Hydrous pyrolysis of New Albany and Phosphoria Shales: production kinetics of carboxylic acids and light hydrocarbons and interactions between the inorganic and organic chemical systems

Hydrous pyrolysis in flexible gold-bag autoclaves was used to study the production of carboxylic acids and light hydrocarbons from two marine type IIb source rocks (New Albany and Phosphoria Shales). Kerogen pyrolysis produced significant amounts of the monocarboxylic acids (acetic > propionic > butyric). The gases were dominated by CO₂ and methane, in that order, and progressively smaller amounts of the alkanes (ethane > propane > butane > pentane). Kinetic analyses of production rates for the New Albany Shale suggest mean activation energies (E) of 51-54 kcal/mol for both the light hydrocarbons and acids. Pressure had little effect on measured production rates for either shale over the pressure range investigated. Chemical thermodynamic speciation modeling suggests that in these experiments metal-organic acid anion complexation had little impact on aluminum speciation/solubility, but was important with respect to the alkaline earths.     

Geochemical variations within a laminated evaporite deposit: evidence for brine composition during formation of the Permian Castile Formation, Texas and New Mexico, USA

The Upper Permian Castile Formation of the Delaware Basin in northwest Texas and New Mexico consists of up to 600 m of evaporites and is subdivided into units of anhydrite overlain by halite. The Castile Formation has commonly been interpreted as a deep-water, deep-basin deposit in which sediments were laid down in several hundred metres of water or brine. Recent textural observations within anhydrite units, in which the thick-bedded anhydrite horizons have been interpreted as being of shallow-water origin, have challenged this assumption. This geochemical study of the oldest anhydrite unit in the Castile Formation (the Anhydrite 1 Member) attempts to resolve some of the problems regarding brine depth and evolution in the basin. The Anhydrite 1 Member has been subdivided into five major cycles on the basis of the distribution of stratigraphic units of thick-bedded anhydrite.

Stable isotopic analyses of sulphur from anhydrite, and oxygen and carbon from calcite show that the basin waters were chemically homogeneous during precipitation of anhydrite, and do not indicate any significant input of meteoric, continental-derived waters. Throughout the section studied progressive enrichment of ¹⁸O upwards within cored intervals indicates continuous evaporation of the water body. Carbon isotopes appear to indicate fluctuations in organic activity within the cycles. Trace elemental analyses of Fe, Mg, Sr, Mn, Al, Ba, Zn, Pb and Cu from the sulphate fraction of the samples show a very high variability. There is a distinct increase in trace elemental abundances at the tops of cycles which may indicate variations in precipitation kinetics. Analyses of texturally defined cycles show that up-core trends for many of the trace elements correlate with changes in δ¹⁸O, indicating a progressive increase in the influence of evaporation. In addition, cyclical variations in trace elemental composition indicate changes in basin conditions with around a 350-year cyclicity. These changes are independent of δ¹⁸O values. The geochemical data do not provide conclusive proof of water depth during deposition of the Castile Formation. The data are interpreted as reflecting small-scale changes in conditions of deposition, despite the fact that water input remained essentially constant in terms of chemical composition.     

Partial molar volume of water in phonolitic glasses and liquids

The volumes and expansivities of four hydrous phonolite glasses and liquids have been measured by dilatometry from 300 K up to the glass transition and over a 50 K interval just above the glass transition. The partial molar volume of water is independent of the water content for the glass and liquid phases, with values of about 11.0ǂ.5 and 17.1ǂ.9 cm³/mol at 300 and 800 K, respectively. The partial molar thermal expansivity of water in phonolite glasses is about 8᎒^-5 K^-1, a result similar to recently published values for different silicate compositions, and about 36.5᎒^-5 K^-1 in phonolite liquids. The implications for melt density and water dissolution are discussed.     

Partial melting of metavolcanics in amphibolite facies regional metamorphism

Metavolcanic rocks containing low-Ca amphiboles (gedrite, cummingtonite) and biotite can undergo substantial dehydration-melting. This is likely to be most prominent in Barrovian Facies Series (kyanite-sillimanite) and occurs at the same time as widespread metapelite dehydrationmelting. In lower pressure facies series, metavolcanics will be represented by granulites rich in orthopyroxene when dehydration occurs at much lower temperatures than melting. In higher pressure facies series it is not well known whether metavolcanic rocks dehydrate or melt at temperatures lower or similar to that of metapelites.     

Extending Participation in the Swaziland Sugar Industry to Small-Scale Growers: Patterns and Prospects

Since its inception in 1956, the Swazi sugar industry has been dominated by large-scale estates. In 1991, due to a combination of political and economic factors, steps were taken to allow the industry to become more accessible to small-scale Swazi farmers. The paper considers the scale and nature of this newly emerging group and discusses its likely impact on employment. Although these developments have been introduced to enable the benefits of the industry to trickle down more effectively to the rural poor, evidence suggests that better off or more organised groups or individuals are best placed to take advantage of the new opportunities. Further growth is now limited by a lack of water and it is likely that the recent rapid increase in this sector will now slow down. Some concern also exists over the impact of sugar cane monoculture on soils.     

Arcs and backarc basins in the Early Paleozoic lapetus Ocean

Abstract Understanding the evolution and destruction of past oceans not only leads to a better understanding of earth history, but permits comparison with extant ocean basins and tectonic processes. This paper reviews the history of the Early Paleozoic circum-Atlantic oceans by analogy with the Pacific Ocean and Mesozoic Tethys. Rifting and continental separation from 620 to 570 Ma led to the development of passive margins along parts of the northern margin of Gondwana (the western coast of South America); eastern Laurentia (eastern North America, NW Scotland and East Greenland), and western Baltica (western Scandinavia). Meagre paleomagnetic data suggest that western South America and eastern North America could have been joined together to form facing margins after breakup. Although western Baltica is an apparently obvious candidate for the margin facing NW Scotland and East Greenland, the paleomagnetic uncertainties are so large that other fragments could have been positioned there instead. The Iapetus Ocean off northeastern Gondwana was probably a relatively wide Pacific-type ocean with, during the late Precambrian to early Ordovician, the northern margin of Gondwana as a site of continentward-dipping subduction zone(s). The 650-500 Ma arc-related igneous activity here and the associated deformation gave rise to the Cadomian, ‘Grampian’, Penobscotian, and Famantinian igneous and orogenic events. By 490-470 Ma, marginal basins had formed along the eastern Laurentian margin as far as NE Scotland, along parts of the northern margin of Gondwana, and off western Baltica, but none are known from the East Greenland margin. These basins closed and parts were emplaced as ophiolites shortly after their formation by processes that, at least in some cases, closely resemble the emplacement of the late Cretaceous Semail ophiolite of Oman. This orogenic phase seems to have involved collision and attempted subduction of the continental margin of Laurentia, Gondwana and Baltica. In Baltica it gave rise to some eclogite facies metamorphism. Marginal basin development may have been preceded by arc formation as early as ca 510 Ma. A double arc system evolved outboard from the eastern Laurentian and western Baltica margins, analogous to some of the arc systems in the present-day western Pacific. At 480-470 Ma, there was a second phase of breakup of Gondwana, affecting the active Gondwanan margin. Eastern and Western Avalonia, the Carolina Slate Belt, Piedmont, and other North American exotic continental blocks rifted away from Gondwana. Farther east, Armorica, Aquitainia, Iberia and several European exotic continental blocks also rifted away, though it is unlikely that they all rifted at the same time. Between 460-430 Ma, peaking at ca 450 Ma, orogenic events involved continuing arc-continent collision(s). From 435-400 Ma the remaining parts of the Eastern Iapetus Ocean were destroyed and the collision of Baltica with Laurentia caused the 430-400 Ma Scandian orogeny, followed by suturing of these continents during the Siluro-Devonian Acadian orogeny or Late Caledonian orogeny to 380 Ma, leaving a smaller but new ocean south of the fragments that had collided with the Laurentian margin farther south. The Ligerian orogeny 390-370 Ma collision of Gondwana-derived Aquitaine-Cantabrian blocks with Eastern Avalonia-Baltica and removed the part of the Iapetus south of Baltica. Prior to any orogenic events, the Eastern Iapetus Ocean between Baltica and Laurentia may have resembled the present-day central Atlantic Ocean between Africa and North America. The ocean appears to have closed asymmetrically, with arcs forming first outboard of the western margin of Baltica while the East Greenland margin was unaffected. The Western Iapetus Ocean between Laurentia and Gondwana also closed asymmetrically with a dual arc system developing off Laurentia and an arc system forming off the northern margin of Gondwana. Like the Pacific Ocean today, the Eastern Iapetus Ocean had a longer and more complex history than the Western Iapetus Ocean: it was already in existence at 560 Ma, probably developed over at least 400 million years, by mid-Cambrian time was many thousands of kilometres wide at maximum extent, and was associated with a < 30 million year phase of marginal basin formation. In contrast, the Western Iapetus Ocean appears to have been much narrower, shorter lived (probably < 100 million years), and associated with the rifting to form two opposing passive carbonate margins, analogous to the Mesozoic Tethys or the present-day Mediterranean.     

The Vendian record of Sr and C isotopic variations in seawater: Implications for tectonics and paleoclimate

New Sr and C isotopic data, both obtained on the same samples of marine carbonates, provide a relatively detailed record of isotopic variation in seawater through the latest Proterozoic and allow, for the first time, direct correlation of these isotopic changes in the Vendian ( 540–610 Ma). The strong isotope variations determined in this study record significant environmental and tectonic changes. Together with a fairly poorly constrained Nd isotopic record, the Sr and C isotopic records can be used to constrain rates of erosion, hydrothermal alteration and organic C burial. Further, comparison of these records with those of the Cenozoic permit investigation of the general relationship between global tectonics and continental glaciation. In particular, results of this study show a very large change in the ⁸⁷Sr/⁸⁶Sr of marine carbonates from low pre-Vendian ( > 610 Ma) values ( 0.7066) to high Middle Cambrian values ( 0.7090). This change is greater in magnitude than the significant increase in seawater ⁸⁷Sr/⁸⁶Sr through the Cenozoic. Both changes are attributed to high erosion rates associated with continent-continent collisions (Pan-African and Himalayan-Tibetan). In the latest Proterozoic these high erosion rates, probably coupled with high organic productivity and anoxic bottom-water conditions, contributed to a significant increase in the burial rate of organic C. Ice ages mark both the Neoproterozoic and Cenozoic, but different stratigraphic relationships between the Sr isotopic increase and continental glaciation indicate that uplift-driven models proposed to explain Cenozoic climatic change cannot account for the latest Proterozoic ice ages.     

Sulfur dioxide and dimethyl sulfide in the central Pacific troposphere

Boundary-layer and free-troposphere measurements of sulfur dioxide, dimethyl sulfide, and carbon disulfide were made during transits of the central and southern Pacific Ocean between Hawaii and Australia. Sulfur dioxide was generally less than 100 pptv and highly variable with no correlation with respect to geographic location or altitude. Dimethyl sulfide in the boundary layer had a concentration range of <10 to 200 pptv. Highest concentrations of DMS were in the equatorial region of the southern hemisphere although the concentrations were dependent on location and meteorological regime. In the region of the Fiji Islands several boundary layer samples had SO₂, DMS, and CS₂. In 1989, additional SO₂ measurements were made between Hawaii and the equator and to the west of Hawaii downwind of the Kilauea volcano plumes.Paper submitted to the 7th International Symposium of the Commission for Atmospheric Chemistry and Global Pollution on the Chemistry of the Global Atmosphere held in Chamrousse, France, from 5 to 11 September 1990.     

Estimation of effective roughness length for heat and momentum from FIFE data

Using aircraft and surface data from the 1987 FIFE experiment in Kansas, we estimate the roughness length for momentum to be 0.19 m (with an error range 0.10–0.35 m), and the ratio of roughness length for momentum to that for heat to be about 16 (with an error range of 7–35).     

Use of general circulation model output in the creation of climate change scenarios for impact analysis

Many scientific studies warn of a rapid global climate change during the next century. These changes are understood with much less certainty on a regional scale than on a global scale, but effects on ecosystems and society will occur at local and regional scales. Consequently, in order to study the true impacts of climate change, regional scenarios of future climate are needed. One of the most important sources of information for creating scenarios is the output from general circulation models (GCMs) of the climate system. However, current state-of-the-art GCMs are unable to simulate accurately even the current seasonal cycle of climate on a regional basis. Thus the simple technique of adding the difference between 2 × CO₂ and 1 × CO₂ GCM simulations to current climatic time series cannot produce scenarios with appropriate spatial and temporal details without corrections for model deficiencies. In this study a technique is developed to allow the information from GCM simulations to be used, while accommodating for the deficiencies. GCM output is combined with knowledge of the regional climate to produce scenarios of the equilibrium climate response to a doubling of the atmospheric CO₂ concentration for three case study regions, China, Sub-Saharan Africa and Venezuela, for use in biological effects models. By combining the general climate change calculated with several GCMs with the observed patterns of interannual climate variability, reasonable scenarios of temperature and precipitation variations can be created. Generalizations of this procedure to other regions of the world are discussed.