Naphthalene and its biomarkers as measures of occupational exposure to polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAH) include compounds with two or more fused benzene rings, many of which are carcinogens. Industrial sources produce hundreds of PAH, notably in the coke- and aluminium-producing industries. Because PAH are distributed at varying levels between gaseous and particulate phases, exposure assessment has been problematic. Here, we recommend that occupational exposures to naphthalene be considered as a potential surrogate for occupational PAH exposure for three reasons. Naphthalene is usually the most abundant PAH in a given workplace; naphthalene is present almost entirely in the gaseous phase and is, therefore, easily measured; and naphthalene offers several useful biomarkers, including the urinary metabolites 1- and 2-hydroxynaphthalene. These biomarkers can be used to evaluate total-body exposure to PAH, in much the same way that 1-hydroxypyrene has been applied. Using data from published sources, we show that log-transformed airborne levels of naphthalene are highly correlated with those of total PAH (minus naphthalene) in several industries (creosote impregnation: Pearson r= 0.815, coke production: r= 0.917, iron foundry: r= 0.854, aluminium production: r= 0.933). Furthermore, the slopes of the log-log regressions are close to one indicating that naphthalene levels are proportional to those of total PAH in those industries. We also demonstrate that log-transformed urinary levels of the hydroxynaphthalenes are highly correlated with those of 1-hydroxypyrene among coke oven workers and controls (r= 0.857 and 0.876), again with slopes of log-log regressions close to one. These results support the conjecture that naphthalene is a useful metric for occupational PAH exposure. Since naphthalene has also been shown to be a respiratory carcinogen in several animal studies, it is also argued that naphthalene exposures should be monitored per se in industries with high levels of PAH.     

Contamination, source identification, and risk assessment of polycyclic aromatic hydrocarbons in agricultural soil of Shanghai, China

The level, distribution, compositional pattern, and possible sources of polycyclic aromatic hydrocarbons (PAHs) in agricultural soil of Shanghai were investigated. The concentrations ranged from 140.7 to 2,370.8 μg kg(?-1) for 21 PAHs and from 92.2 to 2,062.7 μg kg(?-1) for 16 priority PAHs, respectively. The higher level of PAHs was mainly distributed in the south and west of Shanghai region, and the lower concentration was found in Chongming Island. Generally, the composition pattern of PAHs was characterized with high molecular weight PAHs, the seven possible carcinogenic PAHs accounted for 4.8-50.8% of the total PAHs, and fluoranthene, pyrene, and benzo[b]fluoranthene were the most dominant components in soil samples. The correlation analysis suggested that low molecular weight PAHs and high molecular weight PAHs were originated from different sources and further corroborated that total organic carbon was a key soil property affecting the fate of persistent organic pollutants in the environment. The isomer ratios and principal component analysis indicated that PAHs in the investigated areas were derived primarily from combustion of biomass, coal, and petroleum. Compared to the soil quality standards of the Netherlands, all the target PAHs (except Ant) in most samples exceeded their target values. The Nemerow composite index based on the same soil quality standard showed that 69.4% of the soil samples were heavily polluted. The total BaP(eq) of ten Dutch target PAHs in 72% soil samples were higher than the reference total carcinogenic potency. Therefore, the agricultural soil in Shanghai is suffering from serious PAHs contamination.     

Distribution and risk assessment of polycyclic aromatic hydrocarbons (PAHs) from Liaohe estuarine wetland soils

Thirty-one surface soil samples were collected from Liaohe estuarine wetland in October 2008 and May and August 2009. The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs), identified as priority pollutants by the US EPA, were measured by gas chromatography. PAHs were predominated by three- and four-ring compounds. The total PAH concentrations ranged from 704.7 to 1,804.5 μg/kg with a mean value of 1,001.9 μg/kg in October 2008, from 509.7 to 1,936.9 μg/kg with an average of 887.1 μg/kg in May 2009, and from 293.4 to 1,735.9 μg/kg with a mean value of 675.4 μg/kg in August 2009. The PAH concentration detected at most sites shared the same pattern, with maximum concentrations during the autumn (October) and minimum concentrations during the summer (August). The ecological risk assessment of PAHs showed that adverse effects would occasionally occur in the soils from Liaohe estuarine wetland based on the effects range low (ERL)/effects range median and the toxic equivalency factors. The results revealed that some of the individual PAHs were in excess of ERL which implied possible acute adverse biological effects. The BaP(eq) values in some sites surpassed the Dutch target value. Therewith, quite a part of soils in the wetland were subjected to potential ecological risks.     

Assessment of non-occupational exposure to polycyclic aromatic hydrocarbons through personal air sampling and urinary biomonitoring

Non-occupational inhalation and ingestion exposure to polycyclic aromatic hydrocarbons (PAHs) has been studied in 8 non-smoking volunteers through personal air sampling and urinary biomonitoring. The study period was divided into 4 segments (2 days/segment), including weekdays with regular commute and weekends with limited traffic related exposures; each segment had a high or low PAH diet. Personal air samples were collected continuously from the subjects while at home, at work, and while commuting to and from work. All urine excretions were collected as individual samples during the study. In personal air samples, 28 PAHs were measured, and in urine samples 9 mono-hydroxylated metabolites (OH-PAHs) from 4 parent PAHs (naphthalene, fluorene, phenanthrene and pyrene) were measured. Naphthalene was found at higher concentrations in air samples collected at the subjects' residences, whereas PAHs with four or more aromatic rings were found at higher levels in samples taken while commuting. Urinary OH-PAH biomarker levels increased following reported high inhalation and/or dietary exposure. On days with a low PAH diet, the total amount of inhaled naphthalene during each 24-hour period was well correlated with the amount of excreted naphthols, as was, to a lesser extent, fluorene with its urinary metabolites. During days with a high dietary intake, only naphthalene was significantly correlated with its excreted metabolite. These findings suggest that this group of non-occupational subjects were exposed to naphthalene primarily through indoor air inhalation, and exposed to other PAHs such as pyrene mainly through ingestion.     

Occurrence, finger printing and ecological risk assessment of polycyclic aromatic hydrocarbons (PAHs) in the Chenab River, Pakistan

Seventeen polycyclic aromatic hydrocarbons (PAHs) were studied in surface waters (including particulate phase) from the Chenab River, Pakistan and ranged from 289-994 and 437-1290 ng l(-1) in summer and winter (2007-09), respectively. Concentrations for different ring-number PAHs followed the trend: 3-rings > 2-rings > 4-rings > 5-rings > 6-rings. The possible sources of PAHs are identified by calculating the indicative ratios; appropriating petrogenic sources of PAHs in urban and sub-urban regions with pyrogenic sources in agricultural region. Factor analysis based on principal component analysis identified the origins of PAHs from industrial activities, coal and trash burning in agricultural areas and municipal waste disposal from surrounding urban and sub-urban areas via open drains into the riverine ecosystem. Water quality guidelines and toxic equivalent factors highlighted the potential risk of low molecular weight PAHs to the aquatic life of the Chenab River. The flux estimated for PAHs contaminants from the Chenab River to the Indus River was >50 tons/year.     

Characterizing ecological risk for polycyclic aromatic hydrocarbons in water from Lake Taihu, China

Lake Taihu provides vital ecological services for humans in China; it receives a great deal of attention regarding its ecological and environmental conditions. In this study, the ecological risks of eight individual polycyclic aromatic hydrocarbons (PAHs) in water were assessed using probabilistic distributions of the hazard quotient based on Monte Carlo simulation. The results show that the 95th percentile of the hazard quotients ranged from 0.00074 to 2.831, and the ecological risk of Flua was highest, followed by, in descending order of risk, B[a]P?>?Pyr?>?Ant?>?Phe?>?Flu?>?Ace?>?Chr. The probabilities of hazard quotients exceeding a decision criteria of 0.3 were 18.09%, 6.51%, 3.76%, and 2.85% for Flua, B[a]P, Pyr, and Ant, respectively, indicating their potential ecological risks to aquatic organisms. The spatial distribution of hazard quotients for these four individual PAHs with potential ecological risk were obtained using Geographic Information System (GIS), and similar spatial distribution patterns were also observed in the lake. The highest ecological risks of these four individual PAHs to aquatic organisms were found in Meiliang Bay, followed by Gonghu Bay and Xukou Bay. The uncertainty within the ecological risk assessment was also discussed.     

Contributions of deposited particles to pine needle polycyclic aromatic hydrocarbons

The contributions of deposited particles (P) to polycyclic aromatic hydrocarbon (PAH) levels in pine (Cedrus deodar) needles sampled from the Dalian region were evaluated by washing off the particles from pine needle surfaces. P values ranged from 4.4 +/- 2.2% for fluorene to 69.9 +/- 4.0% for indeno(1,2,3-cd)pyrene, and positively correlated with the logarithm of octanol-air partition coefficients (log K OA) of each PAH significantly. P and the total levels of 14 PAHs under study ( summation PAHs), that ranged from 490 to 3241 ng g(-1) dw (dry weight) with median value of 1521 ng g(-1) dw, were high for traffic areas, and low for residential or park areas, implying the significant contributions of PAHs in both gas and particle phases emitted by vehicles. However, PAH profiles in pine needles were not significantly altered by the washing, due to the low fractions (2-5%) of the 5- and 6-ring PAHs in summation PAHs. The high wind speed and frequently alternating wind directions in the Dalian spring could quicken the depuration processes of pine needle PAHs. Thus, the local meteorological conditions and source variations should be taken into account when using pine needles to implicate seasonal variations of atmospheric semi-volatile organic compounds.     

Quantitative assessment of polycyclic aromatic hydrocarbons in sewage sludge from wastewater treatment plants in Qingdao, China

In this study, 16 polycyclic aromatic hydrocarbons (PAHs) were detected in sewage sludge samples from four wastewater treatment plants (WWTPs) in Qingdao, China. These WWTPs differ in the type of treatment used and in the origin of the wastewater. The total amounts of PAHs in digested sludges ranged from 1.9645 to 6.5752 mg/kg, which did not exceed the projected European Union cut-off limits (6 mg/kg) for sludge found in farmland, except for the Haibohe WWTP. Significant differences were observed in overall PAH values between WWTPs receiving domestic effluents and those receiving industrial effluents. The total amounts of PAHs in digested sludge from the Licunhe and Haibohe WWTPs, which mainly received industrial effluents, were markedly higher than those of the Tuandao and Huangdao WWTPs, which received only domestic effluents. The distribution of PAH compounds in digested sludges were analysed. At the Tuandao, Huangdao and Licunhe WWTPs, 2-, 3-, 4-benzene rings were predominant, accounting for 100%, 99.8% and 99.0% of the sum concentration of 16 PAHs (∑PAHs), respectively. At the Haibohe WWTP, a large number of high molecular weight PAHs (5-, 6-benzene rings) were observed, accounting for 30% of the ∑PAHs. The sum of seven carcinogenic PAHs (∑PAHs-c) ranged from 0.8694 to 3.0389 mg/kg in four WWTPs. The highest value was found in the Haibohe WWTP. Moreover, the PAH concentrations in sludges from the different treatment processes in the Licunhe and Tuandao WWTPs are discussed.     

Fugacity approach to evaluate the sediment-water diffusion of polycyclic aromatic hydrocarbons

Diffusion is an important process for sediment-water exchange and plays a vital role in controlling water quality. Fugacity fraction (ff) was used to estimate the sediment-water diffusion of polycyclic aromatic hydrocarbons (PAHs) between seawater and surficial sediment. A total of 33 surface sediment and sea water samples were collected concurrently from the northeast coastal area in China and 25 PAHs were analyzed including the alkylated and chlorated PAHs. Fugacity fraction was calculated based on the PAH concentrations in water and sediment, octanol-water partition coefficient of PAHs, organic matter content in sediment, and density of sediment. The calculated results showed that ff increased with decreasing molecular weight of PAHs. The low molecular weight PAHs (2-3 rings) transferred from sediment to water and the sediment acted as a secondary source to the water. The medium molecular weight PAHs (4-5 rings) were close to the sediment-water equilibrium and the transfer tendency shifted between sediment and water. The high molecular weight PAHs (5-6 rings) transferred from water into sediment and the sediment acted as a sink. Soot carbon and the difference of PAH concentrations between sediment and water were found to be important factors affecting the sediment-water diffusion. This study provided new insight into the process of sediment-water diffusion, which has a great influence on the quality of water, especially in severely-polluted sediment areas.     

Aliphatic and polycyclic aromatic hydrocarbons in the surface sediments of the Mediterranean: assessment and source recognition of petroleum hydrocarbons

Coastal marine sediment samples were collected from ten sampling stations along the Egyptian Mediterranean coast in April 2010. All sediment samples were analyzed for aliphatic (C7 to C34) and polycyclic aromatic hydrocarbons (PAHs) as well as total organic carbon (TOC) contents and grain size analysis. Total aliphatic hydrocarbons ranged from 1621.82 to 9069.99 ng/g (dry weight), while aromatic hydrocarbons (16 PAHs) varied between 208.69 and 1020.02 ng/g with an average of 530.68?±?225.86 ng/g?dwt. Good correlations observed between certain PAH concentrations allowed to identify its origin. The average TOC percent was varied from 0.13 to 1.46 %. Principal component analysis was used to determine the sources of hydrocarbon pollutants in sediments of Mediterranean. Additionally, special PAHs compound ratios suggest the petrogenic origins.     

Lipid peroxidation and antioxidant defense enzymes in Clarias gariepinus as useful biomarkers for monitoring exposure to polycyclic aromatic hydrocarbons

The toxicological evaluations of crude oil, xylene, toluene and benzene were carried out against juvenile stages of Clarias gariepinus. On the basis of LC(50) value, benzene (0.017 ml/l) was found to be the most toxic followed by xylene (0.086 ml/l), toluene (0.398 ml/l) and crude oil (2.219 ml/l) was the least toxic. The results of the lipid peroxidation assay showed that the level of malonaldehyde (MDA) in liver and gills of fish exposed to all the test chemicals increased significantly (P < 0.05) when compared to control. Measurement of activities of antioxidant enzymes, superoxide dismutase (SOD), catalase (CAT) and glutathione-S-transferase (GST) in liver and gill of fishes exposed to sublethal concentration of the test chemicals over a 28-day period was found to decrease significantly (P < 0.05) when compared to control. The observed reduction in the activities of antioxidant defense enzymes such as SOD, CAT and GST in conjunction with an increase in MDA levels in the gill and liver tissues of test animals exposed to aromatic hydrocarbon compounds were recommended as a good battery of biomarkers for early detection of pollution during biomonitoring programmes.     

Personal and indoor exposure to PM2.5 and polycyclic aromatic hydrocarbons in the southern highlands of Tanzania: a pilot-scale study

Sediment-dwelling macrofauna, polycyclic aromatic hydrocarbons (PAH), and abiotic parameters were monitored annually in benthic marine sediments from 1989-2007 in Port Valdez, a period of declining routine discharge of treated marine ballast water containing residual PAH from a major crude oil loading facility. The resulting dataset was used to evaluate associations between macrofauna and environmental characteristics including PAH concentrations. The influences of natural abiotic gradients on macrofauna were stronger than associations between macrofauna and sediment PAH. Though overall associations of PAH with macrofaunal community structure were weak, effects were greater for the tube-dwelling polychaete worms Galathowenia oculata and Melinna cristata which responded negatively to low PAH values near sediment quality criteria (threshold effects concentration: TEC and field-based sediment quality criterion: fb-SQG: ～300 ng g(?-1)). Effects of PAH on benthic fauna may be strongest through poor survival of juveniles and failed recruitment over multiple years. Comparison of measured PAH concentrations to the TEC and field-based fb-SQG suggest that the observed levels of change in Port Valdez are minor and the criteria are ecologically appropriate for environmental monitoring. By demonstrating positive responses of sensitive fauna to reduction of PAH concentration, this study contributes to understanding the temporal change, ecological importance, and size of effects expected on benthic fauna in the presence of continuous exposure to low levels of hydrocarbons.     

Determination of petroleum hydrocarbons and polycyclic aromatic hydrocarbons in sludge from wastewater treatment basins

Screening by gas chromatography with flame ionization detection and gas chromatography-mass spectrometry has been carried out on sludge extracts of wastewater treatment basins. Soxhlet extraction with trichlorotrifluoroethane was applied. The yields for petroleum hydrocarbons and PAH recovery were high, usually in excess of 90%. The proposed investigations permit a quick assessment of petroleum pollutants in the environment.     

Distribution,sources, and toxicity assessment of polycyclic aromatic hydrocarbons in surface soils of a heavy industrial city,Liuzhou, China

As a heavy industrial city, Liuzhou has been facing a serious pollution problem. It is necessary to take steps to control and prevent environmental pollution wherever possible. Surface soil samples were collected from four communities in Liuzhou City, to determine the concentrations, distributions, sources, and toxicity potential of polycyclic aromatic hydrocarbons (PAHs) present. The mean concentrations of total PAHs in the surface soil are 756.43 ng/g for the heavy industrial area, 605.06 ng/g for the industrial area, 481.24 ng/g for the commercial–cum–residential area, and 49.93 ng/g for the rural area. Both the isomer ratio and principal component analyses for the PAHs prove that these pollutants originate mainly from coal, diesel, gasoline, and natural gas combustion. The pollution hierarchies and toxic equivalency factor of BaP prove that the city is subject to heavy pollution caused by industry, transportation, and daily human activities.     

Ecological risk analysis of polycyclic aromatic hydrocarbons (PAHs) in surface sediments from Laizhou Bay

The current research aims at developing predictive models for trihalomethane (THM) formation in Lebanon based on field-scale investigations as well as laboratory controlled experimentations. Statistical analysis on field data revealed significant correlations for TTHM with chlorine dose, Specific UV-A, and UV(254) absorbing organics. Simulated distribution system-THM tests showed significant correlations with applied chlorine dose, total organic carbon, bromides, contact time, and temperature. Predictive models, formulated using multiple regression approaches, exhibiting the highest coefficients of determination were quadratic for the directly after chlorination (DAC; r(2) = 0.39, p < 0.036) and network (r(2) = 0.33, p < 0.064) THM databases, and logarithmic for the laboratory simulated THM database (r(2) = 0.70, p < 0.001). Computed r(2) values implied low correlations for the DAC and network THM database, and high correlation for the laboratory simulated THM database. Significance of the models were at the 0.05 level for DAC database, 0.10 level for the network database, and very high (<0.01 level) for the laboratory simulated THM database. It is noteworthy to mention that no previous attempts to assess, monitor, and predict THM concentrations in public drinking water have been reported for the country although a large fraction of the population consumes chlorinated public drinking water.     

Source apportionment of polycyclic aromatic hydrocarbons in the Dahuofang Reservoir, Northeast China

Polycyclic aromatic hydrocarbons (PAHs) in 24 surface sediments from the Dahuofang Reservoir (DHF), the largest man-made lake in Northeast China, were measured. The results showed that the concentrations of 16 US EPA priority PAHs in the sediments ranged from 323 to 912 ng/g dry weight with a mean concentration of 592?±?139 ng/g. The PAH source contributions were estimated based on positive matrix factorization model. The coal combustion contributed to 31 % of the measured PAHs, followed by residential emissions (22 %), biomass burning (21 %), and traffic-related emissions (10 %). Pyrogenic sources contributed ～84 % of anthropogenic PAHs to the sediments, indicating that energy consumption release was a predominant contribution of PAH pollution in DHF. Compared with the results from the urban atmospheric PAHs in the region, there was a low contribution from traffic-related emissions in the sediments possibly due to the low mobility of the traffic-related derived 5+6-ring PAHs and their rapid deposition close to the urban area.     

A source study of atmospheric polycyclic aromatic hydrocarbons in Shenzhen, South China

Air pollution has become a serious problem in the Pearl River Delta, South China, particularly in winter due to the local micrometeorology. In this study, atmospheric polycyclic aromatic hydrocarbons (PAHs) were monitored weekly in Shenzhen during the winter of 2006. Results indicated that the detected PAHs were mainly of vapor phase compounds with phenanthrene dominant. The average vapor phase and particle phase PAHs concentration in Shenzhen was 101.3 and 26.7 ng m^???3, respectively. Meteorological conditions showed great effect on PAH concentrations. The higher PAHs concentrations observed during haze episode might result from the accumulation of pollutants under decreased boundary layer, slower wind speed, and long-term dryness conditions. The sources of PAHs in the air were estimated by principal component analysis in combination with diagnostic ratios. Vehicle exhaust was the major PAHs source in Shenzhen, accounting for 50.0% of the total PAHs emissions, whereas coal combustion and solid waste incineration contributed to 29.4% and 20.6% of the total PAHs concentration, respectively. The results clearly indicated that the increasing solid waste incinerators have become a new important PAHs source in this region.     

Solid-phase microextraction to monitor the sonochemical degradation of polycyclic aromatic hydrocarbons in water

Solid-phase microextraction (SPME) coupled with GC-MS has been used to monitor the degradation of polycyclic aromatic hydrocarbons (PAHs) by ultrasound treatment. Immersion SPME sampling enabled the fast and solventless extraction of target contaminants at the low microg l(-1) concentration level. The developed protocol was found to be linear in the concentration range from 0.1 to 50 microg l(-1) for most target analytes, with the limits of detection ranging between 0.01 and 0.70 microg l(-1) and the relative standard deviations between 4.31 and 27%. The developed SPME protocol was used to follow concentration profiles of aqueous solutions containing 16 PAHs, which were subject to low frequency ultrasonic irradiation. At the conditions employed in this study (80 kHz of ultrasound frequency, 130 W l(-1) of applied electric power density, 30 microg l(-1) of initial concentration for each of the 16 PAHs), sonochemical treatment was found capable of destroying the lower molecular weight PAHs (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene) within 120-180 min of irradiation. The higher molecular weight PAHs were more recalcitrant to ultrasound treatment.