Waxes and asphaltenes in crude oils

High molecular weight (HMW) hydrocarbons (>C₄₀) and asphaltenes are important constituents of petroleum and can cause problems related to crystallization and deposition of paraffin waxes during production and transportation as well as in the formation of tar mats. However, traditional methods to isolate asphaltene fractions, by adding 40 volumes in excess of low boiling point solvents such as pentane, hexane or heptane, can produce asphaltene fractions which are contaminated with a significant amount of microcrystalline waxes (>C₄₀). The presence of these microcrystalline waxes in the asphaltene fractions has the potential to provide misleading and ambiguous results in modeling and treatment programs. The sub-surface phase behaviour of an asphaltene fraction will be quite different from that of a wax-contaminated asphaltene fraction. Similarly accurate modelling of wax drop-out requires information on pure wax fractions and not asphaltene-dominated fractions. Hence the goal of this paper is to describe a novel method for the preparation of wax-free asphaltene fractions. In addition, this method provides a quantitative subdivision of the wax fraction into pentane soluble and insoluble waxes which, when correlated with physical properties of crude oil such as viscosity, pour point, cloud point, etc., may help explain causes of wax deposition during production, transportation and storage of petroleum.     

Terrigenous plant wax inputs to the Arabian Sea: Implications for the reconstruction of winds associated with the Indian Monsoon

We have determined the accumulation rates and carbon isotopic compositions (δ¹³C) of long-chain (C₂₄-C₃₂) terrigenous plant wax fatty acids in 19 surface sediment samples geographically distributed throughout the Arabian Sea in order to assess the relationship between plant wax inputs and the surrounding monsoon wind systems. Both the accumulation rate data and the δ¹³C data show that there are three primary eolian sources of plant waxes to the Arabian Sea: Africa, Asia, and the Arabian Peninsula. These sources correspond to the three major wind systems in this region: the summer (Southwest) monsoon, the winter (Northeast) monsoon, and the summer northwesterlies that blow over the Arabian Peninsula. In addition, plant waxes are fluvially supplied to the Gulf of Oman and the Eastern African margin by nearby rivers. Plant wax δ¹³C values reflect the vegetation types of the continental source regions. Greater than 75% of the waxes from Africa and Asia are derived from C₄ plants. Waxes delivered by northwesterly winds reflect a greater influence (25-40%) of C₃ vegetation, likely derived from the Mesopotamian region. These data agree well with previously published studies of eolian dust deposition, particularly of dolomite derived from the Arabian Peninsula and the Mesopotamian region, in surface sediments of the Arabian Sea. The west-to-east gradient of plant wax δ¹³C and dolomite accumulation rates are separately useful indicators of the relationship between the northwesterly winds and the winds of the Southwest monsoon. Combined, however, these two proxies could provide a powerful tool for the reconstruction of both southwest monsoon strength as well as Mesopotamian aridity.     

A back-of-the-envelope approach to boudinage mechanics

Smith has shown from linear hydrodynamic stability that pinch-and-swell boudinage is possible only in a non-Newtonian material. By assuming uniaxial stress and strain and large viscosity contrast between the competent layer and the incompetent matrix, Smith's result can be derived in a very simple way. The one-dimensional force balance also predicts growth rates, although not dominant wavelengths. However, we question the ability of even linear stability analysis to accurately predict boudin widths.     

Fault-related fold kinematics recorded by terrestrial growth strata,Sant Llorenç de Morunys,Pyrenees Mountains,NE Spain

Foreland basin growth strata are ideal recorders of deformation rates and kinematics in tectonically active regions. This study develops a high-resolution chronostratigraphic age model to determine folding rates in the Eocene-Oligocene terrestrial growth strata of the Berga Conglomerate Group, NE Spain. The Berga Conglomerate Group was sampled for rock magnetic, magnetostratigraphic, and magnetic susceptibility (χ) cyclostratigraphy analyses. Analysis of rock magnetic measurements indicate a mixed mineral assemblage with both paramagnetic and ferromagnetic minerals. A new magnetic reversal stratigraphy constrains the time frame of folding and is in agreement with previous interpretations. Time series analysis of χ variations show statistically significant power at expected orbital frequencies and provides precession-scale (20 kyr) temporal resolution. Strain measurements including anisotropy of magnetic susceptibility (AMS) fabrics and bedding plane strain worm burrow distortion are consistent with fixed hinge, flexural folding kinematics. Fault-related folding was modeled using χ cyclostratigraphy timing and strain measurement kinematic constraints. The onset of folding was at 33.85 Ma and the end of deformation is less constrained but is younger than 31.06 Ma. Deformation and sediment accumulation rates are unsteady at 20 kyr time scales but appear artificially steady at polarity chron time scales.     

Biomarker lipids of the freshwater fern Azolla and its fossil counterpart from the Eocene Arctic Ocean

Eocene sediments recovered from the Lomonosov Ridge in the central Arctic Ocean during Integrated Ocean Drilling Program Expedition 302 contain high amounts of fossil remains of the free floating freshwater fern Azolla. Both extant Azolla and the sediments from the Arctic Azolla interval were found to contain relatively high quantities of compounds identified as 1,ω20 C₃₀–C₃₆ diols. Furthermore, structurally related mid-chain hydroxy fatty acids, long chain n-alkanols and keto-ols were discovered. The different series have a common feature: there is always a hydroxy group at the ω20 position. In addition, structurally related C₂₉ ω20,ω21 diols, C₂₉ 1,20,21 triols, C₂₉ dihydroxy fatty acids as well as a series of wax esters containing these mono- and dihydroxy lipids are reported. Selective extraction of Azolla surface lipids revealed that these compounds are most likely present in the leaf waxes of the fern. The suite of long-chain, mid-chain ω20 hydroxy wax constituents is described for the first time. As they are well preserved in the Eocene sediments, these lipids may serve as palaeo-environmental indicators of the Arctic Azolla interval and as markers for the past occurrence of Azolla in general.     

Spatial gradients in plant leaf wax D/H across a coastal salt marsh in southern California

Coastal salt marsh ecosystems contain strong environmental gradients that are anticipated to influence the D/H ratios recorded in the leaf waxes of salt-tolerant plants. We characterized the molecular and hydrogen isotopic composition of alkanes in plant and sediment samples as well as the D/H ratios of environmental and plant waters across an elevation and inundation gradient in a southern Californian, coastal salt marsh. We sampled the dominant salt marsh plant species: Salicornia virginica, Arthrocnemum subterminale and Jamuea carnosa (all succulents), as well as Monanthochloe littoralis and Limonium californicum (nonsucculents). Plant xylem water hydrogen isotopic compositions indicate a shift in source waters from meteoric influences at upland sites (δD value −20‰) to seawater dominated values (0‰) at lowland areas. We found leaf water D enrichment relative to xylem water ranging from mean δD values of +54‰ (upland) to +28‰ (lowland), interpreted as a reduction of transpiration with increasing inundation time. This has the effect of increasing the net fractionation between source water and leaf wax product across the environmental gradient from mean values of −101‰ (upland) to −134‰ (lowland), with an attenuated signal recorded in the δD values of plant leaf wax n-alkanes (−122‰ to −136‰). These results constrain the hydrogen isotopic composition of salt marsh organic matter that may contribute to marine carbon budgets of the Santa Barbara Basin, and further indicate the potential for plant leaf waxes to resolve paleoenvironmental change, including sea level change, in sediment cores from salt marsh ecosystems.     

Identification of biogenic paraffins and their thermal phase transitions

Natural normal paraffin hydrocarbons C _n H_{2n + 2} (n = 17–41) of a biological origin were investigated in terms of their composition, structure, polymorph modification, and thermal phase transition. Paraffin compositions were studied from beeswax (honeycombs and their cappings), plant wax (apple and pumpkin rinds), as well as from different parts of rat cerebrum (cortex, subcortex, brainstem, cerebellum, cerebral hemispheres, myelin, chromatin, etc.). X-ray diffraction analysis (XRD), chromatography, and high-temperature XRD, as well as original analytical methods elaborated upon by the authors, were used. The beeswax paraffin composition that corresponds to the six-component solid solution with a superperiodic four-layer orthorhombic cell was subjected to experimental modeling for the first time. The prepared mixture simulated a paraffin composition (n = 23, 25, 27, 29, 31, 33) and the asymmetric distribution of homologues by n.     

Distribution patterns and stable carbon isotopic composition of alkanes and alkan-1-ols from plant waxes of African rain forest and savanna C3 species

Leaf wax components of terrestrial plants are an important source of biomass in the geological records of soils, lakes and marine sediments. Relevant to the emerging use of plant wax derived biomarkers as proxies for past vegetation composition this study provides key data for C₃ plants of tropical and subtropical Africa. We present analytical results for 45 savanna species and 24 rain forest plants sampled in their natural habitats. Contents and distribution patterns of long chain n-alkanes (n-C₂₅ to n-C₃₅) and n-alkan-1-ols (n-C₂₄ to n-C₃₄) as well as bulk and molecular carbon isotopic data are presented. The variations of the analysed parameters among different growth forms (herb, shrub, liana and tree) are small within the vegetation zones, whereas characteristic differences occur between the signatures of rain forest and savanna plants. Therefore, we provide averaged histogram representations for rain forest and savanna C₃ plants.The findings were compared to previously published data of typical C₄ grass waxes of tropical and subtropical Africa. Generally, trends to longer n-alkane chains and less negative carbon isotopic values are evident from rain forest over C₃ savanna to C₄ vegetation. For n-alkanols of rain forest plants the maximum of the averaged distribution pattern is between those of C₃ savanna plants and C₄ grasses. The averaged presentations for tropical and subtropical vegetation and their characteristics may constitute useful biomarker proxies for studies analysing the expansion and contraction of African vegetation zones.     

Structural pattern and strain history of a superposed fold system in the Precambrian of Central Rajasthan,India. II. Strain history

Analysis of shapes of folds, together with other structures such as axial plane foliation boudinage, mullions and cross joints, show that the F₁ folds in the ‘main Raialo syncline’ were formed by buckling, and were subsequently modified by flattening normal to the axial planes and lengthening along the axis. The apparent buckle shortening of the F₁ folds generally ranges between 70 and 80%. The folds were formed by simple shear (giving place to pure shear at certain stages) in an almost north-south direction on subhorizontal beds. Progressive deformation in the later stage of F₁ folding resulted in gentle upright folding of F₁ axial planes on F₁′ axes slightly oblique to F₁. The F₂ folds, whose average shortening ranges from 20 to 30%, were also formed by buckling caused by horizontal compression in a nearly northwest-southeast direction. This folding was preceded and followed in some instances by homogeneous strain, as deduced fro mthe shapes of the F₂ folds and the nature of variation of the F₁ lineations. The F₃ conjugate structures developed when the maximum compressive strain was vertical and the intermediate compressive strain northwest-southeast, almost normal to the subvertical F₂ axial planes. The increase in the amplitude of the F₂ folds in the last phase of F₂ folding in certain zones resulted in an excess of vertical load, which dissipated with the formation of the F₃ structures. In the last stage of movement (F₄) the maximum compressive strain became horizontal along the strike of F₂ axial planes, whereas the minimum compressive strain was normal to them. The F₄ structures, therefore, point to a longitudinal shortening with reference to large scale F₂ folding.     

Variation in n-alkane δD values from terrestrial plants at high latitude: Implications for paleoclimate reconstruction

The molecular hydrogen isotope composition (δD) of leaf waxes from terrestrial plants is increasingly used to infer hydrological characteristics of ancient high latitude climates. Analysis of the hydrogen isotope composition of n-alkanes (δD_n-alkane) from a global dataset of individual plants growing at low and middle latitudes indicates that plant ecological life form is an important factor in determining the hydrogen isotope fractionation. However, environmental and biological controls of high latitudinal leaf wax δD values are poorly understood because of a lack of δD records from modern flora in these regions. We previously noticed smaller apparent hydrogen isotope fractionations between n-alkanes and environmental water (ε_alk-water) in deciduous trees growing at high latitudes (>59°N; Liu, W.-G., Yang, H., 2008. Multiple controls for the variability of hydrogen isotopic compositions in higher plant n-alkanes from modern ecosystems. Global Change Biology 14, 2166-2177.) To further examine these issues, we measured δD_n-alkane from a variety of plants that inhabit high latitude environments and added critically needed leaf wax δD data from grass and herbs to the existing global δD_n-alkane database. Inclusion of these new data with the existing global dataset (n = 408) confirms plant ecological life form as an important control for leaf wax δD variation for terrestrial plants living at high latitudes. Our results suggest that, while precipitation δD is captured in these high latitude plants, physiological characters such as leaf area, venation pattern and hydraulic system, that enhance transpiration rate during summer growth, may impart δD_n-alkane differences among plants with different ecological life forms.     

An automated machine for pure shear deformation of analogue materials in plane strain

A plane strain, pure shear rig has been developed for the deformation of rock-analogue materials under tightly controlled experimental conditions. Shortening of up to 42% is possible, with constant natural strain rates and a predetermined confining side stress (σ₃). Differential stress, side stress, temperature and strain rate are recorded during the experiments, allowing rheological calibration under exactly the same conditions used in the applied studies of mechanical instabilities (folds, boudinage, etc.). The relatively large specimen size, three-piece side plate design and the extensive use of low-friction facing materials in contact with the model result in boundary conditions which closely approximate plane strain, pure shear.     

The metamorphic and structural evolution of the Phyllite-Quartzite Nappe of western Crete

The Phyllite-Quartzite (PQ) Nappe constitutes an external, allochthonous complex of the Hellenides on the island of Crete and shows a polyphase structural history. A first phase of deformation (F 1) produced recumbent isoclinal folds, a penetrative schistosity, and boudinage under high-P/low-T metamorphic conditions. Mylonite formation at the top of the PQ Nappe, below the overriding Tripolitza Nappe, further boudinage, and schistosity (S 2) represent a late tectono-metamorphic episode. Post-metamorphic small folds (F 3), lineations, and a crenulation cleavage were formed synchronously with transport of the PQ Nappe. A last phase (F 4) developed small folds, a fracture/crenulation cleavage, and large-scale folds after nappe movement. It is suggested that high-P/low-T metamorphism in the PQ rocks originated during subduction. Nappe transport of the higher, unmetamorphosed units, which were thrust over the PQ Nappe, began under waning metamorphic conditions. Subsequent transport of the PQ Nappe itself also occurred after the completion of metamorphism and after the formation of the mylonite at its top.     

Strain-dependent rheology and the memory of plasticine

Plasticine and plasticine-like materials have been widely used as analogue materials for experimental deformation, but not many workers have conducted detailed investigations on their rheology. The physical properties of Beck's green and black plasticine, a modelling material made in Gomaringen, Germany, and plasticine/oil mixtures were investigated by means of uniaxial compression and relaxation tests. Beck's plasticine is a non-Newtonian fluid characterised by strain rate-dependent plastic yielding and strain hardening. Strain hardening is more pronounced at low strain rates leading to an increase of both stress exponent and viscosity. The addition of oil leads to an increase of the stress exponent and a decrease in viscosity. The strain dependence of viscosity decreases with increasing oil content. Compression tests on preflattened plasticine were also conducted in order to study possible ‘strain memory’ of the materials. Preflattened plasticine is characterised by a later onset of yielding and an increase in both stress exponent and viscosity. Our results suggest that Beck's green and black plasticine is a suitable analogue material for modelling rocks that deform by dislocation creep and exhibit pronounced strain hardening. Nevertheless, plane strain modelling of boudinage has verified analytical solutions for the dominant wavelength at viscosity contrasts of approximately 1.5 and 2.5.     

北京西山膨缩石香肠流变性质构造研究初探

本文探索了利用膨缩石香肠构造定量估测古岩石流变参数的方法,获得北京西山云母大理岩中的方解石石英脉的应力指数在3.06-7.69之间,与云母大理岩的粘度比在8.74-20.27之间;板岩中的石英脉的应力指数在2.57-4.75之间,与板岩的粘度比在94.8-175.8之间;白云岩中硅质条带的应力指数在2.25-3.93之间,与白云岩的粘度比在2.38-4.26之间.      

Geometrical relationships between unconformities and subsequent folding: the Arro fold system (southern Pyrenees)Relations entre discordances et plissement dans le système de plis et chevauchements d'Arro (bassin de Graus-Tremp,Pyrénées)

The Arro system is an oblique fold system involving the Eocene sediments of the Graus-Tremp basin. It consists of westward-verging folds, trending NNW–SSE, some of them related with thrusts, in piggyback sequence. Seismic profiles allow to infer the geometry of structures at depth: folds and thrusts are ‘decolled’ over an unconformity between turbiditic and platform sediments. Re-activation of bedding surfaces by folding in the underlying units resulted in folding and thrusting in the upper series. To cite this article: A.M. Casas et al., C. R. Geoscience 334 (2002) 765–772.     

Controls on the D/H ratios of plant leaf waxes in an arid ecosystem

The extent to which leaf water D-enrichment (transpiration) and soil water D-enrichment (evaporation) affect the D/H ratio of plant leaf waxes remains a contentious issue, with important implications for paleohydrologic reconstructions. In this study we measure δD values of precipitation (δD_p), groundwater (δD_gw), plant xylem water (δD_xw) and leaf water (δD_lw) to understand their impact on the δD values of plant leaf wax n-alkanes (δD_wax) in an arid ecosystem. Our survey includes multiple species at four sites across an aridity gradient (80-30% relative humidity) in southern California.We find that many species take up groundwater or precipitation without significant fractionation. D-enriched soil water is a minor source even in species known to perform and utilize waters from hydraulic lift, such as Larrea tridentata (+10‰). Measurements of leaf water isotopic composition demonstrate that transpiration is an important mechanism for D-enrichment of leaf waters (+74 ± 20‰, 1σ), resulting in the smallest net fractionation yet reported between source water and leaf waxes (L. tridentata −41‰; multi-species mean value is −94 ± 21‰, 1σ). We find little change in leaf water D-enrichment or net fractionation across the climatic gradient sampled by our study, suggesting that a net fractionation of ca. −90‰ may be appropriate for paleohydrologic reconstructions in semi-arid to arid environments. Large interspecies offsets in net fractionations (1σ = 21‰) are potentially troublesome, given the observed floristic diversity and the likelihood of species assemblage changes with climate shifts.     

Stress and displacement analysis of boudinages by the finite-element method

The paper deals with the displacement and stress distribution in boudinage structures. To analyze this, the finite-element method is used. Four models are examined.The first model treats three homogeneous bands. The displacement of the central band produces a barrel-shaped structure. The tension is greatest in the central part of this band and decreases almost continuously towards the shorter edges. If the band ruptures, the rupture will occur in the central part.The second model treats a quarter of a total structure that is already in part a developed boudinage. This development is followed through 19 iterative steps. The displacement analysis demonstrates that the boudin is displaced towards the free short edge and becomes more barrel-shaped, thinner and wider. The mean stress has two, local, tensilestress maxima inside the boudin at the upper boundary: one in the gap area and the other in the matrix at the outer, short edge of the boudin.The third model treats a quarter of a developed boudinage with two materials in the matrix. Displacement analyses demonstrate that the barrel shape of the boudin becomes more pronounced when the competence contrast between boudin and matrix decreases.One axis of principal stress has a direction in every element close to the x-axis of the model. In the area marked PbS (model 6A), this axis shows a local tensile-stress maximum and a local compressive-stress maximum. In model 6B, these points are still extreme points, but the local compressive-stress maximum has changed to a local tensile-stress maximum.The fourth model treats a boudinage in which one boudin is rotated. Displacement analyses demonstrate that the boudins tend to rotate to a position in which they are parallel, diverging a little from a right angle to the angle of the applied pressure. The mean stress demonstrates a pressure shadow in the PbS area, with a slight displacement downwards in the area beside the rotated boudin.The stress distribution corresponds to the mineral distribution of the boudinage from the Udden Mine. The investigation indicates a direct relationship between grain size and stress distribution.     

Characterization of high molecular weight biomarkers in crude oils

High-temperature gas chromatography (HTGC) has enhanced our ability to characterize hydrocarbons extending to C₁₂₀ in crude oils. As a result, hydrocarbons in waxes (> C₂₀) have been observed to vary significantly between crude oils, even those presumed to originate from the same source. Prior to this development, microcrystalline waxes containing hydrocarbons above C₄₀ were not characterized on a molecular level due to the analytical limitations of conventional gas chromatography. Routine screenings of high pour-point crude oils by high-temperature gas chromatography has revealed that high molecular weight hydrocarbons (> C₄₀) are very common in most oils and may represent 2% of the crude oil. Precise structures, origins, and significance of these high molecular weight compounds remain elusive. As a preliminary step to expand our knowledge of these compounds their general molecular structures and formulas have been investigated in this study. Initial results suggest that the major high molecular weight compounds include a homologous series of n-alkanes, methylbranched alkanes, alkylcyclopentanes, alkylcyclohexanes, alkylbenzenes and alkylcycloalkanes.     

Analytical solutions for the capture zone of a pumping well near a stream

The capture zone for a fully penetrating well in an aquifer with regional flow to a stream boundary under steady-state conditions was delineated using complex algebra and image well theory. Regional flow in the aquifer was allowed to take different directions relative to the stream axis. Two critical pumping rates, Q _C1 and Q _C2, produce three capture-zone pattern scenarios: (1) at low pumping rates (Q?<?Q _C1) water is solely withdrawn from the aquifer and no water from the stream enters the aquifer, (2) at medium pumping rates (Q _C1?<?Q?<?Q _C2) a portion of stream water enters the aquifer but it is not captured by the well, and (3) at high pumping rates (Q?>?Q _C2) pumped water is supplied from both the aquifer and the stream with different proportions. For the second and third scenarios, the stream length interval through which stream water enters the aquifer was determined and found to be more sensitive to pumping rate as the regional flow direction approaches the stream axis. The portion of pumped water supplied by the stream was determined in the third scenario. Finally, the capture-zone asymmetry with respect to its axial line was delineated.