Environmental and biological monitoring of polycyclic aromatic hydrocarbons (PAHs) in coke plants and other workplaces

Primary aldosteronism remains a diagnostic challenge. Certain immunoassay techniques, simplified diagnostic testing, and the introduction of sensitive imaging techniques have facilitated the diagnosis, but obstacles that remain include a lack of optimal screening methods, low sensitivity and specificity of current diagnostic tests, and a growing number of etiological subgroups. A rational approach to the diagnosis of primary aldosteronism is described, as is the differentiation of the surgically correctable lesion (adenoma) from the other etiological subgroups.     

Evaluation of enzyme-linked immunosorbent assay for the determination of polycyclic aromatic hydrocarbons in house dust and residential soil

Two commercially available enzyme-linked immunosorbent assays (ELISA) for total polycyclic aromatic hydrocarbon (PAH) and carcinogenic PAH (C-PAH) were evaluated. The testing procedures were refined for application to screening PAH and C-PAH in house dust and soil samples for human exposure studies. The overall method precision expressed as percent relative standard deviation (%RSD) of triplicate real world dust and soil samples was within +/- 29% (12-29%) for PAH ELISA and +/- 21% (5.9-21%) for C-PAH ELISA. Spike recoveries from real world dust/soil samples were 114 +/- 30% for phenanthrene from PAH ELISA and 120 +/- 8.2% for benzo[a]pyrene from C-PAH ELISA. The overall method accuracy for PAH and C-PAH assays cannot be assessed for multiple PAH components in dust/soil samples (which represent real-world samples), because of the assays' cross reactivities with other PAH components. Over 100 dust/soil samples from 13 North Carolina homes and 22 Arizona homes were analyzed by PAH and C-PAH assays, as well as by the conventional gas chromatography/mass spectrometry (GC/MS) method. Statistical analysis showed that dust/soil PAH data from ELISA and GC/MS methods are significantly different. In general PAH ELISA responses were higher than PAH GC/MS responses. The regression analysis showed that the linear relationship between ELISA and GC/MS measurements is not strong in the combined data. The relationship became stronger for the data from the same type of dust/soil samples. The screening performance of ELISA was evaluated based on the frequency distribution of ELISA and GC/MS data. The results indicated that the ELISA PAH and C-PAH assays cannot be used as a quantitative analytical tool for determining PAH in real-world dust/soil samples. However, the ELISA is an effective screening tool for ranking PAH concentrations in similar types of real world dust/soil samples.     

Benzo(a)pyrene-albumin adducts in humans exposed to polycyclic aromatic hydrocarbons in an industrial area of Poland

Antiarrhythmic drugs administered intravenously run the risk of producing a hemodynamic collapse even when used by expert and well trained hands. The arrhythmias in the focal point of a preexcitation syndrome constitute a very special situation in which extreme caution must be used when using intravenous drugs, because the conduction through accessory channels can vary, depending on multiple factors. We describe a case of a patient with an accessory atrioventricular pathway and orthodromic tachycardia who developed cardiac arrest by wide QRS tachycardia after receiving intravenous amiodarone.     

Cancer risk from occupational and environmental exposure to polycyclic aromatic hydrocarbons

Epidemiologic evidence on the relationship between polycyclic aromatic hydrocarbons (PAH) and cancer is reviewed. High occupational exposure to PAHs occurs in several industries and occupations. Covered here are aluminum production, coal gasification, coke production, iron and steel foundries, tar distillation, shale oil extraction, wood impregnation, roofing, road paving, carbon black production, carbon electrode production, chimney sweeping, and calcium carbide production. In addition, workers exposed to diesel engine exhaust in the transport industry and in related occupations are exposed to PAHs and nitro-PAHs. Heavy exposure to PAHs entails a substantial risk of lung, skin, and bladder cancer, which is not likely to be due to other carcinogenic exposures present in the same industries. The lung seems to be the major target organ of PAH carcinogenicity and increased risk is present in most of the industries and occupations listed above. An increased risk of skin cancer follows high dermal exposure. An increase in bladder cancer risk is found mainly in industries with high exposure to PAHs from coal tars and pitches. Increased risks have been reported for other organs, namely the larynx and the kidney; the available evidence, however, is inconclusive. The results of studies addressing environmental PAH exposure are consistent with these conclusions.     

Exposure to polycyclic aromatic hydrocarbons in occupational versus urban environmental air

OBJECTIVES: To evaluate the balance between occupational and environmental exposure to suspended particulate matter (SPM) and polycyclic aromatic hydrocarbons (PAHs), comparison measurements were performed in a coal-fired power plant and the urban atmosphere from the town nearby. METHODS: The analysis of SPM for PAH content was done according to a high-performance liquid chromatography (HPLC)-based method. The microscopic assessment was performed using scanning electron microscopy (SEM) by silver coverage of the samples derived by air filter. RESULTS: Contrary to expectations, the results showed low levels of particle-bound PAHs in the occupational environment (< 1 ng benzo(a)pyrene/m3 air) and high levels in urban air (range 80-1250 ng benzo(a)pyrene/m3). The SPM collected from the power plant exhibited non-respirable characteristics (particles larger than 10 microm), whereas urban SPM almost exclusively contained respirable airborne particles (<3 microm). CONCLUSIONS: The PAH burden, combined with the enhanced probability of respiratory absorption, confers a much greater hazard potential to the urban SPM. Under these conditions, in areas or countries in which old technologies remain in use, occupational exposure to SPM containing PAHs might represent a severe underestimation of the total risk as it does not take into account the background air pollution.     

索氏抽提-柱层析分离-高效液相色谱法测定煤沥青中多环芳烃

以甲苯为溶剂对煤沥青进行索氏抽提,抽提液经过有机滤膜过滤,过滤后的抽提液用二氯甲烷溶解,将样品溶液用硅胶柱分离,然后用体积比为1∶1的石油醚与甲苯混合液以5.0mL/min的流量进行淋洗,将淋洗液旋干后用乙腈定容至10mL,利用ZORBAX Eclipse PAH柱以不同体积比的乙腈-水体系为流动相对样品溶液进行梯度洗脱,建立了煤沥青中16种多环芳烃(PAHs)的高效液相色谱分离检测方法。结果表明,16种PAHs的线性范围为0.50~20mg/L,相关系数(r)不小于0.999,检出限为0.04~0.33μg/L,按照实验方法对湘钢煤沥青实际样品中16种PAHs进行测定,测得结果的相对标准偏差(RSD,n=6)为0.20%~3.5%,回收率为97%~109%。采用实验方法分别测定湘钢、涟钢两种不同煤沥青中16种PAHs的含量,测得结果与湘钢、涟钢两公司提供的推荐值基本一致。结果表明,每1kg湘钢煤沥青中16种致癌性PAHs质量为107.9g,即质量分数为10.79%;每1kg涟钢煤沥青中16种致癌性PAHs质量为104.1g,即质量分数为10.41%;其中苯并[a]芘分别为11.86g/kg和13.82g/kg,即质量分数为1.186%和1.382%。     

Metabolism and activation of cyclopenta polycyclic aromatic hydrocarbons in isolated human lymphocytes, HL-60 cells and exposed rats

The metabolism of radiolabelled benz(j)aceanthrylene (B(j)A) was studied in suspensions of isolated human peripheral mononuclear blood cells (lymphocytes), using high performance liquid chromatography (HPLC). The only known metabolite found after 24 h exposure to 30 microg/ml (120 microM) B(j)A, was B(j)A-1,2-dihydrodiol, representing approximately 35% of the total metabolites formed. B(j)A, benz(l)aceanthrylene (B(l)A) and benzo(a)pyrene (B(a)P) all caused DNA adducts in human lymphocytes, as well as in the human promyelocytic cell line HL-60 cells, as measured by the 32P-postlabelling technique (30 microg/ml, 24 h). The total DNA adduct levels in human lymphocytes exposed to B(j)A, B(l)A or B(a)P were 0.13 +/- 0.03, 1.10 +/- 0.62 and 0.37 +/- 0.10 fmol/microg DNA, respectively, and similar levels were obtained in HL-60 cells (0.18 +/- 0.14, 0.97 +/- 0.35 and 0.29 +/- 0.17 fmol/microg DNA, respectively). For each compound, the human lymphocytes and HL-60 cells in addition showed similar DNA adduct patterns. Cells exposed to B(j)A revealed only one DNA adduct, which, judged by its TLC properties, resulted from B(j)A-1,2-epoxide. As measured by the alkaline filter elution technique, only low levels of single strand DNA breaks (SSB) were observed in both human lymphocytes and HL-60 cells after exposure to B(j)A, B(l)A or B(a)P (24 h, 30 microg/ml). By adding cytosine-1-beta-D-arabinofuranoside (Are C) and hydroxyurea (HU) 1 h prior to analysis to prevent strand break rejoining, some increase in SSB (2-3 times) was observed in the lymphocytes. Co-incubation of human lymphocytes with liver microsomes from PCB-treated rats for 1 h and exposure to B(j)A or B(l)A, increased the DNA adduct levels in the lymphocytes to 12.3 and 37.8 fmol/microg DNA, respectively. A large increase in SSB was also observed, whereas no such increase was observed after co-incubation with human liver microsomes. In vivo exposure of rats to 30 mg/kg B(j)A (i.p.) for 24 h revealed one major DNA adduct in lymphocytes and lung tissue (only one of three rats showed an adduct in liver tissue), apparently resulting from B(j)A-1,2-epoxide. The total DNA adduct level in the lymphocytes was 0.09 fmol/microg DNA, and in lung tissue between 0.10 and 0.62 fmol/microg DNA. Overall, the present data suggests that oxidation at the cyclopenta-ring is an important activation pathway for B(j)A in rats as well as in humans.     

Cytotoxicity and mutagenicity of polycyclic aromatic hydrocarbon ortho-quinones produced by dihydrodiol dehydrogenase

Eight polycyclic aromatic hydrocarbon (PAH) ortho-quinones that can be generated by dihydrodiol dehydrogenase (DD) were examined for their cytotoxicity in H-4-II-e (rat hepatoma) cells and for their mutagenicity in the Ames test. Seven of the PAH otrtho-quinones were potent cytotoxins yielding IC50 values for cell survival in the range 1-30 microns. PAH ortho-quinones were grouped into three classes based on their cytotoxicity profiles: group I contained ortho-quinones (e.g., naphthalene-1,2-dione and 7,12-dimethylbenz[alpha]anthracene-3,4-dione) which reduced cell viability and cell survival; group II contained ortho-quinones (e.g., benz[alpha]anthracene-3,4-dione and 5-methylchrysene-1,2-dione which reduced cell survival but had no effect on cell viability; and group III contained ortho-quinones (e.g., benzo[alpha]pyrene-7,8-dione) which had a pronounced effect on cell viability but minimal effects on cell survival. Using hepatoma cell suspensions and rat liver subcellular fractions, it was found that ortho-quinones underwent preferential enzymatic one-electron redox-cycling and produced superoxide anion radical (O2-.) and/or ortho-semiquinone anion or alternant radicals. ortho-Quinones that reduced cell viability produced O2-. and caused the most total free radical formation, while those that reduced cell survival produced ortho-semiquinone anion or alternant radicals only. PAH ortho-quinones were also tested as direct-acting mutagens in Salmonella typhimurium tester strains TA97a, TA98, TA100, TA102 and TA104. They were found to be more mutagenic than the test mutagens used for each tester strain, and were predominantly frameshift mutagens. The presence of an activating system (Aroclor-induced rat liver S9 plus NADPH) did not increase the mutagenicity of ortho-quinones in tester strains that are sensitive to oxidative mutagens (TA102 and TA104). These data suggest that PAH ortho-quinones produced by DD are cytotoxic and mutagenic by different mechanisms. The mechanism of cytotoxicity involves the formation of reactive oxygen species and/or ortho-semiquinone anion or alternant radicals. The mechanism of mutagenicity is independent of free radical formation and is related to the ability of PAH orthooffinones to intercalate and covalently modify DNA.     

Bacterial and human cell mutagenicity study of some C18H10 cyclopenta-fused polycyclic aromatic hydrocarbons associated with fossil fuels combustion

Maximal activity of NADP.H-cytochrome c reductase was found in the liver, the lowest one--in the retina. On the contrary, the highest activity of aldose reductase was observed in the retina, the lowest one--in the liver. The activity of NADP.H-cytochrome c reductase in the retina of rats with hereditary degeneration of the retina increased to the 60th day of postnatal life by 33%, the increase reaching 273% to the 90th day. In the brain cortex, the increase in the activity to the 45-60th days amounted to 22-34%, whereas at the age of 90 days the difference between healthy and patient rats, as well as the difference between males and females became less significant. The activity of aldose reductase in the cortex and retina in patient rats at the 20th day was 35% lower than in healthy animals. In the liver of patient rats, to the age of 45 days, the activity of aldose reductase decreased by 38%. At other periods, no significant differences were observed between healthy and patient animals with respect to the activity of this enzyme.     

Observation of indigenous polycyclic aromatic hydrocarbons in 'giant' carbonaceous antarctic micrometeorites

Two-step laser desorption/laser ionization mass spectrometry (microL2 MS) was used to establish the nature and mass distribution of polycyclic aromatic hydrocarbons (PAHs) in fragments of fifteen 'giant' (approximately 200 microns) carbonaceous Antarctic micrometeorites (AMMs). Detectable concentrations of PAHs were observed in all AMMs showing a fine-grained matrix. The range of integrated PAH signal intensities varied between samples by over two orders of magnitude. No evidence of contamination whilst in the Antarctic environment could be found. The dramatic variation of both PAH signal intensities and mass distributions between AMMs along with comprehensive contamination checks demonstrates that particles are not exposed to terrestrial PAHs at or above detection limits, either subsequent, during or prior to collection. Comparison of the observed PAH distributions with those measured in three carbonaceous chondrites [Orgueil (CI1), Murchison (CM2) and Allende (CV3)] under identical conditions demonstrated that marked differences exist in the trace organic composition of these two sources of extraterrestrial matter. In general, AMMs show a far richer distribution of unalkylated 'parent' PAHs with more extended alkylation series (replacement of -H with -(CH2)n-H; n = 1, 2, 3 ...). The degree of alkylation loosely correlates with a metamorphic index that represents the extent of frictional heating incurred during atmospheric entry. A search for possible effects of the chemical composition of the fine-grain matrix of host particles on the observed PAH distributions reveals that high degrees of alkylation are associated with high Na/Si ratios. These results, in addition to other observations by Maurette, indicate that 'giant' micrometeorites survive hypervelocity (> or = 11 km s-1) atmospheric entry unexpectedly well. Because such micrometeorites are believed to represent the dominant mass fraction of extraterrestrial material accreted by the Earth, they may have played a significant role in the prebiotic chemical evolution of the early Earth through the delivery of complex organic matter to the surface of the planet.     

Metabolism of polycyclic aromatic hydrocarbons and covalent binding of metabolites to protein in rat adrenal gland

The metabolism of the carcinogenic and adrenocorticolytic polycyclic aromatic hydrocarbon 7,12-dimethylbenz(a)anthracene in rat adrenals was investigated. Both 7,12-dimethylbenz(a)anthracene and benzo(a)pyrene, which also is a well-known carcinogen but has no short-term effects on rat adrenals, appear to be metabolized by one common type of cytochrome P-450-dependent monooxygenase localized in the endoplasmic reticulum. Studies of the kinetic properties of this cytochrome P-450 reveal that the Km values for 7,12-dimethylbenz(a)anthracene and benzo(a)pyrene are lower than 3 microM. Identification of metabolites indicates that, with both 7,12-dimethylbenz(a)anthracene and benzo(a)pyrene, phenols and diols were formed the relative rates of formation of which were markedly influenced by the expoxide hydrase inhibitor cyclohexane oxide, suggesting that epoxides are intermediate metabolites. Added or endogenous microsomal glutathione S-transferase B had little or no effect on the distribution of metabolites. A rather selective binding of metabolites of 7,12-dimethylbenz(a)anthracene to soluble and microsomal proteins was demonstrated. The adrenal cytochrome P-450 involved in the conversion of these polycyclic aromatic hydrocarbons appears to be unrelated to those responsible for the synthesis of mineralocorticoids and glucocorticoids from cholesterol. Among androgens and estrogens, estradiol proved to be the most inhibitory steroid, suggesting a role of the hydrocarbon-metabolizing cytochrome P-450 in estrogen biosynthesis. However, no such function could be demonstrated conclusively. The metabolite patterns and the effects of nonsteroid inhibitors of liver monooxygenases, e.g., alpha-naphthoflavone, SU 9055, and ellipticine, suggest that the properties of this cytochrome P-450 resemble those of the 3-methyl-cholanthrene-inducible cytochrome P-488 from rat liver.     

Monoclonal antibody-based ELISAs for part-per-billion determination of polycyclic aromatic hydrocarbons: effects of haptens and formats on sensitivity and specificity

BACKGROUND: Mitral annuloplasty is an important element of most mitral repairs, yet the effects of various types of annuloplasty rings on mitral annular dynamics are still debated. Recent studies suggest that flexible rings preserve physiologic mitral annular area change during the cardiac cycle, while rigid rings do not. METHODS: To clarify the effects of mitral ring annuloplasty on mitral annular dynamic geometry, we sutured 8 radiopaque markers equidistantly around the mitral anulus in 3 groups of sheep (n = 7 each: no ring, Carpentier-Edwards semi-rigid Physio-Ring [Baxter Healthcare Corp, Edwards Division, Santa Ana, Calif], and Duran flexible ring [Medtronic, Inc, Minneapolis, Minn]). Ring sizes were selected according to anterior leaflet area and inter-trigonal distance (Physio-Ring 28 mm, n = 7; Duran ring 31 mm, n = 5, and 29 mm, n = 2). After 8 +/- 1 days of recovery, the sheep were sedated and studied by means of biplane videofluoroscopy. Mitral annular area was calculated from 3-dimensional marker coordinates without assuming circular or planar geometry. RESULTS: In the no ring group, mitral annular area varied during the cardiac cycle by 11% +/- 2% (mean +/- SEM; maximum = 7.6 +/- 0.2, minimum = 6.8 +/- 0.2 cm2; P 相似文献   

Evidence for the extraterrestrial origin of polycyclic aromatic hydrocarbons in the Martian meteorite ALH84001

Possible sources of terrestrial contamination are considered for the observation of polycyclic aromatic hydrocarbons (PAHs) in the Martian meteorite ALH84001. Contamination is concluded to be negligible.     

全自动固相萃取—气质联用法对平整液废水中多环芳烃的测定

建立了固相萃取—气相色谱/质谱联用测定平整液废水体系中多种多环芳烃(PAHs)的分析方法。结果表明,用C18固相萃取柱,以二氯甲烷为洗脱剂,在上样速率为5 mL/min的条件下,用于平整液废水中多种PAHs的检测,均有较好的回收率,在5～200μg/L范围内呈良好的线性关系,相关系数>0.99,加标回收率为96%～112%,方法简便可靠且能自动化进行,能够达到对平整废水中19种多环芳烃的检测要求。     

Mutagenicity of mixtures of halogenated aliphatic hydrocarbons and polycyclic aromatic hydrocarbons in the Ames test with TA98 and TA100

Within the framework of the assessment of the genotoxic potential of environment samples the Salmonella-microsome-test (Ames-test) is often used as a screening-test. It is one of the most applied biotest systems and possesses a large scientific acceptance. Because most environment samples are mixtures of various substances, possible effects resulting from the combination should be taken into account with regard to the mutagenic potential. In this context we investigated eight polycyclic aromatic hydrocarbons each combined with six halogenated aliphatic hydrocarbons as to their mutagenicity in the Salmonella-microsome-test with TA98 and TA100. For an exogenous metabolizing system, Arochlor 1254 induced rat liver S9-mix was used. Benz-a-pyrene in combination with bromodichloromethane (Ames neg. in TA98 and TA100 +S9) showed an increase in the number of the revertants up to 25% in TA98 and TA100 (+S9). Carbon tetrachloride (Ames neg. in TA98 and TA100 +S9) showed in TA100 (+S9) an increase in the number of the revertants of 18% at most. In the combination 3-methylcholanthrene with dichloromethane the number of revertants in TA98 (+S9) increased by 25% and in TA100 (+S9) by 18%. Hexachloroethane (weakly mutagenic in TA98 +S9) in combination showed in TA98 (+S9) a slightly increased number of revertants with benz-a-pyrene as well with 3-methylcholanthrene. All the other substances tested (chrysene, phenanthrene, anthanthrene, dibenz-a, i-pyrene, triphenylene, fluoranthene) in combination with either tetrachloroethylene or trichloroethene did not cause an increase in mutagenicity.     

Ambient, biological, and biological effect monitoring of exposure to polycyclic aromatic hydrocarbons (PAHs)

A novel strategy was utilised to assess the risk to health from exposure to polycyclic aromatic hydrocarbons (PAHs). Ambient monitoring was carried out by personal sampling. Urinary thioethers (UTh) and urinary 1-hydroxypyrene (1-HP) were utilised for biological monitoring. Urinary d-glucaric acid (UDGA) and sister chromatid exchange (SCE) in peripheral blood lymphocytes were used as biological effect markers. The population was categorised into exposed and control groups according to the external dose of PAHs. The excretion of 1-HP in the controls over the 3-day period showed a relatively stable baseline, while the exposed showed a significant increase over the same period of time. SCE frequency in the exposed population was significantly different from controls.     

Fungal metabolism of polycyclic aromatic hydrocarbons: past, present and future applications in bioremediation

This article examines the importance of non-ligninolytic and ligninolytic fungi in the bioremediation of polycyclic aromatic hydrocarbon contaminated wastes. The research from the initial studies in Dave Gibson's laboratory to the present are discussed.