Biodegradation of polycyclic aromatic hydrocarbons

The intent of this review is to provide an outline of the microbial degradation of polycyclic aromatic hydrocarbons. A catabolically diverse microbial community, consisting of bacteria, fungi and algae, metabolizes aromatic compounds. Molecular oxygen is essential for the initial hydroxylation of polycyclic aromatic hydrocarbons by microorganisms. In contrast to bacteria, filamentous fungi use hydroxylation as a prelude to detoxification rather than to catabolism and assimilation. The biochemical principles underlying the degradation of polycyclic aromatic hydrocarbons are examined in some detail. The pathways of polycyclic aromatic hydrocarbon catabolism are discussed. Studies are presented on the relationship between the chemical structure of the polycyclic aromatic hydrocarbon and the rate of polycyclic aromatic hydrocarbon biodegradation in aquatic and terrestrial ecosystems.     

Removal of polycyclic aromatic hydrocarbons from oil-contaminated Kuwaiti soil

In the uncontaminated farm soil, more than 80% of the supplemented acenaphthene, fluoranthene, and pyrene (100 mg/100 g soil) decreased in 90 days, while ratio of removal was about 20%, 30%, and 0%, respectively, in the Kuwaiti oil-contaminated soil. Simultaneous addition of naphthalene, phenanthrene, and anthrathene (100 mg of each compound/100 g soil) led the acenaphthene to a decrease of about 20% to 45% but not of fluoranthene and pyrene. Addition of the farm soil to the Kuwaiti soil did not enhance the decrease of these three PAHs.     

Porphinatoiron-mediated oxidation of polycyclic aromatic hydrocarbons

Although porphinatoiron complexes have been used extensively as biomimetic catalysts for oxidation of aliphatic and olefinic hydrocarbons, few oxidations of polycyclic aromatic hydrocarbons (PAH) have been reported. In all cases, heterogeneous iodosobenzene/tetraphenylporphinatoiron(III) systems were employed, oxidations were inefficient and control experiments demonstrating the requirement for catalyst were not described. The current study investigates the oxidation of pyrene, benzo[a]pyrene and benzanthracene in a homogeneous m-chloroperoxybenzoic acid/bifacially hindered porphinatoiron system in which the peroxyacid was shown to be unreactive in the absence of catalyst. Pyrene and benzo[a]pyrene were oxidized efficiently, with pyrene yielding mixtures of 1.6- and 1.8-quinones and benzo[a]pyrene yielding mixtures of phenols and quinones. Benzanthracene was oxidized less efficiently, primarily at the meso positions, to give 7.12-quinone. Initial oxidation of meso carbons of benzo[a]pyrene (confirmed by the presence of the 6-hydroxy derivative as a product) and benzanthracene indicates that PAH-to-catalyst charge transfer may be an important oxidation pathway. Oxidation of pyrene was performed by addition of pyrene to observable oxo iron(V) species as well as in a catalytic reaction where excess peroxyacid was added to a solution of pyrene and catalyst and oxo iron(V) is not generated as an observable intermediate. Yields (based on oxidant consumed), were identical under both conditions, strongly supporting oxo iron(V) as a common intermediate.     

Photoproducts from DNA pyrimidine bases and polycyclic aromatic hydrocarbons

The major photoproduct formed between benzo[a]pyrene and thymine is identified as 1-(benzo[a]pyren-6-yl)-thymine by means of spectroscopic analysis and isotopic syntheses. Irradiation of 1-methylcytosine hydrochloride and anthracene gives two isolable photoproducts of which one is assigned the structure 5-(anthracen-9-yl)-1-methylcytosine.     

Optimized extraction of polycyclic aromatic hydrocarbons from contaminated soil samples

A comparison of Soxhlet extraction and a new extraction technique, fluidized-bed extraction, has been conducted. The extraction of polycyclic aromatic hydrocarbons (PAHs) by this new technique has been optimized considering as experimental variables the variation of the number of extraction cycles and the holding time after reaching the heating temperature by means of a surface response design. The significance of the operational parameters of the fluidized-bed extraction onto the performance characteristics has been investigated. For the determination of the analytes, a cleanup of the extracts followed by gas chromatography with mass spectrometric detection was used. The accuracy of the method was established by extraction and analysis of a reference material, supplied from the European Commission's Joint Research Centre.     

Repair of bulky DNA lesions deriving from polycyclic aromatic hydrocarbons

Genomic DNA is damaged by a variety of factors exerting an adverse effect on human health, such as environmental pollution, UV light, ionizing radiation, and toxic compounds. Air pollution with products of incomplete combustion of hydrocarbon fuels and wastes of various industries are main sources of polycyclic aromatic hydrocarbons, whose metabolites can damage DNA by forming bulky DNA adducts, which potentially lead to mutations and cancer. Nucleotide excision repair is the main pathway that eliminates these lesions in eukaryotic cells. The excision efficiency of bulky adducts depends on many factors, including the structure of a bulky substituent and the degree of DNA double helix distortion induced by a lesion. Clustered DNA lesions are the most dangerous for the cell. Several DNA repair systems cooperate to recognize and remove such lesions. The review focuses on the mechanisms that repair DNA with single and clustered bulky lesions, taking the natural carcinogen benzo[a]pyrene as an example.     

多环芳烃类化合物在土壤上的吸附

研究了几种多环芳烃化合物在土壤上的吸附行为．通过一个连续投药－取样试验装置,在没有任何其它有机试剂干扰的情况下,测定了荧蒽与菲在土壤上的吸附量．研究表明,这两种多环芳烃化合物在土壤上的吸附量与土壤有机质含量之间呈显著相关．对多环芳烃化合物的分子结构及理化特性,如辛醇－水分配系数、溶解度等参数与ＬｏｇＫｏｃ关系的研究发现多环芳烃化合物的ＬｏｇＫｏｃ与化合物的水溶性、辛酸－水分配系数以及分子结构中的苯环数线性相关．     

Detoxification of polycyclic aromatic hydrocarbons by fungi

Summary The polycyclic aromatic hydrocarbons (PAHs) are a group of hazardous environmental pollutants, many of which are acutely toxic, mutagenic, or carcinogenic. A diverse group of fungi, includingAspergillus ochraceus, Cunninghamella elegans, Phanerochaete chrysosporium, Saccharomyces cerevisiae, andSyncephalastrum racemosum, have the ability to oxidize PAHs. The PAHs anthracene, benz[a]anthracene, benzo[a]pyrene, fluoranthene, fluorene, naphthalene, phenanthrene, and pyrene, as well as several methyl-, nitro-, and fluoro-substituted PAHs, are metabolized by one or more of these fungi. Unsubstituted PAHs are oxidized initially to arene oxides,trans-dihydrodiols, phenols, quinones, and tetralones. Phenols andtrans-dihydrodiols may be further metabolized, and thus detoxified, by conjugation with sulfate, glucuronic acid, glucose, or xylose. Although dihydrodiol epoxides and other mutagenic and carcinogenic compounds have been detected as minor fungal metabolites of a few PAHs, most transformations performed by fungi reduce the mutagenicity and thus detoxify the PAHs.     

Methanogenic biodegradation of two-ringed polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAH) are widespread in methane-rich subsurface environments, such as oil reservoirs and fuel-contaminated aquifers; however, little is known about the biodegradation of these compounds under methanogenic conditions. To assess the metabolism of PAH in the absence of electron acceptors, a crude oil-degrading methanogenic enrichment culture was tested for the ability to biodegrade naphthalene, 1-methylnaphthalene (1-MN), 2-methylnaphthalene (2-MN), and 2, 6-dimethylnaphthalene (2, 6-diMN). When methane was measured as an indicator of metabolism, nearly 400 μmol of methane was produced in the 2-MN- and 2, 6-diMN-amended cultures relative to substrate-unamended controls, which is close to the amount of methane stoichiometrically predicted based on the amount of substrate added (51-56 μmol). In contrast, no substantial methane was produced in the naphthalene- and 1-MN-amended enrichments. In time course experiments, metabolite analysis of enrichments containing 2-MN and 2, 6-diMN revealed the formation of 2-naphthoic acid and 6-methyl-2-naphthoic acid, respectively. Microbial community analysis by 454 pyrosequencing revealed that these PAH-utilizing enrichments were dominated by archaeal members most closely affiliated with Methanosaeta and Methanoculleus species and bacterial members most closely related to the Clostridiaceae, suggesting that these organisms play an important role in the methanogenic metabolism of the substituted naphthalenes in these cultures.     

Transfer of polycyclic aromatic hydrocarbons between model membranes: relation to carcinogenicity

Polynuclear aromatic hydrocarbons (PAH), some of which are potent carcinogens, are common environmental pollutants. The transport processes for these hydrophobic compounds into cells and between intracellular membranes are diverse and are not well understood. A common mechanism of transport is by spontaneous desorption and transfer through the aqueous phase. From the partitioning parameters, we have inferred that the rate limiting step involves solvation of the transfer species in the interfacial water at the phospholipid surface. Transfer of 10 PAH (pyrene, 3,4-benzophenanthrene, triphenylene, chrysene, 1,2-benzanthracene, 1,1'-binaphthyl, 9-phenylanthracene, 2,2'-binaphthyl, m-tetraphenyl and 1,3,5-triphenylbenzene) out of phosphatidylcholine vesicles has been examined. Our results show that the molecular volume of the PAH is a rate-determining factor. Moreover, high performance liquid chromatography (HPLC) data confirms the hypothesis that the rate of transfer is correlated with the size of the molecule and with the partitioning of the molecule between a polar and hydrocarbon phase. The kinetics and characteristics of the spontaneous transfer of carcinogens are likely to have a major impact on the competitive processes of PAH metabolism within cells.     

Biomarkers of carcinogenesis in humans exposed to polycyclic aromatic hydrocarbons

The frequencies of micronuclei (MN) in cytokinesis-blocked lymphocytes of 91 steel foundry workers were analysed. On the basis of ambient PAH levels at the work stands and 1-hydroxypyrene concentrations in the urine, the coke-oven workers were the most exposed as compared to the rollers reference group. The difference in results for the two groups studied was not statistically significant, although MN were slightly higher for coke-oven workers. The frequency of MN did not increase with exposure: after some increase in 1-10 years, a decreasing tendency was observed.     

Bacterial metabolism of polycyclic aromatic hydrocarbons: strategies for bioremediation

Polycyclic aromatic hydrocarbons (PAHs) are compounds of intense public concern due to their persistence in the environment and potentially deleterious effects on human, environmental and ecological health. The clean up of such contaminants using invasive technologies has proven to be expensive and more importantly often damaging to the natural resource properties of the soil, sediment or aquifer. Bioremediation, which exploits the metabolic potential of microbes for the clean-up of recalcitrant xenobiotic compounds, has come up as a promising alternative. Several approaches such as improvement in PAH solubilization and entry into the cell, pathway and enzyme engineering and control of enzyme expression etc. are in development but far from complete. Successful application of the microorganisms for the bioremediation of PAH-contaminated sites therefore requires a deeper understanding of the physiology, biochemistry and molecular genetics of potential catabolic pathways. In this review, we briefly summarize important strategies adopted for PAH bioremediation and discuss the potential for their improvement.     

Biomonitoring of polycyclic aromatic hydrocarbons in human urine

Measurement of polycyclic aromatic hydrocarbons (PAH) metabolites in human urine is the method of choice to determine occupational and/or environmental exposure of an individual to PAH, in particular, when multiple routes of exposure have to be taken into account. Requirements for methods of biomonitoring PAH metabolites in urine are presented. Studies using 1-hydroxypyrene or phenanthrene metabolites including its phenols and dihydrodiols are summarized. The role of these PAH metabolites as established biomarkers and also more recent developments of PAH biomonitoring are discussed.     

Chemical rearrangement of phenol-epoxide metabolites of polycyclic aromatic hydrocarbons to quinone-methides

Evidence of the involvement of triol-epoxide and phenol-epoxide metabolites in the metabolic activation of polycyclic hydrocarbons is accumulating. It is proposed that the phenolic OH-groups present in such epoxides will activate the epoxide moieties and permit their rearrangement to quinone-methides. These quinone-methides are highly reactive, potentially-isolable chemical entities with strong alkylating activity. In one resonance form they are resonance-stabilized carbonium ions. Only epoxides that also possess phenolic OH-groups in certain positions will form quinone-methides: these appear to include 9-hydroxybenzo [a] pyrene 4,5-oxide and the triol-epoxides 9-hydroxy-trans-1,2-dihydro-1,2-dihydroxychrysene 3,4-oxide and 2-hydroxy-trans-9,10-dihydro-9,10-dihydroxybenzo[a]pyrene 7,8-oxide.