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.
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.
Petroleum sludge is a hazardous waste that contains various organic compounds including polycyclic aromatic hydrocarbons (PAHs) which have carcinogenic-mutagenic and toxic characteristics. This study focuses on the thermal treatment (indirect heating) of petroleum sludge cake for PAH degradation at 250, 450, and 650 degrees C using Ca(OH)2 + NaHCO3 as an additive. The treatment was conducted in a rotary drum electric heater. All experiments were carried out in triplicate. Concentrations of the 16 priority PAHs in gas (absorbed on Amberlite XAD-4 adsorbent), particulate (on quartz filter) and residue phases were determined using gas chromatography-mass spectrometry (GC-MS). The samples were extracted with acetonitrile by ultra-sonication prior to GC-MS analysis. The use of additive was beneficial and a temperature of 450 degrees C was suitable for PAH degradation. Low levels of PAH emissions, particularly carcinogenic PAH and toxic equivalent concentration (sigma TEC), were observed in gas, particulate and residue phases after treatment.
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.
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.
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 persistent pollutants and chemically a class of structurally similar chemical compounds characterized by the presence of fused aromatic rings. This research was undertaken to find out immunotoxic effects produced by pyrene, phenanthrene and fluoranthene. These chemicals were injected into developing chicks at three dose levels (0.2, 2 and 20 mg per kg) through allantioc route to rule out possible mechanisms involved in immunotoxicity. DNA adduct produced by PAHs in immune organs were analyzed by DNA adduct enzyme-linked immunosorbent assay (ELISA) kit and DNA damage was assessed by comet assay. A significant increase in the DNA adduct levels was found in thymus and bursa in 2 mg and 20 mg dose levels of pyrene, fluoranthene and phenanthrene treated groups, whereas those in spleen simulated the value of controls. Comet assay indicated that PAHs especially pyrene, fluoranthene and phenanthrene were capable of inducing increased level of comet parameters in thymus at all the dose levels. Bursa of Fabricius and spleen also showed a gradual rise in comet parameters corresponding to all dose levels, but the increase was more marked as in thymus. Thus, it can be concluded that DNA adducts produced by PAHs lead to single-strand breaks and reduced DNA repair, which ultimately begin a carcinogenic process. Hence, this experiment can be considered as a strong evidence of genotoxic potential of PAHs like pyrene, phenanthrene and fluoranthene in developing chicks.
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.
Laccases are industrially attractive enzymes and their applications have expanded to the field of bioremediation. The challenge of today's biotechnology in enzymatic studies is to design enzymes that not only have a higher activity but are also more stable and could fit well with the condition requirements. Laccases are known to oxidize non-natural substrates like polycyclic aromatic hydrocarbons (PAHs). We suppose by increasing the hydrophobicity of laccase, it would increase the chance of the enzyme to meet the hydrophobic substrates in a contamination site, therefore increasing the bioremediation efficacy of PAHs from environment. In this attempt, the applications of evolutionary trace (ET), molecular surface accessibility and hydrophobicity analysis on laccase sequences and laccase's crystal structure (1KYA) are described for optimal design of an enzyme with higher hydrophobicity. Our analysis revealed that Q23A, Q45I, N141A, Q237V, N262L, N301V, N331A, Q360L and Q482A could be promising exchanges to be tested in mutagenesis experiments.
The spatial distribution of 19 polycyclic aromatic hydrocarbons (tPAHs) was quantified in aquacultures located in intertidal mudflats of the west coast of Peninsular Malaysia in order to investigate bioaccumulation of PAH in blood cockles, Anadara granosa (A. granosa). Fifty-four samples from environmental matrices and A. granosa were collected. The sampling locations were representative of a remote area as well as PAH-polluted areas. The relationship of increased background levels of PAH to anthropogenic PAH sources in the environment and their effects on bioaccumulation levels of A. granosa are investigated in this study. The levels of PAH in the most polluted station were found to be up to ten-fold higher than in remote areas in blood cockle. These high concentrations of PAHs reflected background contamination, which originates from distant airborne and waterborne transportation of contaminated particles. The fraction and source identification of PAHs, based on fate and transport considerations, showed a mix of petrogenic and pyrogenic sources. The relative biota-sediment accumulation factors (RBSAF), relative bioaccumulation factors from filtered water (RBAFw), and from suspended particulate matter (SPM) (RBAFSP) showed higher bioaccumulations of the lower molecular weight of PAHs (LMWs) in all stations, except Kuala Juru, which showed higher bioaccumulation of the higher molecular weight of PAHs (HMWs). Calculations of bioaccumulation factors showed that blood cockle can accumulate PAHs from sediment as well as water samples, based on the physico-chemical characteristics of habitat and behaviour of blood cockles. Correlations among concentrations of PAHs in water, SPM, sediment and A. granosa at the same sites were also found. Identification of PAH levels in different matrices showed that A. granosa can be used as a good biomonitor for LMW of PAHs and tPAHs in mudflats. Considering the toxicity and carcinogenicity of PAHs, the bioaccumulation by blood cockles are a potential hazard for both blood cockles and their consumers.
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.
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.
A new microextraction procedure termed agarose gel liquid phase microextraction (AG-LPME) combined with gas chromatography-mass spectrometry (GC-MS) was developed for the determination of selected polycyclic aromatic hydrocarbons (PAHs) in water. The technique utilized an agarose gel disc impregnated with the acceptor phase (1-octanol). The extraction procedure was performed by allowing the solvent-impregnated agarose gel disc to tumble freely in the stirred sample solution. After extraction, the agarose gel disc was removed and subjected to centrifugation to disrupt its framework and to release the impregnated solvent, which was subsequently withdrawn and injected into the GC-MS for analysis. Under optimized extraction conditions, the new method offered high enrichment factors (89-177), trace level LODs (9-14ngL(-1)) and efficient extraction with good relative recoveries in the range of 93.3-108.2% for spiked drinking water samples. AG-LPME did not exhibit any problems related to solvent dissolution, and it provided high extraction efficiencies that were comparable to those of hollow fiber liquid phase microextraction (HF-LPME) and significantly higher than those of agarose film liquid phase microextraction (AF-LPME). This technique employed a microextraction format and utilized an environmentally compatible solvent holder that supported the green chemistry concept.
With more than 80 cytochrome P450 (CYP) encoding genes found in the nematode Caenorhabditis elegans (C. elegans), the cyp35 genes are one of the important genes involved in many biological processes such as fatty acid synthesis and storage, xenobiotic stress response, dauer and eggshell formation, and xenobiotic metabolism. The C. elegans CYP35 subfamily consisted of A, B, C, and D, which have the closest homolog to human CYP2 family. C. elegans homologs could answer part of the hunt for human disease genes. This review aims to provide an overview of CYP35 in C. elegans and their human homologs, to explore the roles of CYP35 in various C. elegans biological processes, and how the genes of cyp35 upregulation or downregulation are influenced by biological processes, upon exposure to xenobiotics or changes in diet and environment. The C. elegans CYP35 gene expression could be upregulated by heavy metals, pesticides, anti-parasitic and anti-chemotherapeutic agents, polycyclic aromatic hydrocarbons (PAHs), nanoparticles, drugs, and organic chemical compounds. Among the cyp35 genes, cyp-35A2 is involved in most of the C. elegans biological processes regulation. Further venture of cyp35 genes, the closest homolog of CYP2 which is the largest family of human CYPs, may have the power to locate cyps gene targets, discovery of novel therapeutic strategies, and possibly a successful medical regime to combat obesity, cancers, and cyps gene-related diseases.
The fast pyrolysis of waste lignin derived from biobutanol production process was performed to determine the optimal pyrolysis conditions and pyrolysis product properties. Four types of pyrolysis reactors, e.g.: micro-scale pyrolyzer-gas chromatography/mass spectrometry, lab and bench scale fixed bed (FB) reactors, and bench scale rotary kiln (RK) reactor, were employed to compare the pyrolysis reaction conditions and product properties obtained from different reactors. The yields of char, oil, and gas obtained from lab scale and bench scale reactor were almost similar compared to FB reactor. RK reactor produced desirable bio-oil with much reduced yield of poly aromatic hydrocarbons (cancer precursor) due to its higher cracking reaction efficiency. In addition, char agglomeration and foaming of lignin pyrolysis were greatly restricted by using RK reactor compared to the FB reactor.
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.
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 reconstruction of fire history is essential to understand the palaeoclimate and human history. Polycyclic aromatic hydrocarbons (PAHs) have been extensively used as a fire marker. In this work, the distribution of PAHs in Borneo peat archives was investigated to understand how PAHs reflect the palaeo-fire activity. In total, 52 peat samples were analysed from a Borneo peat core for the PAH analysis. Pyrogenic PAHs consist of 2-7 aromatic rings, some of which have methyl and ethyl groups. The results reveal that the concentration of pyrogenic PAHs fluctuated with the core depth. Compared to low-molecular-weight (LMW) PAHs, the high-molecular-weight (HMW) PAHs had a more similar depth variation to the charcoal abundance. This finding also suggests that the HMW PAHs were mainly formed at a local fire near the study area, while the LMW PAHs could be transported from remote locations.
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.