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.     

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.     

Delay coordinates: a sensitive indicator of nonlinear dynamics in single charged particle motion in magnetic reversals

The delay coordinate technique is examined as an indicator of the regime of particle dynamics for the system of single charged particle motion in magnetic reversals. Examples of numerically integrated trajectories in both static (zero electric field) and time dependent (corresponding nonzero induction electric field) simple models for magnetic reversals are considered. In the static case, the dynamics can in principle be directly classified by constructing Poincaré surfaces of section; here we demonstrate that whilst the Poincaré surface contains the relevant information to classify the dynamics, the corresponding delay coordinate plot can provide a far more sensitive indication of the onset of nonregular behaviour. In the case of nonperiodic time dependence considered here Poincaré plots cannot in general be constructed directly. Nevertheless, delay coordinate plots can still reveal details of the phase space portrait of the system, and here are shown to indicate whether segments of stochastic motion exist in a given trajectory. It is anticipated that the delay coordinate plot technique as realized here will be a valuable tool in characterizing the behaviour in large numbers of trajectories that are evolved in time-dependent systems, thereby giving us insight into the evolution of the distribution function as a whole, either in prescribed fields or in self-consistent numerical simulations.     

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.     

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.     

Mineral-scale Sr-isotope constraints on magma evolution and chamber dynamics in the Rum layered intrusion,Scotland

Sr isotopic zoning within single plagioclase crystals from rocks from Unit 9 of the Rum layered intrusion is used to infer events during crystal growth in a magma undergoing contamination. The ⁸⁷Sr/⁸⁶Sr diversity among minerals and between cores and rims of plagioclase crystals increases as the boundary between unit 9 and the overlying Unit 10 peridotite is approached. Models of near-solidus interaction of the cumulate with a fluid or melt, or large scale textural re-equilibration, cannot easily account for the systematic differences in ⁸⁷Sr/⁸⁶Sr between small crystals and the rims of larger crystals.We propose a simple interpretation in which crystal growth is concentrated along the cool margins of the reservoir. Crystals are subsequently advected to a site of accumulation at the base of the reservoir, probably by episodic plume-like dense downwellings allowing mixing of isotopically zoned and unzoned crystals.If the core-rim isotope variations are inherited from primary magmatic growth, then the small distances over which they are now preserved (1–2 mm) place constraints on the minimum cooling rate of the intrusion. Although the length scale of diffusive equilibration is influenced by a number of poorly-constrained variables (starting temperature, feldspar composition, temperature-time path) cooling was clearly very rapid with cooling to effective closure (~1,000 °C) within a few thousand years.Editorial responsibility: I. Parsons     

Microwave Remote Sensing of the Temperature and Distribution of Sulfur Compounds in the Lower Atmosphere of Venus

A multi-wavelength radio frequency observation of Venus was performed on April 5, 1996, with the Very Large Array to investigate potential variations in the vertical and horizontal distribution of temperature and the sulfur compounds sulfur dioxide (SO₂) and sulfuric acid vapor (H₂SO₄(g)) in the atmosphere of the planet. Brightness temperature maps were produced which feature significantly darkened polar regions compared to the brighter low-latitude regions at both observed frequencies. This is the first time such polar features have been seen unambiguously in radio wavelength observations of Venus. The limb-darkening displayed in the maps helps to constrain the vertical profile of H₂SO₄(g), temperature, and to some degree SO₂. The maps were interpreted by applying a retrieval algorithm to produce vertical profiles of temperature and abundance of H₂SO₄(g) given an assumed sub-cloud abundance of SO₂. The results indicate a substantially higher abundance of H₂SO₄(g) at high latitudes (above 45°) than in the low-latitude regions. The retrieved temperature profiles are up to 25 K warmer than the profile obtained by the Pioneer Venus sounder probe at altitudes below 40 km (depending on location and assumed SO₂ abundance). For 150 ppm of SO₂, it is more consistent with the temperature profile obtained by Mariner 5, extrapolated to the surface via a dry adiabat. The profiles obtained for H₂SO₄(g) at high latitudes are consistent with those derived from the Magellan radio occultation experiments, peaking at around 8 ppm at an altitude of 46 km and decaying rapidly away from that altitude. At low latitudes, no significant H₂SO₄(g) is observed, regardless of the assumed SO₂ content. This is well below that measured by Mariner 10 (Lipa and Tyler 1979, Icarus39, 192-208), which peaked at ∼14 ppm near 47 km. Our results favor ≤100 ppm of SO₂ at low latitudes and ≤50 ppm in polar regions. The low-latitude value is statistically consistent with the results of Bézard et al. (1983, Geophs. Res. Lett.20, 1587-1590), who found that a sub-cloud SO₂ abundance of 130±40 ppm best matched their observations in the near-IR. The retrieved temperature profile and higher abundance of H₂SO₄(g) in polar regions are consistent with a strong equatorial-to-polar, cloud-level flow due to a Hadley cell in the atmosphere of Venus.     

Recharge estimation for transient ground water modeling

Reliable ground water models require both an accurate physical representation of the system and appropriate boundary conditions. While physical attributes are generally considered static, boundary conditions, such as ground water recharge rates, can be highly variable in both space and time. A practical methodology incorporating the hydrologic model HELP3 in conjunction with a geographic information system was developed to generate a physically based and highly detailed recharge boundary condition for ground water modeling. The approach uses daily precipitation and temperature records in addition to land use/land cover and soils data. The importance of the method in transient ground water modeling is demonstrated by applying it to a MODFLOW modeling study in New Jersey. In addition to improved model calibration, the results from the study clearly indicate the importance of using a physically based and highly detailed recharge boundary condition in ground water quality modeling, where the detailed knowledge of the evolution of the ground water flowpaths is imperative. The simulated water table is within 0.5 m of the observed values using the method, while the water levels can differ by as much as 2 m using uniform recharge conditions. The results also show that the combination of temperature and precipitation plays an important role in the amount and timing of recharge in cooler climates. A sensitivity analysis further reveals that increasing the leaf area index, the evaporative zone depth, or the curve number in the model will result in decreased recharge rates over time, with the curve number having the greatest impact.