not directly supplied by nearby rivers/point sources, muddy terrigenous sediments blanket the entire slope and basin, rather than forming localized fans. Slope failures affect the entire slope, rather than localized submarine canyons. Slopes may become destabilized as a result of tectonic activity, inherent sediment weaknesses, and/or during relative sea-level lowstands. For this reason, sediment deposits in this setting reflect tectonic and eustatic events that caused slope instabilities, rather than migration of different submarine fan facies.

Miocene to Pliocene calcareous nannofossil biostratigraphy at ODP Leg 117 Sites 1088 and 1090, Southern Ocean

The calcareous nannofossil biostratigraphy of ODP Leg 177 Sites 1088 and 1090 (Subantarctic sector from the Atlantic Ocean) is discussed. Most nannofossil zonal boundaries of Martini (1971) and Okada and Bukry (1980) were recognized for the studied mid-high-latitude sediments. Conventional low-latitude marker species such as Amaurolithus spp., Discoaster spp., Triquetrorhabdulus spp., Ceratolithus spp. were recorded as rare and scattered, which impeded the development of a detailed nannofossil biostratigraphic zonation of some Miocene and Pliocene intervals. Because of the absence of some primary biostratigraphic marker species, additional second-order bioevents, such as the first occurrence of Calcidiscus macintyrei and the last occurrence of Coccolithus miopelagicus, have been used to approximate the base of zones NN7 and NN8, respectively. Several disconformities disturbing the Pliocene and Miocene intervals of Site 1090 could be determined based on nannofossil distribution although the occurrence of intervals with dissolved nannofloras and low species diversity prevented a reliable age assignment. An acme of small Gephyrocapsa was recognized near the lower/middle Pliocene boundary, close to the NN15-NN16 zonal boundary, presenting an event for further improvement of the calcareous nannofossil biostratigraphy of this interval time. The first occurrence of Pseudoemiliania lacunosa (>4 µm) occurs close to this interval, representing a fairly reliable event to approximate the base of NN15 zone when other biozonal events are absent. A paracme of R. pseudoumbilicus (>7 µm) was detected in the lower Pliocene NN12 and in the upper Miocene NN11. These temporary absences of the species seem to be isochronous between high-latitude and low-middle-latitude areas.

Miocene stable isotope stratigraphy of ODP Hole 120-747A

We correlated Miocene d18O increases at Ocean Drilling Program Site 747 with d18O increases previously identified at North Atlantic Deep Sea Drilling Project Sites 563 and 608. The d18O increases have been directly tied to the Geomagnetic Polarity Time Scale (GPTS) at Site 563 and 608, and thus our correlations at Site 747 provide a second-order correlation to the GPTS. Comparison of the oxygen isotope record at Site 747 with records at Sites 563 and 608 indicates that three as-yet-undescribed global Miocene d18O increases may be recognized and used to define stable isotope zones. The d18O maxima associated with the bases of Zones Mila, Milb, and Mi7 have magnetochronologic age estimates of 21.8, 18.3, and 8.5 Ma, respectively. The correlation of a d18O maximum at 70 mbsf at Site 747 to the base of Miocene isotope Zone Mi3 (13.6 Ma) provides a revised interpretation of four middle Miocene normal polarity intervals observed between 77 and 63 mbsf at Hole 747A. Oxygen isotope stratigraphy indicates that the reversed polarity interval at 70 mbsf, initially interpreted as Chronozone C5AAr, should be C5ABr. Instead of a concatenated Chronozone C5AD-C5AC with distinct Chronozones C5AB, C5AA, and C5A (as in the preliminary interpretation), d18O stratigraphy suggests that these normal polarity intervals are Chronozones C5AD, C5AC, and C5AB, whereas Chronozones C5AA-C5A are concatenated. This interpretation is supported by the d13C correlations. The upper Miocene magnetostratigraphic record at Hole 747A is ambiguous. Two upper Miocene d18O events at Site 747 can be correlated to the oxygen isotope records at Site 563 and 608 using the magnetostratigraphy derived at Hole 747B. Our chronostratigraphic revisions highlight the importance of stable isotope stratigraphy in attaining an integrated stratigraphic framework for the Miocene.