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.
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.
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.
The Changbai (also known as "Baekdu") Mountain, on the border between China and North Korea, is the highest mountain (2750 m) in northeastern China. Recently, this mountain region has experienced a dramatic increase in air pollution, not only because of increasing volumes of tourism-derived traffic but also because of the long-range transport of polluted westerly winds passing through major industrial and urban cities in the eastern region of China. To assess the relative importance of the two sources of pollution, 16 polycyclic aromatic hydrocarbons (PAHs) as model substances were determined in the mountain soil. A total of 32 soil samples were collected from different sides of the mountain at different latitudes between July and August of 2009. The ∑PAH concentrations were within the range 38.5-190.1 ng g(-1) on the northern side, 117.7-443.6 ng g(-1) on the southern side, and 75.3-437.3 ng g(-1) on the western side. A progressive increase in the level of ∑PAHs with latitude was observed on the southern and western sides that face the westerly wind with abundant precipitation. However, a similar concentration gradient was not observed on the northern side that receives less rain and is on the leeward direction of the wind. The high-molecular-weight PAH compounds were predominant in the soils on the southern and western sides, while low-molecular-weight PAHs dominated the northern side soils. These findings show that the distribution of PAHs in the mountain soil is strongly influenced by the atmospheric long-range transport and cold trapping.
This paper aims to review the applications of Fenton based treatments specifically for polycyclic aromatic hydrocarbons-contaminated soils. An overview of the background and principles of Fenton treatment catalysed by both homogenous (conventional and modified Fenton) and heterogeneous (Fenton-like) catalysts is firstly presented. Laboratory and field soil remediation studies are then discussed in terms of efficiency, kinetics and associated factors. Four main scopes of integrated Fenton treatments, i.e. physical-Fenton, biological-Fenton, electro-Fenton and photo-Fenton are also reviewed in this paper. For each of these integrated remediation technologies, the theoretical background and mechanisms are detailed alongside with achievable removal efficiencies for polycyclic aromatic hydrocarbons in contaminated soils compared to sole Fenton treatment. Finally, the environmental impacts of Fenton based soil treatments are documented and discussed.
This study aimed to determine the spatial distribution of PM2.5 and PM10 collected in four regions (North, Central, South and East Coast) of Peninsular Malaysia during the southwest monsoon. Concurrent measurements of PM2.5 and PM10 were performed using a high volume sampler (HVS) for 24 h (August to September 2018) collecting a total of 104 samples. All samples were then analysed for water soluble inorganic ions (WSII) using ion chromatography, trace metals using inductively coupled plasma-mass spectroscopy (ICP-MS) and polycyclic aromatic hydrocarbon (PAHs) using gas chromatography-mass spectroscopy (GC-MS). The results showed that the highest average PM2.5 concentration during the sampling campaign was in the North region (33.2 ± 5.3 μg m-3) while for PM10 the highest was in the Central region (38.6 ± 7.70 μg m-3). WSII recorded contributions of 22% for PM2.5 and 20% for PM10 mass, with SO42- the most abundant species with average concentrations of 1.83 ± 0.42 μg m-3 (PM2.5) and 2.19 ± 0.27 μg m-3 (PM10). Using a Positive Matrix Factorization (PMF) model, soil fertilizer (23%) was identified as the major source of PM2.5 while industrial activity (25%) was identified as the major source of PM10. Overall, the studied metals had hazard quotients (HQ) value of <1 indicating a very low risk of non-carcinogenic elements while the highest excess lifetime cancer risk (ELCR) was recorded for Cr VI in the South region with values of 8.4E-06 (PM2.5) and 6.6E-05 (PM10). The incremental lifetime cancer risk (ILCR) calculated from the PAH concentrations was within the acceptable range for all regions.
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.
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.
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.
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.
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.
Chenab River is one of the most important rivers of Punjab Province (Pakistan) that receives huge input of industrial effluents and municipal sewage from major cities in the Central Punjab, Pakistan. The current study was designed to evaluate the concentration levels and associated ecological risks of USEPA priority polycyclic aromatic hydrocarbons (PAHs) in the surface sediments of Chenab River. Sampling was performed from eight (n = 24) sampling stations of Chenab River and its tributaries. We observed a relatively high abundance of ∑16PAHs during the summer season (i.e. 554 ng g(-1)) versus that in the winter season (i.e. 361 ng g(-1)), with an overall abundance of two-, five- and six-ring PAH congeners. Results also revealed that the nitrate and phosphate contents in the sediments were closely associated with low molecular weight (LMW) and high molecular weight (HMW) PAHs, respectively. Source apportionment results showed that the combustion of fossil fuels appears to be the key source of PAHs in the study area. The risk quotient (RQ) values indicated that seven PAH congeners (i.e. phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)pyrene, chrysene and benzo(a)anthracene) could pose serious threats to the aquatic life of the riverine ecosystem in Pakistan.
Polycyclic aromatic hydrocarbons (PAHs) in soil have been recognised as a serious health and environmental issue due to their carcinogenic, mutagenic and teratogenic properties. One of the commonly employed soil remediation techniques to clean up such contamination is soil washing or solvent extraction. The main factor which governs the efficiency of this process is the solubility of PAHs in the extraction agent. Past field-scale soil washing treatments for PAH-contaminated soil have mainly employed organic solvents or water which is either toxic and costly or inefficient in removing higher molecular weight PAHs. Thus, the present article aims to provide a review and discussion of the alternative extraction agents that have been studied, including surfactants, biosurfactants, microemulsions, natural surfactants, cyclodextrins, vegetable oil and solution with solid phase particles. These extraction agents have been found to remove PAHs from soil at percentages ranging from 47 to 100% for various PAHs.
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.
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.
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 study reports the concentrations and congener partners of polychlorinated biphenyls (PCBs) in commercially available paints. Polycyclic-type pigments containing dioxazine violet (pigment violet (PV) 23, PV37) and diketopyrrolopyrrole (PR254, PR255) were found to contain PCB-56, PCB-77, PCB-40, PCB-5, and PCB-12, and PCB-6, PCB-13, and PCB-15, respectively, as major congeners. Dioxazine violet is contaminated with by-products during synthesis from o-dichlorobenzene, which is used as a solvent during synthesis, and diketopyrrolopyrrole is contaminated with by-products during synthesis from p-chlorobenzonitrile. The concentration of PCBs in paint containing PV23 or PV37 was 0.050-29 mg/kg, and toxic equivalency (TEQ) values ranged 1.1-160 pg-TEQ/g. The concentration of PCBs in paint containing PR254 or PR255 was 0.0019-2.4 mg/kg. Naphthol AS is an azo-type pigment, and PCB-52 was detected in paint containing pigment red (PR) 9 with 2,5-dichloroaniline as its source. PCB-146, PCB-149, and PCB-153 were identified from paint containing PR112 produced from 2,4,5-trichloroaniline, as major congeners. These congeners have chlorine positions similar to aniline, indicating that these congeners are by-products obtained during the synthesis of pigments. The concentrations of PCBs in paints containing PR9 and PR112 were 0.0042-0.43 and 0.0044-3.8 mg/kg, respectively. The corresponding TEQ for PR112 was 0.0039-8.6 pg-TEQ/g.
This study focuses on the feasibility of treating aged polycyclic aromatic hydrocarbons (PAHs)-contaminated soils using ethyl lactate (EL)-based Fenton treatment via a combination of parametric and kinetic studies. An optimised operating condition was observed at 66.7 M H2O2 with H2O2/Fe(2+) of 40:1 for low soil organic carbon (SOC) content and mildly acidic soil (pH 6.2), and 10:1 for high SOC and very acidic soil (pH 4.4) with no soil pH adjustment. The desorption kinetic was only mildly shifted from single equilibrium to dual equilibrium of the first-order kinetic model upon ageing. Pretreatment with EL fc = 0.60 greatly reduced the mass transfer coefficient especially for the slow desorbed fraction (kslow) of high molecular weight (HMW) PAHs, largely contributed by the concentration gradient created by EL-enhanced solubility. As the major desorption obstacle was almost fully overcome by the pretreatment, the pseudo-first-order kinetic reaction rate constant of PAHs degradation of aged soils was statistically discernible from that of freshly contaminated soils but slightly reduced in high SOC and high acidity soil. Stabilisation of H2O2 by EL addition in combination with reduced Fe(2+) catalyst were able to slow the decomposition rate of H2O2 even at higher soil pH.
This study investigated the simultaneous formation of polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatic amines (HCAs) in gas-grilled beef satay at different temperatures (150, 200, 250, 300, and 350°C). Solid-phase extraction (SPE) was used for sample clean-up. Fifteen PAHs were determined using high performance liquid chromatography with fluorescence detection (HPLC-FLD) and nine HCAs were quantified using liquid chromatography tandem-mass spectrometry (LC-MS/MS) with a gradient programme. The lowest significantly concentrations of PAHs and HCAs were generated at 150°C; the formation of PAHs and HCAs simultaneously increased with temperatures. Benzo[a]pyrene was detected in all samples and increased markedly at 300 and 350°C. The sums of 4 PAHs (PAH4) in marinated beef satay at 300 and 350°C exceeded the maximum level in Commission Regulation (EU) 2015/1125. Significant reductions of polar and non-polar HCAs (except PhIP) were found in marinated beef satay across all temperatures. Overall, PAHs and HCAs showed opposite trends of formation in beef satay with marination.
Roasting is an important process in cocoa production which may lead to formation of non-desirable compounds such as polycyclic aromatic hydrocarbons (PAHs). Therefore, PAH4 (sum of four different polycyclic aromatic hydrocarbons; benz[a]anthracene, chrysene, benzo[b]fluoranthene, and benzo[a]pyrene) in roasted cocoa beans was determined using a modified method (combination of QuEChERS and DLLME), and quantified by HPLC-FLD. The modified method was validated and met the performance criteria required by the EU Regulation (No. 836/2011). Results show a significant (p