In this study, the distributions and sources of sediment-associated polycyclic aromatic hydrocarbons (PAHs) and hopanes in the Malaysian rivers and estuaries were evaluated. The concentrations of 16 USEPA PAHs varied from 225.5 to 293.9 (Perlis River), 195.2 to 481.2 (Kedah River), 791.2 to 1995.4 (Merbok River), 231.2 to 426.7 (Perak River), and 3803.2 to 7442.7 ng g(-1) (Klang River) dry weight. PAHs can be classified as moderate in the Perlis, Kedah, and Perak Rivers, moderate to high in the Merbok River, and high to very high in the Klang River. The comparison of PAHs with sediment quality guidelines (SQGs) indicates that occasionally adverse biological effects may occur from total PAHs, low molecular weight (LMW), and high molecular weight (HMW) PAHs at stations 1, 2, and 3 of the Klang River and from total PAHs at station 2 of the Merbok River. The diagnostic ratios of individual PAHs indicate both petrogenic and pyrogenic origin PAHs with significant dominance of pyrogenic sources in the study areas. The results suggest that Malaysian sediments had hopane ratios (C29/C30) similar to MECO suggesting MECO as a major source of the petroleum hydrocarbons found in the sediments, which is consistent with results reported in previous studies. These findings demonstrate that effective and improved environmental regulations in Malaysia have shifted the source of petroleum hydrocarbons from petrogenic to pyrogenic origin.
In this work, crude oil biodegradation has been optimized in a solid-liquid two phase partitioning bioreactor (TPPB) by applying a response surface methodology based d-optimal design. Three key factors including phase ratio, substrate concentration in solid organic phase, and sodium chloride concentration in aqueous phase were taken as independent variables, while the efficiency of the biodegradation of absorbed crude oil on polymer beads was considered to be the dependent variable. Commercial thermoplastic polyurethane (Desmopan®) was used as the solid phase in the TPPB. The designed experiments were carried out batch wise using a mixed acclimatized bacterial consortium. Optimum combinations of key factors with a statistically significant cubic model were used to maximize biodegradation in the TPPB. The validity of the model was successfully verified by the good agreement between the model-predicted and experimental results. When applying the optimum parameters, gas chromatography-mass spectrometry showed a significant reduction in n-alkanes and low molecular weight polycyclic aromatic hydrocarbons. This consequently highlights the practical applicability of TPPB in crude oil biodegradation.
A 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.
A brief review is conducted on the application of vegetable oils in the treatment of PAH-contaminated soils. Three main scopes of treatment strategies are discussed in this work including soil washing by oil, integrated oil-biological treatment and integrated oil-non-biological treatment. For each of these, the arguments supporting vegetable oil application, the applied treatment techniques and their efficiencies, associated factors, as well as the feasibility of the techniques are detailed. Additionally, oil regeneration, the environmental impacts of oil residues in soil and comparison with other commonly employed techniques are also discussed.
Polycyclic aromatic hydrocarbons (PAHs) 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.
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.
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.
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.
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.
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.
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.
Solubility data of recalcitrant contaminants in cosolvents is essential to determine their potential applications in enhanced soil remediation. The solubilities of phenanthrene, anthracene, fluoranthene and benzo[a]pyrene in ethyl lactate/water and ethanol/water mixtures were measured using equilibrium techniques. The cosolvency powers derived from solubility data were then applied to the model developed from the solvophobic approach to predict the capability of ethyl lactate and ethanol in enhancing the desorption of contaminants from soils. Both ethyl lactate and ethanol cosolvents were shown to be able to enhance the solubilisation of the tested four polycyclic aromatic hydrocarbons by > 4 orders of magnitude above the levels obtained with water alone. However, ethyl lactate demonstrated a greater capacity to enhance PAH solubility than ethanol. The cosolvency powers of ethyl lactate/water system obtained from the end-to-end slope (sigma) and the end-to-half slope (sigma0.5) of the solubilisation curve were 1.0-1.5 and 2.0-2.9 higher than ethanol/water system respectively. In line with this, ethyl lactate/water was demonstrated to enhance the desorption of contaminants from soil by 20%-37% and 18%-61% higher compared to ethanol/water system in low organic content and high organic content soils respectively, with a 2:1 (V/W) ratio of solution:soil and with cosolvent fraction as low as 0.4. With the exception of benzo[a]pyrene, the experimental desorption results agreed fairly with the predicted values, under an applied solution:soil ratio that was enough to hold the capacity of released contaminants.
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.
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.
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.
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.
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 present study aimed to determine the degradation and transformation of three-ring PAHs phenanthrene and anthracene by Cryptococcus sp. MR22 and Halomonas sp. BR04 under halophilic conditions. The growth progress of Cryptococcus sp. MR22 and Halomonas sp. BR04 on anthracene and phenanthrene was monitored by colony-forming unit (CFU) technique. The growth of the bacteria was maintained at a maximum concentration of 200 mg/L of all tested hydrocarbon, indicating that Cryptococcus sp. MR22 and Halomonas sp. BR04 significantly perform in the removal of the PAH-contaminated medium at low concentrations. The fit model to represent the biodegradation kinetics of both PAHs was first-order rate equation The extract prepared from cells supplemented with three different substrates exhibited some enzymes such as hydroxylase, dioxygenase, laccase and peroxidase. The results suggest that both strains had an impressive ability in the degradation of aromatic and aliphatic hydrocarbon but also could tolerate in the extreme salinity condition.