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   

GC/MS analysis of polynuclear aromatic hydrocarbons in sediment samples from the Niger Delta region

Thirteen sediment samples from different locations in the Niger Delta region of Nigeria were analyzed for the presence of 16 polynuclear aromatic hydrocarbons (PAHs) via gas chromatography/mass spectrometry. The specific target compounds for this study included naphthalene, acenaphthylene, acenaphthene, flourene, phenanthrene, anthracene, flouranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]flouranthene, benzo[a]pyrene, benzo[ghi]perylene, dibenz[a,h]anthracene, and indeno[1,2,3-cd]pyrene. Four isotopically labeled polynuclear aromatic hydrocarbons (acanaphthene-d10, phenanthrene-d10, chrysene-d12 and perylene-d12) were used for internal standardization. All 16 PAHs were found in most of the thirteen samples with concentration ranging from 0.1 microg/kg to 28 microg/kg. It was also found that the 5 and 6-ring PAHs were present in higher concentrations than all the other compounds, indicating their high resistance to microbial degradation.     

Distribution of polycyclic aromatic hydrocarbons in thirty typical soil profiles in the Yangtze River Delta region, east China

Polycyclic aromatic hydrocarbons (PAHs) were quantified in 30 soil profiles from the Yangtze River Delta Region, in east China. Relative concentrations of PAH compounds with different benzene rings and ratios of fluoranthene to fluoranthene plus pyrene and benz(a)anthracene to benz(a)anthracene plus chrysene were used to identify the possible sources of soil PAHs. Total concentrations of 15 PAHs in topsoils ranged from 8.6 to 3881 microg kg(-1) with an average of 397 microg kg(-1). Half of the soil samples were considered to be contaminated with PAHs (>200 microg kg(-1)) and two sampling sites were heavily polluted by PAHs with concentrations >1000 microg kg(-1). Phenanthrene was found in soils below a depth of 100 cm in half of the sampling sites, but the detectable ratio of benzo(a)pyrene decreased sharply from 100% in topsoil to 0 in the 4th horizon.     

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.     

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.     

PCDD/F, PAH and heavy metals in the sewage sludge from six wastewater treatment plants in Beijing, China

In order to better understand land application of sewage sludge, the characterization of heavy metals, PCDD/F and PAHs in sewage sludge was investigated from six different wastewater treatment plants (WWTP) in Beijing City, China. It was found that the total concentrations of Zn in Wujiacun (WJC) sewage sludge, and Cd and Hg in sewage sludge generated from all of the six different places are higher than Chinese regulation limit of pollutants for sludge to be used for agriculture (GB18918-2002). The levels of 16 PAHs that have been categorized as priority pollutants by US EPA in the sewage sludge samples varied from 2467 to 25923 microg/kg (dry weight), the highest values of 25923 microg/kg being found in WJC WWTP. The concentrations of Benzo[a]pyrene were as high as 6.1mg/kg dry weight in WJC sewage sludge, exceeding the maximum permitted content by GB18918-2002. Individual PAH content varies considerably with sewage samples. The ratios of anthracene to anthracene plus phenanthrene (An/178), benz[a]anthracene to benz[a]anthracene plus chrysene (BaA/228), indene[1,2,3-cd]pyrene to indene[1,2,3-cd]pyrene plus benzo[g,h,i]perylene (In/In+BP), and fluoranthene to fluoranthene plus pyrene (Fl/Fl+Py) suggest that petroleum and combustion of fossil fuel were the dominant contributions for the PAHs in sewage sludge. The concentrations of total PCDD/F in the sewage sludge ranged from 330 to 4245 pg/g d.w. The toxicity equivalent concentrations is between 3.47-88.24 pg I-TEQ according to NATO/CCMS, which is below Chinese legislation limit value proposed for land application. The PCDD/F congener/homologue profiles found in the Beijing samples indicated that the high chlorinated PCDD/F contamination might originate mainly from PCP-related source and depositional sources while the low chlorinated PCDD/F homologues could be originating from incineration or coal combustion. The major source of PCDD/Fs in Beijing sludge is still unclear.     

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。     

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.     

Polycyclic aromatic hydrocarbons in marine organisms from the Adriatic Sea, Italy

Polycyclic aromatic hydrocarbons (PAHs) were analyzed in bivalves (Mitylus galloprovincialis), cephalopods (Todarodes sagittatus), crustaceans (Nephrops norvegicus) and fish (Mullus barbatus, Scomber scombrus, Micromesistius poutassou, Merluccius merluccius) in several pools coming from the Central Adriatic Sea. These marine organisms were selected because of their multitude, wide distribution and common use in the Italian diet, they were sampled and analyzed during the year 2004. Acenaphthene, benzo(a)pyrene, dibenz(a,h)anthracene, benzo(ghi)perylene and indeno(1,2,3-cd)pyrene showed levels below the instrumental detection limit in all samples. Fluorene, phenanthrene, anthracene, fluoranthene, benz(a)anthracene, benzo(b)fluoranthene and benzo(k)fluoranthene were detected at different concentrations in analyzed samples. Chrysene was detected only in mussels with very low values (average 0.74ngg(-1) wet weight). PAHs composition pattern was dominated by the presence of PAHs with 3-rings (62%) followed from those with 4-rings (37%) and 5-rings (1%). Atlantic mackerel, European hake and blue whiting showed the highest PAH concentrations, ranging from 44.1 to 63.3ngg(-1) wet weight, the group of invertebrate organisms showed a level of contamination about three times lower than those of the vertebrate groups. Mediterranean mussels that did not present very high levels of contamination expressed as sum of PAHs showed one of the highest values of benzo(a)pyrene equivalents (BaPEs). Conversely the latter value was very low in Atlantic mackerel even if this species reported the highest total PAH concentrations. No significant correlation was observed between weight, length and trophic levels and total PAHs.     

In vitro EROD induction equivalency factors for the 10 PAHs generally monitored in risk assessment studies in The Netherlands

The ethoxy resorufin dealkylase (EROD) inducing potency of 10 polycyclic aromatic hydrocarbons (PAHs) is measured in the H4IIE in vitro bioassay and the results are compared to those reported in literature. The selected PAHs varied considerably in their potency to induce EROD activity. Anthracene (Ant) and phenanthrene (Phe) showed consistently no response. Naphthalene (Nap) showed no or a very weak response on EROD activity. Fluoranthene (Fla) and benzo[g,h,i]perylene (BghiP) showed weak responses at the highest doses. The other PAHs, including indeno[1,2,3-cd]pyrene (IP), benz[a]anthracene (BaA), benzo[a]pyrene (BaP), chrysene (Chr) and benzo[k]fluoranthene (BkF), showed full bell shaped dose-response curves. BaP EROD induction equivalency factors (BaP-1EF) were calculated and increased in the order Ant approximately Phe < Fla < Nap < BghiP < IP < BaA < BaP < Chr < BkF. Comparison of BaP-IEFs based on 50% effect concentration (EC50) or lowest effect concentration (LEC), yielded a significant relationship between both methods described by the equation log(BaPIEF(EC50) = 0.55 x log(BaPIEF(LEC)) + 0.07 (r2 = 0.913). BaP-IEFs as derived from our measurements and as reported in literature and measured in other in vitro assays deviated up to a factor of 17 among the different studies, but the potency rankings were comparable. For the PAH mixture as on average present in the human diet an overall tetrachlorodibenzo-p-dioxin (TCDD)-IEF of 1 x 10(-4) was estimated. The total PAH based TCDD induction equivalents (IEQ) intake then was calculated 300 pg/day, which is approximately 2 times higher then the PHAH based TCDD-EQ intake reported for humans.     

Distribution characteristics of polycyclic aromatic hydrocarbons with particle size in urban aerosols at the roadside in Ho Chi Minh City,Vietnam

The purpose of this study was to characterize size distributions of atmospheric polycyclic aromatic hydrocarbons (PAHs) with 4–6 rings at the roadside in Ho Chi Minh City, Vietnam. Ten PAHs (fluoranthene, pyrene, triphenylene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene) in atmospheric particulate matters (PM) at the roadside were measured in the dry and rainy seasons in 2005 at Ho Chi Minh City, using a low-pressure cascade impactor. The PM were separated into nine fractions by their aerodynamic diameter, i.e. >9.0, 9.0–5.8, 5.8–4.7, 4.7–3.3, 3.3–2.1, 2.1–1.1, 1.1–0.7, 0.7–0.4 and <0.4 μm (a final filter). PAHs were analyzed by high-performance liquid chromatography with fluorescence detection. Total PAHs measured were higher in the rainy season than in the dry season. The mass of coarse particles occupied a higher fraction than that of fine particles in both seasons. Total PAHs were mainly concentrated in particles with aerodynamic diameter smaller than 0.4 μm. The particle size distributions of PAHs investigated were bi-modal with a peak in fine particle mode (<2.1 μm) and another peak in coarse particle mode (>2.1 μm). Generally, 5,6-ring PAHs associated mainly with fine particles and 4-ring PAHs spread out in both fine and coarse particles.     

Chemical characterization and source identification of polycyclic aromatic hydrocarbons in aerosols originating from different sources

To obtain the characteristic factors or signatures of particulate polycyclic aromatic hydrocarbons (PAHs) to help identify the sources of particulate PAHs in the atmosphere, different carbonaceous aerosols were generated by burning different fossil fuels and biomass under different conditions in the laboratory, and the chemical characteristics of 14 PAHs were studied in detail. The results showed that (1) carbonaceous aerosols derived from domestic burning of coal, diesel fuel, and gasoline have much higher concentrations of PAHs than those derived from domestic burning of biomass; (2) carbonaceous aerosols derived from domestic burning of diesel fuel/gasoline have similar PAH components as those derived from high-temperature combustion of diesel fuel/gasoline, although the former have much higher concentrations of PAHs than the latter, suggesting that the burning temperature obviously affects the emitting amount of particulate PAHs, but only slightly influences the PAHs components; and (3) the ratios of benzo[b]fluoranthene/acenaphthylene, benzo[b]fluoranthene/fluorene, dibenzo[a,h]anthracene/acenaphthylene, dibenzo[a,h]anthracene/fluorine, and benzo[b]fluoranthene/benzo[k]fluoranthene in carbonaceous aerosols are sensitively dependent on their sources, indicating that these ratios are suitable for use as characteristic factors or signatures of particulate PAHs in the atmosphere.     

An oxygenated metabolite of benzo[a]pyrene increases hepatic β-oxidation of fatty acids in chick embryos

Polycyclic aromatic hydrocarbons (PAHs) are well-known carcinogens to humans and ecotoxicological effects have been shown in several studies. However, PAHs can also be oxidized into more water soluble-oxygenated metabolites (Oxy-PAHs). The first purpose of the present project was to (1) assess the effects of a mixture containing three parent PAHs: anthracene, benz[a]anthracene, and benzo[a]pyrene versus a mixture of their oxygenated metabolites, namely: anthracene-9,10-dione, benz[a]anthracene-7,12-dione, and 9,10-dihydrobenzo[a]pyrene-7-(8H)-one on the hepatic fatty acid β-oxidation in chicken embryos (Gallus gallus domesticus) exposed in ovo. The second and also main purpose of the project was to (2) assess the effects of the parent PAHs versus their oxy-PAHs analogues when injected individually, followed by (3) additional testing of the individual oxy-PAHs. The hepatic β-oxidation was measured using a tritium release assay with [9,10-³H]-palmitic acid (16:0) as substrate. The result from the first part (1) showed reduced hepatic β-oxidation after exposure in ovo to a mixture of three PAHs, however, increased after exposure to the mixture of three oxy-PAHs compared to control. The result from the second part (2) and also the follow-up experiment (3) showed that 9,10-dihydrobenzo[a]pyrene-7-(8H)-one was the causative oxy-PAH. The implication of this finding on the risk assessment of PAH metabolite exposure in avian wildlife remains to be determined. To the best of our knowledge, no similar studies have been reported.     

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.     

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.     

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.     

Contents and sources of polycyclic aromatic hydrocarbons and organochlorine pesticides in vegetable soils of Guangzhou, China

We investigated contents, distribution and possible sources of PAHs and organochlorine pesticides (Ops) in 43 surface and subsurface soils around the urban Guangzhou where variable kinds of vegetables are grown. The results indicate that the contents of PAHs (16 US EPA priority PAHs) range from 42 to 3077 microg/kg and the pollution extent is classified as a moderate level in comparison with other investigations and soil quality standards. The ratios of methylphenanthrenes to phenanthrene(MP/P), anthracene to anthracene plus phenanthrene (An/178), benz[a]anthracene to benz[a]anthracene plus chrysene (BaA/228), indeno[1,2,3-cd]pyrene to indeno[1,2,3-cd]pyrene plus benzo[ghi]perylene (In/In+BP) suggest that the sources of PAHs in the soil samples are mixed with a dominant contribution from petroleum and combustion of fossil fuel. The correlation analysis shows that the PAHs contents are significantly related to total organic carbon contents (TOC) (R2=0.75) and black carbon contents (BC) (R2=0.62) in the soil samples. Dichlorodiphenyltrichloroethane and metabolites (DDTs) and hexachlorocyclohexanes and metabolites (HCHs) account largely for the contaminants of OPs. The concentrations of DDTs range from 3.58 to 831 microg/kg and the ratios for DDT/(DDD+DDE) are higher than 2 in some soil samples, suggesting that DDT contamination still exists and may be caused by its persistence in soils and/or impurity in the pesticide dicofol. The concentrations of HCHs are 0.19-42.3 microg/kg.     

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.     

Soil mobility of surface applied polyaromatic hydrocarbons in response to simulated rainfall

Polyaromatic hydrocarbons (PAHs) are emitted from a variety of sources and can accumulate on and within surface soil layers. To investigate the level of potential risk posed by surface contaminated soils, vertical soil column experiments were conducted to assess the mobility, when leached with simulated rainwater, of six selected PAHs (naphthalene, phenanthrene, fluoranthene, pyrene, benzo(e)pyrene and benzo(ghi)perylene) with contrasting hydrophobic characteristics and molecular weights/sizes. The only PAH found in the leachate within the experimental period of 26 days was naphthalene. The lack of migration of the other applied PAHs was consistent with their low mobilities within the soil columns which generally paralleled their log K _oc values. Thus, only 2.3 % of fluoranthene, 1.8 % of pyrene, 0.2 % of benzo(e)pyrene and 0.4 % of benzo(ghi)perylene were translocated below the surface layer. The PAH distributions in the soil columns followed decreasing power relationships with 90 % reductions in the starting levels being shown to occur within a maximum average depth of 0.94 cm compared to an average starting depth of 0.5 cm. A simple predictive model identifies the extensive time periods, in excess of 10 years, required to mobilise 50 % of the benzo(e)pyrene and benzo(ghi)perylene from the surface soil layer. Although this reduces to between 2 and 7 years for fluoranthene and pyrene, it is concluded that the possibility of surface-applied PAHs reaching and contaminating a groundwater aquifer is unlikely.     

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.