Milk--blood transfer of (14)C-tagged polycyclic aromatic hydrocarbons (PAHs) in pigs

Polycyclic aromatic hydrocarbons (PAHs) are lipophilic organic pollutants occurring widely in the terrestrial environment. To study the transfer of PAHs in the food chain, pigs have been fed with milk spiked either with [(14)C]phenanthrene or with [(14)C]benzo[a]pyrene. The analysis of blood radioactivity showed that both PAHs were absorbed with a maximum concentration at 5--6 h after milk ingestion, similar to fat metabolism. The blood radioactivity then decreased to reach background levels 24 h after milk ingestion. Furthermore, the blood radioactivity was higher for phenanthrene (even if the injected load was the lowest) than for benzo[a]pyrene, in agreement with their solubility difference. These findings suggest that milk fat and PAHs were absorbed during the same time period.     

Polycyclic aromatic hydrocarbons in soils of Vasilievsky Island (St. Petersburg)

The composition and accumulation patterns of priority polycyclic aromatic hydrocarbons (PAHs) in soils of Vasilievsky Island in Saint Petersburg were studied. Concentrations of benzo[a]pyrene were found to exceed maximum permissible concentrations in all the samples, and the maximum recorded concentration exceeded the MPC by 50 times. Concentrations of other PAHs also exceeded the background values. The main soil pollutants were found to be fluoranthene, pyrene, benzo[b]fluoranthene, benzo[a]pyrene, and benzo[g, h, i] perylene, the part of which in the total content of PAHs was 65–80%.     

Determination of polycyclic aromatic hydrocarbons in commercial liquid smoke flavorings of different compositions by gas chromatography-mass spectrometry

The presence of polycyclic aromatic hydrocarbons (PAHs) in five commercial liquid smoke flavorings, used in the European food industry, was studied. The samples were subjected to an alkaline treatment, extracted with cyclohexane, cleaned up by means of solid-phase extraction tubes, and analyzed by gas chromatography-mass spectrometry. Three different procedures for the cleanup were tested. The results revealed the presence of 34 PAHs, some of them with methyl substituents. In all cases, the concentrations of compounds of low molecular weight were much higher than those of high molecular weight. Relationships between smoke flavoring compositions and PAH levels were also studied. Three of the samples contained high levels of both total and carcinogenic PAHs. Benzo[a]pyrene was also detected in these three samples, but its concentration did not exceed the 10 microg/kg level fixed by the FAO/WHO. Finally, a relation was found, first between the concentrations of total carcinogenic PAHs and benzo[a]pyrene and also between the concentrations of pyrene and benzo[a]pyrene. The latter ratio reveals that pyrene concentration could be very useful in predicting the level of benzo[a]pyrene and, consequently, in estimating the carcinogenicity arising from the presence of benzo[a]pyrene and other carcinogenic PAHs.     

Rapid, semimicro method for determination of polycyclic aromatic hydrocarbons in shellfish by automated gel permeation/liquid chromatography

A simple, rapid, easily automated method is described for the determination of polycyclic aromatic hydrocarbons (PAHs) in shellfish such as American lobster (Homarus americanus) and blue mussel (Mytilus edulis). PAHs are extracted from small amounts (1-8 g) of tissue by saponification in 1N ethanolic potassium hydroxide followed by partitioning into 2,2,4-trimethylpentane. This solution is evaporated just to dryness by rotary evaporation and the residue is dissolved in cyclohexane-dichloromethane (1 + 1) for gel permeation chromatography (GPC) on Bio-Beads SX-3. The GPC procedure is ideal as a screening method in the range 25-18 000 ng PAHs/g tissue. If individual PAH measurements are required, the appropriate GPC fraction is collected and PAHs are separated by reverse phase liquid chromatography (LC) with fluorometric detection. Individual PAHs at concentrations as low as 0.25-10 ng/g can be determined. Recoveries of added fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[e]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[ghi]perylene, and indeno[1,2,3-cd]pyrene were quantitative, with relative standard deviations ranging from 0.0 to 16.9%.     

Studying the Effects of Two Various Methods of Composting on the Degradation Levels of Polycyclic Aromatic Hydrocarbons (PAHs) in Sewage Sludge

The research comprised of studying the effect composting sewage sludge with sawdust and vermicomposting with earthworm Eisenia fetida has on the degradation of 16 polycyclic aromatic hydrocarbons (PAHs). Raw rural sewage sludge prior composting was more contaminated with PAHs than urban sewage sludge, in both cases exceeding EU cutoff limits of 6 mg/kg established for land application. Dibenzo[a,h]anthracene (DBahAnt), acenaphtylene (Acy) and indeno[1,2,3-c,d]pyrene (IPyr) were predominant in rural sewage sludge, whilst the urban sewage sludge contained the highest concentrations of benzo[b]fluoranthene (BbFl), benzo[k]fluoranthene (BkFl) and indeno[1,2,3-c,d]pyrene (IPyr). Thirty days of composting with sawdust has caused a significant reduction of 16 PAHs on average from 26.07 to 4.01 mg/kg (84.6%). During vermicomposting, total PAH concentration decreased on average from 15.5 to 2.37 mg/kg (84.7%). Vermicomposting caused full degradation of hydrocarbons containing 2 and 6 rings and significant reduction of PAHs with 3 aromatic rings (94.4%) as well as with 5 aromatic rings (83.2%). The lowest rate of degradation (64.4%) was observed for hydrocarbons with 4 aromatic rings such as fluoranthene, benzo(a)anthracene, chrysene and pyrene. On the other hand, the highest level of degradation was determined for PAHs with 2 rings (100%), 3 rings (88%) and 6 aromatic rings in the molecule (86.9%) after composting with sawdust. Acenaphthene and pyrene were found to be the most resistant to biodegradation during both composting methods.     

Characterization and Sources of PAHs and Potentially Toxic Metals in Urban Environments of Sevilla (Southern Spain)

The purpose of this study was to determine the degree of PAH contamination and the association of PAHs with metals in urban soil samples from Sevilla (Spain). Fifteen polycyclic aromatic hydrocarbons-PAHs (naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylene, indeno[1,2,3-c,d]pyrene) and seven metals (Cd, Cr, Cu, Mn, Ni, Pb, Zn) have been evaluated in representative urban soil samples. Forty-one top soils (0–10 cm) under different land use (garden, roadside, riverbank and agricultural allotment) were selected. PAHs from soil samples were extracted by sonication using dichloromethane. The simultaneous quantification of 15 different PAH compounds were carried out by HPLC using multiple wavelength shift in the fluorescence detector. For qualitative analysis a photo diode-array detector was used. Metal (pseudo-total) analysis was carried out by digestion of the soils with aqua regia in microwave oven. The mean concentration of each PAH in urban soils of Sevilla showed a wide range, they are not considered highly contaminated. The results of the sum of 15 PAHs in Sevilla soils are in the range 89.5–4004.2 μg kg^?1, but there seems not to be a correlation between the concentration of PAHs and the land use. Of the 15 PAHs examined, phenanthrene, fluoranthene and pyrene were present at the highest concentrations, being the sum of these PAHs about 40% of the total content. Although metal content were not especially high in most soils, there are significant hints of moderate pollution in some particular spots. Such spots are mainly related with some gardens within the historic quarters of the city. The associations among metals and PAHs content in the soil samples was checked by principal components analysis (PCA). The largest values both for ‘urban’ metals (Pb, Cu and Zn) and for PAHs were mainly found in sites close to the historic quarters of the city in which a heavy traffic of motor vehicles is suffered from years.     

Rapid magnetic solid-phase extraction based on magnetic multiwalled carbon nanotubes for the determination of polycyclic aromatic hydrocarbons in edible oils

In this study, magnetic multiwalled carbon nanotubes were fabricated by a simple method and applied to magnetic solid-phase extraction (MSPE) of eight heavy molecular weight polycyclic aromatic hydrocarbons (PAHs) including chrysene, benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene and benzo[g,h,i]perylene from edible oil samples. Several parameters affecting the extraction efficiency were investigated, including the type and volume of desorption solvent, extraction and desorption time, washing solution and the amount of sorbent. Under the optimized conditions, a simple and effective method for the determination of PAHs in edible oils was developed by coupling with gas chromatography-mass spectrometry (GC-MS). The whole pretreatment process was rapid, and it can be accomplished within 10 min. The limits of quantitation for the target PAHs were found to be 0.34-2.9 ng/g. The recoveries in oil sample were in the range 87.8-122.3% with the RSDs less than 6.8% (intraday) and 9.6% (interday). This method was successfully applied to the analysis of PAHs in seven kinds of edible oils from local markets.     

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.     

某氮肥厂场地土壤PAHs污染特征研究

采用现场采样及室内测试方法对广州某氮肥厂原料车间和油库区土壤中16种优控多环芳烃（PAHs）的含量进行调查研究,分析了EPAHs含量及其组成特征和垂直分布特征,并在此基础上进行了源解析。结果表明,分析样品中∑PAHs范围在10-7795μg·kg,原料车间土壤中的∑PAHs小于油库区土壤中的,菲、芘、荧蒽、并（b）荧蒽、苯并（a）芘为主要污染物;油库土壤0-40cm的样品中16种PAHs均有检出,∑PAHs和单体分布基本一致;原料车间土壤∑PAHs和单体浓度随着地面深度的增加而减少。通过对单组分比值（菲／蒽,荧蒽／芘）的分析可以看出油库区土壤中PAHs来源于石油和燃烧源,而原料车间污染源主要为燃烧源。     

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.     

Effect of soil bacteria on the ability of polycyclic aromatic hydrocarbons (PAHs) removal by Trametes versicolor and Irpex lacteus from contaminated soil

The effect of bacteria represented by indigenous soil microflora or a mixture of soil bacteria Pseudomonas aeruginosa and Rhodococcus erythropolis on fungal growth, extracellular enzyme production and polycyclic aromatic hydrocarbons (PAHs) biodegradation efficiency in soil of white-rot fungi Trametes versicolor and Irpex lacteus was investigated. Both fungi were able to colonize soil. The growth yields measured by ergosterol were about two-fold in I. lacteus after 10 weeks. Laccase was produced in T. versicolor cultures in the presence or absence of bacteria but live bacteria reduced the laccase levels in soil about 5 times. Manganese-dependent peroxidase (MnP) was not detected in T. versicolor cultures. The amounts of MnP and laccase in I. lacteus cultures were not affected by the presence of bacteria. T. versicolor was more efficient in PAH removal for all PAHs tested although its capacity to colonize soil was lower. The removal rates of PAHs by T. versicolor in sterile soil were 1.5-fold, 5.8-fold and 1.8-fold for 2-3-ring, 4-ring and 5-6-ring PAHs, compared to I. lacteus, respectively. I. lacteus showed a low efficiency of removal of pyrene, benzo[a]anthracene and benzo[k]fluoranthene, compared to T. versicolor, whereas chrysene and benzo[b]fluoranthene were degraded by neither fungus. The main effect of the presence of the indigenous microflora or R. erythropolis and P. aeruginosa was a significant decrease of degradation of total PAHs by both T. versicolor and I. lacteus. Weak fungal/bacterial synergistic effects were observed in the case of removal of acenapthylene, benzo[a]pyrene, dibenzo[a,h]anthracene and benzo[g,h,i]perylene by I. lacteus and acenapthylene by T. versicolor. However, the bacterial effects were different in the two fungi. PAH abiotic losses represented 15 and 21% of the total PAHs after 5 and 10 weeks, respectively; naphthalene and acenaphthene were removed from the soil due to volatilization.     

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。     

Input and behavior of polycyclic aromatic hydrocarbons in arable,fallow, and forest soils of the taiga zone (Tver oblast)

Contents of 11 most prevalent polycyclic aromatic hydrocarbons (PAHs) in snow and soils of arable, fallow, and forest areas significantly remote from impact technogenic sources of polyarenes have been examined in the Torzhok district of Tver oblast. From the analysis of snow samples, the volumes and composition of PAHs coming from the atmosphere onto the areas of different land use have been determined. Light hydrocarbons prevail in PAHs. They make up 65–70% of total PAHs; their share in soils reaches almost 95%. An increase in the content of PAHs is revealed in fallow soils compared to arable and afforested areas. A direct relationship is revealed between the lateral distribution of total PAHs and the content of organic carbon. The distribution of total PAHs is surface-accumulative in forest soils, mainly uniform in arable soils, and deepaccumulative in fallow soils. PAH groups characterized by similar radial distributions and ratios between their reserves in snow and soils are distinguished: (1) fluorene and phenanthrene, (2) biphenyl and naphthalene, (3) benzo(a)anthracene, chrysene, perylene, and benzo[a]pyrene, and (4) anthracene and benzo[ghi]pyrene.     

In vitro bioaccessibility of soil-bound polycyclic aromatic hydrocarbons in successive digestive compartments in cows

Ruminants, which have a central place in the food chain, ingest soil that may contain pollutants. The bioaccessibility of three different polycyclic aromatic hydrocarbon compounds from soil was studied using an in vitro model based on the digestive tract of cows. For this purpose, pasture soil was spiked with (14)C radio-labeled compounds, aged, and then exposed to conditions which simulated the digestive compartments of the rumen, abomasum, and intestines. Our results show that aging generally reduced the bioaccessibility of all the compounds tested. Total bioaccessibilty in the first digestive compartment, i.e., the rumen, depended on the considered compound: elevated for phenanthrene (17-24%), moderate for pyrene (6.6-8.1%), and low for benzo[ a]pyrene (2.3-3.6%). Bioaccessibility was very low in abomasal acidity (generally <2%) and intestinal colloids (<8%). The liquid phases of intestinal medium successfully extracted compounds from freshly contaminated soil (25-28%), but the bioaccessibilty dropped markedly after aging (17% for phenanthrene and <9% for the more lipophylic compounds). Total bioaccessibilty in this in vitro model ranged from 11% for benzo[ a]pyrene in aged soil to 58% for phenanthrene in freshly contaminated soil, and the bioaccessibility of this latter compound was always higher compared to pyrene or benzo[ a]pyrene. Residual soil contained around half of the initial load, the highest residual levels being of benzo[ a]pyrene, which confirms the observed bioaccessibility.     

Hydrocarbon status of soils under atmospheric pollution from a local industrial source

Contents and compositions of bitumoids, polycyclic aromatic hydrocarbons (PAHs), and free and retained hydrocarbon gases in soils along a transect at different distances from the local industrial source of atmospheric pollution with soot emissions have been studied. The reserves of PAHs progressively decrease when the distance from the source increases. Among the individual PAHs, the most significant decrease is observed for benzo[a]pyrene, tetraphene, pyrene, chrysene, and anthracene. On plowlands, the share of heavy PAHs—benzo[ghi]perylene, benzo[a]pyrene, perylene, etc.—is lower than in the forest soils. In automorphic soils of the park zone adjacent to the industrial zone, the penetration depth of four-, five-, and sixring PAHs from the atmosphere is no more than 25 cm. In soils under natural forest vegetation, heavy PAHs do not penetrate deeper than 5 cm; in tilled soils, their penetration depth coincides with the lower boundary of plow horizons. Analysis of free gases in the soil air revealed hydrocarbons only under forest. From the quantitative and qualitative parameters of the content, reserves, and compositions of different hydrocarbons, the following modification types of hydrocarbon status in the studied soils were revealed: injection, atmosedimentation–injection, atmosedimentation–impact, atmosedimentation–distant, and biogeochemical types.     

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.     

农药企业搬迁土地多环芳烃的风险评价

以常州市某农药厂搬迁土地为研究对象,在监测分析土壤中16种多环芳烃（PAHs）的基础上,对该区域土壤进行健康风险和生态风险评价。结果表明,研究区域土壤中∑PAHs的含量范围为0～1.546mg·kg-1,优势化合物中萘、菲等低环化合物含量大于高环的荧蒽、苯并[k]荧蒽和芘等化合物,且土壤中PAHs可能来源于石油源。健康风险评价结果在可接受的10-6～10-4范围内,而生态风险评价表明,尽管研究区域土壤中的多环芳烃不存在严重的生态风险,但是化合物苊和芴含量超出了风险评价低值（ER-L和ISQV-L）,存在着对生物的潜在危害。     

长江三角洲地区污泥中多环芳烃的污染研究

To ascertain the contaminated conditions of polycyclic aromatic hydrocarbons （PAHs） in sludge and to evaluate the risk of application of this sludge for agricultural purposes, 44 sludge samples obtained from 15 cities in the Yangtze River Delta area of China were investigated using capillary gas chromatography/mass spectrometry （GC/MS） after ultrasonic extraction and silica gel cleanup. PAHs＇ contents ranged from 0.0167 to 15.4860 mg kg^-1 （dry weight, DW） and averaged 1.376 mg kg^-1, with most samples containing 〈 1.5 mg kg^-1. Pyrene （PY）, fluoranthene （FL）, benzo[b]fluoranthene （BbF）, indeno[1,2,3-cd]pyrene （IND）, benzo[a]pyrene （B[a]P）, and benzo[g,h,i]perylene （BghiP） were the most dominant compounds, ranging from 0.1582 to 0.2518 mg kg^-1. Single PAH, such as naphthalene （NAP, 2-benzene rings）, phenanthrene （PA, 3-benzene rings）, PY （4-benzene rings）, and FL （3-benzene rings）, had high detection rates （76.1%-93.5%）. The distribution patterns of PAHs were found to vary with the sludge samples; however, the patterns showed that a few compounds with 2- and 3-benzene rings were commonly found in the samples, whereas those with 4-, 5-, and 6-benzene rings were usually less commonly found. All the 44 sludge samples were within the B[a]P concentration limit for sludge applied to agricultural land in China （〈 3.0 rag kg^-1）. The probable sources of PAH contamination in the sludge samples were petroleum, petroleum products, and combustion of liquid and solid fuel. The concentrations and distributions of the 16 PAHs in sludge were related to sludge type, source, and treatment technology, together with the physicochemical properties.