Alkanes and hopanes for pollution source apportionment in coking plant soils

Polluted soils of former coking plants are characterized by multiple organic contributions, e.g. coal tar, coal, coke, soot, and natural organic matter, that can either be sources of polycyclic aromatic hydrocarbons (PAHs) or act as sorption surfaces for pollutants. The contamination level is usually based on the quantification of 16 PAHs but it does not provide any information on PAH sources. We studied the aliphatic fractions of 25 soil samples from a former coking plant site by microscopy and gas chromatography-mass spectrometry (GC-MS). The microscopic investigation allowed to identify four main organic contributions: coal tar, coal, coke, and natural organic matter. These isolated sources were analyzed and considered as reference materials. Although the PAH distributions were very similar in the 25 contaminated soils, alkanes and hopanes distributions were representative from various contributions characterizing the relative enrichment in coal, coal tars, or natural organic matter. Two principal component analyses based on n-alkanes and hopanes showed that three molecular indices, the carbon preference index, the low molecular weight/high molecular weight n-alkanes ratio, and the 18α(H)-22,29,30-trisnorhopane/(18α(H)-22,29,30-trisnorhopane+17α(H)-22,29,30-trisnorhopane) ratio allow to classify polluted soils according to various organic contributions.     

Screening for plants and rhizospheral fungi with bioremediation potency of petroleum-polluted soils in a Tehran oil refinery area

The contamination of soils by toxic and/or hazardous organic pollutants, especially with crude oil, is a widespread problem. This study was conducted in a petroleum-contaminated area in a Tehran oil refinery to find petroleum-resistant plants and their rhizospheral fungal strains with bioremediation potency. The plants growing in the oil-polluted area were collected and determined taxonomically. Root samples of the plant species were collected from a polluted area and fungal strains determined by laboratory methods and taxonomical keys. The growth ability of the isolated fungal strains was studied in media containing 1%–15% crude oil. Results showed that seven plant species were of the highest density in the contaminated area: Alhagi persarum, Hordeum marinum, Peganum harmala, Phragmites australis, Prosopis farcta, Salsola kali, and Senecio glaucus. The root-associated fungi were isolated and showed that the fungal variation in the oil-polluted area is higher than that in a non-polluted area. The growth assay of isolated fungal strains showed that all studied fungal strains were able to form colonies at the applied concentrations but Alternaria sp. and Rhizopus sp. were the most resistant ones. Some plants were resistant to oil pollution, which also had positive effects on the fungal strains.     

京津潮白河多环芳烃及其衍生物分布

采用固相萃取-气相色谱质谱联用仪测定京津潮白河中的多环芳烃(PAHs)及其衍生物(SPAHs)的污染水平,并采用絮凝法分析水样中自由态PAHs/SPAHs和结合态PAHs/SPAHs的分布。结果表明,京津潮白河中PAHs和SPAHs总质量浓度分别为55.06～215.02 ng·L~(-1)和92.37～227.33 ng·L~(-1),上游河段PAHs和SPAHs质量浓度均低于下游河段。7种致癌PAHs占比为22%～41%,需引起重视。本研究中的SPAHs包括三类物质:氧化PAHs(OPAHs)、甲基PAHs(MPAHs)和氯代PAHs(Cl PAHs)。其中,OPAHs对SPAHs贡献最大(59%～71%),其次是Cl PAHs(22%～32%)和MPAHs(7%～14%)。京津潮白河中PAHs和SPAHs主要以自由态形式存在,总浓度可以准确估计污染物的环境风险。     

Hydrocarbons contamination and microbial degradation in mangrove sediments of the Niger Delta region (Nigeria)

The distribution of aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs), and their degradability by bacteria in epipelic and benthic sediments from Qua Iboe Estuary mangrove ecosystem and associated creeks were investigated. The research findings revealed that total aliphatic hydrocarbons in sediments ranged from 16.82 mg·kg ^?1 to 210 mg kg ^?1, wheras total PAHs ranged from 6.30 to 35.55 mg·kg ^?1 dry weight of sediment. Low molecular mass (i.e. the 2–3-ring) PAHs were predominant in almost all the sampling points, whereas the higher molecular masses (4-, 5- and 6-ring PAHs) had the lowest concentrations. In general, the sediment samples ES ₂ (39.7%), ES ₃ (24.8%), BS ₁ (46.7%), BS ₂ (49.9%) and BS ₃ (44.2%) showed<50% contributions of Σ combustion–derived PAH (COMP-PAH) concentration to the Σ PAH concentrations, whereas ES ₁ (57%) contained>50% of COMP-PAHs. Our results have also shown that many mangrove bacteria have strong capacity to utilise Qua Iboe Light (QL) crude oil as the sole source of carbon and energy, while lower number of bacterial species including Bacillus sp., Micrococcus sp., Pseudomonas aeruginosa, Alcaligenes sp. and Flavobacterium sp. exhibited detectable PAHs degradability; and as such may serve as efficient degraders of QL crude oil contamination of mangrove ecosystem.     

Toxic equivalency factor approach for risk assessment of polycyclic aromatic hydrocarbons

The toxic equivalency factor (TEF) method has been developed to evaluate structurally related compounds, sharing a common mechanism of action. Because certain polycyclic aromatic hydrocarbons (PAHs) appear to fit this requirement and are ubiquitous environmental contaminants, these compounds are TEF candidates. Toxicity is often expressed relative to benzo[a]pyrene (BaP), the reference standard (e.g., TEF = EC50_BaP/EC50_PAH). BaP‐like toxicity or toxic equivalents (TEQs) can then be calculated: TEQ = S(PAH _i × TEF _i ), where PAH _i and TEF _i are the concentration and TEF, respectively, for individual PAH congeners. Representative TEFs for PAHs were compiled from studies measuring carcinogenic potency and surrogate biomarkers. This review examines the application of TEFs to PAHs with established criteria (i.e., demonstrated need, defined chemical grouping, broad toxicological database, endpoint consistency, additivity, common mechanism of action, consensus). Although all criteria are not satisfied (e.g., endpoint inconsistency, nonadditivity) and more rigorous validation studies are needed, the TEF method is useful when limitations are recognized. Refinements of the method might include incorporation of pharmacokinetic factors and segregation of TEFs derived from mammalian vs. nonmammalian systems to increase endopoint consistency. Probabilistic analysis may also prove useful to assess the range of TEF values reported both within and between human health and ecological risk assessments.     

Uptake,metabolism and discharge of polycyclic aromatic hydrocarbons by marine fish

The uptake, metabolism and discharge of two polycyclic aromatic hydrocarbons, ¹⁴C-naphthalene and ³H-3,4-benzopyrene, were studied in 3 species of marine fish (mudsucker or sand goby, Gillichthys mirabilis; sculpin, Oligocottus maculosus; sand dab, Citharichthys stigmaeus). The path of hydrocarbons through the fish included entrance through the gills, metabolism by the liver, transfer of hydrocarbons and their metabolites to the bile, and, finally, excretion. The gall bladder was a major storage site of labeled hydrocarbons and their metabolites. The major product of ²H-3,4-benzypyrene metabolism was tentatively identified as 7,8-dihydro-7,8-dihydroxybenzopyrene. The ¹⁴C-naphthalene was metabolized to 1,2-dihydro-1,2-dihydroxynaphthalene after 24 h exposure. The urine appeared to the major avenne for discharge of labeled hydrocarbon from the body. Our laboratory results indicated that certain polycyelic aromatic hydrocarbons were rapidly taken up from seawater by the above fish, but detoxification mechanisms existed for efficient removal of these compounds from their body tissues.     

基于统计方法的辽东湾沉积物中多环芳烃来源特征分析

为研究辽东湾表层沉积物中多环芳烃(PAHs)的来源特征,2014年5月采集了20个辽东湾海域表层沉积物样品,并利用气相色谱质谱联用仪对优先控制的16种PAHs进行测定,采用聚类分析、主成分分析-多元线性回归分析、异构体比值3种统计方法对辽东湾表层沉积物中PAHs来源特征进行了研究。结果表明,辽东湾表层沉积物中PAHs含量范围88.5~199.3 ng·g-1,平均值为(126.3±35.3)ng·g-1,其中,萘、菲和荧蒽是PAHs优势组分。通过统计分析结果表明,辽东湾北部表层沉积物中PAHs含量低于西南部,沉积物中PAHs的来源包括石油燃烧来源、煤炭、木材等生物质燃烧来源和石油来源,其中燃烧来源是主要来源,煤炭、木材等生物质燃烧来源占49.9%,石油燃烧来源和石油来源占50.1%。     

Occurrence of and risk posed by highly carcinogenic dibenzo[def,p]chrysene isomers in urban soil

Dibenzopyrene and its isomers are considered the most potent carcinogens of all polycyclic aromatic hydrocarbons tested to date. However, despite public concerns over their deleterious effects, they have not been extensively studied. The occurrence of four highly carcinogenic isomers of dibenzopyrene – dibenzo[def,p]chrysene, dibenzo[a,e]pyrene, dibenzo[a,i]pyrene, and dibenzo[a,h]pyrene in urban soil samples from Shanghai, China, have been determined in this study, as well as that of benzo[a]pyrene and coronene. A total of 14 peaks with ions at m/z 302 were detected by gas chromatography-mass spectrometry. Although the concentrations of benzo[a]pyrene and the sum of the 16 priority polycyclic aromatic hydrocarbons were greater than that of dibenzopyrene and its isomers, the carcinogenic potency of the latter was higher than that of benzo[a]pyrene. The results also indicate that the relative carcinogenic potency of the four dibenzopyrene isomers in the samples is higher than that of the 16 priority polycyclic aromatic hydrocarbons.     

Biodegradation kinetics of cymoxanil in aquatic system

A potential method to detoxify pesticides in aquatic system is using bioremediation. In this study, four microorganisms (Pseudomonas sp (EB11), Streptomyces sp. (EB12), Aspergillus niger (EB13) and Trichoderma viride (EB14) were isolated from cucumber leaves previously treated with cymoxanil using enrichment technique. These strains were evaluated for their potential to detoxify cymoxanil in aquatic system at the concentration level of 5×10^?4M. The effect of pH and temperature on the growth ability of the tested strains was also investigated by measuring the intracellular protein and mycelia dry weight for bacterial and fungal strains, respectively. Moreover, the remaining toxicity of cymoxanil after 28 days of incubation with tested strains was evaluated to confirm the complete removal of any toxic materials (cymoxanil and its metabolites). The results showed that the optimum pH for the growth of cymoxanil degrading strains (bacteria and fungi) was 7. A temperature of 30°C appears to be the optimum for the growth of either fungal or bacterial strains. Pseudomonas sp. (EB11) was the most effective strain in cymoxanil degradation followed Streptomyces sp (EB12), Trichoderma viride (EB14) and Aspergillus niger (EB13), with half-lives of 4.33, 9.5, 17.3 and 24.7 days, respectively. The degradation of cymoxanil by bacterial strains was much faster than fungal one. There is no remaining toxicity of cymoxanil detected in aqueous media previously treated with Pseudomonas sp. (EB11) for 28 days. The results suggest that bioremediation by Pseudomonas sp. (EB11) are promising for the detoxification of cymoxanil in aqueous media.     

Arsenic detoxification potential of <Emphasis Type="Italic">aox</Emphasis> genes in arsenite-oxidizing bacteria isolated from natural and constructed wetlands in the Republic of Korea

Arsenic is subject to microbial interactions, which support a wide range of biogeochemical transformations of elements in natural environments such as wetlands. The arsenic detoxification potential of the bacterial strains was investigated with the arsenite oxidation gene, aox genotype, which were isolated from the natural and constructed wetlands. The isolates were able to grow in the presence of 10 mM of sodium arsenite (As(III) as NaAsO₂) and 1 mM of d+glucose. Phylogenetic analysis based on 16S rRNA gene sequencing indicated that these isolated strains resembled members of the genus that have arsenic-resistant systems (Acinetobacter sp., Aeromonas sp., Agrobacterium sp., Comamonas sp., Enterobacter sp., Pantoea sp., and Pseudomonas sp.) with sequence similarities of 81–98%. One bacterial isolate identified as Pseudomonas stutzeri strain GIST-BDan2 (EF429003) showed the activity of arsenite oxidation and existence of aoxB and aoxR gene, which could play an important role in arsenite oxidation to arsenate. This reaction may be considered as arsenic detoxification process. The results of a batch test showed that P. stutzeri GIST-BDan2 (EF429003) completely oxidized in 1 mM of As(III) to As(V) within 25–30 h. In this study, microbial activity was evaluated to provide a better understanding of arsenic biogeochemical cycle in both natural and constructed wetlands, where ecological niches for microorganisms could be different, with a specific focus on arsenic oxidation/reduction and detoxification.     

Source characterisation and mid-term spatial and temporal distribution of polycyclic aromatic hydrocarbons in molluscs along the Basque coast (northern Spain)

The variability of polycyclic aromatic hydrocarbons (PAH) measured in the soft tissues of Mediterranean mussels (Mytilus galloprovincialis) and Pacific oysters (Crassostrea gigas) are investigated. Samples were collected from estuarine waters within the Basque Country (Bay of Biscay), between 2003 and 2011. PAH bioaccumulation showed some seasonality and significant differences were observed between cold (autumn–winter) and warm (spring–summer) seasons. Sites located within the ports of Bilbao and Pasaia showed the highest PAH concentrations in molluscs, and the highest percentages of samples above the established Environmental Quality Standards and Environmental Assessment Criteria. Probably due to human activities carried out in the area, no clear trends were observed, between 2003 and 2011, for the autumn data. Since the Basque coast is an area with high population density and industrial activity, the congener profiles (which reveal the predominance of tetra-aromatics) and the diagnostic ratios identified urban/industrial combustion processes as the main PAH sources. However, natural and petrogenic sources cannot be disregarded.     

Quantification of polyphenols during retting and characterization of bacteria from the Kadinamkulam Backwaters, Kerala

The retting environment which provides a competitive niche for specialized microbes is speculated to harbour a variety of microbes with high biodegradation potential. In this context, an effort has been made to isolate and identify bacterial species having high tolerance to phenol In vitro. Maximum polyphenol (1.897 mg l(-1)) as observed during the initial period of retting, which decreased as retting proceeded. Based on biochemical characterization, the isolated bacterial strains were identified as Micrococcus sp., Moraxella sp. strain MP1, Moraxella sp. strain MP2 and Moraxella sp. strain MP3, Pseudomonas sp. strain PP1 and Pseudomonas sp. strain PP2, Amphibacillus sp., Brucella sp. strain BP1 and Brucella sp. strain BP2, Aquaspirillum sp., Escherichia coli strain EP1 and Escherichia coli strain EP2, Campylobacter sp., Aeromonas sp., Neisseria sp., Vibrio sp., Erwinia sp. and Mesophilobacter sp. These strains were found to tolerate maximum concentration of phenol viz. 200 to 1000 mg l(-1). Plasmid analysis of phenol resistant bacterial isolates showed that almost all the cultures had at least one plasmid of size > 1Kb. Studies on the protein profile of isolated bacterial cultures showed the presence of proteins with molecular sizes ranging from 10 to 85 KDa with exception of Mesophilobacter and Neisseria having still high molecular weight protein (95 KDa). Bacterial strains isolated from coir-ret-liquor showed tolerance to high phenol concentration.     

Bioavailability of hydrophobic organic contaminants and quality of organic carbon

U.S. laws require that contaminant bioaccumulation potential be evaluated before dredged material can be recycled. Simple fugacity models, e.g. organic contaminant aqueous partition coefficient (K _oc)-derived theoretical bioaccumulation potential, are commonly used to estimate the partitioning of hydrophobic organic contaminants between sediment organic matter and organism lipid. K _oc-derived models, with or without the addition of a soot carbon term, did not accurately or consistently predict total polycyclic aromatic hydrocarbons (PAHs) and polychlorobiphenyls partitioning of eight sediments from ongoing dredging operations onto C₁₈-coated filter paper. These models also failed to predict the partitioning of individual PAHs from these eight sediments. These data underscore the trade-offs between the ease of using simple models and the uncertainty of predicted partitioning values.     

Molecular characterisation of high-strength polycyclic aromatic hydrocarbon (PAH)-degrading and phenol-tolerant bacteria obtained from thermal power plant wastewater

This article reports the successful isolation and molecular characterisation of nine different phenol-tolerant and polycyclic aromatic hydrocarbon (PAH)-degrading Gram-positive bacterial species of diverse genera from the effluents of various industries. Based on similarity matrix studies, isolates Corynebacterium sp. DST1, Lysinibacillus sp. and Planococcus sp. showed<97% similarity, suggesting the possibility of new species in their respective genera.     

Strengthening effects of ammonia nitrogen on the harmless biological treatment of oily sludge

To improve the efficiency of oil degradation and strengthen the harmless treatment of oily sludge, three dominant strains identified as Chryseomicrobium sp. YL2, Gordonia sp. YL3 and Acinetobacter sp. YL5 were isolated from soil near a refinery, and the effects on the bioremediation of the oily sludge from the refinery were investigated. The results showed that the efficiency of oil degradation increased by 31.5% compared with the control when the dominant strains were added to the treatment of oily sludge. Furthermore, the dominant strains could use oil as a carbon source for heterotrophic nitrification–aerobic denitrification. The addition of ammonia nitrogen resulted in a large number of remaining microbes and heightened dehydrogenase activity in the oily sludge, further accelerating oil degradation, mainly for C₁₁ to C₂₅ saturated hydrocarbons, and the oil degradation efficiency increased by 40.8%. After 120 days of bioremediation, the biotoxicity of oily sludge, which was expressed by the equivalent phenol concentration, decreased by 40.0% compared with that of the control, indicating that the addition of ammonia nitrogen enhanced the biodegradation of oil. This method can be used to strengthen the harmless treatment of oily sludge in practical engineering applications.     

Carbon black-benzo(a)pyrene complex-induced apoptosis and autophagy blockage in rat alveolar macrophages

Abstract

Cooking of foods and the burning of biomass and fossil fuels in stoves are the main sources of cooking fumes, with carbon black and polycyclic aromatic hydrocarbons as main components. The toxicity of carbon black and polycyclic aromatic hydrocarbons has been well studied individually, but the combined toxicity is much less understood. Carbon black can adsorb benzo(a)pyrene to form a complex which displays an altered physical form which in this study has been constructed to simulate particles in the cooking fumes and explore the combined toxic effect on rat alveolar macrophages. The complex-induced cell apoptosis and blocked cell autophagy flux compared with both individually. The mechanism of toxicity may be by intracellular reactive oxygen species generation, impairing the mitochondrial membrane potential and activating apoptosis signaling pathways.     

Analyses of PAHs (polycyclic aromatic hydrocarbons) and mutagenicity in raw and chlorinated water

Both raw water and chlorinated drinking water samples were collected from and the Liu‐Du water treatment plant in northern Taiwan from October 1990 to April 1992. The polycyclic aromatic hydrocarbons (PAHs) and mutagenicity in these water samples were analyzed by GC/MS and Ames test. The Mutagenicity/DMSO (Dimethyl Sulfoxide) ratio in S. typhimurium TA98 and TA100 with or without S9 mixture increased, even higher than 2, following the sequence of unit process. It was observed that the mutagenicity with TA98 (S9+) was highly related to most of PAHs in the raw water; while the mutagenicity with TA98 (S9+) was only correlated with DbA and BghiPr in the treated water. It could be expected that the mutagenicity level was controlled by other predominant components after the raw water was treated, for example, the chlorination process.     

Microbiological degradation of polycyclic aromatic hydrocarbons: Anthracene,benzo(K)fluoranthene,dibenzothiophene, benzo(H) quinoline and 2‐nitronaphthalene

Biodegradation experiments of various polycyclic aromatic hydrocarbons were studied with mixed bacteria culture under aerobic conditions. An easy‐to‐handle clean‐up procedure was developed for PAH and their metabolites simultaneously as well as a gc‐ms‐method to identify and quantify these compounds.

Anthracene and dibenzothiophene are completely degradable in an aqeous system, whereas biodegradation of benzo(k)fluoranthene and benzo(h)quinoline is possible only in an oil‐in‐water‐system with dodecane as cosubstrate. No degradation of nitronaphthalene was observed in aqueous systems. New metabolites are 2,3‐dihydroxybenzothiophene, hydroxybenzothiophenecarbonic acid and benzothiophenequinone for dibenzothiophene and hydroxyfluoranthenic acid for benzo(k)flouranthene. Whereas the former metabolites are degradable under the experimental conditions, the latter accumulates during the degradation experiment.

The results are important for microbiological wastewater treatment, since knowledge of biodegradation processes is indespensable for the successful treatment of PAH‐containing wastewater.     

The deployment of γ-irradiation for reducing polycyclic aromatic hydrocarbons and microbial load in wheat kernels

Food contamination may contribute to serious human health problems. In this work, the effect of γ-irradiation 0, 5, 10, and 15 kGy doses on the removal of polycyclic aromatic hydrocarbons from wheat kernels was investigated. Additionally, variations in the contents of 16 congeners on bacterial load and other chemical parameters were studied. Polycyclic aromatic hydrocarbons concentrations were determined by high-performance liquid chromatography followed by fluorescence detection. The effects of γ-irradiation on the concentrations varied for each congener, with the highest irradiation dose being the most effective. Benzo[a]pyrene was reduced by ～50%, and the total concentration of all congeners decreased dramatically from 154 to 21 µg.kg^?1 upon 15 kGy irradiation at a dose rate of 8.49 kGy h^?1. The total bacterial load was reduced from 2.4 to < 1 log₁₀ cfu g^?1, while wheat chemical properties were not affected.     

Cellular damage of plant pathogenic fungi by antifungal compounds produced by Bacillus spp. isolates

The use of microorganisms as biological control agents (BCAs) has become an effective alternative to chemical means of controlling plant pathogens. The antagonistic and inhibitory activity of 71 Bacillus spp. strains, which were isolated from different Mexican sites, were tested against several phytopathogen fungi, Fusarium oxysporum, Fusarium equiseti, Fusarium avenaceum, Bipolaris spp. and Alternaria spp. From the antagonism study, the strain ELI149 showed a marked inhibition of growth against all tested fungi; therefore crude metabolites from this strain were extracted using ethyl acetate and amberlite resin and probed against the same fungi as well as strains of Mucor sp., Penicillium spp. and Paecilomyces spp. The results indicated that amberlite was more suitable for extraction of secondary metabolites with antifungal activity. Finally, observation of cell damage in the tested pathogenic fungi showed marked morphological changes on reproductive structures in all tested fungi indicating that antibiosis was the mechanism of the antagonistic effect. These results suggest that metabolites from the Bacillus strains have a wide spectrum of antibiotic activities, which can be used as biocontrol agents for controlling fungal plant diseases of agricultural importance.