Accumulation of polycyclic aromatic hydrocarbons (PAH) poses significant dangers to the environment and human health. The advancement of technology for cleaning up PAH-contaminated environments is receiving more attention. Adsorption is the preferred and most favorable approach for cleaning up sediments polluted with PAH. Due to their affordability and environmental friendliness, carbonaceous adsorbents (CAs) have been regarded as promising for adsorbing PAH. However, adsorbent qualities, environmental features, and factors may all significantly impact how well CAs remove PAH. According to growing data, CAs, most of which come from laboratory tests, may be utilized to decontaminate PAH in aquatic setups. However, their full potential has not yet been established, especially concerning field applications. This review aims to concisely summarize recent developments in CA, PAH stabilization processes, and essential field application-controlling variables. This review analysis emphasizes activated carbon, biochar, Graphene, carbon nanotubes, and carbon-nanomaterials composite since these CAs are most often utilized as adsorbents for PAH in aquatic systems.
Abundance of fine particulate-bound 16 priority polycyclic aromatic hydrocarbons (PAHs) was investigated to ascertain its sources and potential carcinogenic health risks in Varanasi, India. The city represents a typical urban settlement of South Asia having particulate exposure manyfold higher than standard with reports of pollution induced mortalities and morbidities. Fine particulates (PM2.5) were monitored from October 2019 to May 2020, with 32% of monitoring days accounting ≥100 μgm-3 of PM2.5 concentration, frequently from November to January (99% of monitoring days). The concentration of 16 priority PAHs varied from 24.1 to 44.6 ngm-3 (mean: 33.1 ± 3.2 ngm-3) without much seasonal deviations. Both low (LMW, 56%) and high molecular weight (HMW, 44%) PAHs were abundant, with Fluoranthene (3.9 ± 0.4ngm-3) and Fluorene (3.5 ± 0.3ngm-3) emerged as most dominating PAHs. Concentration of Benzo(a)pyrene (B(a)P, 0.5 ± 0.1ngm-3) was lower than the national standard as it contributed 13% of total PAHs mass. Diagnostic ratios of PAH isomers indicate predominance of pyrogenic sources including emissions from biomass burning, and both from diesel and petrol-driven vehicles. Source apportionment using receptor model revealed similar observation of major PAHs contribution from biomass burning and fuel combustion (54% of source contribution) followed by coal combustion for residential heating and cooking purposes (44%). Potential toxicity of B[a]P equivalence ranged from 0.003 to 1.365 with cumulative toxicity of 2.13ngm-3. Among the PAH species, dibenzo[h]anthracene contributed maximum toxicity followed by B[a]P, together accounting 86% of PAH induced carcinogenicity. Incremental risk of developing cancer through lifetime exposure (ILCR) of PAHs was higher in children (3.3 × 10-4) with 56% contribution from LMW PAHs, primarily through ingestion and dermal contact. Adults in contrast, were more exposed to inhale airborne PAHs with cumulative ILCR of 2.2 × 10-4. However, ILCR to PM2.5 exposure is probably underestimated considering unaccounted metal abundance thus, require source-specific control measures.
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.
Zeolite socony mobil-5 (ZSM-5) is a common catalyst used for biomass pyrolysis. Nevertheless, the quantitative information on the catalytic behavior of ZSM-5 on biomass pyrolysis is absent so far. This study focuses on the catalytic pyrolysis phenomena and mechanisms of biomass wastes using ZSM-5 via thermogravimetric analyzer and pyrolysis-gas chromatography/mass spectrometry, with particular emphasis on catalytic level identification and aromatic hydrocarbons (AHs) formation. Two biomass wastes of sawdust and sorghum distillery residue (SDR) are investigated, while four biomass-to-catalyst ratios are considered. The analysis suggests that biomass waste pyrolysis processes can be divided into three zones, proceeding from a heat-transfer dominant zone (zone 1) to catalysis dominant zones (zones 2 and 3). The indicators of the intensity of difference (IOD), catalytic effective area, catalytic index (CI), and aromatic enhancement index are conducted to measure the catalytic effect of ZSM-5 on biomass waste pyrolysis and AHs formation. The maximum IOD occurs in zone 2, showing the highest intensity of the catalytic effect. The CI values of the two biomass wastes increase with increasing the biomass-to-catalyst ratio. However, there exists a threshold for sawdust pyrolysis, indicating a limit for the catalytic effect on sawdust. The higher the catalyst addition, the higher the AHs proportion in the vapor stream. When the biomass-to-catalyst ratio is 1/10, AHs formation is intensified significantly, especially for sawdust. Overall, the indexes conducted in the present study can provide useful measures to identify the catalytic pyrolysis dynamics and levels.
The main focus of this study is exploring the spatial distribution of polyaromatics hydrocarbon links between oil spills in the environment via Support Vector Machines based on Kernel-Radial Basis Function (RBF) approach for high precision classification of oil spill type from its sample fingerprinting in Peninsular Malaysia. The results show the highest concentrations of Σ Alkylated PAHs and Σ EPA PAHs in ΣTAH concentration in diesel from the oil samples PP3_liquid and GP6_Jetty achieving 100% classification output, corresponding to coherent decision boundary and projective subspace estimation. The high dimensional nature of this approach has led to the existence of a perfect separability of the oil type classification from four clustered oil type components; i.e diesel, bunker C, Mixture Oil (MO), lube oil and Waste Oil (WO) with the slack variables of ξ ≠ 0. Of the four clusters, only the SVs of two are correctly predicted, namely diesel and MO. The kernel-RBF approach provides efficient and reliable oil sample classification, enabling the oil classification to be optimally performed within a relatively short period of execution and a faster dataset classification where the slack variables ξ are non-zero.
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.
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.
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.
Poly(β-cyclodextrin-ionic liquid) grafted magnetic nanoparticles combined with 1-octanol as supramolecular solvents (SUPRASs) presenting new ferrofluid was developed and successfully applied in the dispersive liquid-phase microextraction of seven representative polycyclic aromatic hydrocarbons. One variable at-a-time (OVAT) analysis and response surface methodology (RSM) were used for efficient optimization of the main variables. The calibration curves were found to be linear in the range of 0.1-150 ng mL-1 with correlation of determinations (R2) ranging from 0.9944 to 0.9986. Detection limits ranged at 0.02-0.07 ng mL-1 for all studied PAHs. The intra and inter-day precision values (RSD %) were in the range of 1.80%-7.56% and 2.97%-8.23%, respectively. The ferrofluid showed a satisfactory reproducibility between 1.72% and 5.90%, and acceptable recovery values at 84%-110% were obtained for the real samples analysis. The optimized method was successfully applied to access the content safety of the PAHs studied in a variety of commercial food and beverages available in Malaysia.
Perak River basin is in Perak state of Peninsular Malaysia. In this research, the river stretch serves as water intake for domestic, agricultural and industrial purposes in Perak Tengah, Hilir Perak and Manjung regions. It is located in mixed use area whilst exposing the river to anthropogenic elements. The sampling locations were conducted at selected points of Perak River namely Tanjung Belanja Bridge (TBB), Water Treatment Plant Parit (WTPP), Parit Town discharge (PTD), Water Treatment Plant Senin (WTPS) and Water Treatment Plant Kepayang (WTPK). The existence of aromatic hydrocarbons in freshwater samples was pre-assessed via qualification analysis; specific ultraviolet absorbance (SUVA254) method at 254 nm of wavelength. The SUVA dataset were 48.38 L/mg-m (TBB), 50.54 L/mg-m (WTPP), 8.05 L/mg-m (PTD), 85.75 L/mg-m (WTPS) and 217.39 L/mg-m (WTPK). The SUVA254 values of fresh water at the river basin have exceeded the water quality standards value equivalent to 2.0 L/mg-m permitted by the Environmental Protection Agency of United States. The exceeding values were an indication of a large portion of aromatic compounds in the water. Qualification analyses evident the existence of water pollutants at treacherous concentrations for public health in freshwater samples of Perak River basin. Thus, this research has presented important findings towards further research and countermeasure for a better alternative of water treatment in Malaysia.
Catalytic co-pyrolysis (CCP) of spent coffee ground (SCG) and cellulose over HZSM-5 and HY was characterized thermogravimetrically, and a catalytic pyrolysis of two samples was conducted using a tandem micro reactor that directly connected with gas chromatography-mass spectrometry. To access the more fundamental investigations on CCP, the effects of the zeolite pore structure, reaction temperature, in-situ/ex-situ reaction mode, catalyst to feedstock ratio, and the SCG and cellulose mixing ratio were experimentally evaluated. The temperature showing the highest thermal degradation rate of cellulose with SCG slightly delayed due to the interactions during the thermolysis of two samples. HZSM-5 in reference to HY produced more aromatic hydrocarbons from CCP. With respect to the reaction temperature, the formation of aromatic hydrocarbons increased with the pyrolytic temperature. Moreover, the in-situ/ex-situ reaction mode, catalyst/feedstock, and cellulose/SCG ratio were optimized to improve the aromatic hydrocarbon yield.
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.
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
Polycyclic aromatics hydrocarbons (PAHs) are ubiquitous and toxic pollutants that are dangerous to humans and living organism in aquatic environment. Normally, PAHs has lower molecular weight such as phenanthrene and naphthalene that are easy and efficient to degrade, but high-molecular-weight PAHs such as chrysene and pyrene are difficult to be biodegraded by common microorganism. This study investigated the isolation and characterization of a potential halophilic bacterium capable of utilizing two high-molecular-weight PAHs. At the end of the experiment (25-30 days of incubation), bacterial counts have reached a maximum level (over 40 × 1016 CFU/mL). The highest biodegradation rate of 77% of chrysene in 20 days and 92% of pyrene in 25 days was obtained at pH 7, temperature 25 °C, agitation of 150 rpm and Tween 80 surfactant showing to be the most impressive parameters for HMWPAHs biodegradation in this research. The metabolism of initial compounds revealed that Hortaea sp. B15 utilized pyrene to form phthalic acid while chrysene was metabolized to form 1-hydroxy-2-naphthoic acid. The result showed that Hortaea sp. B15 can be promoted for the study of in situ biodegradation of high molecular weight PAH.
Poly(β-cyclodextrin functionalized ionic liquid) immobilized magnetic nanoparticles (Fe3O4@βCD-Vinyl-TDI) as sorbent in magnetic µ-SPE was developed for the determination of selected polycyclic aromatic hydrocarbons (PAHs) in rice samples coupled with gas chromatographic-flame ionization detector (GC-FID). The nanocomposite was characterized by various tools and significant parameters that affected the extraction efficiency of PAHs were investigated. The calibration curves were linear for the concentration ranging between 0.1 and 500 μg kg-1 with correlation determinations (R2) from 0.9970 to 0.9982 for all analytes. Detection limits ranged at 0.01-0.18 μg kg-1 in real matrix. The RSD values ranged at 2.95%-5.34% (intra-day) and 4.37%-7.05% (inter-day) precision for six varied days. The sorbents showed satisfactory reproducibility in 2.9% to 9.9% range and acceptable recovery values at 80.4%-112.4% were obtained for the real sample analysis. The optimized method was successfully applied to access content safety of selected PAHs for 24 kinds of commercial rice available in 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.
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 penalized quantitative structure-property relationship (QSPR) model with adaptive bridge penalty for predicting the melting points of 92 energetic carbocyclic nitroaromatic compounds is proposed. To ensure the consistency of the descriptor selection of the proposed penalized adaptive bridge (PBridge), we proposed a ridge estimator ([Formula: see text]) as an initial weight in the adaptive bridge penalty. The Bayesian information criterion was applied to ensure the accurate selection of the tuning parameter ([Formula: see text]). The PBridge based model was internally and externally validated based on [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], the Y-randomization test, [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text] and the applicability domain. The validation results indicate that the model is robust and not due to chance correlation. The descriptor selection and prediction performance of PBridge for the training dataset outperforms the other methods used. PBridge shows the highest [Formula: see text] of 0.959, [Formula: see text] of 0.953, [Formula: see text] of 0.949 and [Formula: see text] of 0.959, and the lowest [Formula: see text] and [Formula: see text]. For the test dataset, PBridge shows a higher [Formula: see text] of 0.945 and [Formula: see text] of 0.948, and a lower [Formula: see text] and [Formula: see text], indicating its better prediction performance. The results clearly reveal that the proposed PBridge is useful for constructing reliable and robust QSPRs for predicting melting points prior to synthesizing new organic compounds.
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.
In this study, caged calcium alginate-caged multiwalled carbon nanotubes dispersive microsolid phase extraction was described for the first time for the extraction of polycyclic aromatic hydrocarbons (PAHs) from water samples prior to gas chromatographic analysis. Fluorene, phenanthrene and fluoranthene were selected as model compounds. The caged calcium alginate-caged multiwalled carbon nanotubes was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy and thermal gravimetry analyses. The effective parameters namely desorption solvent, solvent volume, extraction time, desorption time, the mass of adsorbent and sample volume were optimized. Under the optimum extraction conditions, the developed method showed good linearity in the range of 0.5-50 ng mL-1 (R2 ≥ 0.996), low limits of detection and quantification (0.42-0.22 ng mL-1) (0.73-1.38 ng mL-1) respectively, good relative recoveries (71.2-104.2%) and reproducibility (RSD 1.8-12.4%, n = 3) for the studied PAHs in water sample. With high enrichment factor (1,000), short extraction time (<30 min), low amounts of adsorbent (100 mg) and low amounts of solvent (0.1 mol) have proven that the microsolid phase extraction method based on calcium alginate-caged multiwalled carbon nanotubes are environmentally friendly and convenient extraction method to use as an alternative adsorbent in the simultaneous preconcentration of PAHs from environmental water samples.