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.
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.
The concentration of carcinogenic poly aromatic hydrocarbons (c-PAHs) present in water and sediment of Klang Strait as well as in the edible tissue of blood cockle (Anadara granosa) was investigated. The human health risk of c-PAHs was assessed in accordance with the standards of the United States Environmental Protection Agency (US EPA). The cancer risks of c-PAHs to human are expected to occur through the consumption of blood cockles or via gastrointestinal exposure to polluted sediments and water in Kalng Strait. The non-carcinogenic risks that are associated with multiple pathways based on ingestion rate and contact rates with water were higher than the US EPA safe level at almost all stations, but the non-carcinogenic risks for eating blood cockle was below the level of US EPA concern. A high correlation between concentrations of c-PAHs in different matrices showed that the bioaccumulation of c-PAHs by blood cockles could be regarded as a potential health hazard for the consumers.
Concentration, source, and ecological risk of polycyclic aromatic hydrocarbons (PAHs) were investigated in 22 stations from surface sediments in the areas of anthropogenic pollution in the Klang Strait (Malaysia). The total PAH level in the Klang Strait sediment was 994.02±918.1 µg/kg dw. The highest concentration was observed in stations near the coastline and mouth of the Klang River. These locations were dominated by high molecular weight PAHs. The results showed both pyrogenic and petrogenic sources are main sources of PAHs. Further analyses indicated that PAHs primarily originated from pyrogenic sources (coal combustion and vehicular emissions), with significant contribution from petroleum inputs. Regarding ecological risk estimation, only station 13 was moderately polluted, the rest of the stations suffered rare or slight adverse biological effects with PAH exposure in surface sediment, suggesting that PAHs are not considered as contaminants of concern in the Klang Strait.
Major concern about the presence of fluoranthene, which consists of four fused benzene rings, in the environment has been raised in the past few years due to its toxic, mutagenic, and persistent organic pollutant properties. In this study, we investigated the removal of fluoranthene under static and agitated conditions. About 89% fluoranthene was removed within 30 days under the agitated condition, whereas under the static condition, only 54% fluoranthene was removed. We further investigated the behavior and mechanism of fluoranthene biosorption and biotransformation by Pleurotus eryngii F032 to accelerate the elimination of fluoranthene. The optimum conditions for the elimination of fluoranthene by P. eryngii F032 included a temperature of 35 °C, pH 3, 0.2% inoculum concentration, and a C/N ratio of 16. Under these conditions at the initial fluoranthene concentration of 10 mg/L, more than 95% of fluoranthene was successfully removed within 30 days. Of those factors influencing the biodegradation of fluoranthene, salinity, glucose, and rhamnolipid content were of the greatest importance. Degradation metabolites identified using gas chromatography-mass spectrometry were 1-naphthalenecarboxylic acid and salicylic acid, suggesting possible metabolic pathways. Finally, it can be presumed that the major mechanism of fluoranthene elimination by white-rot fungi is to mineralize polycyclic aromatic hydrocarbons via biotransformation enzymes like laccase.
This study aims to investigate the impacts of ethyl lactate (EL) based Fenton treatment on soil quality for polycyclic aromatic hydrocarbons (PAHs)-contaminated soils. Accumulation of oxygenated-polycyclic aromatic hydrocarbons (oxy-PAHs) was observed, but quantitative measurement on the most abundant compound 9,10-anthraquinone (ATQ) showed lower accumulation of the compound than that reported for ethanol (ET) based Fenton treatment. In general, as compared to conventional water (CW) based Fenton treatment, the EL based Fenton treatment exerted either a lower or higher negative impact on soil physicochemical properties depending on the property type and shared the main disadvantage of reduced soil pH. For revegetation, EL based Fenton treatment was most appropriately adopted for soil with native pH >/~ 6.2 in order to obtain a final soil pH >/~ 4.9 subject to the soil buffering capacity.
Armillaria sp. F022 is a white-rot fungus isolated from a tropical rain forest in Indonesia that is capable of utilizing pyrene as a source of carbon and energy. Enzymes production during the degradation process by Armillaria sp. F022 was certainly related to the increase in biomass. In the first week after incubation, the growth rate rapidly increased, but enzyme production decreased. After 7 days of incubation, rapid growth was observed, whereas, the enzymes were produced only after a good amount of biomass was generated. About 63 % of pyrene underwent biodegradation when incubated with this fungus in a liquid medium on a rotary shaker (120 rpm, 25 °C) for 30 days; during this period, pyrene was transformed to five stable metabolic products. These metabolites were extracted in ethyl acetate, isolated by column chromatography, and then identified using thin layer chromatography (TLC) and gas chromatography-mass spectrometry (GC-MS). 1-Hydroxypyrene was directly identified by GC-MS, while 4-phenanthroic acid, 1-hydroxy-2-naphthoic acid, phthalic acid, and protocatechuic acid were identified to be present in their derivatized forms (methylated forms and silylated forms). Protocatechuic acid was the end product of pyrene degradation by Armillaria sp. F022. Dynamic profiles of two key enzymes, namely laccase and 1,2-dioxygenase, were revealed during the degradation process, and the results indicated the presence of a complicated mechanism in the regulation of pyrene-degrading enzymes. In conclusion, Armillaria sp. F022 is a white-rot fungus with potential for application in the degradation of polycyclic aromatic hydrocarbons such as pyrene in the environment.
We collected surface sediment samples from 174 locations in India, Indonesia, Malaysia, Thailand, Vietnam, Cambodia, Laos, and the Philippines and analyzed them for polycyclic aromatic hydrocarbons (PAHs) and hopanes. PAHs were widely distributed in the sediments, with comparatively higher concentrations in urban areas (Sigma PAHs: approximately 1000 to approximately 100,000 ng/g-dry) than in rural areas ( approximately 10 to approximately 100g-dry), indicating large sources of PAHs in urban areas. To distinguish petrogenic and pyrogenic sources of PAHs, we calculated the ratios of alkyl PAHs to parent PAHs: methylphenanthrenes to phenanthrene (MP/P), methylpyrenes+methylfluoranthenes to pyrene+fluoranthene (MPy/Py), and methylchrysenes+methylbenz[a]anthracenes to chrysene+benz[a]anthracene (MC/C). Analysis of source materials (crude oil, automobile exhaust, and coal and wood combustion products) gave thresholds of MP/P=0.4, MPy/Py=0.5, and MC/C=1.0 for exclusive combustion origin. All the combustion product samples had the ratios of alkyl PAHs to parent PAHs below these threshold values. Contributions of petrogenic and pyrogenic sources to the sedimentary PAHs were uneven among the homologs: the phenanthrene series had a greater petrogenic contribution, whereas the chrysene series had a greater pyrogenic contribution. All the Indian sediments showed a strong pyrogenic signature with MP/P approximately 0.5, MPy/Py approximately 0.1, and MC/C approximately 0.2, together with depletion of hopanes indicating intensive inputs of combustion products of coal and/or wood, probably due to the heavy dependence on these fuels as sources of energy. In contrast, sedimentary PAHs from all other tropical Asian cities were abundant in alkylated PAHs with MP/P approximately 1-4, MPy/Py approximately 0.3-1, and MC/C approximately 0.2-1.0, suggesting a ubiquitous input of petrogenic PAHs. Petrogenic contributions to PAH homologs varied among the countries: largest in Malaysia whereas inferior in Laos. The higher abundance of alkylated PAHs together with constant hopane profiles suggests widespread inputs of automobile-derived petrogenic PAHs to Asian waters.
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.
Concentrations of 12 hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) were determined in 306 urine samples collected from seven Asian countries (China, India, Japan, Korea, Kuwait, Malaysia, and Vietnam) by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The total concentrations of OH-PAHs found in the seven Asian countries were in the following increasing order: Malaysia (median: 2260 pg/mL) < Japan (4030 pg/mL) < China (5770 pg/mL) < India (6750 pg/mL) < Vietnam (8560 pg/mL) < Korea (9340 pg/mL) < Kuwait (10170 pg/mL). The measured urinary concentrations of 1-hydroxypyrene (1-PYR) in samples from Malaysia, Korea, and Japan (∼ 100 pg/mL) were similar to those reported for North America and Western Europe. The concentrations of 1-PYR in urine samples from China, India, and Vietnam were 4-10 times higher than those reported for other countries, thus far. Among the 12 OH-PAH compounds analyzed, hydroxynaphthalene (NAP: sum of 1-hydroxynaphthalene and 2-hydroxynaphthalene) was the dominant compound (accounting for 60-90% of total OH-PAHs), followed by hydroxyphenanthrene (PHEN: sum of 2-hydroxyphenanthrene, 3-hydroxyphenanthrene, 4-hydroxyphenanthrene, and 9-hydroxyphenanthrene [3-16%]), 2-hydroxyfluorene (3-20%), and 1-PYR (2-8%). The total daily intakes (DIs) of PAHs were estimated based on the urinary concentrations of their metabolites. The DIs of naphthalene were found to be higher for populations in Korea, Kuwait, and Vietnam (> 10 μg/day) than those of the other countries studied (∼ 5 μg/day). The DIs of phenanthrene and pyrene (> 10 μg/day) in the populations of China, India, and Vietnam were higher than those estimated for the populations in the other countries studied (∼ 5 μg/day).
Malaysian coasts are subjected to various threats of petroleum pollution including routine and accidental oil spill from tankers, spillage of crude oils from inland and off-shore oil fields, and run-off from land-based human activities. Due to its strategic location, the Straits of Malacca serves as a major shipping lane. This paper expands the utility of biomarker compounds, hopanes, in identifying the source of tar-balls stranded on Malaysian coasts. 20 tar-ball samples collected from the east and west coast were analyzed for hopanes and polycyclic aromatic hydrocarbons (PAHs). Four of the 13 tar-ball samples collected from the west coast of Peninsular Malaysia were identified as the Middle East crude oil (MECO) based on their biomarker signatures, suggesting tanker-derived sources significantly contributing the petroleum pollution in the Straits of Malacca. The tar-balls found on the east coast seem to originate from the offshore oil platforms in the South China Sea. The presence of South East Asian crude oil (SEACO) tar-balls on the west coast carry several plausible explanations. Some of the tar-balls could have been transported via sea currents from the east coast. The tankers carrying SEACO to other countries could have accidentally spilt the oil as well. Furthermore, discharge of tank washings and ballast water from the tankers were suggested based on the abundance in higher molecular weight n-alkanes and the absence of unresolved complex mixture (UCM) in the tar-ball samples. The other possibilities are that the tar-balls may have been originated from the Sumatran oil fields and spillage of domestic oil from oil refineries in Port Dickson and Malacca. The results of PAHs analysis suggest that all the tar-ball samples have undergone various extent of weathering through evaporation, dissolution and photooxidation.
A novel adsorbent, palm fatty acid coated magnetic Fe3O4 nanoparticles (MNP-FA) was successfully synthesized with immobilization of the palm fatty acid onto the surface of MNPs. The successful synthesis of MNP-FA was further confirmed by X-Ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and Energy dispersive X-Ray spectroscopy (EDX) analyses and water contact angle (WCA) measurement. This newly synthesized MNP-FA was applied as magnetic solid phase extraction (MSPE) adsorbent for the enrichment of polycyclic aromatic hydrocarbons (PAHs), namely fluoranthene (FLT), pyrene (Pyr), chrysene (Cry) and benzo(a)pyrene (BaP) from environmental samples prior to High Performance Liquid Chromatography- Diode Array Detector (HPLC-DAD) analysis. The MSPE method was optimized by several parameters such as amount of sorbent, desorption solvent, volume of desorption solvent, extraction time, desorption time, pH and sample volume. Under the optimized conditions, MSPE method provided a low detection limit (LOD) for FLT, Pyr, Cry and BaP in the range of 0.01-0.05 ng mL(-1). The PAHs recoveries of the spiked leachate samples ranged from 98.5% to 113.8% with the RSDs (n = 5) ranging from 3.5% to 12.2%, while for the spiked sludge samples, the recoveries ranged from 81.1% to 119.3% with the RSDs (n = 5) ranging from 3.1% to 13.6%. The recyclability study revealed that MNP-FA has excellent reusability up to five times. Chromatrographic analysis demonstrated the suitability of MNP-FA as MSPE adsorbent for the efficient extraction of PAHs from environmental samples.
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 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.
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.
Amending polycyclic aromatic hydrocarbon (PAH)-contaminated soils with biochar may be cheaper and environmentally friendly than other forms of organic materials. This has led to numerous studies on the use of biochar to either bind or stimulate the microbial degradation of organic compounds in soils. However, very little or no attention have been paid to the fact that biochars can give simultaneous impact on PAH fate processes, such as volatilization, sorption and biodegradation. In this review, we raised and considered the following questions: How does biochar affect microbes and microbial activities in the soil? What are the effects of adding biochar on sorption of PAHs? What are the effects of adding biochar on degradation of PAHs? What are the factors that we can manipulate in the laboratory to enhance the capability of biochars to degrade PAHs? A triphasic concept of how biochar can give simultaneous impact on PAH fate processes in soils was proposed, which involves rapid PAH sorption into biochar, subsequent desorption and modification of soil physicochemical properties by biochar, which in turn stimulates microbial degradation of the desorbed PAHs. It is anticipated that biochar can give simultaneous impact on PAH fate processes in soils.
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.
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.
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.
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