This study investigated the concentrations of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in the particulate and dissolved phase, as well as concentrations of PAHs in the sediment in Kaohsiung Harbor lagoon. Sources of PAHs in the water column were determined by isomer ratios, hierarchical cluster analysis (HCA) and principal components analysis (PCA). The net and annual fluxes of PAHs were calculated after a lagoon-wide water sampling campaign and compared with those found in a previous study (Fang, 2007) in which data from only one water sampling station was used. ¡@¡@In rain season, total PAH concentrations ranged from 21.6 to 36.2 ng/L for water samples, with dissolved and particulate phase concentrations ranged from 15.5 to 27.2 ng/L and from 3.4 to 8.6 ng/L, respectively. In dry season, total PAH concentrations ranged from 13.2 to 31.5 ng/L for water samples, with dissolved and particulate phase concentrations ranged from 8.0 to 21.1 ng/L and from 5.3 to 10.5 ng/L, respectively. Total PAH concentrations were found higher in rain season than in dry season. The highest total PAH concentration in dry season was observed in Chianjen River estuary. Relatively high PAH concentrations were also observed in these southern stations of Kaohsiung Harbor because of their location near Dalin industrial park. Total PAH concentrations ranged from 81.7 to 2279 ng/g for sediment samples, with average of 895 ng/g. The correlations between PAH concentrations and organic carbons, water temperature, salinity and suspended particles were also examined in this study. PAH concentration in dissolved phase was negatively correlated with water temperature (p<0.05). PAH concentration in sediment was positively correlated with organic carbons (p<0.05), and negatively correlated with median diameter (p<0.01). The logKoc¡ÐlogKow relationship in rain and dry season was compared with literature. It was found that the logKoc values were higher than those reported in literature, suggesting that soot particles might play an important role in the transport and distribution of PAHs in the study area. In rain season, PAHs in dissolved phase were mainly from pyrogenic origins; while mainly from petrogenic origins in particulate phase. In contrast, in dry season, PAHs in dissolved phase were mainly from petrogenic origins; while mainly from pyrogenic origins in particulate phase. In addition, it was found, relatively, that petrogenic pollution was introduced maily from the northern area of the lagoon. In rain season, total PCB concentrations ranged from 1.1 to 2.7 ng/L for water samples, with dissolved and particulate phase concentrations ranged from 0.42 to 2.1 ng/L and from 0.24 to 1.4 ng/L, respectively. In dry season, total PCB concentrations ranged from 0.54 to 1.3 ng/L for water samples, with dissolved and particulate phase concentrations ranged from 0.20 to 0.74 ng/L and from 0.32 to 0.76 ng/L, respectively. The direction of net fluxes of PAHs in this study are from water to air (net volatilization) in summer. In winter, however, the absorptive PAH fluxes obtained for four to six-ring PAH, such as fluoranthrene, chrysene + triphenylene and benzo[a]anthracene, indicating that PAHs were absorbed into surface waters. According to our results, it was suggested that the results from previous study (Fang, 2007) might underestimate the net fluxes of Pyrene and total fluxes in dry season. The annual fluxes of PAHs estimated in this study were 212 mg/m2 /year and 5.7 kg of PAHs were emitted annually from the harbor lagoon surface waters to the ambient atmosphere.

The aim of this study is to investigate the distributions of polycyclic aromatic hydrocarbons (PAHs) in sediment and water (suspended particles and dissolved phase) samples collected from Dapeng Bay(coast¡Bbay¡Bwetland and mangrove). Chemical fingerprinting techniques and statistical analysis were applied to delineate the possible sources of PAHs in sediment and water samples. The average concentrations of total PAHs (£U51PAHs) ranged from 143 to 1595 ng/g dry weight (dw) in the sediments. Total PAH (£U46PAHs) concentrations varied from 11 to 38 ng/L in dissolved phase and from 1.4 to 15ng/L (252 to 772 ng/g dw) in suspended particulate phase, respectively. Comparing with sediment quality guidelines (SQGs), the total PAH concentrations in all sediment samples were below the criteria, suggesting that no adverse biological effects would arise from the PAHs in these sediments. The partition coefficients¡]KOC¡^values of PAHs were higher than predicted values. It might be attributed to soot particles which have extremely high sorption capacities. Total organic carbon¡]POC¡^and black carbon (BC) were significantly correlated with combustion PAH concentrations in Dapeng Bay. Combustion PAHs (Flt¡ÏPyr¡ÏBaA¡ÏChr¡ÏBbF¡ÏBkFa¡ÏBeP¡ÏBaP¡ÏIP¡ÏBghiP) concentrations were significantly correlated with black carbon (BC) in mangroves sediment cores and wetland A. In addition, total PAH concentrations were significantly correlated with combustion PAHs concentrations in dissolved phase. In suspended particulate phase, total PAH concentrations and combustion PAHs concentrations were significantly correlated with suspended solid (SS). Results from diagnostic ratios and hierarchical cluster analysis (HCA) both indicate that PAHs in the coast of Dapeng Bay were mainly from petrogenic sources, but from petrogenic and pyrogenic mixed sources in the wetland and mangrove inside the Dapeng Bay. In addition, the origin of perylene in Dapeng Bay and coastal sediments was mainly from the biogenic and pyrogenic, while it was from biogenic origin in wetland A and wetland B. However, the origin of perylene in mangrove M1 and mangrove M2 tended to be diagenetic.

Coastal atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs) were measured at top of a building on campus of the National Sun Yat-sen University of Kaohsiung. Concentrations of 52 PAH compounds were analyzed in both gaseous and particulate phases in air samples collected from May 2008 through April 2009. PAHs diagnostic, Hierarchical Analysis (HCA) and Principal Component Analysis (PCA) were employed to determine the potential sources of PAHs. The Group Method of Data Handling (GMDH) was applied to relate atmospheric PAH concentration to air quality variables like SO2 and O3, as well as meteorological conditions like precipitation and temperature. During the sampling period the mean of total PAH concentrations was 14.2 ng/m3. Over all, PAH concentrations in winter were higher than summer, with the lowest concentrations of PAHs occurred in June (2.22 ng/m3), while the highest occurred in January (32.4 ng/m3). The night-time concentrations of PAHs are higher than daytime. The 2, 3-ring PAHs were mostly present in the gaseous phase, 4-ring were dominant in the gaseous phase, while 5, 6, 7-ring PAHs were mostly present in the particulate phase. During the Ghost festival and Asian dust storm events, atmospheric concentrations of PAHs and PAHs/TSP ratios were both found increased. Meteorological conditions, such as temperature and relative humidity, may strongly affect PAH concentrations, the gaseous and particulate PAHs correlate significantly with SO2, NOx, and PM10. Result from analyses of diagnostic rations, HCA and PCA, indicates the major sources of PAHs include gasoline and diesel exhaust. By using GMDH, a reasonable appraisal index was obtained for the pattern forecast potency with the meteorological and air quality variables. The GMDH algorithm obtained during 2008~2009 was tested in predictions and compared with what measured in 2007~2008.

The distribution of butyltin compounds (BTs) in the sediments and seawater, at the river outfalls, fishing ports, shipyards, and industrial zone docks of Kaohsiung Harbor, Taiwan were investigated. Twenty sediment and seawater samples were collected from various locations in the Harbor in 2006, and analyzed for monobutyltin (MBT), dibutyltin (DBT), and tributyltin (TBT). Results showed that the concentration of total BTs varied from 1.5 to 151 ng/g in sediment samples, with TBT being the major component of the sediment samples. This suggests that sediments could be the most possible sink of TBT brought by the sorption mechanism. The concentrations of BTs ranged from 9.7 to 270 ng/L in seawater samples, whereas DBT and MBT, the degradation byproducts of TBT, were mainly the most abundant BT compounds of the seawater samples. This indicates that the abiotic or biotic degradation potential of TBT was significant. Spatially, the highest concentrations of BTs were observed in both water and sediment samples collected from the shipyard and fishing port areas. This indicates that the shipping related activities (e.g., navigation, ship repair, and ship building), would contribute most of BTs in the environment. Results show that the concentrations of degradation products (DBT and MBT) were related closely to temperature, salinity, dissolved oxygen (DO), and chlorophyll-a of the seawater. This implies that seasonal changes of the water parameters controlled the degradation of TBT in seawater. The observed levels of BT compounds in both seawater and sediments were much higher than those required to induce toxic effects on marine organisms suggesting that appropriate TBT control strategies should be taken in Kaohsiung Harbor. Sediment samples were collected from the river outfalls, fishing ports, shipyards, and industrial zone docks of Kaohsiung Harbor, Taiwan to evaluate the distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments. Collected sediment samples from 12 locations were analyzed for 17 different PAHs, organic content, and grain size. The results show that the total PAH concentrations varied from 472 to 16,201 ng/g dry wt, with a mean concentration of 5,764 ng/g dry wt The highest PAH concentrations were from the industrial zone docks situated in south Kaohsiung Harbor, ranging from 8,788 to 16,201 ng/g dry wt Among those sediment samples, the 5-, 6-ring PAHs were predominant PAH congeners in sediments, ranging from 42 to 71%. However, the dominant PAH congeners were 2-, 3-ring PAHs (37 to 42%) collected from steel industrial zone docks. This indicates that the sources for the PAH contamination at steel industrial zone docks were different from the other zones in Kaohsiung Harbor. According to the diagnostic ratios, the possible source of PAHs in the industrial zone dock could be coal combustion while in the other zones it could be petroleum combustion. The total PAH levels were expressed as the total toxic equivalent (TEQcarc). The total TEQcarc varied from 55 to 1,964 ng TEQ/g dry wt. Higher total TEQcarc values were found at industrial zone docks (from 1,404 to 1,964 ng TEQ/g dry wt). As compared with the US Sediment Quality Guidelines (SQGs), the observed levels of PAHs at industrial zone docks exceeded the effects range low (ERL), and could thus cause acute biological damage. However, the lower levels of PAHs at the other zones would not exert adverse biological effects. Results would be helpful in developing strategies for sediment remediation in Kaohsiung Harbor.

In this study our purposes were to investigate the spatial distribution and seasonal variation of polycyclic aromatic hydrocarbons (PAHs) in the dissolved and particulate phase of PAHs in Er-Jen River. In addition, the potential sources of PAHs in Er-Jen River were investigated not only by finger printing, but also principal component analysis (PCA) and hierarchical cluster analysis (HCA). ¡@¡@Concentrations of dissolved and particulate PAHs ranged from 13.8 to 516 ng/L and from 4.05 to 55.9 ng/L, respectively. In March (dry season), concentrations of dissolved and particulate PAHs ranged from 38.3 to 186 ng/L and from 4.05 to 25.9 ng/L, respectively. In addition, concentrations of dissolved and particulate PAHs ranged from 32.3 to 82.8 ng/L and from 14.8 to 85.3 ng/L, respectively in September (wet season). The highest total PAH concentration in this area was found in Station Er-3 which is located on a tributary of Er-Jen River. Total PAH concentrations in wet season were higher than those found in dry season for all stations in Er-Jen River, except for station Er-3, which suggesting that different geography might be the reason. ¡@¡@Results from correlation analysis indicated that distributions of PAH concentrations for particulate phase in Er-Jen River correlated well with flow rate, suspended solid concentrations and salinity. Total PAH concentration of station Er-2, which was located at the downstream Er-Jen River, was highly correlated with salinity; while total PAH concentrations in other stations were mainly affected by flow rate, suspended solid concentrations and some potential sources of pollution. Results from PCA, HCA and finger printing all indicated the origins of PAHs were complex sources in the study area, including pyrogenic, petrogenic and diagenetic/biogenic origins. The origins of PAHs in dissolved phase were mainly from both pyrogenic and petrogenic sources; while those in particulate phase were mainly from pyrogenic sources. In addition, the pyrogenic origins in both dissolved and particulate phase were mostly from liquid fuel combustion. In wet season, howerer, diagenetic/biogenic origins were also found in particulate phase at the sampling sites of Er-Jen River. ¡@¡@The annual total PAH fluxes of Er-Jen River were estimated to be 23.1 kg For dissolved phase, the average daily fluxes in dry and wet season were 5.9 g/day and 65.8 g/day, respectively, with an annual mean fluxe of 11.3 kg/year. For particulate phase, the mean daily fluxes in dry and wet season were 0.8 g/day and 76.2 g/day, respectively, with an annual mean flux of 11.8 kg/year. In general, the total PAH fluxes in wet season were higher than dry season. The total annual PAH fluxes in Er-Jen River were generally less than those reported worldwide, and comparable to those in San Francisco River in USA, but higher than those in Le Havre River in France.

Water, suspended particle and sediment samples from Kao-ping estuary were collected and measured for concentrations of polycyclic aromatic hydrocarbons (PAHs) during March 2004 and April 2005. In addition, sediments from neighboring coastal area were also analyzed to estimate distribution, transportation and possible sources of PAHs. Total PAH concentrations varied from 33.0 to 910 ng/g dry weight (dw) in coastal sediments, and diagnostic ratios reflect a mixed sources of petrogenic and pyrolytic inputs. Due to the contribution of Kao-ping River, spatial distribution of PAH concentrations at coastal sediments near river mouth varied dramatically. Results of hierachical cluster analysis showed that PAH concentration distribution was influenced by Kao-ping canyon, and biogenic source might be the major PAH source for offshore sediments. Total PAH concentrations in river sediment varied from 63.0 to 720 ng/g dw. Higher concentration was measured between the Water Main pipe and Shuang-yuan Bridge, and possible sources were from both petrogenic and pyrolytic sources. Sediment of Dung-gang harbour had highest concentration, 28,000ng/g dw, in this study, which was contributed from petrogenic sources due to its intensive boating activities. Except fluorene and phenanthrene in harbour sediments, individual PAH concentrations of other sediments are lower or near the Effect Range Low value, concentrations might lead to possible adverse effects upon organism. Total PAH concentrations varied from 5.0 to 82.0 ng/L in suspended particulate phase and from 5.5ng/L to 46.0ng/L in dissolved phase, respectively. Most of high molecular weight PAH concentrations (>5-ring PAHs) in dissolved phase were below method detection limits. The partition coefficients¡]Koc¡^values of PAHs were 1 to 2 orders higher than predicted values. It might be attributed to soot particles which have extremely high sorption capacities. Correlation coefficients between total PAH concentrations in sediments versus total organic carbon¡]TOC¡^ and fine particle content¡]<63£gm%¡^were significant ¡]R=0.575, 0.800, 0.851 and 0.657, P<0.01¡^. In addition, PAHs in suspended particulate phase and dissolved phase were also significantly correlated to particulate organic carbon¡]POC¡^ and dissolved organic carbon¡]DOC¡^, respectively. The distribution of calculated PAH concentrations from organic carbon was higher in surface water than bottom water. Unlike salinity, there was no decreasing or increasing trend of these concentrations among river samples. It is possible that contamination was not come from upstream, but from estuary area where plume was lifted and diffused upstream by neat seawater. The flux in Wan-da Bridge was higher than downstream estuary area that might be due to PAH concentrations reduction by sedimentation or degradation.

Refinery operations have been associated with a wide variety of atmospheric emissions consisting of criteria air pollutants, volatile organic components, hazardous air pollutants as well as other pollutants. With approximately 100 oil refineries in the Wider Caribbean region (WCR), hydrocarbons in this region pose significant environmental and human health risks. One of the oldest and largest refineries in the WCR is the Isla Refineriá, which is located on the island of Curaçao, and has been the basis of historical debates and conflict between the public and the local government over the environmental and human health risks. This research aims to establish baseline levels of ambient petrochemical emissions in Curaçao, specifically polycyclic aromatic hydrocarbons (PAHs), inhalable particulate matter (PM10) and sulfur dioxide (SO2), and to evaluate through comparative literature analysis and recommended public health guidelines the potential health risks in Curaçao. In addition, source elucidation of PAHs was conducted using concentration profiles, distribution profiles, binary diagnostic ratios and factor analysis. Passive air samplers with polyurethane foam collection disks (PAS-PUFs) were deployed in 2011 (n=43) and in 2014 (n=30) to measure ambient PAH concentrations. Ambient PAH concentrations ranged from 1.2 ng/m3 in 2011 and 27.3 to 660.1 ng/m3 in 2014, demonstrating no temporal differences. However, there were highly significant spatial differences, with the samples downwind of the refinery having significantly higher ambient PAH concentrations than those upwind in 2014. Source elucidation revealed the ambient PAHs were dominated by petrogenic emission sources (i.e., refinery) in the 2011 and the 2014 downwind samples, whereas the 2014 upwind locations were equally influenced by both petrogenic (i.e., refinery) and pyrogenic (i.e., vehicle emissions) sources. Available hourly, daily and monthly PM10 and SO2 measurements were downloaded from June 2010 through December 2014 from two local air monitoring stations. Concentrations of both PM10 and SO2 in Curaçao are among the highest reported globally, demonstrating an increasing trend over time and exceed current public health guidelines recommended by local and international agencies. It is plausible that the residents of Curaçao may experience health effects often associated with PM10 and SO2, however the epidemiological evidence is inadequate to infer causality between health effects and long-term exposures. Using the USEPA’s risk analysis methodology the resulting cumulative lifetime cancer risk estimates from PAH inhalation were below the level of concern (1.0 x 10-4). In contrast, by evaluating the potency adjusted concentrations relative to the most toxic compound (benzo[a]pyrene), age class (children and adults) extrapolated and site specific risks indicated levels exceeding the upper bound acceptable risk (1.0 x 10-4) by almost two orders of magnitude suggesting the need for remediation.

The overall objective of the present study was to evaluate the effectiveness of using a variety of hydrophobic biopolymers and hydrophobic biopolymer-coated sands as technically and economically feasible in-situ sediment amendments or alternative capping materials on a laboratory scale. Cutin from tomato peels, cellulolytic enzyme lignin from sitka spruce chips, and keratin azure from commercially dyed sheeps wool were isolated, prepared, tested, and evaluated as feasible hydrophobic biopolymers for the removal of selected Polycyclic Aromatic Hydrocarbons (PAHs). Testing included chemical and physical characterization, as well as the measurement of kinetics and equilibrium sorption parameters for the sorbates naphthalene, phenanthrene, and pyrene as model hydrophobic organic contaminants. Tomato peel cutin exhibited the largest overall affinity for PAHs, however, keratin azure was selected for further evaluation as the most feasible material due to its low preparation cost. Amendment of industrial sand with a stable, uniform, cross-linked keratin azure derivative was achieved to produce hydrophobic biopolymer-coated sand products containing zero, moderate, and high mass fractions of sand. Chemical and physical material parameters, as well as kinetics and equilibrium sorption parameters for the sorbates naphthalene, phenanthrene, and pyrene, were then obtained for the coated sand products. This allowed simple finite difference modeling of PAH fate and transport through a thin cap comprised of the same, insight into the specific sorption mechanisms involved, and information which could prove useful in predicting potential of keratin products to provide a suitable capping material. Conclusions and recommendations for future research focus on the technical and economical feasibility of the prepared hydrophobic biopolymers and hydrophobic biopolymer-coated sand products as capping or in-situ sediment amendments. / text

North American petroleum refineries use landfarming to dispose of hydrocarbon-containing wastes for bioremediation by indigenous soil microorganisms. In this study, we isolated PAH-degrading bacteria from landfarm soil by enrichment with hydrocarbon-containing effluent. One isolate, Arthrobacter sp. UG50, was capable of using phenanthrene and anthracene as sole carbon sources. The strain degraded phenanthrene (200 mg/L) within 24 h in pure culture at high cell density (10e8 cells/mL). Anthracene (50 mg/L) was slowly degraded, with 29% degraded within 21 days. The strain could not use naphthalene, pyrene, chrysene or benzo(a)pyrene as sole carbon sources, but could degrade pyrene (50 mg/L) cometabolically when phenanthrene was provided. Anthracene degradation (50 mg/L) was enhanced by phenanthrene, with 100% degraded within 6 days. The addition of strain UG50 to petroleum sludge in baffled flasks increased total hydrocarbon degradation and degradation of low concentrations of fluorene, phenanthrene, pyrene and chrysene compared to flasks with limited aeration or containing sludge alone. / NOVA Chemicals and the Ontario Centres of Excellence

The accumulation of persistent contaminants is a significant issue for the health of aquatic environments. This study aims to determine the effects of polycyclic aromatic hydrocarbons (PAH) on the stress response of fish by monitoring plasma cortisol levels and the expression of key hypothalamic-pituitary-interrenal (HPI) stress axis regulators. Injection of benzo(a)pyrene (BaP), a ubiquitous PAH, induced a differential dose- and time-dependentcortisol response in rainbow trout and brown bullhead. BaP exposure also elicited a species-specific transcriptional response at all levelsof the HPI axis.Similarly, the HPI axis response to a standardized emersionstressor revealed species-specific differences. In the field, exposure of different brown bullhead populations to sediment with complex PAH mixtures did not consistently affect cortisol levels and providedno evidence of genetic adaptation of the stress response. Thus, future studies are needed to bridge the gap in our understanding between the laboratory and field effects of PAHs on the stress response of fish.