Sand production remains a huge obstacle in many oil and gas fields around the world, but the hazards of contaminants riding on the produced sand are often not emphasised. Improper disposal of the sand could see the toxic leaching into the environment including the food chain, endangering all living organisms. The impending sand production from an oilfield offshore Sabah also suffers from the lack of hazards identification; hence, this study was conducted to assess the contaminant on the produced sand. Sand samples were collected from multiple wells in the area, with the contaminants extracted using n-hexane and subjected to chemical and thermal analyses. FTIR and GC-MS detected traces of harmful pollutants like naphthalene, amine substances, cyclohexanol, and short-chain alkanes. It was discovered that the volatile fraction of the contaminants was able to evaporate at 33 °C, while high energy was needed to remove 100% of the contaminants from the sand. Overall, the produced sand from the oilfield was unsafe and required treatment before it could be dumped or used.
A systematic process is introduced to compare (13)C NMR spectra of two (or more) candidate samples of known structure to a natural product sample of unknown structure. The process is designed for the case where the spectra involved can reasonably be expected to be very similar, perhaps even identical. It is first validated by using published (13)C NMR data sets for the natural product 4,6,8,10,16,18-hexamethyldocosane. Then the stereoselective total syntheses of two candidate isomers of the related 4,6,8,10,16-pentamethyldocosane natural product are described, and the process is applied to confidently assign the configuration of the natural product as (4S,6R,8R,10S,16S). This is accomplished even though the chemical shift differences between this isomer and its (16R)-epimer are only ±5-10 ppb (±0.005-0.01 ppm).
The distribution of aliphatic hydrocarbons in three sediment cores from Brunei Bay was investigated in order to understand their sources and the biogeochemical processes of these hydrocarbons. The total concentrations of C15 to C37n-alkanes ranged from 0.70 to 16.5 μg g-1. Traces of hopanes with C29-C31 carbon homologs were detected in the study area. The carbon preference index (CPI15-37) ranged from 1.23 to 3.42 coupled with the natural n-alkane ratio (NAR19-32) ratios (1.52 to 5.34), and the presence of unresolved complex mixtures and hopanes, suggested slight contamination by anthropogenic hydrocarbons, presumably derived from activities along the coasts. The presence of C27 trisnorhopene and diploptene, as well as their association with long-chain and short-chain n-alkanes, revealed a depositional environment of organic matter in the sediment cores.
Waxy crude oil is a problem to the oil and gas industry because wax deposition in pipelines reduces the quality of the crude oil. Currently, the industry uses chemicals to solve the problem but it is not environmentally friendly. As an alternative, the biodegradation approach is one of the options. Previously eleven thermophilic bacteria were isolated and exhibited high ability to degrade hydrocarbon up to 70% of waxy crude oil. However, despite the successful study on these single bacteria strains, it is believed that biodegradation of paraffin wax requires more than a single species. Five consortia were developed based on the biodegradation efficiency of 11 bacterial strains. Consortium 3 showed the highest biodegradation (77.77%) with more long-chain alkane degraded throughout the incubation compared to other consortia. Enhancement of hydrocarbon degradation was observed for all consortia especially in long chain alkane (C18-C40). Consortium 3 exhibited higher alkane monooxygenase, alcohol dehydrogenase, lipase, and esterase activities. Moreover, the dominant bacteria in the consortia were determined by denaturing gradient gel electrophoresis (DGGE), which showed the domination of genera Geobacillus, Parageobacillus, and Anoxybacillus. It can be concluded that the bacterial consortia showed higher biodegradation and improved degrading more long-chain hydrocarbon compared to a single isolate.
We have designed new derivatives of naphtha [2 ,1-b:6 ,5-13V difuran as DPNDF-CN1 and DPNDF-CN2. The molecular structures of DPNDF, its derivatives DPNDF-CN1 and DPNDF-CN2 have been optimized at the ground (So) and first excited (S1) states using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), respectively. Then the highest occupied molecular orbitals (HOMOs), the lowest unoccupied molecular orbitals (Lumos), photoluminescence properties, electron affinities (EELS), reorganization energies (.1.$) and ionization potentials (iPs) have been investigated. The balanced A(h) and A(e) showed that DPNDF, DPNDF-CN1 and DPNDF-CN2 would be better charge transport materials for both hole and electron. The effect of attached acceptors on the geometrical parameters, electronic, optical and charge transfer properties have also been investigated.
In the title adduct, 1,3,5,7-tetraazatricyclo[3.3.1.1(3,7)]decane-4-nitrobenzene-1,2-diol-water (1/2/1), C(6)H(12)N(4).2C(6)H(5)NO(4).H(2)O, the hexamethylenetetramine molecule acts as an acceptor of intermolecular O-H.N hydrogen-bonding interactions from the water molecule and the hydroxy groups of one of the two symmetry-independent 4-nitrocatechol molecules. The structure is built from molecular layers which are stabilized by three intermolecular O-H.O, two intermolecular O-H.N and four intermolecular C-H.O hydrogen bonds. The layers are further interconnected by one additional intermolecular O-H.N and two intermolecular C-H.O hydrogen bonds.
Adulteration of lard with other fats and oils in food production affects many areas including economics, religion, and health. Previous studies discriminated lard based on major components of fats, i.e. triglycerides and fatty acids. This study aimed to differentiate lard and other animal fats (beef, chicken and mutton fat) based on n-alkane profiles established by gas chromatography-mass spectrometry (GC-MS). Principal Component Analysis (PCA) and Hierarchical Clustering Analysis (HCA) were able to initiate clustering of lard and other animal fats. Good result was obtained using Random Forest (RF) and Partial Least Squares-Discriminant Analysis (PLS-DA). Statistical models propose tetracosane (C24) as a potential n-alkane marker and it was found that C24 was the major alkane with composition of 15.72% (GC-MS) of total alkanes identified. Based on this finding, more interesting study may potentially be explored for the interest of various fats and oils consumers in vast applications especially using chemometrics analysis.
The seasonal variation of petroleum pollution including n-alkanes in surface sediments of the Selangor River in Malaysia during all four climatic seasons was investigated using GC-MS. The concentrations of n-alkanes in the sediment samples did not significantly correlate with TOC (r = 0.34, p > 0.05). The concentrations of the 29 n-alkanes in the Selangor River ranged from 967 to 3711 µg g-1 dw, with higher concentrations detected during the dry season. The overall mean per cent of grain-sized particles in the Selangor River was 85.9 ± 2.85% sand, 13.5 ± 2.8% clay, and 0.59 ± 0.34% gravel, respectively. n-alkanes are derived from a variety of sources, including fresh oil, terrestrial plants, and heavy/degraded oil in estuaries. The results of this study highlight concerns and serve as a warning that hydrocarbon contamination is affecting human health. As a result, constant monitoring and assessment of aliphatic hydrocarbons in coastal and riverine environments are needed.
The Straits of Malacca is one of the world's busiest shipping routes where frequent oil spills occur. Rapid development in the west coast of Peninsular Malaysia is the other major source of petroleum pollution in this narrow waterway. In order to identify occurrence and origin of hydrocarbons in the Straits, mangrove oysters (Crassostrea belcheri) were collected from five sampling locations and analysed for n-alkanes and biomarkers. Soxhlet apparatus and two step column chromatography were used for extraction, purification and fractionation of the oysters. Petroleum origin n-alkanes were detected in majority of the sampling locations which is indicative of anthropogenic activities in this region. Using source and maturity diagnostic ratios for hopanes revealed used crankcase oil as the main source of petroleum hydrocarbons in oysters from all sampling locations except for the Pulau Merambong where signature of South East Asia crude oil (SEACO) was detected.
Insufficient power generation from a microbial fuel cell (MFC) hampers its progress towards utility-scale development. Electrode modification with biopolymeric materials could potentially address this issue. In this study, medium-chain-length poly-3-hydroxyalkanoates (PHA)/carbon nanotubes (C) composite (CPHA) was successfully applied to modify the surface of carbon cloth (CC) anode in MFC. Characterization of the functional groups on the anodic surface and its morphology was carried out. The CC-CPHA composite anode recorded maximum power density of 254 mW/m2, which was 15-53% higher than the MFC operated with CC-C (214 mW/m2) and pristine CC (119 mW/m2) as the anode in a double-chambered MFC operated with Escherichia coli as the biocatalyst. Electrochemical impedance spectroscopy and cyclic voltammetry showed that power enhancement was attributed to better electron transfer capability by the bacteria for the MFC setup with CC-CPHA anode.
Peninsular Malaysia has gone through fast development during recent decades resulting in the release of large amounts of petroleum and its products into the environment. Aliphatic hydrocarbons are one of the major components of petroleum. Surface sediment samples were collected from five rivers along the west coast of Peninsular Malaysia and analyzed for aliphatic hydrocarbons. The total concentrations of C10 to C36 n-alkanes ranged from 27,945 to 254,463ng·g(-1)dry weight (dw). Evaluation of various n-alkane indices such as carbon preference index (CPI; 0.35 to 3.10) and average chain length (ACL; 26.74 to 29.23) of C25 to C33 n-alkanes indicated a predominance of petrogenic source n-alkanes in the lower parts of the Rivers, while biogenic origin n-alkanes from vascular plants are more predominant in the upper parts, especially in less polluted areas. Petrogenic sources of n-alkanes are predominantly heavy and degraded oil versus fresh oil inputs.
Methanolic extracts of the leaves, stems, and roots of Phyllagathis rotundifolia collected in Malaysia yielded seven galloylated cyanogenic glucosides based on prunasin, with six of these being new compounds, prunasin 2',6'-di-O-gallate (3), prunasin 3',6'-di-O-gallate (4), prunasin 4',6'-di-O-gallate (5), prunasin 2',3',6'-tri-O-gallate (6), prunasin 3',4',6'-tri-O-gallate (7), and prunasin 2',3',4',6'-tetra-O-gallate (8). Also obtained was a new alkyl glycoside, oct-1-en-3-yl alpha-arabinofuranosyl-(1-->6)-beta-glucopyranoside (9). For compounds 3-8, the galloyl groups were individually linked to the sugar moieties via ester bonds. All new structures were established on the basis of NMR and MS spectroscopic studies. In addition, prunasin (1), gallic acid and its methyl ester, beta-glucogallin, 3,6-di-O-galloyl-D-glucose, 1,2,3,6-tetra-O-galloyl-beta-D-glucose, strictinin, 6-O-galloyl-2,3-O-(S)-hexahydroxydiphenoyl-D-glucose, praecoxin B, and pterocarinin C were isolated and identified. The isolation of 1 and its galloyl derivatives (3-8) from a Melastomataceous plant are described for the first time.
Central composite design (CCD) and response surface methodology (RSM) were employed to optimize four important variables, i.e. amounts of oil, bacterial inoculum, nitrogen and phosphorus, for the removal of selected n-alkanes during bioremediation of weathered crude oil in coastal sediments using laboratory bioreactors over a 60 day experimentation period. The reactors contained 1 kg soil with different oil, microorganisms and nutrients concentrations. The F Value of 26.89 and the probability value (P < 0.0001) demonstrated significance of the regression model. For crude oil concentration of 2, 16 and 30 g per kg sediments and under optimized conditions, n-alkanes removal was 97.38, 93.14 and 90.21% respectively. Natural attenuation removed 30.07, 25.92 and 23.09% n-alkanes from 2, 16 and 30 g oil/kg sediments respectively. Excessive nutrients addition was found to inhibit bioremediation.
The chlorine radical is a potent atmospheric oxidant, capable of perturbing tropospheric oxidative cycles normally controlled by the hydroxyl radical. Significantly faster reaction rates allow chlorine radicals to expedite oxidation of hydrocarbons, including methane, and in polluted environments, to enhance ozone production. Here we present evidence, from the CARIBIC airborne dataset, for extensive chlorine radical chemistry associated with Asian pollution outflow, from airborne observations made over the Malaysian Peninsula in winter. This region is known for persistent convection that regularly delivers surface air to higher altitudes and serves as a major transport pathway into the stratosphere. Oxidant ratios inferred from hydrocarbon relationships show that chlorine radicals were regionally more important than hydroxyl radicals for alkane oxidation and were also important for methane and alkene oxidation (>10%). Our observations reveal pollution-related chlorine chemistry that is both widespread and recurrent, and has implications for tropospheric oxidizing capacity, stratospheric composition and ozone chemistry.
The preparation of activated carbon using palm kernel shells as the precursor (PKSAC) was successfully accomplished after the parametric optimization of the carbonization temperature, carbonization holding time, and the ratio of the activator (H₃PO₄) to the precursor. Optimization at 500 °C for 2 h of carbonization with 20% H₃PO₄ resulted in the highest surface area of the activated carbon (C20) of 1169 m² g-1 and, with an average pore size of 27 Å. Subsequently, the preparation of shape-stabilized phase change material (SSPCM-C20) was done by the encapsulation of n-octadecane into the pores of the PKSAC, C20. The field emission scanning electron microscope images and the nitrogen gas adsorption-desorption isotherms show that n-octadecane was successfully encapsulated into the pores of C20. The resulting SSPCM-C20 nano-composite shows good thermal reliability which is chemically and thermally stable and can stand up to 500 melting and freezing cycles. This research work provided a new strategy for the preparation of SSPCM material for thermal energy storage application generated from oil palm waste.
Different extraction procedures were evaluated to assess their potential for measuring volatile organic compounds (VOCs) from raw rubber materials. Four headspace sampling techniques (SHS, DHS, HS-SPME and µ-CTE) were studied. Each method was firstly optimised to ensure their reliability in performance. Passive sampling was also compared as a rapid identification of background VOCs. 352 VOCs were identified, 71 from passive sampling and 281 from active headspace sampling, with 62 not previously reported (hexanenitrile, octanone, decanal, indole, aniline, anisole, alpha-pinene as well as pentanol and butanol). The volatiles belonged to a broad range of chemical classes (ketones, aldehydes, aromatics, acids, alkanes, alcohol and cyclic) with their thermal effects (lower boiling points) greatly affecting their abundance at a higher temperature. Micro-chamber (µ-CTE) was found to be the most suitability for routine assessments due to its operational efficiency (rapidity, simplicity and repeatability), identifying 115 compounds from both temperatures (30 °C and 60 °C). Whereas, HS-SPME a widely applied headspace technique, only identified 75 compounds and DHS identified 74 VOCs and SHS only 17 VOCs. Regardless of the extraction technique, the highest extraction efficiency corresponded to aromatics and acids, and the lowest compound extraction were aldehyde and hydrocarbon. The interaction between techniques and temperature for all chemical groups were evaluated using two-way ANOVA (p-value is 0.000197) explaining the highly significant interactions between factors.
Wax appearance temperature (WAT), defined as the temperature at which the first solid paraffin crystal appears in a crude oil, is one of the key flow assurance indicators in the oil industry. Although there are several commonly-used experimental techniques to determine WAT, none provides unambiguous molecular-level information to characterize the phase transition between the homogeneous fluid and the underlying solid phase. Molecular Dynamics (MD) simulations employing the statistical associating fluid theory (SAFT) force field are used to interrogate the incipient solidification states of models for long-chain alkanes cooled from a melt to an arrested state. We monitor the phase change of pure long chain n-alkanes: tetracosane (C24H50) and triacontane (C30H62), and an 8-component surrogate n-alkane mixture (C12-C33) built upon the compositional information of a waxy crude. Comparison to Diffusion Ordered Spectroscopy Nuclear Magnetic Resonance (DOSY NMR) results allows the assessment of the limitations of the coarse-grained models proposed. We show that upon approach to freezing, the heavier components restrict their motion first while the lighter ones retain their mobility and help fluidize the mixture. We further demonstrate that upon sub-cooling of long n-alkane fluids and mixtures, a discontinuity arises in the slope of the self-diffusion coefficient with decreasing temperature, which can be employed as a marker for the appearance of an arrested state commensurate with conventional WAT measurements.
Crotalaria pallida Aiton is an herbaceous legume from the family Fabaceae. In the present study, one new cyclopentyliene, crotolidene (1) and seven known compounds, i.e. hydroxydihydrobovolide (2), octacosane (3), trans-phytyl palmitate (4), linoleic acid (5), methyl oleate (6), ethyl palmitate (7), and palmitic acid (8) were isolated from the C. pallida collected from Perak, Malaysia. These compounds were isolated and characterized using extensive chromatographic and spectroscopic methods.
One of the techniques to increase oil recovery from hydrocarbon reservoirs is the injection of low salinity water. It is shown that the injection of low salinity water changes the wettability of the rock. However, there are argumentative debates concerning low salinity water effect on changing the wettability of the oil/brine/rock system in the oil reservoirs. In this regard, molecular dynamics simulation (MDS) as a tool to simulate the phenomena at the molecular level has been used for more than a decade. In this study, the Zisman plot (presented by KRUSS Company) was simulated through MDS, and then, contact angle experiments for n-decane interactions on the Bentheimer substrate in the presence of different concentrations of sodium ions were conducted. MDS was then used to simulate experiments and understand the wettability trend based on free-energy calculations. Hereafter, a new model was developed in this study to correlate free energies with contact angles. The developed model predicted the experimental results with high accuracy (R2 ∼ 0.98). A direct relation was observed between free energy and water contact angle. In contrast, an inverse relation was noticed between the ion concentration and the contact angle such that an increase in the ion concentration resulted in a decrease in the contact angle and vice versa. In other terms, increasing brine ionic concentrations in the presence of n-decane is linked to a decrease in free energies and an increase in the wetting state of a sandstone. The comparison between the developed model's predicted contact angles and experimental observations showed a maximum deviation of 14.32%, which is in satisfactory agreement to conclude that MDS can be used as a valuable and economical tool to understand the wettability alteration process.
The title compound, 3,5,7-triaza-1-azoniatricyclo[3.3.1.1(3,7)]decane 2,4-dinitrophenolate monohydrate, C6H13N4+*C6H3N2O5-*H2O, the 1:1 hydrate adduct of hexamethylenetetramine (HMT) and 2,4-dinitrophenol, undergoes a temperature phase transition. In the room-temperature phase, the adduct crystallizes in the monoclinic P2(1)/m space group, whereas in the low-temperature phase, the adduct crystallizes in the triclinic P1 space group. This phase transition is reversible, with the transition temperature at 273 K, and the phase transition is governed by hydrogen bonds and weak interactions. In both these temperature-dependent polymorphs, the crystal structure is alternately layered with sheets of hexamethylenetetramine and sheets of dinitrophenol stacked along the c axis. The hexamethylenetetramine and dinitrophenol moieties are linked by intermolecular hydrogen bonds. The water molecule in the adduct plays an important role, forming O-H...O hydrogen bonds which, together with C-H...O hydrogen bonds, bridge the adducts into molecular ribbons. Extra hydrogen bonds and weak interactions exist for the low-temperature polymorph and these interconnect the molecular ribbons into a three-dimensional packing structure. Also in these two temperature-dependent polymorphs, dinitrophenol acts as a hydrogen-bond acceptor and HMT acts as a hydrogen-bond donor.