Effect of exposure to soil-bound polycyclic aromatic hydrocarbons on milk contaminations of parent compounds and their monohydroxylated metabolites

The aim of this study was to determine the transfer kinetics of soil-bound polycyclic aromatic hydrocarbons to milk in lactating cows. Soil (500 g/day) fortified with fluorene (104 microg/g dry soil), phenanthrene (82 microg/g), pyrene (78 microg/g), and benzo[a]pyrene (33 microg/g) was administered to three dairy cows via a rumen cannulas for 28 consecutive days. Parent compounds and their major metabolites in milk were measured using gas chromatography-mass spectrometry. Secretion of parent compounds in milk did not increase significantly (P > 0.05) over the control values measured before supply. Target monohydroxylated metabolites were not detected in control samples, but 2-hydroxy fluorene, 3-hydroxy phenanthrene, and 1-hydroxy pyrene were present in milk by the second day of dosing. The highest concentrations of metabolites in milk (31-39 ng/mL) were for 1-hydroxy pyrene at days 7 and 14 of dosing. The observed plateaus for 3-hydroxy phenanthrene and 2-hydroxy fluorene were lower (respectively, 0.69 and 2.79 ng/mL) but significantly increased in comparison to the control samples. Contrarily, 3-hydroxy benzo[a]pyrene was not detected in milk at any sampling time. These results suggested a notable metabolism of the parent compounds after their extraction from soil during the digestive transfer. Thus, the metabolization of fluorene and pyrene can lead to higher concentrations of metabolites than of parent compounds in milk. Despite the absence of a significant transfer of parent PAHs to milk, the appearance of metabolites raises the questions of their impact on human health.     

Availability of polycyclic aromatic hydrocarbons in aging soils

Purpose  

The soil contamination by hydrophobic organic contaminants (HOCs), such as polycyclic aromatic hydrocarbons (PAHs), poses great threats to human health and ecological security and attracts worldwide concerns. The total HOC concentrations overestimate its available fraction to the soil biota. Increased understanding of the availabilities of PAHs in soil environment will have considerable benefits for their risk assessment and be very instructive to food safety and remediation strategies in contaminated sites. However, the availability of PAHs in aging soils and particularly the correlations of the availabilities with their forms in soils have yet to be elucidated. In this work, the availabilities of PAHs in aging soils were evaluated using a sequential mild extraction technique.     

Distribution of polycyclic aromatic hydrocarbons in the soil-plant system

The content and composition of the polycyclic aromatic hydrocarbons (PAHs) in the conjugated systems of [arable soil]-[above-ground plant organs] in background (reference) and contaminated regions were studied. The coefficients of the biological uptake of PAHs by plants (K _bPAH) were determined for different PAH concentrations in the soil. Correlations of the PAH accumulation rate in plants with the physicochemical properties of the PAHs—the solubility, hydrophobicity, volatility, and chemical activity (polarizability and ionization potential)—were revealed. The high accuracy, sensitivity, and information value of the standardized parameters K _b were shown (with K _bPAH as an example) for the quantitative study of the accumulation mechanisms of substances by plants compared to the average arithmetic values of their concentrations in the plants.     

Sorption of polycyclic aromatic hydrocarbons to mineral surfaces

Minerals contribute crucially to the retention of polycyclic aromatic hydrocarbons (PAHs) in subsurface environments. To investigate the sorption behaviour to mineral surfaces batch sorption experiments were conducted using three PAHs (phenanthrene, pyrene, benzo(a)pyrene) and three mineral sorbents that were representative of subsurface materials (quartz, goethite‐coated quartz, quartz‐montmorillonite mixture). Sorption kinetics showed an instantaneous, considerable PAH sorption to all minerals, except for phenanthrene sorption to quartz at small aqueous‐phase concentrations. Apparent sorption equilibrium was achieved after 4 hours of contact time. The sorption characteristics were fitted to six isotherm models by applying Monte Carlo simulation and nonlinear regression. Best‐fit models were obtained by a model discrimination approach. Phenanthrene and pyrene sorption were best described by the Freundlich isotherm model, with the exception of phenanthrene sorption to quartz (linear isotherm). Good fit results for quartz were also obtained for the combined linear‐Freundlich isotherm. Benzo(a)pyrene sorption to all minerals followed linear high‐affinity isotherms. In the case of phenanthrene and pyrene, the Monte Carlo simulations resulted in mean values with small standard deviations for the isotherm parameters, indicating a negligible influence of the experimental uncertainties on the accuracy of the fitted parameters. For phenanthrene, (i) linear isotherms to quartz and goethite‐coated quartz and (ii) a nonlinear concave‐shaped isotherm to quartz–montmorillonite, assuming a pore‐filling process to micropores formed by clay aggregates, were confirmed. For pyrene, nonlinear convex‐shaped isotherms to the mineral surfaces were assessed. A specific sorption affinity of pyrene to the goethite surface indicated a non‐covalent cation‐π interaction. Small sorption affinities to quartz–montmorillonite support an unfavourable partitioning into the adjacent water.     

Phytotoxicity of polycyclic aromatic hydrocarbons to willow trees

The toxicity of PAH to willow trees(Salix alba, S. viminalis, S. viminalis x schwerinii) was investigated. Willow cuttings were grown in PH-saturated hydroponic solution (naphthalene NAP, phenanthrene PHEN and benzo(a)pyrene BaP). Toxicity was related to aqueous solubility and was highest for NAP. PHEN did not show significant effects, except in one case. Exposure of trees to BaP showed no effect in two cases, but increased transpiration and growth in two others. High dosages of NAP were fatal for the trees, the lowest dosage significantly stimulated growth. Soil samples were taken from several PAH contaminated sites, among them gas works sites and a former sludge basin. The PAH contents ranged from 1.76 mg/kg to 1451 mg/kg. None of the soils was lethally toxic to the trees, and difference between growth in control soils and growth in PAH contaminated soils was not apparent. Growth and water use efficiency were positively, but not significantly correlated to the PAH content of the soils. Outdoor growth of willows and poplars on the former sludge basin in Valby was monitored, with willows growing faster than poplars(Fopulus trichocarpa). Phytotoxic effects could be observed at some willows at the Valby sludge basin, but it is not sure whether these effects can be contributed to PAH.     

多环芳烃微生物降解机理研究进展

主要阐述了微生物降解PAHs的机理,比较了典型微生物种类芽孢杆菌(Bacillus)和分支杆菌(M.vanbaalenii PYR-1)对同种PAHs菲的代谢过程不同之处,并分析了分支杆菌(M.vanbaalenii PYR-1)对菲和芘的代谢机理,指出微生物氧化降解PAHs主要从其K区和湾区开始,而K区氧化是有毒PAHs降解的主要可能途径,资料显示真菌比细菌对苯并[a]芘的降解能力更强,同时给出了微生物代谢菲、芘和苯并[a]芘的降解图,以便做进一步研究。     

Extraction of polycyclic aromatic hydrocarbons from spiked soil

A homogenization method was evaluated for extracting polycyclic aromatic hydrocarbons (PAHs) from soils. Fifteen PAHs were spiked and recovered from 2 soils at concentrations ranging from 1 to 1000 micrograms/g, using the homogenization method and a Soxhlet extraction method. Each extraction method performed well in removing the 15 PAHs from both soils over a broad range of concentrations. In general, Soxhlet extraction yielded slightly but significantly (P less than 0.05) higher recoveries than did the homogenization method. The homogenization method, however, was easy to use, and the extraction step turnaround time was less than 15 min/sample. The method should be suitable for other applications requiring the extraction of hydrophobic organic compounds from soils.     

Determination of monocyclic and polycyclic aromatic hydrocarbons in fish tissue

An analytical method is presented in which fish tissue is analyzed for neutral monocyclic and polycyclic aromatic hydrocarbons (AHs) and aromatic sulfur heterocycles (ASHs) by capillary column gas chromatography (CGC) with photoionization detection. The sample enrichment procedure includes saponification with aqueous KOH, acidification of the digestates, and extraction of the aromatic compounds into cyclopentane-dichloromethane. Adsorption chromatography on tandem segments of potassium silicate and silica gel removes 99% of the coextracted lipid. Final enrichment by gel permeation chromatography eliminates residual biogenic material and potentially interfering alkanes. Relatively volatile monoaromatics are included among the analytes by virtue of the efficiency of the complementary enrichment steps, the use of small quantities of only low-boiling solvents, and the selectivity of the detector. Most targeted compounds (AHs ranging in size from C3-alkylbenzenes through benzo[g,h,l]perylene and ASHs within the same size range) can be determined in 5 g (wet weight) samples of fish tissue at concentrations as low as 20 ng/g. Comparisons are made of recoveries of selected AHs under ordinary and gold fluorescent lighting conditions.     

Selenium enhances Conyza canadensis phytoremediation of polycyclic aromatic hydrocarbons in soil

Journal of Soils and Sediments - To determine whether supplemental selenium (Se) enhances the tolerance of Conyza canadensis (C. canadensis) to polycyclic aromatic hydrocarbons (PAHs) and thereby...     

Formation of polycyclic aromatic hydrocarbons in northern and middle taiga soils

An integrated study of the qualitative and quantitative composition of polycyclic aromatic hydrocarbons (PAHs) in the atmospheric precipitation-soil-lysimetric water system was performed using high performance liquid chromatography. It was shown that the accumulation of low-molecular PAHs (phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, and chrysene) in soils is due to the transformation of organic matter and the regional transport and deposition of PAHs with atmospheric precipitation on the underlying surface. High-molecular polyarenes (benz[b]fluoranthene, benz[k]fluoranthene, benz[a]pyrene, dibenz[a,h]anthracene, benzo[ghi]perylene, and indeno[1,2,3-cd]pyrene) mainly result from the decomposition of soil organic matter.     

Determination of polycyclic aromatic hydrocarbons in fumes from fried chicken legs

The amount and variety of polycyclic aromatic hydrocarbons (PAHs) in fumes during frying of chicken legs in edible oils were determined using a modified smoke collection device and a GC-MS technique. Chicken legs were fried in soybean oil, canola oil, or sunflower oil at 163 degrees C for 1-4 h. Results showed that most smoke (99%) was collected in the condensation apparatus, whereas the rest (1%) was adsorbed onto adsorption wool. A large proportion of PAHs in the smoke were detected in adsorption wool, whereas a small portion was found in the condensation apparatus. Canola oil generated the largest content (500.9 g for a frying time of 4 h) of smoke, followed by soybean oil, and sunflower oil. A similar trend was observed for PAH formation in fumes, with the exception that soybean oil produced a higher level than canola oil.     

Liquid chromatographic determination of polycyclic aromatic hydrocarbons in fish and shellfish

A simple and accurate analytical method for determination of polycyclic aromatic hydrocarbons (PAHs) in fish and shellfish is presented, which is considered to be useful for routine analyses and for screening purposes. The procedure involves alkaline digestion, extraction with n-hexane, silica gel column chromatography, and liquid chromatographic (LC) determination with fluorometric detection. During development of the analytical method for determination of PAHs, it was found that benzo[a]pyrene, a representative PAH, was decomposed easily by the analytical procedure, and this tendency was investigated for the experimental conditions used. Benzo[a]pyrene was decomposed by the coexistence of alkaline conditions, light, and oxygen; by peroxides in aged ethyl ether; and by oxygen when absorbed on silica gel. Thus, to obtain good recoveries and precise analytical results, these decomposition conditions must be avoided. The following precautions are recommended: protection from light through all analytical steps; addition of Na2S to alkaline digestion mixture as an antioxidant; complete removal of peroxides from ethyl ether just before use; quick column chromatography on silica gel; and prevention of air from contact with adsorbent. When this simple method was applied to fish and shellfish samples, very good recoveries of PAHs from fortified fish samples were obtained, and no serious interferences were observed in fish and shellfish extracts.     

Determination of 10 carcinogenic polycyclic aromatic hydrocarbons in mainstream cigarette smoke

Polycyclic aromatic hydrocarbons (PAHs) are one class of chemical compounds that (1) are present at low to trace levels in unburned cigarette filler, and (2) are predominantly generated during combustion. According to a recent report of the International Agency for Research on Cancer, 10 carcinogenic PAHs together with 53 other known carcinogens are present in cigarette smoke. Accurate quantification of these chemicals helps assess public health risk to both smokers and nonsmokers exposed to second-hand smoke. We have developed and validated a specific and sensitive method for measuring these 10 carcinogenic PAHs in the particulate phase of mainstream tobacco smoke. Cigarette smoke particulate, produced using standard machine smoking protocols, was collected on glass fiber Cambridge filter pads. The particulate matter was solvent extracted, purified by solid-phase extraction, and analyzed by liquid chromatography/atmospheric pressure photoionization tandem mass spectrometry using isotopically labeled analogues as internal standards. Our method's limits of detection ranged from 11 to 166 pg and achieved sufficient reproducibility and accuracy to provide useful information on a range of cigarettes having dramatically different machine-smoked tar and nicotine deliveries. The identity of each PAH analyte was established from chromatographic retention time, analyte-specific fragmentation patterns, and relative peak area ratios of the product/precursor ion pairs. This new method provides higher sensitivity, specificity, and throughput than did earlier methods. We found relatively consistent PAH levels among a selection of domestic full-flavor cigarettes. The PAH levels in smoke from highly ventilated light and ultralight cigarettes were low when smoked using ISO (International Organization for Standardization) conditions. However, if highly ventilated cigarettes were smoked under more intense conditions (e.g., larger or more frequent puffs, vents blocked), their PAH levels equaled or exceeded their full-flavor counterparts under ISO conditions.     

Determination of polycyclic aromatic hydrocarbons in coffee brew using solid-phase extraction

The presence of polycyclic aromatic hydrocarbons (PAHs) in coffee has been reported and is suspected to be due to the degradation of coffee compounds during the roasting step. Due to the high toxicity of these compounds, among which benzo[a]pyrene is known to be the most carcinogenic, their presence in the coffee, especially the coffee brew that is directly ingested by the consumer, is of prime importance. However, due to the low solubility of these compounds, their concentrations are expected to be rather low. As a consequence, reliable and sensitive analytical methods are required. The aim of this study was to develop a reliable and fast analytical procedure to determine these organic micropollutants in coffee brew samples. PAHs were retained on a 0.5 g polystyrene-divinylbenzene cartridge before being eluted by a mixture of methanol/tetrahydrofuran (10:90 v/v), concentrated, and directly analyzed by reversed-phase high-performance liquid chromatography coupled to a fluorescence detector. Application to the determination of PAHs in several coffee brew samples is also given, with mean estimated concentrations in the range of 0-100 ng L(-1) for suspected benzo[b]fluoranthene and benzo[a]pyrene, whereas no fluoranthene could be detected. Tentative identification was made on the basis of UV spectra. However, identification of the suspected traces of PAHs could not be achieved due to matrix effects, so that the presence of coeluting compounds may not be excluded.     

Microtox技术检测多环芳烃生物毒性的研究

利用Microtox技术检测 5种多环芳烃化合物生物毒性结果表明 ,二甲亚砜配制的测试液中萘、菲及荧蒽均对发光细菌具有一定生物毒性 ,且随浓度的增大而增强 ,相同浓度下毒性菲 >萘 ;测试液中当萘浓度小于其溶解度时即产生 10 0 %的抑光率 ,萘EC50 为 4 .32mg/L ,而菲及荧蒽浓度近其溶解度时所产生的最大抑光率分别为 <5 0 %和15 %左右 ;芘及蒽最大浓度时则对发光细菌无生物毒性显示。表明Microtox技术可有效检测低环化合物萘的生物毒性 ,但对高环化合物 (≥ 3环 )的检测因受其低水溶性的限制而灵敏度降低 ,利用二甲亚砜获取多环芳烃污染物提取液的生物毒性主要与低分子化合物萘及菲有关     

Annual rates of deposition of polycyclic aromatic hydrocarbons in different forest ecosystems

Using the flux balance of the forest canopy of a beech and a spruce stand annual rates of total deposition — divided into precipitation and interception deposition — were derived for 4 polycyclic aromatic hydrocarbons (PAH). The deposition of PAH is in general higher under spruce because of higher rates of interception deposition as compared to beech. The rate of interception deposition of the various PAH compounds (3.4-Benzopyrene, Indeno (1,2,3-cd)pyrene,1.12 Benzoperylene, Fluoranthene) are significantly different. Substantial amounts of PAH are transferred to the soil by litterfall, which indicates adsorption of PAH on leaf and needle surfaces. The storage of PAH in the soil is equivalent to 34 to 48 yr of the actual deposition for 3.4 Benzopyrene and Indeno (1,2,3-cd)pyrene and is equivalent to 14 to 26yr of actual deposition for the amount of 1.12 Benzoperylene and Fluoranthene in the soil.     

大型海藻基生物炭中多环芳烃分布特征及毒性评价

研究大型海藻基生物炭中多环芳烃（Polycyclic Aromatic Hydrocarbons,PAHs）分布特征及毒性可为其资源化利用提供重要的依据。该研究利用索氏提取结合气相色谱质谱法分析了不同热解温度（200、300、400、500和600 ℃）的大型海藻（瓦氏马尾藻（Sagassum vachellianum）、羊栖菜（Sargassum fusiforme）、鼠尾藻（Sargassum thunbergii）、带形蜈蚣藻（Grateloupia turuturu）、粗枝软骨藻（Chondria crassicaulis）及孔石莼（Ulva pertusa））基生物炭中16种PAHs含量并对其毒性进行评价。结果表明,大型海藻基生物炭中均能检出PAHs（总量浓度为78.2～2 244.2 μg/kg）,且其生成量整体随热解温度升高先增加后降低。大型海藻基生物炭中PAHs含量均低于欧洲生物炭标准（European Biochar Certificate,EBC,10.1版）规定的EBC-AgroOrganic等级限量值（4±2）mg/kg。大型海藻基生物炭中PAHs以2环和3环为主,4环PAHs在所有生物炭中均存在,而5环和6环PAHs仅在部分生物炭中被检出。此外,不同大型海藻基生物炭呈现各异的苯并[a]芘毒性当量浓度（BaP- Toxic Equivalence Quantity, TEQBaP）（0.196～46.151 μg/kg）,其TEQBaP不仅依赖于生物炭中PAHs含量还与其环数和类型分布有关。在生物炭修复效果且潜在环境风险相近的基础上,结合产率及热解温度耗能,可选择热解温度较低的生物炭材料,为大型海藻基生物炭制备与应用的优化提供重要指导。