Solid-phase extraction (SPE) of organochlorine pesticide residues from environmental water samples was evaluated using octadecyl (C18)-bonded porous silica. The efficiency of SPE of these pesticide residues from reagent water samples at 1-5 micrograms dm-3 levels was compared with those obtained by solvent extraction with hexane and Freon TF (trichlorotrifluoroethane). Average recoveries exceeding 80% for these organochlorine pesticides were obtained via the SPE method using small cartridges containing 100 mg of 40 microns C18-bonded porous silica. The average recovery by solvent extraction with hexane and Freon TF exceeded 90% in both instances. It was concluded that the recoveries and precision for the SPE of organochlorine pesticides were poorer than those for the solvent extraction method. Organochlorine pesticide residue levels in environmental water samples from two major rivers flowing through predominantly rice-growing areas were monitored by gas chromatography using the solvent extraction method with hexane. Exceptionally high levels of organochlorine pesticide residues such as BHC, DDT, heptachlor, endosulfan and dieldrin were found in these water samples.
Exploring new renewable energy sources as a substitute of petroleum reserves is necessary due to fulfilling the oncoming energy needs for industry and transportation systems. In this quest, a lot of research is going on to expose different kinds of new biodiesel sources. The non-edible oil from candlenut possesses the potential as a feedstock for biodiesel production. The present study aims to produce biodiesel from crude candlenut oil by using two-step transesterification process, and 10%, 20%, and 30% of biodiesel were mixed with diesel fuel as test blends for engine testing. Fourier transform infrared (FTIR) and gas chromatography (GC) were performed and analyzed to characterize the biodiesel. Also, the fuel properties of biodiesel and its blends were measured and compared with the specified standards. The thermal stability of the fuel blends was measured by thermogravimetric analysis (TGA) and differential scan calorimetry (DSC) analysis. Engine characteristics were measured in a Yanmar TF120M single cylinder direct injection (DI) diesel engine. Biodiesel produced from candlenut oil contained 15% free fatty acid (FFA), and two-step esterification and transesterification were used. FTIR and GC remarked the biodiesels' existing functional groups and fatty acid methyl ester (FAME) composition. The thermal analysis of the biodiesel blends certified about the blends' stability regarding thermal degradation, melting and crystallization temperature, oxidative temperature, and storage stability. The brake power (BP), brake specific fuel consumption (BSFC), and brake thermal efficiency (BTE) of the biodiesel blends decreased slightly with an increasing pattern of nitric oxide (NO) emission. However, the hydrocarbon (HC) and carbon monoxides (CO) of biodiesel blends were found decreased.
Chlorinated compounds such as sphingolipid-based organochlorine compounds are precursors for the formation of 3-monochlororopanediol (3-MCPD) esters in palm oil. This study evaluates the effects of several factors within the palm oil supply chain on the levels of sphingolipid-based organochlorine, which in turn may influence the formation of 3-MCPD esters during refining. These factors include application of inorganic chlorinated fertiliser in the oil palm plantation, bruising and degradation of oil palm fruits after harvest, recycling of steriliser condensate as water for dilution of crude oil during oil palm milling, water washing of palm oil and different refining conditions. It was observed that bruised and degraded oil palm fruits showed higher content of sphingolipid-based organochlorine than control. In addition, recycling steriliser condensate during milling resulted in elevated content of sphingolipid-based organochlorine in palm oil. However, the content of sphingolipid-based organochlorine compounds was reduced by neutralisation, degumming and bleaching steps during refining. Although water washing of crude palm oils (CPO) prior to refining did not reduce the content of sphingolipid-based organochlorine, it did reduce the formation of 3-MCPD esters through the removal of water-soluble chlorinated compounds. It was found that the use of inorganic chlorinated fertiliser in plantations did not increase the content of chlorinated compounds in oil palm fruits and extracted oil, and hence chlorinated fertiliser does not seem to play a role in the formation of 3-MCPD esters in palm oil. Overall, this study concluded that lack of freshness and damage to the fruits during transport to mills, combined with water and oil recycling in mills are the major contributors of chlorinated precursor for 3-MCPD esters formation in palm oil.
The ageing of the bitumen during storage, mixing, transport and laying on the road, as well as in service life, are the most important problems presented by the use of bitumen in pavements. This paper investigates the possibility of using waste cooking oil (WCO), which is a waste material that pollutes landfills and rivers, as an alternative natural rejuvenating agent for aged bitumen to a condition that resembles the original bitumen. With this target, the physical and chemical properties of the original bitumen, aged bitumen and rejuvenated bitumen were measured and compared by the bitumen binder tests - softening point, penetration, Brookfield viscosity, dynamic shear rheometer and Fourier transform infrared spectroscopy. In addition, the behaviour of the WCO rejuvenated bitumen is investigated and compared with virgin bitumen after using the rolling thin film oven ageing process. In general, the results showed that using 3-4% of WCO the aged bitumen group 40/50 was rejuvenated to a condition that closely resembled the physical, rheological properties of the original bitumen (80/100), however, there was a difference in the tendency to ageing between the WCO rejuvenated bitumen and the virgin bitumen during mixing, transport and laying on the road.
The concentrations of polycyclic aromatic hydrocarbons (PAHs) in soil samples were measured at five different sites within Klang Valley, Malaysia. The results showed that the total concentrations of the fourteen priority PAHs ranged from 64 to 155 μg/kg. Irrespective of the land use, all the measured soil PAH concentrations in this study were significantly lower than that found in soil samples in temperate regions. The profile of PAHs in the soils was dominated by the LMW PAHs. The PAHs in Klang Valley soils originated from pyrogenic sources, with a combination of petroleum and biomass combustion in vehicles, industries and non-point sources.
This study investigated the optimum conditions for total petroleum hydrocarbon (TPH) removal from diesel-contaminated water using phytoremediation treatment with Scirpus grossus. In addition, TPH removal from sand was adopted as a second response. The optimum conditions for maximum TPH removal were determined through a Box-Behnken Design. Three operational variables, i.e. diesel concentration (0.1, 0.175, 0.25% Vdiesel/Vwater), aeration rate (0, 1 and 2 L/min) and retention time (14, 43 and 72 days), were investigated by setting TPH removal and diesel concentration as the maximum, retention time within the given range, and aeration rate as the minimum. The optimum conditions were found to be a diesel concentration of 0.25% (Vdiesel/Vwater), a retention time of 63 days and no aeration with an estimated maximum TPH removal from water and sand of 76.3 and 56.5%, respectively. From a validation test of the optimum conditions, it was found that the maximum TPH removal from contaminated water and sand was 72.5 and 59%, respectively, which was a 5 and 4.4% deviation from the values given by the Box-Behnken Design, providing evidence that S. grossus is a Malaysian native plant that can be used to remediate wastewater containing hydrocarbons.
In this work, crude oil biodegradation has been optimized in a solid-liquid two phase partitioning bioreactor (TPPB) by applying a response surface methodology based d-optimal design. Three key factors including phase ratio, substrate concentration in solid organic phase, and sodium chloride concentration in aqueous phase were taken as independent variables, while the efficiency of the biodegradation of absorbed crude oil on polymer beads was considered to be the dependent variable. Commercial thermoplastic polyurethane (Desmopan®) was used as the solid phase in the TPPB. The designed experiments were carried out batch wise using a mixed acclimatized bacterial consortium. Optimum combinations of key factors with a statistically significant cubic model were used to maximize biodegradation in the TPPB. The validity of the model was successfully verified by the good agreement between the model-predicted and experimental results. When applying the optimum parameters, gas chromatography-mass spectrometry showed a significant reduction in n-alkanes and low molecular weight polycyclic aromatic hydrocarbons. This consequently highlights the practical applicability of TPPB in crude oil biodegradation.
A lab-scale granular activated carbon sequencing batch biofilm reactor (GAC-SBBR), a combined adsorption and biological process, was developed to treat real wastewater from a recycled paper mill. In this study, one-consortia of mixed culture (4000-5000 mg/L) originating from recycled paper mill activated sludge from Kajang, Malaysia was acclimatized. The GAC-SBBR was fed with real wastewater taken from the same recycled paper mill, which had a high concentration of chemical oxygen demand (COD) and adsorbable organic halides (AOX). The operational duration of the GAC-SBBR was adjusted from 48 h to 24, 12 and finally 8 h to evaluate the effect of the hydraulic retention time (HRT) on the simultaneous removal of COD and AOX. The COD and AOX removals were in the range of 53-92% and 26-99%, respectively. From this study, it was observed that the longest HRT (48 h) yielded a high removal of COD and AOX, at 92% and 99%, respectively.
A brief review is conducted on the application of vegetable oils in the treatment of PAH-contaminated soils. Three main scopes of treatment strategies are discussed in this work including soil washing by oil, integrated oil-biological treatment and integrated oil-non-biological treatment. For each of these, the arguments supporting vegetable oil application, the applied treatment techniques and their efficiencies, associated factors, as well as the feasibility of the techniques are detailed. Additionally, oil regeneration, the environmental impacts of oil residues in soil and comparison with other commonly employed techniques are also discussed.
Polycyclic aromatic hydrocarbons (PAHs) in a sediment core collected from Langkawi Island of the Andaman Sea, Malaysia were determined by GC/MS, the vertical variations of concentration and distributions of PAHs were investigated. In combining with 210Pb-dating, the PAHs sedimentary record in the last 100 years was reconstructed and their possible sources were also discussed. The sigmaPAH concentration ranged from 13.2-60.1 ng x g(-1) in the whole sedimentary section (0-56 cm) with the dominant compounds of phenanthrene, naphthalene and perylene. The sediments contaminated to a lesser extent comparing with the surrounding waters. Before the 1920s, the concentrations of PAHs were considered to be the background level, which was implied from the natural inputs. The historical records of PAHs in the core showed that two distinct peaks which represented the input time of 1960s and 1980s, respectively, inferred that there were some relatively dramatically land-based inputs, and human activities leaded a clear impact to these waters during these periods. Furthermore, PAHs diagnostic ratios indicated that PAHs in the core sediments were mainly of pyrolytic origin (combustion), accompanied with minor petroleum origin. These were related with agriculture, industry, ocean import and export, and shipping activities in the surrounding regions. Meanwhile as the vital communication line, the marine transportation of the Strait of Malacca had influenced the environmental quality of the Andaman Sea. Meanwhile, based on the sedimentary record, PAHs concentrations were found to correlate positively with humanism activities and socioeconomic development (Gross Domestic Production) in the surrounding regions.
In Malaysia, rivers are the main source of public water supplies. This study was conducted from 2002 to 2003 to determine the levels of selected organochlorine and organophosphate pesticides in the Selangor River in Malaysia. Surface water samples have been collected seasonally from nine sites along the river. A liquid-liquid extraction followed by gas chromatography-mass spectrometry technique was used to determine the trace levels of these pesticide residues. The organochlorine pesticides detected were lindane, heptachlor, endosulfan, dieldrin, endosulfan sulfate, o,p'-DDT, p,p'-DDT, o,p'-DDE and p,p'-DDE whereas for organophosphate pesticides, they were chlorpyrifos and diazinon. At the river upstream where a dam is located for public water supply, incidents of pesticide levels exceeding the European Economic Community Directive of water quality standards have occurred. Furthermore, the wetland ecosystems located at the downstream of the river which houses the fireflies community is being threatened by occasional pesticide levels above EPA limits for freshwater aquatic organisms. The occurrence of these residual pesticides in the Selangor River can be attributed to the intense agriculture and urban activity.
The concentrations and distributions of particle bound polycyclic aromatic hydrocarbons (PAHs) collected over a 10 month period in ambient environment, at street levels as well as during a hazy episode are reported. Ambient and street level distributions of PAHs were similar and their occurrence was attributed to vehicular emissions. However, in haze particles, a different pattern of PAHs was observed, characterized by relatively low levels of benzo[a]pyrene (BaP) and high levels of benzofluoranthenes (BFs). The BaP equivalency results showed that the potential health risk associated with haze smoke particles was 4 times higher than that of street level particles whereas the lowest health risk was associated with ambient atmospheric particles.
Polycyclic aromatic hydrocarbons (PAHs) are present in both gaseous and particulate phases. These compounds are considered to be atmospheric contaminants and are human carcinogens. Many studies have monitored atmospheric particulate and gaseous phases of PAH in Asia over the past 5 years. This work compares and discusses different sample collection, pretreatment and analytical methods. The main PAH sources are traffic exhausts (AcPy, FL, Flu, PA, Pyr, CHR, BeP) and industrial emissions (BaP, BaA, PER, BeP, COR, CYC). PAH concentrations are highest in areas of traffic, followed by the urban sites, and lowest in rural sites. Meteorological conditions, such as temperature, wind speed and humidity, strongly affect PAH concentrations at all sampling sites. This work elucidates the characteristics, sources and distribution, and the healthy impacts of atmospheric PAH species in Asia.
New coumarin derivatives, namely 7-[(5-amino-1,3,4-thiadiazol-2-yl)methoxy]-2H-chromen-2-one, 5-[(2-oxo-2H-chromen-7-yloxy)methyl]-1,3,4-thiadiazol-2(3H)-one, 2-[2-(2-oxo-2H-chromen-7-yloxy)acetyl]-N-phenylhydrazinecarbothioamide, 7-[(5-(phenylamino)-1,3,4-thiadiazol-2-yl)methoxy]-2H-chromen-2-one and 7-[(5-mercapto-4-phenyl-4H-1,2,4-triazol-3-yl)methoxy]-2H-chromen-2-one were prepared starting from the natural compound umbelliferone. The newly synthesized compounds were characterized by elemental analysis and spectral studies (IR, ¹H-NMR and ¹³C-NMR).
PM10 airborne particles and soot deposit collected after a fire incident at a chemical store were analyzed in order to determine the concentrations of polycyclic aromatic hydrocarbons (PAHs). The samples were extracted with 1:1 hexane-dichloromethane by ultrasonic agitation. The extracts were then subjected to gas chromatography-mass spectrometric (GC-MS) analysis. The total PAHs concentrations in airborne particles and soot deposit were found to be 3.27 +/- 1.55 ng/m3 and 12.81 +/- 24.37 microg/g, respectively. Based on the molecular distributions of PAHs and the interpretation of their diagnostic ratios such as PHEN/(PHEN + ANTH), FLT/(FLT + PYR) and BeP/(BeP + BaP), PAHs in both airborne particles and soot deposit may be inferred to be from the same source. The difference in the value of IP/(IP + BgP) for these samples indicated that benzo[g, h, i] perylene and coronene tend to be attached to finer particles and reside in the air for longer periods. Comparison between the molecular distributions of PAHs and their diagnostic ratios observed in the current study with those reported for urban atmospheric and roadside soil particles revealed that they are of different sources.
In this study, the distributions and sources of sediment-associated polycyclic aromatic hydrocarbons (PAHs) and hopanes in the Malaysian rivers and estuaries were evaluated. The concentrations of 16 USEPA PAHs varied from 225.5 to 293.9 (Perlis River), 195.2 to 481.2 (Kedah River), 791.2 to 1995.4 (Merbok River), 231.2 to 426.7 (Perak River), and 3803.2 to 7442.7 ng g(-1) (Klang River) dry weight. PAHs can be classified as moderate in the Perlis, Kedah, and Perak Rivers, moderate to high in the Merbok River, and high to very high in the Klang River. The comparison of PAHs with sediment quality guidelines (SQGs) indicates that occasionally adverse biological effects may occur from total PAHs, low molecular weight (LMW), and high molecular weight (HMW) PAHs at stations 1, 2, and 3 of the Klang River and from total PAHs at station 2 of the Merbok River. The diagnostic ratios of individual PAHs indicate both petrogenic and pyrogenic origin PAHs with significant dominance of pyrogenic sources in the study areas. The results suggest that Malaysian sediments had hopane ratios (C29/C30) similar to MECO suggesting MECO as a major source of the petroleum hydrocarbons found in the sediments, which is consistent with results reported in previous studies. These findings demonstrate that effective and improved environmental regulations in Malaysia have shifted the source of petroleum hydrocarbons from petrogenic to pyrogenic origin.
Members of the catadromous eel live in various fresh, brackish and marine habitats. Therefore, these eels can accumulate organic pollutants and are a suitable bioindicator species for determining the levels of organic contaminants within different water bodies. The ecological risk for organochlorine compounds (OCs) in Anguilla japonica with various migration patterns, such as freshwater, estuarine and marine residences, was examined to understand the specific accumulation patterns. The concentrations of HCB, ∑HCHs, ∑CHLs and ∑DDTs in the silver stage (maturing) eel were significantly higher than those in the yellow stage (immature) eel, in accordance with the higher lipid contents in the former versus the latter. The OC accumulations were clearly different among migratory types in the eel. The ecological risk of OCs increased as the freshwater residence period in the eel lengthened. The migratory histories and the lipid contents directly affected the OC accumulation in the catadromous eel species.
One of the appropriate development technology options for the treatment of wastewater contaminated with diesel is constructed wetlands (CWs). Throughout 72 days of exposure, sampling was carried out for monitoring of physical parameters, plant growth and the efficiency of total petroleum hydrocarbon (TPH) removal, as an indication for diesel contamination, to assess the pilot-scale performance. Four pilot CWs with a horizontal sub-surface flow system were applied using the bulrush of Scirpus grossus. The CWs were loaded with different diesel concentrations of 0, 0.1, 0.2 and 0.25% (Vdiesel/Vwater). The TPH removal efficiencies were 82, 71, and 67% at the end of 72 days for diesel concentrations of 0.1, 0.2, and 0.25% respectively. In addition, the high removal efficiency of total suspended solids and chemical oxygen demand (COD) were 100 and 75.4% respectively, for a diesel concentration of 0.1%. It was concluded that S. grossus is a potential plant that can be used in a well-operated CW for restoring 0.1% diesel-contaminated water.
Two types of flow system, free surface flow (FSF) and sub-surface flow (SSF), were examined to select a better way to remove total petroleum hydrocarbons (TPH) using diesel as a hydrocarbon model in a phytotoxicity test to Scirpus grossus. The removal efficiencies of TPH for the two flow systems were compared. Several wastewater parameters, including temperature (T, °C), dissolved oxygen (DO, mgL(-1)), oxidation-reduction potential (ORP, mV), and pH were recorded during the experimental runs. In addition, overall plant lengths, wet weights, and dry weights were also monitored. The phytotoxicity test using the bulrush plant S. grossus was run for 72 days with different diesel concentrations (1%, 2%, and 3%) (Vdiesel/Vwater). A comparison between the two flow systems showed that the SSF system was more efficient than the FSF system in removing TPH from the synthetic wastewater, with average removal efficiencies of 91.5% and 80.2%, respectively. The SSF system was able to tolerate higher diesel concentrations than was the FSF system.
The bioaccumulation and bioavailability of polycyclic aromatic hydrocarbons (PAHs) were characterized in sediment and Paphia undulata (short-neck clam) from six mudflat areas in the west coasts of Peninsular Malaysia. The concentrations of total PAHs varied from 357.1 to 6257.1 and 179.9 ± 7.6 to 1657.5 ± 53.9 ng g -1 dry weight in sediment and short-neck clam samples, respectively. PAHs can be classified as moderate to very high level of pollution in sediments and moderate to high level of pollution in short-neck clams. The diagnostic ratios of individual PAHs and principal component analysis indicate both petrogenic and pyrogenic sources with significant dominance of pyrogenic source. The first PAHs biota-sediment accumulation factors and relative biota-sediment accumulation factors data for short-neck clam were obtained in this study, indicating a preferential accumulation of lower molecular weight PAHs. Evaluation of PAH levels in sediments and short-neck clams indicates that short-neck clam could be introduced as a good biomonitor in mudflats. The results also demonstrated that under environmental conditions, the sedimentary load of hydrocarbons appears to be one of the factors controlling their bioavailability to biota.