Rapid increase in industrialization and urbanization in the west coast of Peninsular Malaysia has led to the intense release of petroleum and products of petroleum into the environment. Surface sediment samples were collected from the Selangor River in the west coast of Peninsular Malaysia during four climatic seasons and analyzed for PAHs and biomarkers (hopanes). Sediments were soxhlet extracted and further purified and fractionated through first and second step column chromatography. A gas chromatography-mass spectrometry (GC-MS) was used for analysis of PAHs and hopanes fractions. The average concentrations of total PAHs ranged from 219.7 to 672.3 ng g-1 dw. The highest concentrations of PAHs were detected at 964.7 ng g-1 dw in station S5 in the mouth of the Selangor River during the wet inter-monsoonal season. Both pyrogenic and petrogenic PAHs were detected in the sediments with a predominance of the former. The composition of hopanes was homogeneous showing that petroleum hydrocarbons share an identical source in the study area. Diagnostic ratios of hopanes indicated that some of the sediment samples carry the crankcase oil signature.
Oily wastewater, especially water-oil emulsion has become serious environmental issue and received global attention. Chemical demulsifiers are widely used to treat oil-water emulsion, but the toxicity, non-recyclable and non-environmental friendly characteristic of chemical demulsifiers had limited their practical application in oil-water separation. Therefore, it is imperative to develop an efficient, simple, eco-friendly and recyclable demulsifiers for breaking up the emulsions from the oily wastewater. In this study, a magnetic demulsifier, magnetite-reduced graphene oxide (M-rGO) nanocomposites were proposed as a recyclable demulsifier to break up the surfactant stabilized crude oil-in-water (O/W) emulsion. M-rGO nanocomposites were prepared via in situ chemical synthesis by using only one type Fe salt and GO solid as precursor at room temperature. The prepared composites were fully characterized by various techniques. The effect of demulsifier dosage and pH of emulsion on demulsification efficiency (ED) has been studied in detailed. The demulsification mechanism was also proposed in this study. Results showed that M-rGO nanocomposites were able to demulsify crude O/W emulsion. The ED reaches 99.48% when 0.050 wt.% of M-rGO nanocomposites were added to crude O/W emulsion (pH = 4). Besides, M-rGO nanocomposites can be recycled up to 7 cycles without showing a significant change in terms of ED. Thus, M-rGO nanocomposite is a promising demulsifier for surfactant stabilized crude O/W emulsion.
It is known that in Padang, Rantau, Rangsang, Merbau and Bengkalis islands, Riau Province, the deposit of oil was found in a huge quantity. The drilling concession belongs to Kondur Petroleum Company. To operate an exploitation, hundreds of workers not only Indonesian but also the workers from foreign countries come and go to that area. It was recorded that the workers from foreign countries come from Singapore, Malaysia, Thailand, The Philippines, Taiwan, Japan, Korea. United States of America and from France, Britain, Australia and Germany. These workers have a close interaction with about 50,00 local population distributed with a high concentration in some places. The high risk of DHF was determined since the significant density of Aedes aregypti larvae, the main vector of DHF, were found in Lukit, Mengkikip and Melibur, three locations of survey. Of 104 (53.3%) of 195 houses in these three survey locations were found positive for the larvae. Even though there were no positive of larvae in 65 houses in Lukit, in Melibur and Mengkikip, the House Index (HI) was 61.7% and 95.7%. Outside the houses 521 containers were examined in three locations of survey and 329 (63.1%) were positive for Ae. aegypti larvae. The highest number of containers positive for Ae. aegypti larvae were 213 (94.7%) out of 225 and found in Mengkikip. In Melibur, 114 (68.3%) out of 167 of containers were positive and in Lukit only 2 (1.56%) out of 129 containers were positive of Ae. aegypti larvae. These larvae density constitute a high risk of DHF outbreak, and unfortunately is supported by the rainfall situation recorded in Kurau and BZ Climatology Stations. It was recorded that all along the year, at least one day in a month there was the rain which the rainfall volume was 30 ml.
This is the first publication on the distribution and sources of polycyclic aromatic hydrocarbons (PAHs) in riverine and coastal sediments in South East Asia where the rapid transfer of land-based pollutants into aquatic environments by heavy rainfall and runoff waters is of great concern. Twenty-nine Malaysian riverine and coastal sediments were analyzed for PAHs (3-7 rings) by gas chromatography mass spectrometry. Total PAHs concentrations in the sediment ranged from 4 to 924 ng/g. Alkylated homologues were abundant for all sediment samples. The ratio of the sum of methylphenanthrenes to phenanthrene (MP/P), an index of petrogenic PAHs contribution, was more than unity for 26 sediment samples and more than 3 for seven samples for urban rivers covering a broad range of locations. The MP/P ratio showed a strong correlation with the total PAHs concentrations, with an r2 value of 0.74. This ratio and all other compositional features indicated that Malaysian urban sediments are heavily impacted by petrogenic PAHs. This finding is in contrast to other studies reported in many industrialized countries where PAHs are mostly of pyrogenic origin. The MP/P ratio was also significantly correlated with higher molecular weight PAHs such as benzo[a]pyrene, suggesting unique PAHs source in Malaysia which contains both petrogenic PAHs and pyrogenic PAHs. PAHs and hopanes fingerprints indicated that used crankcase oil is one of the major contributors of the sedimentary PAHs. Two major routes of inputs to aquatic environments have been identified: (1) spillage and dumping of waste crankcase oil and (2) leakage of crankcase oils from vehicles onto road surfaces, with the subsequent washout by street runoff. N-Cyclohexyl-2-benzothiazolamine (NCBA), a molecular marker of street dust, was detected in the polluted sediments. NCBA and other biomarker profiles confirmed our hypothesis of the input from street dust contained the leaked crankcase oil. The fingerprints excluded crude oil, fresh lubricating oil, asphalt, and tire-particles as major contributors.
Malaysian coasts are subjected to various threats of petroleum pollution including routine and accidental oil spill from tankers, spillage of crude oils from inland and off-shore oil fields, and run-off from land-based human activities. Due to its strategic location, the Straits of Malacca serves as a major shipping lane. This paper expands the utility of biomarker compounds, hopanes, in identifying the source of tar-balls stranded on Malaysian coasts. 20 tar-ball samples collected from the east and west coast were analyzed for hopanes and polycyclic aromatic hydrocarbons (PAHs). Four of the 13 tar-ball samples collected from the west coast of Peninsular Malaysia were identified as the Middle East crude oil (MECO) based on their biomarker signatures, suggesting tanker-derived sources significantly contributing the petroleum pollution in the Straits of Malacca. The tar-balls found on the east coast seem to originate from the offshore oil platforms in the South China Sea. The presence of South East Asian crude oil (SEACO) tar-balls on the west coast carry several plausible explanations. Some of the tar-balls could have been transported via sea currents from the east coast. The tankers carrying SEACO to other countries could have accidentally spilt the oil as well. Furthermore, discharge of tank washings and ballast water from the tankers were suggested based on the abundance in higher molecular weight n-alkanes and the absence of unresolved complex mixture (UCM) in the tar-ball samples. The other possibilities are that the tar-balls may have been originated from the Sumatran oil fields and spillage of domestic oil from oil refineries in Port Dickson and Malacca. The results of PAHs analysis suggest that all the tar-ball samples have undergone various extent of weathering through evaporation, dissolution and photooxidation.
A biosurfactant-producing and hydrocarbon-utilizing bacterium, Pseudomonas aeruginosa USM-AR2, was used to assist conventional distillation. Batch cultivation in a bioreactor gave a biomass of 9.4 g L(-1) and rhamnolipid concentration of 2.4 g L(-1) achieved after 72 h. Biosurfactant activity (rhamnolipid) was detected by the orcinol assay, emulsification index and drop collapse test. Pretreatment of crude oil TK-1 and AG-2 with a culture of P. aeruginosa USM-AR2 that contains rhamnolipid was proven to facilitate the distillation process by reducing the duration without reducing the quality of petroleum distillate. It showed a potential in reducing the duration of the distillation process, with at least 2- to 3-fold decreases in distillation time. This is supported by GC-MS analysis of the distillate where there was no difference between compounds detected in distillate obtained from treated or untreated crude oil. Calorimetric tests showed the calorie value of the distillate remained the same with or without treatment. These two factors confirmed that the quality of the distillate was not compromised and the incubation process by the microbial culture did not over-degrade the oil. The rhamnolipid produced by this culture was the main factor that enhanced the distillation performance, which is related to the emulsification of hydrocarbon chains in the crude oil. This biotreatment may play an important role to improve the existing conventional refinery and distillation process. Reducing the distillation times by pretreating the crude oil with a natural biosynthetic product translates to energy and cost savings in producing petroleum products.
The characteristics and water/oil sorption effectiveness ofkapok fibre, sugarcane bagasse and rice husks have been compared. The three biomass types were subjected to field emission scanning electron microscopy-energy dispersive X-ray spectroscopy and surface tension analyses for liquid-air and oil-water systems were conducted. Both kapok fibre and sugarcane bagasse exhibit excellent oil sorption capabilities for diesel, crude, new engine and used engine oils as their oil sorption capacities all exceed 10 g/g. The synthetic sorbent exhibits oil sorption capacities comparable with sugarcane bagasse, while rice husks exhibit the lowest oil sorption capacities among all the sorbents. Kapok fibre shows overwhelmingly high oil-to-water sorption (O/W) ratios ranging from 19.35 to 201.53 while sugarcane bagasse, rice husks and synthetic sorbent have significantly lower O/W ratios (0.76-2.69). This suggests that kapok fibre is a highly effective oil sorbent even in well-mixed oil-water media. An oil sorbent suitability matrix is proposed to aid stakeholders in evaluating customized oil removal usage of the natural sorbents.
The distribution of total petrogenic hydrocarbon was investigated in the subsurface water of Setiu Wetland from July to October 2008. The concentration was quantified by UV-fluorescence spectroscopy and ranged from 4 to 121 μg/L (mean 60 ± 41 μg/L). Higher total petrogenic hydrocarbon concentrations were found in area with high boating activities suggesting that the contribution is likely related to fossil fuel combustion. The present study also revealed that the total petrogenic hydrocarbon values are still lower that those reported in Malaysian coastal waters.
This study analyzes the effects of toxic, hydraulic, and organic shocks on the performance of a lab-scale sequencing batch reactor (SBR) with a capacity of 5L. Petroleum refinery wastewater (PRWW) was treated with an organic loading rate (OLR) of approximately 0.3 kg chemical oxygen demand (COD)/kg MLSSd at 12.8h hydraulic retention time (HRT). A considerable variation in the COD was observed for organic, toxic, hydraulic, and combined shocks, and the worst values observed were 68.9, 77.1, 70.2, and 57.8%, respectively. Improved control of toxic shock loads of 10 and 20mg/L of chromium (VI) was identified. The system was adversely affected by the organic shock when a shock load thrice the normal value was used, and this behavior was repeated when the hydraulic shock was 4.8h HRT. The empirical recovery period was greater than the theoretical period because of the inhibitory effects of phenols, sulfides, high oil, and grease in the PRWW. The system recovery rates from the shocks were in the following order: toxic, organic, hydraulic, and combined shocks. System failure occurred when the combined shocks of organic and hydraulic were applied. The system was resumed by replacing the PRWW with glucose, and the OLR was reduced to half its initial value.
Produced water is the largest waste stream generated in oil and gas industries. It is a mixture of different organic and inorganic compounds. Due to the increasing volume of waste all over the world in the current decade, the outcome and effect of discharging produced water on the environment has lately become a significant issue of environmental concern. Produced water is conventionally treated through different physical, chemical, and biological methods. In offshore platforms because of space constraints, compact physical and chemical systems are used. However, current technologies cannot remove small-suspended oil particles and dissolved elements. Besides, many chemical treatments, whose initial and/or running cost are high and produce hazardous sludge. In onshore facilities, biological pretreatment of oily wastewater can be a cost-effective and environmental friendly method. As high salt concentration and variations of influent characteristics have direct influence on the turbidity of the effluent, it is appropriate to incorporate a physical treatment, e.g., membrane to refine the final effluent. For these reasons, major research efforts in the future could focus on the optimization of current technologies and use of combined physico-chemical and/or biological treatment of produced water in order to comply with reuse and discharge limits.
Addition of nitrogen sources as supplementary nutrient into MSM medium to enhance biodegradation by stimulating the growth four isolates, Acinetobacter faecalis, Staphylococcus sp., Pseudomonas putida and Neisseria elongata isolated from petroleum contaminated groundwater, wastewater aeration pond and biopond at the oil refinery Terengganu Malaysia was investigated. The organic nitrogen sources tested not only supported growth but also enhances biodegradation of 1% Tapis crude oil. All four isolates showed good growth especially when peptone was employed as the organic nitrogen compared to growth in the basal medium. Gas chromatography showed that more then 91, 93, 94 and 95% degradation of total hydrocarbon was observed after 5 days of incubation by isolates Pseudomonas putida, Neisseria elongate, Acinetobacter faecalis and Staphylococcus sp., respectively.
Oil and gas field wastewater or produced water is a significant waste stream in the oil and gas industries. In this study, the performance of a membrane sequencing batch reactor (MSBR) and membrane sequencing batch reactor/reverse osmosis (MSBR/RO) process treating produced wastewater were investigated and compared. The MSBR was operated in different hydraulic residence time (HRT) of 8, 20 and 44 h. Operation results showed that for a HRT of 20 h, the combined process effluent chemical oxygen demand (COD), total organic carbon (TOC) and oil and grease (O&G) removal efficiencies were 90.9%, 92% and 91.5%, respectively. The MSBR effluent concentration levels met the required standard for oil well re-injection. The RO treatment reduced the salt and organic contents to acceptable levels for irrigation and different industrial re-use. Foulant biopsy demonstrated that the fouling on the membrane surface was mainly due to inorganic (salts) and organic (microorganisms and their products, hydrocarbon constituents) matters.
Soil contamination by used lubricating oil from automobiles is a growing concern in many countries, especially in Asian and African continents. Phytoremediation of this polluted soil with non-edible plant like Jatropha curcas offers an environmental friendly and cost-effective method for remediating the polluted soil. In this study, phytoremediation of soil contaminated with 2.5 and 1% (w/w) waste lubricating oil using J. curcas and enhancement with organic wastes [Banana skin (BS), brewery spent grain (BSG) and spent mushroom compost (SMC)] was undertaken for a period of 180 days under room condition. 56.6% and 67.3% loss of waste lubricating oil was recorded in Jatropha remediated soil without organic amendment for 2.5% and 1% contamination, respectively. However addition of organic waste (BSG) to Jatropha remediation rapidly increases the removal of waste lubricating oil to 89.6% and 96.6% in soil contaminated with 2.5% and 1% oil, respectively. Jatropha root did not accumulate hydrocarbons from the soil, but the number of hydrocarbon utilizing bacteria was high in the rhizosphere of the Jatropha plant, thus suggesting that the mechanism of the oil degradation was via rhizodegradation. These studies have proven that J. curcas with organic amendment has a potential in reclaiming hydrocarbon-contaminated soil.
The effects of initial oil concentration and the Corexit 9500 dispersant on the rate of bioremediation of petroleum hydrocarbons were investigated with a series of ex-situ seawater samples. With initial oil concentrations of 100, 500, 1,000 and 2,000 mg/L, removal of total petroleum hydrocarbons (TPHs) with dispersant were 67.3%, 62.5%, 56.5% and 44.7%, respectively, and were 64.2%, 55.7%, 48.8% and 37.6% without dispersant. The results clearly indicate that the presence of dispersant enhanced crude oil biodegradation. Lower concentrations of crude oil demonstrated more efficient hydrocarbon removal. Based on these findings, bioremediation is not recommended for crude oil concentrations of 2,000 mg/L or higher.
This study examined the capacity of immobilized bacteria to degrade petroleum hydrocarbons. A mixture of hydrocarbon-degrading bacterial strains was immobilized in alginate and incubated in crude oil-contaminated artificial seawater (ASW). Analysis of hydrocarbon residues following a 30-day incubation period demonstrated that the biodegradation capacity of the microorganisms was not compromised by the immobilization. Removal of n-alkanes was similar in immobilized cells and control cells. To test reusability, the immobilized bacteria were incubated for sequential increments of 30 days. No decline in biodegradation capacity of the immobilized consortium of bacterial cells was noted over its repeated use. We conclude that immobilized hydrocarbon-degrading bacteria represent a promising application in the bioremediation of hydrocarbon-contaminated areas.
The synthesis of fatty acid methyl esters (FAME) as a substitute to petroleum diesel was investigated in this study from crude jatropha oil (CJO), a non-edible, low-cost alternative feedstock, using aluminium modified heterogeneous basic oxide (Mg-Zn) catalyst. The transesterification reaction with methanol to methyl esters yielded 94% in 6h with methanol-oil ratio of 11:1, catalyst loading of 8.68 wt.% at 182°C and the properties of CJO fuel produced were determine and found to be comparable to the standards according to ASTM. In the range of experimental parameters investigated, it showed that the catalyst is selective to production of methyl esters from oil with high free fatty acid (FFA) and water content of 7.23% and 3.28%, respectively in a single stage process. Thus, jatropha oil is a promising feedstock for methyl ester production and large scale cultivation will help to reduce the product cost.
To determine the influence of nutrients on the rate of biodegradation, a five-level, three-factor central composite design (CCD) was employed for bioremediation of seawater artificially contaminated with crude oil. Removal of total petroleum hydrocarbons (TPH) was the dependent variable. Samples were extracted and analyzed according to US-EPA protocols. A significant (R(2)=0.9645, P<0.0001) quadratic polynomial mathematical model was generated. Removal from samples not subjected to optimization and removal by natural attenuation were 53.3% and 22.6%, respectively. Numerical optimization was carried out based on desirability functions for maximum TPH removal. For an initial crude oil concentration of 1g/L supplemented with 190.21 mg/L nitrogen and 12.71 mg/L phosphorus, the Design-Expert software predicted 60.9% hydrocarbon removal; 58.6% removal was observed in a 28-day experiment.
Weathered crude oil (WCO) removals in shoreline sediment samples were monitored for 60 days in bioremediation experimentation. Experimental modeling was carried out using statistical design of experiments. At optimum conditions maximum of 83.13, 78.06 and 69.92% WCO removals were observed for 2, 16 and 30 g/kg initial oil concentrations, respectively. Significant variations in the crude oil degradation pattern were observed with respect to oil, nutrient and microorganism contents. Crude oil bioremediation were successfully described by a first-order kinetic model. The study indicated that the rate of hydrocarbon biodegradation increased with decrease of crude oil concentrations.
In this work, a genetic algorithm is applied for the automatic detection of oil spills. The procedure is implemented using sequences from RADARSAT-2 SAR ScanSAR Narrow single-beam data acquired in the Gulf of Mexico. The study demonstrates that the implementation of crossover allows for the generation of an accurate oil spill pattern. This conclusion is confirmed by the receiver-operating characteristic (ROC) curve. The ROC curve indicates that the existence of oil slick footprints can be identified using the area between the ROC curve and the no-discrimination line of 90%, which is greater than that of other surrounding environmental features. In conclusion, the genetic algorithm can be used as a tool for the automatic detection of oil spills, and the ScanSAR Narrow single-beam mode serves as an excellent sensor for oil spill detection and survey.