Benzo[b]fluoranthene,a Potential Alternative to Benzo[a]pyrene as an Indicator of Exposure to Airborne PAHs in the Vicinity of Söderberg Aluminum Smelters

ABSTRACT

Benzo[b]fluoranthene (B[b]F) was used in relative abundance ratios (RARs), a parameter obtained by dividing the concentration of individual polycyclic aromatic hydrocarbons (PAHs) found in a given sample by the concentration of B[b]F in the same sample. The B[b]F RARs were derived for PAH concentrations measured at stacks and sampling stations in the vicinity of two Söderberg aluminum horizontal stud smelters (HSSs). The samples collected were analyzed by high-performance liquid chromatography using UV and fluorescence detection. A total of 15 PAHs were analyzed, but, due to the inefficiency of the sampling method used in collecting gaseous PAHs, only particulate PAHs were considered. Comparisons between the B[b]F RARs obtained simultaneously at the source (stack) and those obtained at sampling stations at the two smelters showed that B[b]F degrades more slowly than or at the same rate as most other particulate PAHs monitored. Twenty-three months of urban sampling in the vicinity of one of the aluminum HSSs are also presented, and the results indicate that B[b]F is more stable than all other particulate PAHs investigated. Sampling conducted during a smelter shutdown period confirmed that B[b]F was a much better marker of this source than was benzo[a]pyrene (B[a]P), the usual indicator. The remarkable stability of the benzo[k]fluoranthene (B[k]F)/B[b]F ratio is also discussed.     

Benzo[b]fluoranthene, a potential alternative to benzo[a]pyrene as an indicator of exposure to airborne PAHs in the vicinity of Söderberg aluminum smelters

Benzo[b]fluoranthene (B[b]F) was used in relative abundance ratios (RARs), a parameter obtained by dividing the concentration of individual polycyclic aromatic hydrocarbons (PAHs) found in a given sample by the concentration of B[b]F in the same sample. The B[b]F RARs were derived for PAH concentrations measured at stacks and sampling stations in the vicinity of two S?derberg aluminum horizontal stud smelters (HSSs). The samples collected were analyzed by high-performance liquid chromatography using UV and fluorescence detection. A total of 15 PAHs were analyzed, but, due to the inefficiency of the sampling method used in collecting gaseous PAHs, only particulate PAHs were considered. Comparisons between the B[b]F RARs obtained simultaneously at the source (stack) and those obtained at sampling stations at the two smelters showed that B[b]F degrades more slowly than or at the same rate as most other particulate PAHs monitored. Twenty-three months of urban sampling in the vicinity of one of the aluminum HSSs are also presented, and the results indicate that B[b]F is more stable than all other particulate PAHs investigated. Sampling conducted during a smelter shutdown period confirmed that B[b]F was a much better marker of this source than was benzo[a]pyrene (B[a]P), the usual indicator. The remarkable stability of the benzo[k]fluoranthene (B[k]F)/B[b]F ratio is also discussed.     

Dynamics of PAH deposition, cycling and storage in a mixed-deciduous (Quercus-Fraxinus) woodland ecosystem

Estimates of standing biomass and fluxes of biomass in a mixed-deciduous woodland were derived, and used with results for concentrations of seven polycyclic aromatic hydrocarbons (PAHs) in different compartments of the woodland system to quantitatively assess some of the key fluxes and burdens of PAHs in this complex system. We quantified PAH burdens in air, in leaves of three deciduous tree species, in leaf litter and in soil, and uptake of PAHs by the tree leaves; PAH fluxes in litterfall, and deposition to the litter layer on the woodland floor during winter were calculated from these data. Air burdens exhibited marked seasonal variations for all compounds, with lowest values in summer when combustion-related emissions were low. Leaves did not accumulate large burdens of PAHs while on the trees and consequently, litterfall-associated fluxes of PAHs were small, representing only a fraction of the burdens in the litter layer to which they were deposited. Higher PAH burdens in air in winter, combined with the organic-matter-rich nature of the litter layer, are thought to be responsible for fluxes of PAHs to the litter layer in winter being 20-170 times the peak litterfall fluxes. The soil compartment was calculated to contain 25 years' worth of deposition of benzo[ghi]perylene, the most recalcitrant PAH in this study. Storage quotients for fluoranthene, pyrene, benzo[k]fluoranthene and benzo[a]pyrene burdens in soil represented 7-10 years' worth of deposition, while fluorene and phenanthrene storage in soil approached unity with inputs (1 and 3 years' worth of deposition, respectively). The relative importance of storage and loss processes was therefore closely related to the physico-chemical properties of the PAH, and is discussed in relation to the cycling of carbon in the woodland.     

Bioaccumulation of cyclopenta[cd]pyrene and benzo[ghi]fluoranthene by mussels transplanted in a coastal lagoon

The bioaccumulation of two isomeric non-alternant non-priority polycyclic aromatic hydrocarbons (PAHs), namely cyclopenta[cd]pyrene and benzo[ghi]fluoranthene, was investigated in caged mussels (Mytilus galloprovincialis) exposed for 30 days in three sites of a coastal lagoon (Pialassa Baiona, Ravenna, Italy) contaminated by pyrogenic PAHs. The concentration of cyclopenta[cd]pyrene and benzo[ghi]fluoranthene increased from undetectable levels in reference mussels withdrawn from the Adriatic sea to 10-30 ng g(-1) dry weight in transplanted mussels. Other contaminants bioaccumulated by caged mussels included pyrene, fluoranthene and mercury. Whilst the isomer concentration ratio pyrene/fluoranthene in biota was comparable to that observed in sediments, the cyclopenta[cd]pyrene/benzo[ghi]fluoranthene ratio was much lower in mussels than in sediments. The lower sediment biota accumulation factor of cyclopenta[cd]pyrene with respect to that of benzo[ghi]fluoranthene was tentatively attributed to the greater biological activity of the former compound, which contains a reactive olefinic bond in the cyclopenta fused ring moiety. Given the higher mutagenic activity of cyclopenta[cd]pyrene with respect to other priority PAHs, its bioaccumulation from contaminated sediments may rise considerably the overall toxicity of PAH residues in exposed biota.     

Contamination of polycyclic aromatic hydrocarbons (PAHs) in microlayer and subsurface waters along Alexandria coast,Egypt

The residues of seven polycyclic aromatic hydrocarbons (PAHs) pollutants in microlayer and subsurface seawater samples collected from Alexandria coast, Egypt, were analyzed by gas chromatography–electron-impact mass spectrometry-selected ion monitoring mode (GC–MS-SIM). The pollutants studied were, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene and benzo[a]pyrene. Total PAH levels in microlayer ranged from 103 to 523 ng/l, while it ranged in subsurface samples from 13 to 120 ng/l. The Western Harbor location recorded the highest level of PAHs pollutant over all the other location for both subsurface and microlayer waters. The two major PAHs in microlayer water at the Western Harbor were fluorene and phenanthrene, making up 27% and 20% of the total PAHs, while the two major PAHs in subsurface water at the Eastern Harbor were phenanthrene and fluoranthene recording up 21% each of the total PAHs. The total PAH levels were generally in the nano-gram per liter for microlayer and subsurface seawater samples. The dominant PAHs in both subsurface and microlayer samples were fluoranthene, pyrene and benzo[a]pyrene. The microlayer enrichment factor at Alexandria’s Mediterranean coast was ranged from 29 for fluorene to 3 for phenanthrene and benzo[a]pyrene which showed PAHs concentration in the microlayer with an average of five times more than the total PAH in the subsurface samples.     

Leaves of Quercus ilex L. as biomonitors of PAHs in the air of Naples (Italy)

Polycyclic aromatic hydrocarbons (PAHs) were determined by the GC-MS chromatography in the leaves of Quercus ilex L., an evergreen Mediterranean oak, to monitor the degree of pollution in the urban area of Naples compared to remote areas. Leaf samples were collected in July 1998 from four urban parks, six roadsides and two sites in remote areas. The total PAH contents in Q. ilex leaves ranged from 106.6 in a control site to 4607.5 ng/g d.w. along a road with a high traffic flow. The mean concentration factors (urban/control) were 3.8 for the parks and 15 for the roads. The contribution of carcinogenic PAHs (benz[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, indeno[1,2,3-c,d]pyrene) was higher in urban area and differed according to the site, ranging from 6.7% to 21.3%. The total PAH burden in control sites was dominated by the low molecular weight PAHs, whilst along the urban roads fluoranthene, pyrene and benz[a]anthracene among the measured PAHs showed the highest values. PAHs were positively correlated (P<0.01) to trace metals measured in a previous study.     

Rapid quantification of polycyclic aromatic hydrocarbons in hydroxypropyl-beta-cyclodextrin (HPCD) soil extracts by synchronous fluorescence spectroscopy (SFS)

Synchronous fluorescence spectroscopy (SFS) was directly applied to rapidly quantify selected polycyclic aromatic hydrocarbons (PAHs: benzo[a]pyrene and pyrene) in aqueous hydroxypropyl-beta-cyclodextrin (HPCD) soil extract solutions from a variety of aged contaminated soils containing four different PAHs. The method was optimized and validated. The results show that SFS can be used to analyse benzo[a]pyrene and pyrene in HPCD based soil extracts with high sensitivity and selectivity. The linear calibration ranges were 4.0x10(-6)-1.0x10(-3)mM for benzo[a]pyrene and 6.0x10(-6)-1.2x10(-3)mM for pyrene in 10mM HPCD aqueous solution alone. The detection limits according to the error propagation theory for benzo[a]pyrene and pyrene were 3.9x10(-6) and 5.4x10(-6)mM, respectively. A good agreement between SFS and HPLC was reached for both determinations of PAHs in HPCD alone and in soil HPCD extracts. Hence, SFS is a potential means to simplify the present non-exhaustive hydroxypropyl-beta-cyclodextrin (HPCD)-based extraction technique for the evaluation of PAH bioavailability in soil.     

Occurrence and assessment of polycyclic aromatic hydrocarbons in soils from vegetable fields of the Pearl River Delta, South China

Surface soil (0-20 cm) samples from nine representative vegetable fields located in Guangzhou, Shenzhen, Zengcheng and Huadu within the Pearl River Delta, South China were collected and analyzed for 16 USEPA priority polycyclic aromatic hydrocarbons (PAHs) using gas chromatography coupled to mass spectrometry (GC-MS). Total concentrations of 16 PAHs (Sigma(PAHs)) ranged from 160 to 3700 microg kg(-1). Large variations were observed also between concentrations of individual PAHs from different vegetable fields and within the site as well. Acenapthylene, benzo[b]fluoranthene, fluoranthene, benzo[a]pyrene and benzo[k]fluoranthene were consistently the most prevalent individual PAHs. The values of PAH isomer ratios [anthracene/(anthracene+phenanthrene) and fluoranthene/(fluoranthene+pyrene)] indicate that combustion processes are the major sources of PAHs. Concentrations of PAHs were poorly correlated with organic carbon concentrations of soils, suggesting different sources and also indicating that the PAH pollution of this area is recent. The same outcome is confirmed by the predominance of PAHs with fewer rings (相似文献   

The temporal variability of the profile of carcinogenic polycyclic aromatic hydrocarbons in urban air: a study in a medium traffic area in Rome, 1993–1998

The constancy, both temporal and spatial, of the profile of polycyclic aromatic hydrocarbons (PAHs) relative to benzo[a]pyrene (BaP) is a prerequisite to using the BaP-indicator approach in the carcinogenic risk assessment for PAHs. The principal aim of this study was to provide a contribution to validate this approach, by studying the variability of the profile at a typical urban site through a multi-year data set and by comparing the profiles available for different cities. Seven carcinogenic PAHs (benz[a]anthracene, benzo[b+j+k]fluoranthenes, BaP, indeno[1,2,3-cd]pyrene, dibenz[a,h]anthracene) were determined in PM₁₀ 24-h samples collected every third day at a road site; moreover, benzo[e]pyrene was determined as a reference PAH due to its stability. The profile was found stable from year to year. Besides, it was similar to those recently found in other European cities (observed differences within a factor of four) and to those elaborated from earlier (1970s–1980s) investigations. The substantial similarity of profiles, both temporal (on an annual basis) and spatial, supports the validity of the BaP-indicator approach. Large PAH-to-PAH differences were, however, found in the seasonal pattern of profile: they were explained by the different atmospheric degradability of PAHs, whose effect is enhanced under the meteoclimatic conditions typical of the European Mediterranean countries. PAH annual means showed a slight declining trend since 1994. In the last sampling year, mean concentration of BaP was 1.2 ng m⁻³. Within-year differences among monthly averaged PAH concentrations were observed, as large as up to 44-fold for BaP, underlining the need for whole-year monitoring.     

Polycyclic aromatic hydrocarbons in the sediments of the South China Sea

Sixteen sediment samples, collected from the South China Sea, were analyzed for 11 parent polycyclic aromatic hydrocarbons (PAHs) using gas chromatography and gas chromatography-mass spectrometry. Total concentrations of the 11 PAHs studied in the sediments ranged from 24.7 to 275.4 ng/g with a mean of 145.9 ng/g dry sediment. PAH concentrations displayed a consistent distribution trend with the sediment organic carbon content. The linear regression analysis showed that the total concentration of PAHs in the sediment was significantly correlated to the sediment organic carbon content with a correlation coefficient of 0.735 (n=16). Special PAH compound ratios, such as phenanthrene/anthracene and fluoranthene/pyrene, were calculated to evaluate the relative importance of different origins. The collected data showed that pyrolytic input from anthropogenic combustion processes was predominant at almost all the stations investigated. Only one station, located in the proximity of oil wells, appeared to be contaminated predominantly by petrogenic input. Three anthropogenic PAHs, i.e. pyrene, benzo[a]pyrene and benzo[e]pyrene, exhibited similar distribution patterns in the studied area, implying that these compounds possess identical sources. However, perylene did not entirely follow the distribution trend of the three PAHs, suggesting that the sediment perylene probably derived from other sources such as in situ biogenic origins. Dibenzothiophene, a sulfur heterocyclic aromatic compound, was also measured in this study.     

Treatment of PAHs in contaminated soil by extraction with aqueous DNA followed by biodegradation with a pure culture of Sphingomonas sp

The biodegradation of polycyclic aromatic hydrocarbons (PAHs) in aqueous deoxyribonucleic acid (DNA) solution from contaminated soil washing was investigated. Initial data with a model effluent consisting of anthracene, phenanthrene, pyrene and benzo[a]pyrene that were individually dissolved in 1% aqueous DNA solution confirmed their positive degradation by Sphingomonas sp. at around 10(8)CFU mL(-1) initial cell loading. For anthracene and phenanthrene, complete removal was achieved within 1h treatment. Degradation of pyrene and benzo[a]pyrene took a relatively longer time of a few days and weeks, respectively. DNA-dissolved PAHs were also degraded relatively faster than PAH crystals in aqueous medium to suggest that the binding of the PAHs in the polymer does not pose serious constraint to bacterial uptake. The DNA was stable against the PAH-degrading bacteria. Parallel experiments with actual DNA solutions obtained during pyrene extraction from an artificially spiked soil also showed similar results. Close to 100% pyrene degradation was achieved after 1d treatment. With its chemical stability, the cell-treated DNA was re-used up to four cycles without a considerable decline in extraction performance.     

Seasonal variations of hydrophobic organic contaminant concentrations in the water-column of the Seine Estuary and their transfer to a planktonic species Eurytemora affinis (Calanoïda, copepoda). Part 1: PCBs and PAHs

Hydrophobic organic contaminants (HOC) (i.e. PAHs and PCBs) were measured in the water column and in Eurytemora affinis samples from the Seine Estuary collected from November 2002 to February 2005. Results showed seasonal variations of both total PCB and PAH levels in the suspended particulate matter (SPM) and in the copepods with maximum levels during winter times. PAH and PCB concentrations in the SPM ranged from 499 to 5819ngg(-1) and from 58 to 463ngg(-1), respectively. Phenanthrene, pyrene and benzo[b+j+k]fluoranthene (B[b+j+k]F) were the predominant PAH compounds in the water column, while CB 101, 118, 153 and 138 were the most abundant PCB congeners. PCBs and PAHs bioaccumulated by E. affinis (EA) varied between 383 and 1785ngg(-1) and 165-3866ngg(-1). CB101, 153, 138 and B[b+j+k] were, respectively, the major compounds of PCB and PAH fingerprints in EA. Thereby, the copepods could reach high accumulation factor (ACF) (91000 for PCBs and 17000 for PAHs). The principal component analyses of contaminant concentrations and environmental parameter datasets distinguished two groups of copepods. The winter time cluster, with high percentage of adult copepods, which bioaccumulated the highest PCB and PAH body-burdens, and the second cluster with juveniles showing the lowest HOC concentrations. Thus, PAH and PCB concentrations in EA exhibited significant correlations with the percentage of adults making up the samples.     

Removal of sorbed polycyclic aromatic hydrocarbons from soil, sludge and sediment samples using the Fenton's reagent process

The use of the Fenton's reagent process has been investigated for the remediation of environmental matrices contaminated by polycyclic aromatic hydrocarbons (PAHs). Laboratory experiments were first conducted in aqueous solutions, to study the kinetics of oxidation and adsorption of PAHs. Benzo[a]pyrene was more rapidly degraded than adsorbed, while only partial oxidation of fluoranthene occurred. In the case of benzo[b]fluoranthene, its adsorption prevented its oxidation. Besides competition effects between PAHs were found, with slower oxidation of mixtures as compared to single PAH solutions. Apparition of some by-products was observed, and a di-hydroxylated derivative of benzo[a]pyrene could be identified under our conditions. Consequently, application to solid environmental matrices (soil, sludge and sediment samples) was performed using large amounts of reagents. The efficiency of the Fenton treatment was dependent on the matrix characteristics (such as its organic carbon content) and the PAH availability (correlated to the date and level of contamination). However, no pH adjustment was required, as well as no iron addition due to the presence of iron oxides in the solid matrices, suggesting the potential application of Fenton-like treatment for the remediation of PAH-contaminated environmental solids.     

Evaluation of new surfactant expanded zirconium and titanium phosphates for polycyclic aromatic hydrocarbons extraction from waters

A newly synthesized family of materials prepared with surfactant as organic template were tested for the extraction of polycyclic aromatic hydrocarbons (PAHs) from water, using pyrene (Pyr) and benzo[a]pyrene (B[a]P) as PAHs representatives. Particular attention was paid to the evaluation of the recovery factors with dichloromethane as eluent in order to estimate their potential as adsorbing solid phases for PAH remediation or analysis. Eleven lamellar MCM-50 type materials incorporating n-alkyl- (n = 12, 16, 18) trimethylammonium bromide molecules with different concentrations and chain lengths and two hexagonal MCM-41 type materials incorporating octadecyl-trimethyl ammonium bromide were tested. Best results were obtained by preparing lamellar MCM-50 zirconium and titanium phosphates in the presence of n-dodecyl-trimethylammonium at a relative molar concentration (surfactant/phosphate) of 1.     

Inclusion of vegetable oils in Fenton's chemistry for remediation of PAH-contaminated soils

Pre-treatment with vegetable oils prior to treatment with Fenton's reagent led to increased oxidation by the latter of polycyclic aromatic hydrocarbons (PAHs) in a pair of model manufactured gas plant soils. This effect was frequently most pronounced in the cases of high-molecular-weight (HMW) PAH species, indicating a preferential "targeting" of oxidative equivalents toward these compounds. In both cases, addition of oils--either corn oil containing unsaturated lipids or palm kernal oil (PKO) comprised primarily of saturated fats--at the 5% dosage was required; supplementation with 1% oil apparently did not sufficiently facilitate PAH desorption and mass-transfer to have a notable effect on degradation efficiency. In PKO-supplemented reactions, replacement of H2O2 with calcium peroxide (CaO2) further increased the extent of PAH removal. Again, this was most pronounced in the cases of several HMW PAHs; among a suite of four 5- and 6-ring PAH (benzo[a]pyrene, dibenz[a, h]anthracene, benzo[g, h, i]perylene and indeno[c, d]pyrene), average removal efficiency increased from 5% in PKO-supplemented reactions in which H2O2 served as the oxidant, compared to 44% in CaO2-containing reactions. This last finding is consistent with other reports which have indicated that slower-release oxidants are better suited to degradation of contaminants which, despite vegetable oil treatment, remain soil-sorbed.     

Profiles of PAH emission from steel and iron industries

In order to characterize the polycyclic aromatic hydrocarbons (PAHs) emission from steel and iron industries, this study measured the stack emission of twelve steel and iron plants in southern Taiwan to construct a set of source fingerprints. The study sampled the emissions by the USEPA's sampling method 5 with the modification of Graseby for the gas and particulate phase PAH and, then, used Hewlett-Packard 5890 gas chromatograph equipped with mass spectrometer detector to analyze the samples. The steel and iron industries are classified into three categories on the basis of auxiliary energy source: Category I uses coal as fuel, Category II uses heavy oil as fuel and Category III uses electric arc furnace. The pollution source profiles are obtained by averaging the ratios of individual PAH concentrations to the total concentration of 21 PAHs and total particulate matter measured in this study. Results of the study show that low molecular weight PAHs are predominant in gas plus particulate phase for all three categories. For particulate phase PAHs, however, the contribution of large molecular weight compounds increases. Two-ring PAHs account for the majority of the mass, varying from 84% to 92% with an average of 89%. The mass fractions of 3-, 4-, 5-, 6-ring PAHs in Category I are found to be more than those of the other two categories. The mass of Category III is dominated by 7-ring PAHs. Large (or heavy) molecular weight PAHs (HMW PAHs) are carcinogenic. Over all categories, these compounds are less than 1% of the total-PAH mass on the average. The indicatory PAHs are benz[a]anthracene, benzo[k]fluoranthene, benzo[ghi]perylene for Category I, benzo[a]pyrene, acenaphthene, acenaphthylene for Category II and coronene, pyrene, benzo[b]chrycene for Category III. The indicatory PAHs among categories are very different. Thus, dividing steel and iron industry into categories by auxiliary fuel is to increase the precision of estimation by a receptor model. Average total-PAH emission factors for coal, heavy oil and electric arc furnace were 4050 μg/kg-coal, 5750 μg/l-oil, 2620 μg/kW h, respectively. Carcinogenic benzo[a]pyrene for gas plus particulate phase was 2.0 g/kg-coal, 2.4 μg/l-oil and 1.4 μg/kW h for Category I, II and III, respectively.     

Characterization and concentrations of polycyclic aromatic hydrocarbons in emissions from different heating systems in Damascus,Syria

Traffic has long been recognized as the major contributor to polycyclic aromatic hydrocarbon (PAH) emissions to the urban atmosphere. Stationary combustion sources, including residential space heating systems, are also a major contributor to PAH emissions. The aim of this study was to determine the profile and concentration of PAHs in stack flue gas emissions from different kinds of space heaters in order to increase the understanding of the scale of the PAH pollution problem caused by this source. This study set out to first assess the characteristics of PAHs and their corresponding benzo[a]pyrene equivalent emissions from a few types of domestic heaters and central heating systems to the urban atmosphere. The study, enabled for the first time, the characterization of PAHs in stationary combustion sources in the city of Damascus, Syria. Nine different types of heating systems were selected with respect to age, design, and type of fuel burned. The concentrations of 15 individual PAH compounds in the stack flue gas were determined in the extracts of the collected samples using high-performance liquid chromatography system (HPLC) equipped with ultraviolet–visible and fluorescence detectors. In general, older domestic wood stoves caused considerably higher PAH emissions than modern domestic heaters burning diesel oil. The average concentration of ΣPAH (sum of 15 compounds) in emissions from all types of studied heating systems ranged between 43?±?0.4 and 316?±?1.4 μg/m³. Values of total benzo[a]pyrene equivalent ranged between 0.61 and 15.41 μg/m³.     

Pinus nigra and Pinus pinaster needles as passive samplers of polycyclic aromatic hydrocarbons

Nine polycyclic aromatic hydrocarbons (PAHs) were analysed in pine needles of different ages (from 6 to 30 months) collected from two species, Pinus nigra and Pinus pinaster, in seven sites located along a transect from a suburban to a rural area of Genoa (Italy). In all sites and for both species, concentrations of more volatile PAHs (phenanthrene, anthracene, fluoranthene, pyrene) were higher than those for other less volatile PAHs, which are preferentially sorbed to airborne particulates (benzo[a]anthracene, chrysene, benzofluoranthenes, benzo[a]pyrene). Concentrations of total PAHs found in P. nigra in the rural sites were, on the average, 2.3 times higher than those in P. pinaster growing nearby. In both pine species, concentrations of volatile PAHs increased according to needle age. Annual trends of other PAHs were more variable, with a general decrease in older needles. P. pinaster needles are shown to be more reliable passive samplers, since they are more resistant to plant diseases, and considerable variation in PAH concentration was observed in P. nigra needles with moulds and fungi.     

采油废水中多环芳烃的生态风险评价

先利用C-18固相萃取小柱富集大港油田港东联合处理站污水处理站的采油废水中16种多环芳烃(PAHs,即萘、苊烯、苊、芴、菲、蒽、荧蒽、芘、、苯并[a]蒽、苯并[b]荧蒽、苯并[k]荧蒽、苯并[a]芘、茚并[1,2,3-cd]芘、二苯并[a,h]蒽和苯并[g,h,i]苝),再用气相色谱/质谱(GC/MS)分析测定其浓度,以评价PAHs的去除率和生态风险。结果表明:(1)采油废水经处理后,COD、石油类去除率分别达到82.27%、91.06%;外排水COD、石油类达到《污水综合排放标准》(GB 8978—1996)一级标准要求,优于中国采油废水处理的一般水平。(2)采油废水主要以2、3环的PAHs为主,约占总量的93%以上。(3)苯并[a]芘超过《地表水环境质量标准》(GB 3838—2002)中限值。(4)处理前的采油废水中蒽、菲和苯并[a]芘具有一定的生态风险;处理后的外排水中萘、蒽、菲、荧蒽、苯并[a]芘的暴露浓度(PEC)/预测无效应浓度(PNEC)均小于1,目前尚未对环境造成威胁。但是8种PAHs(苊烯和苯并类PAHs除外)总和表现出较大的毒性,需要引起重视。     

The effect of ryegrass (Lolium perenne) on decrease of PAH content in long term contaminated soil

The biodegradation of polycyclic aromatic hydrocarbons in microecosystems containing long-term contaminated soil was investigated. Soil was contaminated by different chemicals, including PAHs since World War II. Aging of the soil was expected to act as a principal factor limiting biodegradation. Half of the microecosystems contained ryegrass (Lolium perenne) and long-term selected natural soil microflora originally present in contaminated soil. The others contained contaminated soil with natural microflora only. Half of the microecosystems in each parallel experiment was fertilised with N-P-K fertiliser. Cultivation was carried out at 12 and 18 months in a greenhouse with a natural photoperiod and the ability to degrade 15 chosen PAH was investigated. For analysis, the soil from each pot was divided into three horizontal layers for mutual comparison among layers and each layer was further divided into four equal samples. Soil extracts were analysed using HPLC. After a one-year-cultivation period the content of the monitored PAHs declined to 50%. Mostly, there were no significant differences between the microecosystems. Best degraded were fluoranthene and pyrene, which were the major contaminants present in original soil. Also, other compounds were successfully degraded, even benzo[a]pyrene and benzo[ghi]perylene. Dibenz[a,h]anthracene and indeno[1,2,3-cd]pyrene were the only PAHs, examined that showed no significant degradation. Although some differences between the soil layers were detected, no conclusive trends could be found. However, significantly lower concentrations of PAHs were determined mostly in the bottom layer of the analysed profiles. In vegetated microecosystems the decline of PAHs concentrations was more remarkable after 18 months cultivation.