Molecular simulation of temperature-programmed desorption

We use accelerated molecular dynamics to probe the thermal desorption of n-alkanes from the Au(1 1 1) and C(0 0 0 1) surfaces. Studying an alkane series ranging from CH₄ to C₁₆H₃₄, we find that the desorption prefactor increases with increasing chain length for the short chains until a certain chain length is reached when it becomes essentially constant and independent of chain length. We can understand the dependence of the preexponential factor on alkane chain length in terms of conformational changes within the alkane molecules. For the shorter molecules, the desorption temperatures probed in experimental temperature-programmed desorption studies lie below those for which torsional motion is activated. Thus, the short alkanes can be treated as rigid rods, and the loss in translational and rotational entropy upon adsorption leads to a preexponential factor that increases with increasing chain length. As the alkane chain length increases, the binding energy and the experimental desorption temperatures also increase. Thus, torsional motion is activated to an extent that increases with increasing chain length. This torsional activation increases the entropy of adsorption and counteracts the entropy decrease due to a loss of translation and rotation. This leads to a virtually constant prefactor for sufficiently long chains. Our findings are consistent with experimental data for the thermal desorption of alkanes from the Au(1 1 1), Pt(1 1 1), MgO(1 0 0) and C(0 0 0 1) surfaces.     

Oil Families and Their Potential Sources in the Southern Gulf of Suez, Egypt

Four oil families are identified in the southern Gulf of Suez, through high-resolution geochemical studies including gas chromatography, gas chromatography-mass spectrometry, and carbon isotope analyses. Biological features characterize oils in family 1a, suggesting tertiary carbonate source rocks for these oils, rich in type II organic matter and deposited under anoxic depositional environment. Family 1b oil shows minor variations in the source of organic matter and the depositional environment, as it was derived from carbonate source rock with more algal and bacterial contribution and minor input of terrestrial organic sources, deposited under less saline condition compared to family 1a oil. Family 2 oil, although genetically related to family 1a oil, has some distinctive features, such as diasterane to sterane and pristane to phytane ratios, which suggest clay-rich source rocks and a more oxic depositional environment. Also, the lack of oleanane indicates pre-tertiary source rocks for this oil. In contrast, family 3 oil is of mixed sources (marine and non-marine), generated from low sulfur and clay-rich source rock of tertiary and/or younger age. Family 4 oil seems to be mixed from family 1b and family 3 oils, sourced mainly from carbonate source rocks rich in clay minerals with algal and bacterial contributions. Family 4 oil is highly mature, family 1b oil lies within equilibrium values (peak oil generation stage), while the other families are more or less near equilibrium.     

Applications of biological markers in assessing the organic richness of the surface sediments of Suez Gulf,Egypt

The semienclosed Suez Gulf records various signals of high anthropic pressures from surrounding regions and the industrialized Suez countries. The sedimentary hydrocarbons have been studied in six coastal stations located in the Gulf of Suez. Nonaromatic hydrocarbons were analyzed by GC/FID and GC/MS to assess organic content in surface sediments of Suez Gulf, Egypt, depending on alkane, terpane, and sterane biological marker indicators. The results showed that the hydrocarbons are originated from multiple terrestrial inputs, biogenic and pyrolytic. Several ratios hydrocarbons indicated the predominance of petrogenic in combination with biogenic hydrocarbons.     

A correlation for predicting diffusion coefficients in alkanes

A correlation was developed for predicting limiting mutual diffusion coefficients of gaseous and liquid solutes in normal alkane solvents with carbon numbers ranging from 7 to 28 at temperatures to 570 K. The functional form of the correlation is based on the rough hard sphere theory. The parameters needed in the correlation are the molecular weights and hard sphere diameters of the solute and solvent molecules and molar volume of the solvent. The data used in the development of the correlation included 143 measurements with solute/solvent molecular mass ratios ranging from 0.005 to 2.26 and size ratios ranging from 0.3 to 1.3. The average absolute error in predictions was only 6.3%. When the correlation was used to predict literature values for binary n-alkane systems, the average absolute error was 16.7%.     

Plant tolerance to diesel minimizes its impact on soil microbial characteristics during rhizoremediation of diesel-contaminated soils

Soil contamination due to petroleum-derived products is an important environmental problem. We assessed the impacts of diesel oil on plants (Trifolium repens and Lolium perenne) and soil microbial community characteristics within the context of the rhizoremediation of contaminated soils. For this purpose, a diesel fuel spill on a grassland soil was simulated under pot conditions at a dose of 12,000 mg diesel kg^− 1 DW soil. Thirty days after diesel addition, T. repens (white clover) and L. perenne (perennial ryegrass) were sown in the pots and grown under greenhouse conditions (temperature 25/18 °C day/night, relative humidity 60/80% day/night and a photosynthetic photon flux density of 400 μmol photon m^− 2 s^− 1) for 5 months. A parallel set of unplanted pots was also included. Concentrations of n-alkanes in soil were determined as an indicator of diesel degradation. Seedling germination, plant growth, maximal photochemical efficiency of photosystem II (F_v/F_m), pigment composition and lipophylic antioxidant content were determined to assess the impacts of diesel on the studied plants. Soil microbial community characteristics, such as enzyme and community-level physiological profiles, were also determined and used to calculate the soil quality index (SQI). The presence of plants had a stimulatory effect on soil microbial activity. L. perenne was far more tolerant to diesel contamination than T. repens. Diesel contamination affected soil microbial characteristics, although its impact was less pronounced in the rhizosphere of L. perenne. Rhizoremediation with T. repens and L. perenne resulted in a similar reduction of total n-alkanes concentration. However, values of the soil microbial parameters and the SQI showed that the more tolerant species (L. perenne) was able to better maintain its rhizosphere characteristics when growing in diesel-contaminated soil, suggesting a better soil health. We concluded that plant tolerance is of crucial importance for the recovery of soil health during rhizoremediation of contaminated soils.     

Polymer-cosolvent systems: 5. Upper and lower critical solution temperatures of polystyrene in n-alkanes

The demixing behaviour of low molecular weight polystyrene in three n-alkanes (hexane, heptane and octane) has been established. Critical solution behaviour is a function of alkane chain length, and application of free volume theory shows this to be an entropic effect. The quality of n-alkanes, up to twenty carbons in length, as solvents for polystyrene has been estimated.     

正构烷烃单体烃的氢同位素分析方法及应用

以渤海湾盆地东营凹陷古近系沙河街组烃源岩及原油为研究对象,通过气相色谱仪—GC/TC接口—同位素质谱仪的联用,构建了正构烷烃单体烃氢同位素在线分析方法,对正构烷烃的单体烃氢同位素组成进行了测定,揭示了不同沉积环境中氢同位素的组成特征。沙四上亚段烃源岩的正构烷烃单体烃氢同位素组成较重,分布于-161‰^-111‰,沙三下亚段烃源岩的氢同位素组成较轻,分布在-186‰^-134‰,指示了从微咸水到咸水的沉积环境,随着沉积环境水体盐度的增加,氢同位素值具有明显变重的趋势,成熟度差异较大的样品,其氢同位素组成的差异相对较小。表明在正常生油窗范围内,正构烷烃单体烃的氢同位素受成熟度影响相对较小,主要与母质来源和沉积环境有关,可为油源对比、母质来源和古沉积环境判识提供科学依据。     

Correlating and Predicting the Solubilities of Solid n-Alkanes in Supercritical Ethane Using Carnahan-Starling-van der Waals Model

The solubilities of some solid n-alkanes in supercritical ethane were correlated and predicted in this paper using the Carnahan-Starling-van der Waals model with a density-dependent parameter of a12. At a given temperature, the linear fit of the parameter of a12 and the density of the supercritical solvent was used for solubility correlation, resulting in an average absolute average relative deviation（AARD） of 8.68%, which was between the values of the semiempirical models and the other compressed gas models used in this article. In the linear fit of the parameter of a12 and the density of the solvent, the regressed slope m and intercept n of the linear fit can be correlated with the carbon atom number of solid n-alkanes and then the solubilities of solid n-alkanes in supercritical ethane can be predicted with the intercept n and slope m. The average AARD in solubility prediction was 26.99%.     

优化温度相关力场预测正构烷烃热力学性质

为了实现不同温度下正构烷烃及其混合物热力学性质的准确预测,以正构烷烃（n-C₄~C₁₀）为训练集,通过对全原子OPLS-AA力场中非键相互作用参数（ε）的模拟优化,得到了ε与对比温度（T_r）以及正构烷烃碳原子个数（N_C）的经验关系式。利用该关系式计算出不同温度不同种类的正构烷烃的ε值,预测了正构烷烃纯物质及其混合物的黏度、密度、扩散系数等物性,并将新力场模拟计算值与理论估算值以及实验值进行比较。结果表明,采用优化温度相关力场预测烷烃及其混合物的物性与实验值最为吻合。密度、黏度和扩散系数的预测值与实验值的相对偏差分别小于2%、5%和10%,显著优于目前的理论方法和原OPLS-AA力场模拟计算的预测值。上述温度相关力场参数的确立,对于利用分子动力学模拟方法准确地预测正构烷烃及其混合物的热力学性质具有重要的实际应用价值。