Agarose film liquid phase microextraction (AF-LPME) procedure for the extraction and preconcentration of polycyclic aromatic hydrocarbons (PAHs) in water has been investigated. Agarose film was used for the first time as an interface between donor and acceptor phases in liquid phase microextraction which allowed for selective extraction of the analytes prior to gas chromatography-mass spectrometry. Using 1-octanol as acceptor phase, high enrichment factors in the range of 57-106 for the targeted analytes (fluorene, phenanthrene, fluoranthene and pyrene) were achieved. Under the optimum extraction conditions, the method showed good linearity in the range of 0.1-200 μgL(-1), good correlation coefficients in the range of 0.9963-0.9999, acceptable reproducibility (RSD 6.1-9.2%, n=3), low limits of detection (0.01-0.04 μgL(-1)) and satisfactory relative recoveries (92.9-104.7%). As the AF-LPME device was non-expensive, reuse or recycle of the film was not required, thus eliminating the possibility of analytes carry-over between runs. The AF-LPME technique is environment-friendly and compatible with the green chemistry concept as agarose is biodegradable polysaccharide extracted from seaweed and the procedure requires small volume of organic solvent and generates little waste. The validated method was successfully applied to the analysis of the four analytes in river water samples.
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.
Polycyclic aromatic hydrocarbons (PAHs) and linear alkylbenzenes (LABs) were used as anthropogenic markers of organic chemical pollution of sediments in the Selangor River, Peninsular Malaysia. This study was conducted on sediment samples from the beginning of the estuary to the upstream river during dry and rainy seasons. The concentrations of ƩPAHs and ƩLABs ranged from 203 to 964 and from 23 to 113 ng g(-1) dry weight (dw), respectively. In particular, the Selangor River was found to have higher sedimentary levels of PAHs and LABs during the wet season than in the dry season, which was primarily associated with the intensity of domestic wastewater discharge and high amounts of urban runoff washing the pollutants from the surrounding area. The concentrations of the toxic contaminants were determined according to the Sediment Quality Guidelines (SQGs). The PAH levels in the Selangor River did not exceed the SQGs, for example, the effects range low (ERL) value, indicating that they cannot exert adverse biological effects.
Tourism-related activities such as the heavy use of boats for transportation are a significant source of petroleum hydrocarbons that may harm the ecosystem of Langkawi Island. The contamination and toxicity levels of polycyclic aromatic hydrocarbon (PAH) in the sediments of Langkawi were evaluated using sediment quality guidelines (SQGs) and toxic equivalent factors. Ten samples were collected from jetties and fish farms around the island in December 2010. A gas chromatography/flame ionization detector (GC/FID) was used to analyse the 18 PAHs. The concentration of total PAHs was found to range from 869 ± 00 to 1637 ± 20 ng g⁻¹ with a mean concentration of 1167.00 ± 24 ng g⁻¹, lower than the SQG effects range-low (3442 ng g⁻¹). The results indicated that PAHs may not cause acute biological damage. Diagnostic ratios and principal component analysis suggested that the PAHs were likely to originate from pyrogenic and petrogenic sources. The toxic equivalent concentrations of the PAHs ranged from 76.3 to 177 ng TEQ/g d.w., which is lower compared to similar studies. The results of mean effects range-median quotient of the PAHs were lower than 0.1, which indicate an 11% probability of toxicity effect. Hence, the sampling sites were determined to be the low-priority sites.
The objective of this research was to investigate the relationship between lung cancer mortality rates, carcinogenic polycyclic aromatic hydrocarbon (PAH) emissions, and smoking on a global scale, as well as for different socioeconomic country groups. The estimated lung cancer deaths per 100,000 people (ED100000) and age standardized lung cancer death rate per 100,000 people (ASDR100000) in 2004 were regressed on PAH emissions in benzo[a]pyrene equivalence (BaPeq), smoking prevalence, cigarette price, gross domestic product per capita, percentage of people with diabetes, and average body mass index using simple and multiple linear regression for 136 countries. Using stepwise multiple linear regression, a statistically significant positive linear relationship was found between loge(ED100000) and loge(BaPeq) emissions for high (p-value <0.01) and for the combination of upper-middle and high (p-value <0.05) socioeconomic country groups. A similar relationship was found between loge(ASDR100000) and loge(BaPeq) emissions for the combination of upper-middle and high (p-value <0.01) socioeconomic country groups. Conversely, for loge(ED100000) and loge(ASDR100000), smoking prevalence was the only significant independent variable in the low socioeconomic country group (p-value <0.001). These results suggest that reducing BaPeq emissions in the U.S., Canada, Australia, France, Germany, Brazil, South Africa, Poland, Mexico, and Malaysia could reduce ED100000, while reducing smoking prevalence in Democratic People's Republic of Korea, Nepal, Mongolia, Cambodia, and Bangladesh could significantly reduce the ED100000 and ASDR100000.
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.
In this study, the surface sediments of the Malacca and Prai Rivers were analyzed to identify the distributions, and sources of Polycyclic Aromatic Hydrocarbons (PAHs). The total PAH concentrations varied from 716 to 1210 and 1102 to 7938 ng g(-1)dw in the sediments of the Malacca and Prai Rivers, respectively. The PAH concentrations can be classified as moderate and high level of pollution in the sediments of the Malacca and Prai Rivers, respectively. The comparison of PAHs with the Sediment Quality Guidelines (SQGs) indicates that the PAHs in the sediments of the Malacca and Prai Rivers may have the potential to cause adverse toxicity effects on the sampled ecosystems. The diagnostic ratios of individual PAHs indicate both petrogenic- and pyrogenic-origin PAHs with dominance of pyrogenic source in both rivers. These findings demonstrate that the environmental regulations in Malaysia have effectively reduced the input of petrogenic petroleum hydrocarbons into rivers.
Bioremediation is an effective strategy for cleaning up organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs). Advanced bioremediation implies that biotic agents are more efficient in degrading the contaminants completely. Bioremediation by microbial degradation is often employed and to make this process efficient, natural and cost-effective materials can serve as supportive matrices. Clay/modified clay minerals are effective adsorbents of PAHs/VOCs, and readily available substrate and habitat for microorganisms in the natural soil and sediment. However, the mechanism underpinning clay-mediated biodegradation of organic compounds is often unclear, and this requires critical investigation. This review describes the role of clay/modified clay minerals in hydrocarbon bioremediation through interaction with microbial agents in specific scenarios. The vision is on a faster, more efficient and cost-effective bioremediation technique using clay-based products. This review also proposes future research directions in the field of clay modulated microbial degradation of hydrocarbons.
In this study, caged calcium alginate-caged multiwalled carbon nanotubes dispersive microsolid phase extraction was described for the first time for the extraction of polycyclic aromatic hydrocarbons (PAHs) from water samples prior to gas chromatographic analysis. Fluorene, phenanthrene and fluoranthene were selected as model compounds. The caged calcium alginate-caged multiwalled carbon nanotubes was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy and thermal gravimetry analyses. The effective parameters namely desorption solvent, solvent volume, extraction time, desorption time, the mass of adsorbent and sample volume were optimized. Under the optimum extraction conditions, the developed method showed good linearity in the range of 0.5-50 ng mL-1 (R2 ≥ 0.996), low limits of detection and quantification (0.42-0.22 ng mL-1) (0.73-1.38 ng mL-1) respectively, good relative recoveries (71.2-104.2%) and reproducibility (RSD 1.8-12.4%, n = 3) for the studied PAHs in water sample. With high enrichment factor (1,000), short extraction time (<30 min), low amounts of adsorbent (100 mg) and low amounts of solvent (0.1 mol) have proven that the microsolid phase extraction method based on calcium alginate-caged multiwalled carbon nanotubes are environmentally friendly and convenient extraction method to use as an alternative adsorbent in the simultaneous preconcentration of PAHs from environmental water samples.
Increasing urbanization and changes in land use in Langat river basin lead to adverse impacts on the environment compartment. One of the major challenges is in identifying sources of organic contaminants. This study presented the application of selected chemometric techniques: cluster analysis (CA), discriminant analysis (DA), and principal component analysis (PCA) to classify the pollution sources in Langat river basin based on the analysis of water and sediment samples collected from 24 stations, monitored for 14 organic contaminants from polycyclic aromatic hydrocarbons (PAHs), sterols, and pesticides groups. The CA and DA enabled to group 24 monitoring sites into three groups of pollution source (industry and urban socioeconomic, agricultural activity, and urban/domestic sewage) with five major discriminating variables: naphthalene, pyrene, benzo[a]pyrene, coprostanol, and cholesterol. PCA analysis, applied to water data sets, resulted in four latent factors explaining 79.0% of the total variance while sediment samples gave five latent factors with 77.6% explained variance. The varifactors (VFs) obtained from PCA indicated that sterols (coprostanol, cholesterol, stigmasterol, β-sitosterol, and stigmastanol) are strongly correlated to domestic and urban sewage, PAHs (naphthalene, acenaphthene, pyrene, benzo[a]anthracene, and benzo[a]pyrene) from industrial and urban activities and chlorpyrifos correlated to samples nearby agricultural sites. The results demonstrated that chemometric techniques can be used for rapid assessment of water and sediment contaminations.
This study investigated polycyclic aromatic hydrocarbons (PAHs) pollution in surface sediments within aquaculture areas in Peninsular Malaysia using chemometric techniques, forensics and univariate methods. The samples were analysed using soxhlet extraction, silica gel column clean-up and gas chromatography mass spectrometry. The total PAH concentrations ranged from 20 to 1841 ng/g with a mean of 363 ng/g dw. The application of chemometric techniques enabled clustering and discrimination of the aquaculture sediments into four groups according to the contamination levels. A combination of chemometric and molecular indices was used to identify the sources of PAHs, which could be attributed to vehicle emissions, oil combustion and biomass combustion. Source apportionment using absolute principle component scores-multiple linear regression showed that the main sources of PAHs are vehicle emissions 54%, oil 37% and biomass combustion 9%. Land-based pollution from vehicle emissions is the predominant contributor of PAHs in the aquaculture sediments of Peninsular Malaysia.
In this study, the ranges of pollutants found in the soft tissues of Perna viridis collected from Kg. Masai and Kg. Sg. Melayu, both located in the Straits of Johore, were 0.85-1.58 μg/g dry weight (dw) for Cd, 5.52-12.2 μg/g dw for Cu, 5.66-8.93 μg/g dw for Ni and 63.4-72.3 μg/g dw for Zn, and 36.4-244 ng/g dry weight for ∑PAHs. Significantly (p < 0.05) higher concentrations of Cd, Cu, Ni, Zn and ∑PAHs in the mussels were found in the water of a seaport site at Kg. Masai than a non-seaport site at Kg. Sg. Melayu population. The ratios of low molecular weight/high molecular weight hydrocarbons (2.94-3.42) and fluoranthene/pyrene (0.43-0.45) in mussels from both sites indicated the origin of the PAHs to be mainly petrogenic. This study has demonstrated the utility of using the soft tissues of P. viridis as a biomonitor of PAH contamination and bioavailability in the coastal waters of Peninsular Malaysia.
In this work, a two-phase hollow fiber liquid-phase microextraction (HF-LPME) method combined with gas chromatography-mass spectrometry (GC-MS) is developed to provide a rapid, selective and sensitive analytical method to determine polycyclic aromatic hydrocarbons (PAHs) in fresh milk. The standard addition method is used to construct calibration curves and to determine the residue levels for the target analytes, fluorene, phenanthrene, fluoranthene, pyrene and benzo[a]pyrene, thus eliminating sample pre-treatment steps such as pH adjustment. The HF-LPME method shows dynamic linearity from 5 to 500 µg/L for all target analytes with R(2) ranging from 0.9978 to 0.9999. Under optimized conditions, the established detection limits range from 0.07 to 1.4 µg/L based on a signal-to-noise ratio of 3:1. Average relative recoveries for the determination of PAHs studied at 100 µg/L spiking levels are in the range of 85 to 110%. The relative recoveries are slightly higher than those obtained by conventional solvent extraction, which requires saponification steps for fluorene and phenanthrene, which are more volatile and heat sensitive. The HF-LPME method proves to be simple and rapid, and requires minimal amounts of organic solvent that supports green analysis.
Land application of sludge as fertilizers is a way of disposal and recycling of sludge. However, public concern has arisen due to the fact that organic contaminants in sludge may ultimately enter the food chain. Hence the need arises to analyse the organic contaminants such as PAHs and OCPs in sludge. In this study, Soxhlet was utilised as the extraction method and the extracts subjected to extensive cleanup via either silica columns or solid phase extraction cartridges prior to analysis using gas chromatography or high performance liquid chromatography. Sludge samples were collected from the drying beds of oxidation ponds in three locations in South Johore. OCPs such as heptachlor, dieldrin and pp-DDT were detected in low amounts (52-159 mg/kg) whereas PAHs such as naphthalene, phenanthrene, fluoranthene and benzo(a)pyrene were detected in the range of 0.2-5.5 mg/kg dry mass. Subcritical water extraction (SWE) recovery studies of PAHs were also performed from spiked sludge samples. Although a recovery range of 41-68% was obtained using the SWE method, the results indicated the usefulness of the technique as an alternative to Soxhlet extraction for the analysis of PAHs in sludge samples.
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.
A comprehensive monitoring survey for polycyclic aromatic hydrocarbons (PAHs) and phenolic endocrine disrupting chemicals (EDCs) utilizing mussels as sentinel organisms was conducted in South and Southeast Asia as a part of the Asian Mussel Watch project. Green mussel (Perna viridis) samples collected from a total of 48 locations in India, Indonesia, Singapore, Malaysia, Thailand, Cambodia, Vietnam, and the Philippines during 1994-1999 were analyzed for PAHs, EDCs including nonylphenol (NP), octylphenol (OP) and bisphenol A (BPA), and linear alkylbenzenes (LABs) as molecular markers for sewage. Concentrations of NP ranged from 18 to 643 ng/g-dry tissue. The highest levels of NP in Malaysia, Singapore, the Philippines, and Indonesia were comparable to those observed in Tokyo Bay. Elevated concentrations of EDCs were not observed in Vietnam and Cambodia, probably due to the lower extent of industrialization in these regions. No consistent relationship between concentrations of phenolic EDCs and LABs were found, suggesting that sewage is not a major source of EDCs. Concentrations of PAHs ranged from 11 to 1,133 ng/g-dry, which were categorized as "low to moderate" levels of pollution. The ratio of methylphenanthrenes to phenanthrene (MP/P ratio) was >1.0 in 20 out of 25 locations, indicating extensive input of petrogenic PAHs. This study provides a bench-mark for data on the distribution of anthropogenic contaminants in this region, which is essential in evaluating temporal and spatial variation and effect of future regulatory measures.
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.
This is the first report on bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) and their derivatives (oxygen, nitrogen, sulfur, hydroxyl, carbonyl and methyl-containing PAHs) in three edible marine fishes, namely Lutjanus argentimaculatus, Lethrinus microdon and Scomberomorus guttatus, from Kharg Island, Persian Gulf, Iran. The concentrations (ng g-1dw) of Σ39PAHs resulted significantly higher in fish liver than muscle, with the PAH composition pattern dominated by low molecular weight compounds (naphthalene, alkyl-naphthalenes and phenanthrene). The highest mean concentrations of ∑9 oxygenated and ∑15 hydroxylated PAHs (ng g-1dw) were found ound in L. microdon and L. argentimaculatus, respectively, while the lowest values in S. guttatus. Additionally, the highest mean concentrations of Σ5 carbonylic PAHs (ng g-1dw) were found in L. argentimaculatus, followed by L. microdon. The PAHs levels and distribution in fish liver and muscle were dependent on both the Kow of PAHs congeners and fish lipid contents. Overall, the present findings provide important baseline data for further research on the ecotoxicity of PAHs in aquatic organisms, and consequent implications for human health.
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.
The distribution, sources, and human health risk assessment of polycyclic aromatic hydrocarbons (PAHs) in surface sediment and the edible tissue of short-neck clam (Paphia undulata) from mudflat ecosystem in the west coast of Malaysia were investigated. The concentrations of ∑16 PAHs varied from 347.05 to 6207.5 and 179.32 to 1657.5 ng g-1 in sediment and short-neck clam samples, respectively. The calculations of mean PEL quotients (mean-PELQs) showed that the ecological risk of PAHs in the sediment samples was low to moderate-high level, whereas the total health risk through ingestion and dermal contact was considerably high. The PAHs biota sediment accumulation factors data for short-neck clam were obtained in this study, indicating a preferential accumulation of lower molecular weight PAHs. The source apportionment of PAHs in sediment using positive matrix factorization model indicated that the highest contribution to the PAHs was from diesel emissions (30.38%) followed by oil and oil derivate and incomplete coal combustion (23.06%), vehicular emissions (16.43%), wood combustion (15.93%), and natural gas combustion (14.2%). A preliminary evaluation of human health risk using chronic daily intake, hazard index, benzo[a]pyrene-equivalent (BaPeq) concentration, and the incremental lifetime cancer risk indicated that PAHs in short-neck clam would induce potential carcinogenic effects in the consumers.