Vertical column abundances and seasonal cycle of acetylene,C2H2, above the Jungfraujoch station,derived from IR solar observations

Monthly mean total vertical column abundances of acetylene have been determined from series of infrared solar spectra recorded at the Jungfraujoch station, Switzerland, between June 1986 and April 1991. The data have been obtained by nonlinear least-squares fittings of the ₅ band R19 transition of C₂H₂ at 776.0818 cm^-1. The average of 22 monthly mean total vertical columns of C₂H₂ retrieved during that time interval of almost 5 years was found to be equal to (1.81±0.12)×10¹⁵ molec/cm², which corresponds to an average mixing ratio of (0,22±0.013) ppbv (parts per billion by volume) in a troposphere extending from the altitude of the station (3.58 km), up to 10.5 km. Despite the large variability found from year to year, a least-squares sine fit to the data reveals a seasonal variation with an amplitude of about ±40% of the mean; the maximum occurs during mid-winter and the minimum in the summer. The present results are compared critically with similar in-situ data found in the literature. A sinusoidal fit to all such free troposphere measurements made in-situ between 30°N and 60°N indicates good agreement in shape and phase with the seasonal variation derived above the Jungfraujoch, but their average column abundance, 2.3×10¹⁵ molec/cm², is about 30% higher; this difference is explained on the basis of non-upwelling meteorological conditions generally prevailing during ground-based remote solar observations.     

Reviews

F. L. Stillwell Anniversary Volume. Australian Institute of Mining and Metallurgy, Melbourne, 302 pages, many plates and figures. 1958.

Our Mineral Resources, by Charles M. Riley; x + 338 pages; 102 figures; John Wiley and Sons, Inc., New York and London. $6.95.

Researches in Geochemistry, edited by P. H. Abelson; John Wiley and Sons Inc., New York, 1959. $11.00.

Basic Geology for Science and Engineering, by Edward C. Dapples; vii + 609 pages; 231 figures. John Wiley and Sons Inc., New York, 1959. $9.50.

Historical Geology, by Carl O. Dunbar; xi + 500 pages; 406 figures. Second Edition, publication date August, 1960; John Wiley and Sons Inc., New York. $7.95.

Time, Life and Man, by R. A. Stirton; xi + 558 pages; 291 figures. John Wiley and Sons Inc., New York, 1958.

Vector Space, by Martin J. Buerger; xiv + 347 pages; numerous line drawings; John Wiley and Sons Inc., New York and London. $12.00.

Geology of the Country Around Polonnaruwa, by Piyadasa W. Vtkanage. 1959. Memoir No. 1, Department of Mineralogy, Geological Survey of Ceylon; ix + 75 pages; 11 figures; 12 plates.     

Ordovician system

Rocks in the Brungle‐Darbalara area of the Tumut Trough form two distinct domains: basement (mainly Bullawyarra Schist), of Cambrian‐Ordovician age, and an Ordovician ‐ Early Silurian sedimentary and volcanic cover sequence. These two domains are separated by a sharp discontinuity that marks an abrupt change in rock type, structure, metamorphic grade and deformation style. Cover sequences have undergone only one major penetrative deformation during the Late Silurian, involving sub‐greenschist facies metamorphism and upright folding. In contrast, the basement also underwent at least two older deformations at greenschist facies and contains distinct high‐strain zones subconcordant with the basement‐cover contact. The high‐strain zones, characterized by a ubiquitous south‐southeast trending mineral lineation, record a discontinuous history of ductile followed by brittle behaviour, consistent with an extensional origin.

The structural and metamorphic discontinuity separating basement from Silurian cover is characterized by widespread cataclasis and alteration and is interpreted as a major detachment fault associated with lithospheric extension and the development of the Tumut Trough in the Early Silurian. During the main period of movement on the detachment, which took place prior to intrusion of the Blacks Flat Diorite into the Bullawyarra Schist, mafic and serpentinized ultramafic rocks either were tectonically emplaced or intruded into the high strain zones. This preceded and accompanied extensional faulting of the cover and deposition of Silurian trough sediments and volcanics which unconformably overlie and onlap older units.

The development of the Tumut Trough, in the Brungle‐Darbalara area, bears many similarities with that of Cordilleran metamorphic core complexes. Such a model is consistent with environments suggested for the trough by previous workers. The south‐southeast extension direction parallels the trough‐bounding faults and implies an overall strike‐slip tectonic setting.     

Well vulnerability: a quantitative approach for source water protection

The concept of vulnerability of drinking water sources is reviewed, and a quantitative approach for assessing well vulnerability for complex three-dimensional ground water systems is developed. The approach focuses on the relative expected impact of potential contaminant sources at unknown locations within a well capture zone, providing relative measures of intrinsic well vulnerability, including the expected times of arrival of a contaminant, the dispersion-related reduction in concentration, the time taken to breach a certain quality objective, and the corresponding exposure times. Thus, the result of the analysis includes the usual advective travel time information used in conventional wellhead protection analysis, plus a set of selected quantitative measures expressing the expected impact. The technique is based on adjoint theory and combines forward- and backward-in-time transport modeling using a standard numerical flow and transport code. The methodology is demonstrated using the case study of a complex glacial multiaquifer system in Ontario. The new approach will be useful in helping water managers develop more physically based and quantitative wellhead protection strategies.     

A molecular stratigraphic approach to palaeoenvironmental assessment and the recognition of changes in source inputs in marls of the Mulhouse Basin (Alsace, France)

Principal components analysis (PCA) has been used to investigate changes in concentrations of the components of the hydrocarbon fractions extracted from 71 marl samples, selected to cover two total organic carbon (TOC) maxima in the lower part of the Salt IV formation, a Lower Oligocene evaporitic sequence from the Mulhouse Basin, France. The analysis indicates that the fractions can be ascribed as lying between two end member distributions. The changes in these distributions are gradual, suggesting that they resulted from fairly gradual changes in the depositional palaeoenvironment. These changes are related to increased algal productivity associated with the evolution of a restricted lacustrine environment through to one with a greater marine influence. Systematic variations in the concentrations of selected components relative to the TOC profile point to a repeated sequential evolution in the biological assemblage during deposition of the sequence.     

Analysis of steranes and triterpanes in geolipid extracts by automatic classification of mass spectra

A computer method is described for the automatic classification of triterpanes and steranes into gross structural type from their mass spectral characteristics. The method has been applied to the spectra obtained by GC-MS analysis of two mixtures of standards and of hydrocarbon fractions isolated from the Green River and Messel oil shales. Almost all of the steranes and triterpanes identified previously in both shales were classified, in addition to a number of new components. The results indicate that classification of such alkanes is possible with a laboratory computer system. The method has application to diagenesis and maturation studies, and to oil/oil and oil/source rock correlations, in which rapid screening of large numbers of samples is required.     

Evaluation of fractionation effects during the early stages of primary migration

A stepwise extraction technique, based on that of Beletskaya (1972), has been aplied to sedimentary rock samples of variable grain size and maturity from a Neogene sequence in the Pannonian Basin (S.E. Hungary). The resulting chloroform extracts, claimed by Beletskaya (1978) to sample “open” and mineralogically “closed” pores, have been analysed by gas chromatography and gas chromatography-mass spectrometry. Differences in the concentrations of the two extracts and the concentrations of their hydrocarbon fractions, and in the distributions of $\text{n}$-alkanes and steroid hydrocarbons suggest that either the “open” pores are impregnated with mature oil which has migrated from depth, or that movement of organic material from the “closed” to “open” pores occurs with considerable fractionation based on both polarity and molecular size. The implications of these differences for source rock-oil correlation studies are discussed and an assessment of mechanisms for primary migration is given.     

Laboratory Studies of the Hydrogen Kinetic Isotope Effects (KIES) of the Reaction of Non-Methane Hydrocarbons with the OH Radical in the Gas Phase

The hydrogen kinetic isotope effects (KIEs) of the reactions of 15 non-methane hydrocarbons (NMHCs) with the OH radical were measured at 298 ± 2 K. The measurements were made using NMHCs without artificial isotopic labeling or enrichment. The following average hydrogen KIE values, in per mil (), were obtained: 29.8 ± 2.1 (toluene),51.6 ± 2.1 (n-butane), 97.3± 12.5 (i-butane), 63.2 ± 5.9 (cyclopentane), 10.5 (p-xylene), 26.8 ± 3.5 (ethylbenzene), 65.9± 7.0 (n-pentane), 79.5 ± 9.6 (cyclohexane), 52.8 ± 5.0(n-hexane), 38.9 ± 7.8 (n-heptane), 33.4 ± 3.1 (n-octane), 29.6 ± 1.6(n-nonane), and 29.0 ± 5.3 (n-decane). The KIEs for reactions of two alkenes (cyclohexene and 1-heptene) could not be determined accurately due to interference from reaction with ozone, but nevertheless the results clearly show that the KIEs for reaction of alkenes with OH are significantly lower than those for saturated hydrocarbons. The KIEs for reaction of alkanes are smaller than isotope effects reported in literature for the reactions of NMHCs artificially labeled with deuterium. The main reason for this difference is the reduced probability for reaction at a labeled site for compounds with close to natural deuterium abundance, although some impact of secondary isotope effects cannot be ruled out. Still, the KIEs for NMHCs with natural or close to natural abundance of deuterium are of sufficient magnitude to allow determination of the extent of chemical processing of hydrocarbons in the atmosphere using methods analogous to stable carbon KIE studies. Furthermore, it is shown that combining stable hydrogen and stable carbon isotope ratio data has the potential to also provide valuable information regarding the stable isotope ratios of emissions, and specifically to test one of the key assumptions of the stable isotope hydrocarbon clock, the absence of significant variations of the stable isotope ratio for the emitted NMHCs.