Structure proof and significance of stereoisomeric 28,30-bisnorhopanes in petroleum and petroleum source rocks

Two C₂₈H₄₈-pentacyclic triterpanes were isolated from Monterey shale. X-ray crystallography of a crystal containing both compounds proved their structures as 17β,18α,21α(H)-28,30-bisnorhopane and 17β,18α,21β(H)-28,30-bisnorhopane. Several differences are found between 28,30-bisnorhopanes and the regular hopanes. Unlike the regular hopane epimers, for practical purposes the three epimeric 28,30-bisnorhopanes [17α,21β(H)-, 17β,21α(H)-, and 17β,21β(H)-]cannot be distinguished by their mass spectra. Special conditions are needed to separate them by gas chromatography. The diagenetically first-formed epimer is thought to be 17α,21β(H)- because it predominates in immature shales. The order of thermodynamic stability is 17β,2lα(H) < > 17α,21β(H) > 17β,21β(H), and all three epimers are present in petroleum. 25,28,30-Trisnorhopanes can be analyzed in similar fashion and are found to have similar thermodynamic characteristics. The percent of the ring D/E cis epimer of 28,30-bisnorhopane and/or 25,28,30-trisnorhopane is a useful maturation parameter similar to the 20S/20R sterane ratio. Evidence indicates 25-demethylation of 28,30-bisnorhopane to 25,28,30-trisnorhopane during advanced stages of biodegradation. Hence, percent ring $\text{D}\text{E}$cis 25,28,30-trisnorhopane has an application to maturation assessment in heavily biodegraded oils.     

Carbohydrates in recent marine sediments—II. Occurrence and fate of carbohydrates in a recent stromatolitic deposit: Solar Lake,Sinai

In a study on the diagenesis of carbohydrates in a recent stromatolitic deposit (Solar Lake, Sinai) monosaccharides are quantitated after mild acid hydrolysis and gas chromatographic analysis as alditol acetates. From the depth profiles of the individual monosaccharides relative to the total organic carbon three categories of carbohydrates can be distinguished. The behaviour of the various categories upon burial is discussed in terms of their potential to become a part of the organic matter that survives geological periods. The distribution patterns of especially the mono-O-methyl monosaccharides at various depths are characteristics for the bacterial communities present in the corresponding parts of the sediment column.     

OCCURRENCE OF VOLATILE ORGANIC CHEMICALS IN NEBRASKA GROUND WATER

Abstract. This report summarizes results of monitoring programs for volatile synthetic organic chemicals (VOCs) in Nebraska's private and public water-supply wells conducted by two State agencies. Of 97 community water-supply systems sampled as of June 1984, 16.5 percent (16 systems) showed quantifiable levels of at least one VOC. Detectable amounts of one or more VOCs were measured in samples from 15.9 percent (10) of 63 private wells sampled in 1982. These percentages are consistent with results of other State and national surveys.     

O, S, Sr, and Pb isotope variations in volcanic rocks from the Northern Mariana Islands: implications for crustal recycling in intra-oceanic arcs

Quaternary lavas from the Northern Mariana Islands have respective O- and S-isotope ranges ofδ¹⁸O = +5.7 to +6.6 (‰ SMOW) andδ³⁴S = +2.0to+20.7 (‰ CDT). Chemically evolved andesites and dacites with meanδ¹⁸O = +6.3 ± 0.2 are slightly enriched in¹⁸O with respect to unfractionated basalts of<53%SiO₂ with meanδ¹⁸O = +6.0 ± 0.1. This¹⁸O enrichment can be explained in terms of differentiation of parental mafic magmas havingδ¹⁸O values between +5.7 to +6.2‰ through closed-system crystal fractionation because the lavas from all nine islands of the arc define a coherentδ¹⁸OSiO₂ trend. The S-isotope composition of oxidized magmas is not modified extensively through the degassing of SO₂; therefore, the meanδ³⁴S value of ca. +11‰ for the Mariana lavas is considered to be representative of their source region.The enrichment of¹⁸O and³⁴S in Mariana Arc parental magmas relative to ocean floor basalts withδ¹⁸O ca. + 5.7‰ andδ³⁴S = ca.0.3‰ is attributed to the recycling of¹⁸O- and³⁴S-rich crustal components (sediment withδ¹⁸O = ca. + 25‰ and seawater sulfate withδ³⁴S = ca. +20‰ into the upper mantle source region for these arc magmas. This interpretation is consistent with enrichments of radiogenic Sr and Pb in the same lavas relative to ocean-floor basalts erupted either side of the arc, which are presumed to share a common upper mantle source. This enrichment is considered to reflect the mixing of two components, one having a typical upper mantle composition and the other having a more radiogenic character similar to that of western Pacific pelagic sediments.     

Progress in Carrier Phase Time Transfer

The progress of the joint Pilot Project for time transfer, formed by the International GPS Service (IGS) and the Bureal International des Poids et Mesures (BIPM), was recently reviewed. Three notable milestones were set. (1) The IGS will implement, at least in a test mode, an internally realized time scale based on an integration of combined frequency standards within the IGS network. This will eventually become the reference time scale for all IGS clock products (instead of the current GPS broadcast time). (2) A new procedure for combined receiver and satellite clock products will be implemented officially in November 2000. Receiver clocks are an entirely new product of the IGS. (3) The BIPM will coordinate an effort to calibrate all Ashtech Z12-T (and possibly other) receivers suitable for time transfer applications, either differentially or absolutely. Progress reports will be presented publicly in the spring 2001. ? 2001 John Wiley & Sons, Inc.     

Trace metals in acid sediments and waters, Pimpama catchment, southeast Queensland, Australia

The Pimpama River floodplain has developed over the last several thousand years as a result of sea-level fluctuations that shaped the lower catchment and enabled the formation of sedimentary pyrite. The subsequent production of sulfuric acid due to the oxidation of this pyrite enhances the breakdown of metal-bearing sediments and can lead to leaching of major and trace metals into the waters of the region. The seasonal pattern of rainfall and current land-use activities are important aspects that intensify the natural production of acid and influence the release and distribution of metals. To identify the source and migration of metals in the Pimpama catchment and to understand the impact of pyrite oxidation on the distribution of metals in sediments and waters, several components of the drainage system were analyzed: bedrock, sediments from river bed and bank, and water. The elements analyzed in this study (V, Cr, Co, Ni, Cu, Zn and Pb) are all present in the bedrock material which explains their occurrence in the unconsolidated sediments of the floodplain. These metals concentrate in the upper section of the sedimentary sequence and their presence is related to clay minerals such as smectite, organic matter and iron phases. However, Zn, Mo and Co occur in higher amounts than the local background and within standard shale. This comparison suggests that the diagenetic processes alone cannot explain the higher concentrations and it is concluded that these metals also have an anthropogenic source. The formation of sulfuric acid creates conditions for higher mobility of some metals, such as Cr, Co, Ni, Cu, Zn, but does not affect less mobile ones such as Mo and Pb. Over the longterm, the production of acid influences the breakdown of mineral phases and enhances the process of weathering. Over the short term, every rain event leaches acid from sediments and mobilizes metals resulting in a substantial reduction in the quality of river water. Received: 2 October 1998 · Accepted: 16 February 1999     

Two-dimensional modelling of some CFC replacement compounds

The Cambridge 2-D Eulerian model has been used to study the potential atmospheric distributions and lifetimes of a number of CFC replacement compounds and their degradation products. The study has focused on HFC 134a and HCFCs 123, 141b and 142b and the major products formed by their atmospheric degradation. The loss of these compounds and their products by hydroxyl radical attack, photolysis and in-cloud hydrolysis have been investigated. The study has shown that HCFCs 141b and 142b have sufficiently long lifetimes to enter the stratosphere in significant quantities, where degradation leads to an increase in the total stratospheric chlorine concentration. The study has also highlighted areas where further experimental work would be valuable, in particular characterisation of the product channels for the degradation reactions and determination of the removal rates of the products in the aqueous phase.     

The volcanic and magmatic evolution of Volcán Ollagüe, a high-K, late quaternary stratovolcano in the Andean Central Volcanic Zone

Volcán Ollagüe is a high-K, calc-alkaline composite volcano constructed upon extremely thick crust in the Andean Central Volcanic Zone. Volcanic activity commenced with the construction of an andesitic to dacitic composite cone composed of numerous lava flows and pyroclastic deposits of the Vinta Loma series and an overlying coalescing dome and coulée sequence of the Chasca Orkho series. Following cone construction, the upper western flank of Ollagüe collapsed toward the west leaving a collapse-amphitheater about 3.5 km in diameter and a debris avalanche deposit on the lower western flank of the volcano. The deposit is similar to the debris avalanche deposit produced during the May 18, 1980 eruption of Mount St. Helens, U.S.A., and was probably formed in a similar manner. It presently covers an area of 100 km² and extends 16 km from the summit. Subsequent to the collapse event, the upper western flank was reformed via eruption of several small andesitic lava flows from vents located near the western summit and growth of an andesitic dome within the collapse-amphitheater. Additional post-collapse activity included construction of a dacitic dome and coulée of the La Celosa series on the northwest flank. Field relations indicate that vents for the Vinta Loma and post-collapse series were located at or near the summit of the cone. The Vinta Loma series is characterized by an anhydrous, two-pyroxene assemblage. Vents for the La Celosa and Chasca Orkho series are located on the flanks and strike N55 W, radial to the volcano. The pattern of flank eruptions coincides with the distribution in the abundance of amphibole and biotite as the main mafic phenocryst phases in the rocks. A possible explanation for this coincidence is that an unexposed fracture or fault beneath the volcano served as a conduit for both magma ascent and groundwater circulation. In addition to the lava flows at Ollagüe, magmas are also present as blobs of vesiculated basaltic andesite and mafic andesite that occur as inclusions in nearly all of the lavas. All eruptive activity at Ollagüe predates the last glacial episode ( 11.000 a B.P.), because post-collapse lava flows are overlain by moraine and are incised by glacial valleys. Present activity is restricted to emission of a persistent, 100-m-high fumarolic steam plume from a vent located within the summit andesite dome.Sr and Nd isotope ratios for the basaltic andesite and mafic andesite inclusions and lavas suggest that they have assimilated large amounts of crust during crystal fractionation. In contrast, narrow ranges in ¹⁴³Nd/¹⁴⁴Nd and ⁸⁷Sr/⁸⁶Sr in the andesitic and dacitic lavas are enigmatic with respect to crustal contamination.