Biomarker distributions in asphaltenes and kerogens analysed by flash pyrolysis-gas chromatography-mass spectrometry

Biomarker distributions in a suite of asphaltenes and kerogens have been analysed by flash pyrolysis directly coupled to a GCMS system. Attention has been focussed on biomarkers of the sterane and triterpane types. The sample suite under investigation consists of sediments with different kerogen types and some crude oils. Biomarker distributions in the pyrolysates have been compared with the “free” biomarkers in the corresponding saturated hydrocarbon fractions.The analyses show significant differences between the distributions of the free biomarkers and those in the pyrolysates. The latter have lower amounts of steranes while diasteranes are absent or present at low concentrations only. In the triterpane traces a shift of maximum intensity from C₃₀ (free compounds) to C₂₇/C₂₉ is observed. Furthermore, the pyrolysates contain a set of triterpenes (not present among the free compounds), and there is a selective loss of “non-regular” triterpanes that are present in the saturated hydrocarbon fractions. The observed differences between pyrolysates and free hydrocarbons can be explained partly by the processes occurring during pyrolysis such as bond rupture and subsequent stabilisation of primary pyrolysis products. To a certain extent these differences also show that maturation processes occurring in sediments have effects on free biomarker molecules different from those on molecules that are enclosed in a macromolecular matrix (kerogen or asphaltenes).Differences between biomarker distributions of asphaltene and kerogen pyrolysates are relatively small. A comparison with the pyrolysates from extracted whole sediments suggests that these differences are mainly caused by interactions between the organic material and the mineral matrix during pyrolysis.Oil asphaltenes behave differently from sediment asphaltenes as their pyrolysates are more similar to the corresponding saturated hydrocarbon fractions, i.e. the differences described above are observed to a much smaller extent. This different behaviour appears to be the result of coprecipitation of a part of the maltene fraction with the oil asphaltenes.     

ON THE USE OF MOVABLE-BED MODELS FOR RIVER PROBLEMS:A STATE-OF-THE-ART

I. INTRODUCTIONMore than a decade ago, under tile auspices of DELFT HYDRAULICS an overview on the use ofmodels for river problems was given (de Vries & van der Zwaard. 1975). Since then a better understanding of morphological processes in rivers has been obtained, their mathematical formulation hasbeen improved and computer facilities have been expended. Scale models and mathematical models arein use. but their field of application is gradually changing. It seems that the better ma…     

Land cover change and soil organic carbon stocks in the Republic of Ireland 1851–2000

Using both historic records and CORINE land cover maps, we assessed the impact of land cover change on the stock of soil organic carbon (SOC) in the Republic of Ireland from 1851 to 2000. We identified ten principal land cover classes: arable land, forest, grassland, heterogeneous agricultural areas/other, nonvegetated semi-natural areas, peatland, suburban, urban, water bodies, and wetland. For each land cover class, the SOC stock was estimated as the product of SOC density and land cover area. These were summed to calculate a national SOC budget for the Republic of Ireland. The Republic of Ireland’s 6.94 million hectares of land have undergone considerable change over the past 150 years. The most striking feature is the decrease in arable land from 1.44 million ha in 1851 to 0.55 million ha in 2000. Over the same time period, forested land increased by 0.53 million ha. As of 2000, agricultural lands including arable land (7.85%), grassland (54.33%), and the heterogeneous agricultural areas/other class (7.91%) account for 70.09% of Irish land cover. We estimate that the SOC stock in the Republic of Ireland, to 1 m depth, has increased from 1,391 Tg in 1851 to 1,469 Tg in 2000 despite soil loss due to urbanization. This increase is largely due to the increase of forested land with its higher SOC stocks when compared to agricultural lands. Peatlands contain a disproportionate quantity of the SOC stock. Although peatlands only occupy 17.36% of the land area, as of 2000, they represented 36% of the SOC stock (to 1 m depth).     

Theoretical organic geochemistry. I. The thermodynamic stability of several cholestane isomers calculated by molecular mechanics

The thermodynamic stabilities of thirteen cholestane isomers have been computed using molecular mechanics. The calculated composition of a mixture of these isomers at thermodynamic equilibrium is in agreement with the composition of a cholestane isomerate. From the calculated stabilities the extent to which isomerisation reactions can proceed during maturation can be predicted. The GLC retention order on non-polar phases of 20R/S isomeric pairs has been estimated from the preferred geometries of the molecules which are also obtained by molecular mechanics.     

Ohne Fallgewicht arbeitender Fernauslöser

A device is described which can be used where working equipment has to be instantly activated (i.e. without time delay) under water. The latch with an adjustable spring, on which the instrument is fastened, can be released by jerking on the supporting cable or by suddenly stopping the lowering motion, thereby instantly activating the working equipment.      

Increased heat fluxes near a forest edge

Summary ?Observations of sensible and latent heat flux above forest downwind of a forest edge show these fluxes to be larger than the available energy over the forest. The enhancement averages to 56 W m⁻², or 16% of the net radiation, at fetches less than 400 m, equivalent to fetch to height ratios less than 15. The enhancement of turbulent energy fluxes is explained by advection and increases with the difference in temperature and humidity of the air over the upwind area as compared to the forest. The relatively high temperature and humidity of the upwind air are not caused by high surface heat fluxes, but are explained by the relatively low aerodynamic roughness of the upwind surface. Although the heat fluxes over forest are enhanced, the momentum fluxes are almost adjusted to the underlying forest. The different behaviour of heat and momentum fluxes is explained by absorption of momentum by pressure gradients near the forest edge. It is concluded that fetch requirements to obtain accurate surface fluxes from atmospheric observations need to be more stringent for scalar fluxes as compared to momentum fluxes. Received November 23, 2001; accepted May 13, 2002     

Eine neue Netzgarnitur mit Kipp-Schliessmechanismus für quantitative Zooplanktonfänge in Seen

A new set of nets in twin arrangement for quantitative layer-sampling of crustaceans is presented and compared to a volume sampler, as regards capturing characteristics. Due to a favorable geometry and clearly defined opening of the net, there is no loss due to flight reaction nor water backup.      

Hemispheric Imaging of Galactic Neutral Hydrogen with a Phased Array Antenna System

The thousand element array (THEA) system is a phased array system consisting of 1 m² tiles having 64 Vivaldi elements each, arranged on a regular 8-by-8 grid, which has been developed as a demonstrator of technology and applicability for SKA. In this paper we present imaging results of Galactic neutral hydrogen with THEA. Measurements have been taken using a dense 2-by-2 array of four tiles as a four tile adder. The results are compared with results from the Leiden-Dwingeloo Survey, showing qualitative agreement, but also indicating that further studies are needed on the instrumental characteristics.     

Regionalization of heavy rainfall to improve climatic design values for infrastructure: case study in Southern Ontario,Canada

Abstract

Southern Ontario, Canada, has been impacted in recent years by many heavy rainfall and flooding events that have exceeded existing historical estimates of infrastructure design rainfall intensity–duration–frequency (IDF) values. These recent events and the limited number of short-duration recording raingauges have prompted the need to research the climatology of heavy rainfall events within the study area, review the existing design IDF methodologies, and evaluate alternative approaches to traditional point-based heavy rainfall IDF curves, such as regional IDF design values. The use of additional data and the regional frequency analysis methodology were explored for the study area, with the objective of validating identified clusters or homogeneous regions of extreme rainfall amounts through Ward's method. As the results illustrate, nine homogeneous regions were identified in Southern Ontario using the annual maximum series (AMS) for daily and 24-h rainfall data from climate and rate-of-rainfall or tipping bucket raingauge (TBRG) stations, respectively. In most cases, the generalized extreme value and logistic distributions were identified as the statistical distributions that provide the best fit for the 24-h and sub-daily rainfall data in the study area. A connection was observed between extreme rainfall variability, temporal scale of heavy rainfall events and location of each homogeneous region. Moreover, the analysis indicated that scaling factors cannot be used reliably to estimate sub-daily and sub-hourly values from 24- and 1-h data in Southern Ontario.

Citation Paixao, E., Auld, H., Mirza, M.M.Q., Klaassen, J. & Shephard, M.W. (2011) Regionalization of heavy rainfall to improve climatic design values for infrastructure: case study in Southern Ontario, Canada. Hydrol. Sci. J. 56(7), 1067–1089.