Spatial distribution,potential risk assessment,and source apportionment of polycyclic aromatic hydrocarbons (PAHs) in sediments of Lake Chaohu,China

Twenty-nine sediment samples were collected from Lake Chaohu, a shallow eutrophic lake in Eastern China, and were analyzed for 15 priority polycyclic aromatic hydrocarbons (PAHs) to determine the spatial distribution and exposure risks of PAHs. Three receptor models, the principal component analysis-multiple linear regression (PCA-MLR) model, the positive matrix factorization (PMF) model, and the Unmix model, were used in combination with the PAHs diagnostic ratios to investigate the potential source apportionment of PAHs. A clear gradient in the spatial distribution and the potential toxicity of PAHs was observed from west to east in the sediments of Lake Chaohu. ∑₁₅PAH concentrations and the TEQ were in the range of 80.82-30 365.01 ng g^?1 d.w. and 40.77-614.03, respectively. The highest values of the aforementioned variables were attributed to urban–industrial pollution sources in the west lake region, and the levels decreased away from the river inlets. The three different models yielded excellent correlation coefficients between the predicted and measured levels of the 15 PAH compounds. Similarly, source apportionment results were derived from the three receptor models and the PAH diagnostic ratios, suggesting that the highest contribution to the PAHs was from coal combustion and wood combustion, followed by vehicular emissions. The PMF model yielded the following contributions to the PAHs from gasoline combustion, diesel combustion, unburned petroleum emissions, and wood combustion: 34.49, 24.61, 16.11, 13.01, and 11.78 %, respectively. The PMF model produced more detailed source apportionment results for the PAHs than the PCA-MLR and Unmix models.     

Toxicity of atmospheric particle-bound PAHs: an environmental perspective

Atmospheric polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants that represent a risk not only to humans, but to all living organisms. High-molecular weight PAHs are more toxic than lighter relatives, and also have a higher tendency to bind onto air particles (i.e., particle matter, PM). PM is a major constituent of air pollution. Adequate assessment of the biological impact of PM requires the analysis, not only of the effects on human health, but also on the environment. Since the aquatic systems work as a natural sink to these air pollutants, assessing the effects of particle-bound PAHs on aquatic organisms may further characterize its potential aquatic toxicity, also providing simple and low-cost alternative assays to investigate PM biological effects in vivo. We review the current scientific literature, addressing the atmospheric PAHs fate, transformation and deposition, pertinent particle-bound PAHs toxicity data, and the potential aquatic toxic burden. Conceptual and experimental procedures that could improve future investigations and risk assessments are also considered.     

Potential source apportionment of polycyclic aromatic hydrocarbons in surface sediments from the middle and lower reaches of the Yellow River,China

In this work, principal component analysis/multiple linear regression (PCA/MLR), positive matrix factorization (PMF), and UNMIX model were employed to apportion potential sources of polycyclic aromatic hydrocarbons (PAHs) in surface sediments from middle and lower reaches of the Yellow River, based on the measured PAHs concentrations in sediments collected from 22 sites in November 2005. The results suggested that pyrogenic sources were major sources of PAHs. Further analysis indicated that source contributions of PAHs compared well among PCA/MLR, PMF, and UNMIX. Vehicles contributed 25.1–36.7 %, coal 34.0–41.6 %, and biomass burning and coke oven 29.2–33.2 % of the total PAHs, respectively. Coal combustion and traffic-related pollution contributed approximately 70 % of anthropogenic PAHs to sediments, which demonstrated that energy consumption was a predominant factor of PAH pollution in middle and lower reaches of the Yellow River. In addition, the distributions of contribution for each identified source category were studied, which showed similar distributed patterns for each source category among the sampling sites.     

Genotoxicity of oxy-PAHs to Japanese medaka (Oryzias latipes) embryos assessed using the comet assay

Polycyclic aromatic hydrocarbons (PAHs) have long been recognized as important environmental toxicants. Despite a plethora of information on the fate and effects of parent PAHs, relatively little is known about the environmental fate and toxicity of ketone- and quinone-substituted PAH oxidation products (termed oxy-PAHs), particularly in the aquatic environment. This study begins to fill that gap using embryos of the Japanese medaka (Oryzias latipes) as a model species. The genotoxic potential of two environmentally relevant oxy-PAHs, acenaphthenequinone and 7,12-benz[a]anthracenquinone, was assessed using the comet assay. We found that both oxy-PAHs could cause significant increases in DNA damage after only 48 h of exposure at the lowest concentrations tested (5 μg/L). Comparisons of the genotoxic potential between these oxy-PAHs and their corresponding parent PAHs (acenaphthene and benz[a]anthracene) and a well-known mutagenic PAH, benzo[a]pyrene, indicated similar potencies among all five of these compounds, particularly after longer (7 day) exposures. This study demonstrates the mutagenic potential of oxy-PAHs to an in vivo fish embryo model and points out the need for further study of their environmental occurrence and biologic effects.     

Contamination and distribution of parent,nitrated, and oxygenated polycyclic aromatic hydrocarbons in smoked meat

Smoked meat is widely consumed in many areas, particularly in rural southwest China. High concentrations of polycyclic aromatic hydrocarbons (PAHs) in smoked meat could lead to adverse dietary exposure and health risks. In this study, 27 parent PAHs (pPAHs), 12 nitrated PAHs (nPAHs), and 4 oxygenated PAHs (oPAHs) were measured in coal- and wood-smoked meats. The median concentrations of pPAHs, nPAHs, and oPAHs were as high as 1.66?×?10³, 4.29, and 20.5 ng/g in the coal-smoked meat and 2.54?×?10³, 7.32, and 9.26 ng/g in the wood-smoked meat, respectively. Based on the relative potency factors of individual PAHs, the calculated toxic equivalent (TEQ) values of all pPAHs were 22.1 and 75.1 ng TEQ/g for the wood- and coal-smoked meats, respectively. The highest concentrations of PAHs can be found in the surface layer of skin and decrease exponentially with depth. Surface PAH concentrations correlated with concentrations of PAHs in household air and with the concentration in emission exhaust. Migration of PAHs from surface to interior portions of meat is faster in lean than in fat or skin, and oPAHs and pPAHs can penetrate deeper than pPAHs. The penetration ability of PAHs is negatively correlated with the molecular weight.     

Oxidation of polycyclic aromatic hydrocarbons by horseradish peroxidase in water containing an organic cosolvent

Polycyclic aromatic hydrocarbons (PAHs) are environmental contaminants that are toxic, mutagenic, and carcinogenic. We investigated the horseradish peroxidase (HRP)-catalyzed oxidation of PAHs in water containing N,N-dimethylformamide. Four PAHs (anthracene, phenanthrene, pyrene, and fluoranthene) were investigated using single-PAH and mixed-PAH systems. The results provide useful information regarding the preferential oxidation of anthracene over other PAHs regardless of the reaction time, enzyme dosage, and hydrogen peroxide concentration. The removal of PAHs was found to be very strongly correlated with the ionization potential (IP), and much greater PAH oxidation was observed at a lower IP. The oxidation of anthracene was specifically pH- and temperature-dependent, with the optimal pH and temperature being 8.0 and 40 °C, respectively. The redox mediators 1-hydroxybenzotriazole and veratryl alcohol promoted the transformation of anthracene by HRP; 9,10-anthraquinone was the main product detected from the anthracene oxidation system. The results of this study not only provide a better understanding of the oxidation of PAHs by utilizing a plant biocatalyst, but also provide a theoretical basis for establishing the HRP-catalyzed treatment of PAH-contaminated wastewater.     

Evaluation of heavy metal and polycyclic aromatic hydrocarbons accumulation in plants from typical industrial sites: potential candidate in phytoremediation for co-contamination

The heavy metal and polycyclic aromatic hydrocarbons (PAHs) contents were evaluated in surface soil and plant samples of 18 wild species collected from 3 typical industrial sites in South Central China. The accumulative characteristics of the plant species for both heavy metal and PAHs were discussed. The simultaneous accumulation of heavy metal and PAHs in plant and soil was observed at all the investigated sites, although disparities in spatial distributions among sites occurred. Both plant and soil samples were characterized by high accumulation for heavy metal at smelting site, moderate enrichment at coke power and coal mining sites, whereas high level of PAHs (16 priority pollutants according to US Environmental Protection Agency) at coke power site, followed sequentially by coal mining and smelting sites. Based on the differences of heavy metal and PAH accumulation behaviors of the studied plant species, heavy metal and PAH accumulation strategies were suggested: Pteris vittata L. and Pteris cretica L. for As and PAHs, Boehmeria nivea (L.) Gaud for Pb, As, and PAHs, and Miscanthus floridulu (Labnll.) Warb for Cu and PAHs. These native plant species could be proposed as promising materials for heavy metal and PAHs combined pollution remediation.     

Degradation of polycyclic aromatic hydrocarbons in a coking wastewater treatment plant residual by an O3/ultraviolet fluidized bed reactor

Coking wastewater treatment plant (CWWTP) represents a typical point source of polycyclic aromatic hydrocarbons (PAHs) to the water environment and threatens the safety of drinking water in downstream regions. To enhance the removal of residual PAHs from bio-treated coking wastewater, a pilot-scale O₃/ultraviolet (UV) fluidized bed reactor (O₃/UV FBR) was designed and different operating factors including UV irradiation intensity, pH, initial concentration, contact time, and hydraulic retention time (HRT) were investigated at an ozone level of 240 g h^?1 and 25?±?3 °C. A health risk evaluation and cost analysis were also carried out under the continuous-flow mode. As far as we know, this is the first time an O₃/UV FBR has been explored for PAHs treatment. The results indicated that between 41 and 75 % of 18 target PAHs were removed in O₃/UV FBR due to synergistic effects of UV irradiation. Both increased reaction time and increased pH were beneficial for the removal of PAHs. The degradation of the target PAHs within 8 h can be well fitted by the pseudo-first-order kinetics (R ²?>?0.920). The reaction rate was also positively correlated with the initial concentrations of PAHs. The health risk assessment showed that the total amount of carcinogenic substance exposure to surface water was reduced by 0.432 g day^?1. The economic analysis showed that the O₃/UV FBR was able to remove 18 target PAHs at a cost of US$0.34 m^?3. These results suggest that O₃/UV FBR is efficient in removing residuals from CWWTP, thus reducing the accumulation of persistent pollutant released to surface water.     

Semivolatile PAH and n-alkane gas/particle partitioning using the dual model: up-to-date coefficients and comparison with experimental data

The gas/particle partitioning coefficient K _p , of a semivolatile compound is a key parameter for its atmospheric fate. The most complete method of predicting K _p for polycyclic aromatic hydrocarbons (PAHs) is offered by the dual model, as it describes both the adsorption on soot and absorption into organic matter processes. However, experimental and model data exist almost exclusively for PAHs. In order to bridge this gap, experimental data on the phase partitioning of both PAHs and n-alkanes were collected at an urban and a remote site. Moreover, all the necessary parameters (e.g., octanol–air and soot–air partitioning coefficients) for the dual model have been collected and updated or (if missing) estimated for the first time. The results point out that both absorption and adsorption seem to contribute to the partitioning of PAHs and n-alkanes. However, it seems that the dual model always underestimates the particle sorption not only for PAHs but also for n-alkanes.     

Combined effects of DOM and biosurfactant enhanced biodegradation of polycylic armotic hydrocarbons (PAHs) in soil–water systems

This study systematically investigated the interactive effects of dissolved organic matter (DOM) and biosurfactant (rhamnolipid) on the biodegradation of phenanthrene (PHE) and pyrene (PYR) in soil–water systems. The degradations of two polycyclic aromatic hydrocarbons (PAHs) were fitted well with first order kinetic model and the degradation rates were in proportion to the concentration of biosurfactant. In addition, the degradation enhancement of PHE was higher than that of PYR. The addition of soil DOM itself at an environmental level would inhibit the biodegradation of PAHs. However, in the system with co-existence of DOM and biosurfactant, the degradation of PAHs was higher than that in only biosurfactant addition system, which may be attributed to the formation of DOM–biosurfactant complex micelles. Furthermore, under the combined conditions, the degradation of PAH increased with the biosurfactant concentration, and the soil DOM added system showed slightly higher degradation than the compost DOM added system, indicating that the chemical structure and composition of DOM would also affect the bioavailability of PAHs. The study result may broaden knowledge of biosurfactant enhanced bioremediation of PAHs contaminated soil and groundwater.     

Children and elders exposure assessment to particle-bound polycyclic aromatic hydrocarbons (PAHs) in the city of Rome,Italy

It has been amply demonstrated that exposure to fine particulate matter, containing polycyclic aromatic hydrocarbons (PAHs), may have adverse effects on human health, affecting especially the respiratory and cardiovascular systems. Among population, school-age children and elders present particular susceptibilities and unique exposures to environmental factors. The study presented in this paper belongs to the Project EXPAH, founded by the European (EU) LIFE+ instrument, and consists of the personal monitoring of five elementary school children and four elders during the spring and the summer/autumn of the year 2012 in the city of Rome, Italy. The average exposure, expressed as the sum of eight high-molecular-weight PAHs, resulted equal to 0.70 ng/m³ (SD?=?0.37) for children and 0.59 ng/m³ (SD?=?0.23) for the elderly people. The mean levels of gravimetric PM_2.5 were equal to 23 μg/m³ (SD?=?10) and 15 μg/m³ (SD?=?4) for children and elders, respectively. During spring and summer seasons, personal BaP_eq resulted well below the EU Air Quality reference value of 1 ng/m³. The personal monitoring average values were in the same order of magnitude with available indoor and outdoor environmental data in Rome during the same periods, for both PAHs and PM_2.5. The results suggest that, during non-heating seasons, the personal exposure to PAHs in the city of Rome can be mainly ascribed to the urban background, especially traffic emissions and road dust resuspension; secondhand cigarette smoke can be also considered another possible source of PAHs personal exposure.     

Influence of sediment composition on PAH toxicity using zebrafish (Danio rerio) and Japanese medaka (Oryzias latipes) embryo-larval assays

Due to hydrophobic and persistent properties, polycyclic aromatic hydrocarbons (PAHs) have a high capacity to accumulate in sediment. Sediment quality criteria, for the assessment of habitat quality and risk for aquatic life, include understanding the fate and effects of PAHs. In the context of European regulation (REACH and Water Framework Directive), the first objective was to assess the influence of sediment composition on the toxicity of two model PAHs, benzo[a]pyrene and fluoranthene using 10-day zebrafish embryo-larval assay. This procedure was undertaken with an artificial sediment in order to limit natural sediment variability. A suitable sediment composition might be then validated for zebrafish and proposed in a new OECD guideline for chemicals testing. Second, a comparative study of toxicity responses from this exposure protocol was then performed using another OECD species, the Japanese medaka. The potential toxicity of both PAHs was assessed through lethal (e.g., survival, hatching success) and sublethal endpoints (e.g., abnormalities, PMR, and EROD) measured at different developmental stages, adapted to the embryonic development time of both species. Regarding effects observed for both species, a suitable artificial sediment composition for PAH toxicity testing was set at 92.5 % dry weight (dw) silica of 0.2–0.5-mm grain size, 5 % dw kaolin clay without organic matter for zebrafish, and 2.5 % dw blond peat in more only for Japanese medaka. PAH bioavailability and toxicity were highly dependent on the fraction of organic matter in sediment and of the K _ow coefficients of the tested compounds. The biological responses observed were also dependent of the species under consideration. Japanese medaka embryos appeared more robust than zebrafish embryos for understanding the toxicity of PAHs following a sediment contact test, due to the longer exposure duration and lower sensitivity of sediment physical properties.     

Chronic dietary exposure to pyrolytic and petrogenic mixtures of PAHs causes physiological disruption in zebrafish - part I: Survival and growth

The release of polycyclic aromatic hydrocarbons (PAHs) into the environment has increased very substantially over the last decades leading to high concentrations in sediments of contaminated areas. To evaluate the consequences of long-term chronic exposure to PAHs, zebrafish were exposed, from their first meal at 5 days post fertilisation until they became reproducing adults, to diets spiked with three PAH fractions at three environmentally relevant concentrations with the medium concentration being in the range of 4.6–6.7 μg g^?1 for total quantified PAHs including the 16 US-EPA indicator PAHs and alkylated derivatives. The fractions used were representative of PAHs of pyrolytic (PY) origin or of two different oils of differing compositions, a heavy fuel (HO) and a light crude oil (LO). Fish growth was inhibited by all PAH fractions and the effects were sex specific: as determined with 9-month-old adults, exposure to the highest PY inhibited growth of females; exposure to the highest HO and LO inhibited growth of males; also, the highest HO dramatically reduced survival. Morphological analysis indicated a disruption of jaw growth in larvae and malformations in adults. Intestinal and pancreatic enzyme activities were abnormal in 2-month-old exposed fish. These effects may contribute to poor growth. Finally, our results indicate that PAH mixtures of different compositions, representative of situations encountered in the wild, can promote lethal and sublethal effects which are likely to be detrimental for fish recruitment.     

Heavy metals and polycyclic aromatic hydrocarbons in sediments from the Shenzhen River,South China

With the analysis of eight heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn) and sixteen polycyclic aromatic hydrocarbons (PAHs) in sediments from the Shenzhen River, South China, the ecological risks associated were evaluated using Hakanson’s method (for the metals) and the Effect Range Low/Effect Range Median (ERL/ERM) method (for the PAHs). The result shows concentrations of heavy metal in the order Zn?>?Cu?>?Cr?>?Ni?>?Pb?>?As?>?Cd?>?Hg, and among which the Zn, Cu, Ni, and Pb are exceeding the maximum contaminant level for sediments while those of PAHs are far below. The potential ecological risk index value for the heavy metals in the sediment samples was 261.90, which is in the moderate risk category. Total PAH concentrations in the sediments ranged from 1,028 to 1,120 ng/g, which are all far lower than the sediment guideline concentration of 4,022 ng/g, indicating that the risks of biological impacts caused by PAHs in Shenzhen River sediments are, therefore, relatively low. Besides, the fluorene concentration was above the ERL, and would potentially cause negative biological effects in the Shenzhen River. Heavy metals risks are suggested among the most important concerns that the environmental recover measures pay attention to.     

Polycyclic aromatic hydrocarbon distribution in serum of Saudi children using HPLC-FLD: marker elevations in children with asthma

Diesel exhaust consists of a complex mixture of chemicals which contain known genotoxicants, one of which is polycyclic aromatic hydrocarbons (PAHs) which may be associated with adverse respiratory health outcomes. This study aimed to evaluate the distribution patterns of PAHs (anthracene, naphthalene, fluorene, phenanthrene, cyclopentaphenanthrene, pyrene, fluoranthene, benzanthracene, chrysene, benzo(e)pyrene, benzoacephenanthrylene, and benzo(a)pyrene) in serum collected from asthmatic and healthy control children. PAH serum levels were measured in samples collected from children who lived in 11 different locations in/round Riyadh, Saudi Arabia (Al-yarmouk, Usaibi, Sultana Al-kadema, Omrrojam, Kof, Janoob Dawdmi, Guberah, Arabbuah, Al-mozahemyah, Iskan Al-mazzer, and Al-gharabi) during the period 2010–2011. Our results showed that the highest total mean concentrations of PAH were found in serum samples collected from people who lived in Sultana Aljadhida, Almozahemyah, Guberah, and Omrrojam and were 663.9, 486.17, 412.18, and 258.6 ng ml^?1, respectively. The most prevalent PAHs in serum samples were naphthalene, bezanthracene, benzoacephenanthrylene, phenanthrene, chrysene, and benzo(a)pyrene with a frequency that ranged from 54.5 to 90.9 % positive samples. A close monitoring of PAH pollution is strongly recommended, especially in food and plant samples, because of their high bioaccumulation capacity.     

Aerobic metabolism and cardiac activity in the descendants of zebrafish exposed to pyrolytic polycyclic aromatic hydrocarbons

The increase of anthropogenic activities on coastal areas induces discharges of polycyclic aromatic hydrocarbons (PAHs) in aquatic ecosystem. PAH effects depend not only on their concentration and the way of contamination but also on the different developmental stages of the organism. Zebrafish were exposed to relevant concentration of pyrolytic PAHs from the first meal (i.e., 5-day post fertilization, dpf) to mature adults. Parental effect of this type of exposure was evaluated through the assessment of aerobic metabolic scope, cardiac frequency, and cardiac mRNA expression on larval and/or embryo progeny of contaminated fish. Our results suggest that cardiac frequency increased in larval descendants of fish exposed to the environmental concentration of pyrolytic PAHs (i.e., 5 ng.g^?1 of food), while a lack of effect on aerobic metabolism in 5 dpf larvae was highlighted. A surexpression of mRNA related to the cardiac calcium transporting ATPase atp2a2a, a protein essential for contraction, is in accordance with this increasing cardiac frequency. Even if cardiac development genes cmlc1 and tnnt2a were not affected at early life stages tested, complementary work on cardiac structure could be interesting to better understand PAHs action.     

Chronic dietary exposure of zebrafish to PAH mixtures results in carcinogenic but not genotoxic effects

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous contaminants that can be present at high levels as mixtures in polluted aquatic environments. Many PAHs are potent mutagens and several are well-known carcinogens. Despite numerous studies on individual compounds, little is known about the toxicity of PAHs mixtures that are encountered in environmental situations. In the present work, zebrafish were continuously fed from 5 days post-fertilisation to 14 months post-fertilisation (mpf) with a diet spiked with fractions of either pyrolytic (PY), petrogenic light oil (LO), or petrogenic heavy oil (HO) origin at three concentrations. A decrease in survival was identified after 3 mpf in fish fed with the highest concentration of HO or LO, but not for PY. All PAH fractions caused preneoplastic and neoplastic disorders in long-term-exposed animals. Target tissues were almost exclusively of epithelial origin, with the bile duct epithelium being the most susceptible to chronic exposure to all PAH fractions, and with germ cells being the second most responsive cells. Significantly higher incidences of neoplasms were observed with increasing PAH concentration and exposure duration. The most severe carcinogenic effects were induced by dietary exposure to HO compared to exposure to LO or PY (45, 30 and 7 %, respectively, after 9 to 10 months of exposure to an intermediate concentration of PAHs). In contrast, earliest carcinogenic effects were detected as soon as 3 mpf after exposure to LO, including the lowest concentration, or to PY. PAH bioactivation and genotoxicity in blood was assessed by ethoxyresorufin-O-deethylase activity quantification and comet and micronuclei assays, respectively, but none of these were positive. Chronic dietary exposure of zebrafish to PAH mixtures results in carcinogenotoxic events that impair survival and physiology of exposed fish.     

EROD activity and antioxidant defenses of sea bass (Dicentrarchus labrax) after an in vivo chronic hydrocarbon pollution followed by a post-exposure period

Chronic concentrations of polycyclic aromatic hydrocarbons (PAHs) have been commonly detected in international estuaries ecosystems. Reliable indicators still need to be found in order to properly assess the impact of PAHs in fish. After an in vivo chronic exposure to hydrocarbons, the enzymatic activity of 7-ethoxyresorufin O-deethylase (EROD) and the antioxidant defense system were assessed in sea bass, Dicentrarchus labrax. A total of 45 fish were exposed to the water-soluble fraction of Arabian crude oil, similar to a complex pollution by hydrocarbons chronically observed in situ, while 45 other control fish sustained the same experimental conditions in clean seawater. Fish samples were made after a 21-day exposure period and after a 15-day recovery period in clean fresh water. Throughout the experiment, liver EROD activity was significantly higher in contaminated fish than in control fish. In addition, nonenzymatic (total glutathione) and enzymatic (GPx, SOD, and CAT) antioxidant defense parameters measured in liver were not significantly different in fish. Furthermore, in gills, glutathione content had significantly increased while SOD activity had significantly decreased in contaminated fish compared to controls. On the other hand, CAT and GPx activities were not affected. Chronic exposure to PAHs disturbing the first step (SOD) and inhibiting the second step (GPx and CAT) could induce oxidative stress in tissues by the formation of oxygen radicals. After the postexposure period, there was no significant difference between control and contaminated fish in any of the antioxidant defense parameters measured in gills, attesting to the reversibility of the effects.     

Contribution of harbour activities and ship traffic to PM2.5, particle number concentrations and PAHs in a port city of the Mediterranean Sea (Italy)

In this work, an assessment of the impact of ship traffic and related harbour activities (loading/unloading of ships and hotelling in harbour) on PM 2.5 and particle number concentrations (PNC) separating the contribution associated to ship traffic from that of harbour-related activities is reported. Further, an assessment of the impact and environmental risks associated to polycyclic aromatic hydrocarbon (PAH) concentrations was performed. Results refer to the city of Brindisi (88,500 inhabitants) in the south-eastern part of Italy and its harbour (with yearly 9.5 Mt of goods, over 520,000 passengers and over 175,000 vehicles). PM2.5 and PNC concentrations show a clear daily pattern correlated with daily ship traffic pattern in the harbour. High temporal resolution measurements and correlations with wind direction were used to estimate the average direct contribution to measured concentrations of this source. The average relative contribution of ship traffic was 7.4 % (±0.5 %) for PM2.5 and 26 % (±1 %) for PNC. When the contribution associated to harbour-related activities is added, the percentages become 9.3 % (±0.5 %) for PM2.5 and 39 % (±1 %) for PNC. In the site analysed, air coming from the harbour/industrial sector was richer in PAHs (5.34 ng/m³) than air sampled from all directions (3.89 ng/m³). The major compounds were phenanthrene, fluoranthene and pyrene, but the congener profiles were different in the two direction sectors: air from the harbour/industrial sector was richer in phenanthrene and fluorene, which are the most abundant PAHs in ship emissions. Results showed that lighter PAHs are associated to the gas phase, while high molecular weight congeners are mostly present in the particulate phase. The impact on the site studied of the harbour/industrial source to PAHs was 56 % (range, 29–87 %).     

Response of bacterial pdo1, nah,and C12O genes to aged soil PAH pollution in a coke factory area

Soil pollution caused by polycyclic aromatic hydrocarbons (PAHs) is threatening human health and environmental safety. Investigating the relative prevalence of different PAH-degrading genes in PAH-polluted soils and searching for potential bioindicators reflecting the impact of PAH pollution on microbial communities are useful for microbial monitoring, risk evaluation, and potential bioremediation of soils polluted by PAHs. In this study, three functional genes, pdo1, nah, and C12O, which might be involved in the degradation of PAHs from a coke factory, were investigated by real-time quantitative PCR (qPCR) and clone library approaches. The results showed that the pdo1 and C12O genes were more abundant than the nah gene in the soils. There was a significantly positive relationship between the nah or pdo1 gene abundances and PAH content, while there was no correlation between C12O gene abundance and PAH content. Analyses of clone libraries showed that all the pdo1 sequences were grouped into Mycobacterium, while all the nah sequences were classified into three groups: Pseudomonas, Comamonas, and Polaromonas. These results indicated that the abundances of nah and pdo1 genes were positively influenced by levels of PAHs in soil and could be potential microbial indicators reflecting the impact of soil PAH pollution and that Mycobacteria were one of the most prevalent PAHs degraders in these PAH-polluted soils. Principal component analysis (PCA) and correlation analyses between microbial parameters and environmental factors revealed that total carbon (TC), total nitrogen (TN), and dissolved organic carbon (DOC) had positive effects on the abundances of all PAH-degrading genes. It suggests that increasing TC, TN, and DOC inputs could be a useful way to remediate PAH-polluted soils.