Concentrations Of Chlorinated Polycyclic Aromatic Hydrocarbons Research Articles

Simultaneous determination of polycyclic aromatic hydrocarbons and their chlorinated derivatives in grilled foods

Polycyclic aromatic hydrocarbons (PAHs) are unintentionally generated in foods that are cooked, and dietary ingestion of these PAHs is regarded as the dominant route of exposure to PAHs. Some chlorinated PAHs (ClPAHs) are more toxic than their corresponding parent PAHs and can also be generated in food during cooking. Knowledge of the concentrations of ClPAHs in cooked foods has been limited by the lack of an adequate analytical method for measuring ClPAH concentrations in cooked foods. In this study, we developed an analytical method for simultaneous determination of PAHs and ClPAHs in lipid-rich foods. The combination of a potassium hydroxide silica gel column and an activated carbon cartridge enabled us to simultaneously measure PAH and ClPAH concentrations in raw and grilled fish and meats. Twelve kinds of PAHs (e.g., fluorene [Fle], phenanthrene [Phe], fluoranthene [Flu], and pyrene [Pyr]) were detected in grilled foods. The concentrations ranged from below the limit of quantitation (<LOQ) to 310 ng g−1. We also detected 9-monochlorinated Phe (9-ClPhe), 3-monochlorinated Flu (3-ClFlu), 8-monochlorinated Flu (8-ClFlu), and 1-monochlorinated Pyr (1-ClPyr); those concentrations ranged from <LOQ to 0.16 ng g−1. The total concentrations of PAHs were significantly lower in gas-grilled meats than in charcoal-grilled meats. In contrast, the concentrations of ClPAHs were significantly higher in gas-grilled meats than in the charcoal-grilled meats. This pattern could be attributed to the difference of reaction temperatures needed to generate them. Toxic equivalent (TEQ) concentrations, which were calculated based on toxicities relative to benzo[a]pyrene (BaP), were much higher in the grilled foods (0.12–12 ng-BaPeq g−1) for PAHs than for ClPAHs (<LOQ to 0.026 ng-BaPeq g−1).

Distributions and multiple sources of chlorinated polycyclic aromatic hydrocarbons in the air over Japan

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) have been detected in the air at discrete sites in Japan, but there is no information on their distributions throughout Japan. This study was a widespread survey of atmospheric concentrations of ClPAHs throughout Japan. The majority of 24 species of ClPAHs were detected in either the gas or particle phase at all sampling sites. The concentrations were weakly related to human population densities. The relationships between total concentrations of ClPAHs and PAHs suggested that atmospheric ClPAHs at ~70% of the sites were derived from common sources of PAHs. A ternary diagram based on diagnostic ratios of 1-chloropyrene, 7-chlorobenz[a]anthracene, and 6-chlorobenzo[a]pyrene normalized to 3-chlorofluoranthene suggested that waste combustion was the likely source of ClPAHs in summer and that vehicular emissions and coal burning were the likely sources of ClPAHs in winter. A heat map analysis estimated from the concentrations of individual compounds at each site suggested that there were three categories of sources at the sites: i) common sources of ClPAHs and PAHs that had moderate impacts, ii) common sources of ClPAHs and PAHs that had high impacts, and iii) specific sources of ClPAHs.

Occurrence, profiles, and toxic equivalents of chlorinated and brominated polycyclic aromatic hydrocarbons in E-waste open burning soils

We conducted this study to assess the occurrence, profiles, and toxicity of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) and brominated polycyclic aromatic hydrocarbons (Br-PAHs) in e-waste open burning soils (EOBS). In this study, concentrations of 15 PAHs, 26 Cl-PAHs and 14 Br-PAHs were analyzed in EOBS samples. We found that e-waste open burning is an important emission source of Cl-PAHs and Br-PAHs as well as PAHs. Concentrations of total Cl-PAHs and Br-PAHs in e-waste open burning soil samples ranged from 21 to 2800 ng/g and from 5.8 to 520 ng/g, respectively. Compared with previous studies, the mean of total Cl-PAH concentrations of the EOBS samples in this study was higher than that of electronic shredder waste, that of bottom ash, and comparable to fly ash from waste incinerators in Korea and Japan. The mean of total Br-PAH concentrations of the EOBS samples was generally three to four orders of magnitude higher than those in incinerator bottom ash and comparable to incinerator fly ash, although the number of Br-PAH congeners measured differed among studies. We also found that the Cl-PAH and Br-PAH profiles were similar among all e-waste open burning soil samples but differed from those in waste incinerator fly ash. The profiles and principal component analysis results suggested a unique mechanism of Cl-PAH and Br-PAH formation in EOBS. In addition, the Cl-PAHs and Br-PAHs showed high toxicities equivalent to PCDD/Fs measured in same EOBS samples when calculated based on their relative potencies to benzo[a]pyrene. Along with chlorinated and brominated dioxins and PAHs, Cl-PAHs and Br-PAHs are important environmental pollutants to investigate in EOBS.

Atmospheric chlorinated polycyclic aromatic hydrocarbons in East Asia

This study estimates atmospheric concentrations of chlorinated polycyclic aromatic hydrocarbons (ClPAHs) and polycyclic aromatic hydrocarbons (PAHs) in East Asia using a Gas Chromatograph with High Resolution Mass Spectrometer (GC-HRMS). ClPAHs are ubiquitously generated from PAHs through substitution, and some ClPAHs show higher aryl hydrocarbon receptor (AhR)-mediated activities than their parent PAHs. Atmospheric particles were collected using a high-volume air sampler equipped with a quartz-fiber filter. We determined the ClPAH concentrations of atmospheric particles collected in Japan (Sapporo, Sagamihara, Kanazawa, and Kitakyushu), Korea (Busan), and China (Beijing). The concentrations of ClPAHs were highest in the winter Beijing sample, where the total mean concentration was approximately 15–70 times higher than in the winter samples from Japan and Korea. The concentrations of Σ19ClPAHs and Σ9PAHs were significantly correlated in the Kanazawa and the Busan samples. This indicates that within those cities ClPAHs and PAHs share the same origin, implying direct chlorination of parent PAHs. Toxic equivalent concentrations (TEQs) of the total ClPAHs and PAHs were lowest in Kanazawa in the summer, reaching 1.18 and 2610fg-TEQm−3 respectively, and highest in Beijing in the winter, reaching 627 and 4240000fg-TEQm−3 respectively.

Diurnal variability of chlorinated polycyclic aromatic hydrocarbons in urban air, Japan

Concentrations of 3- to 5-ring chlorinated polycyclic aromatic hydrocarbons (ClPAHs) and corresponding PAHs were quantified in 3-h integrated air samples, taken serially over 3-day periods in December 2009 (winter) and August 2010 (summer) in the urban area of Shizuoka, Japan. Twenty species of targeted ClPAHs were detected in both gas and particle phases throughout each campaign. Mean concentrations of total ClPAHs in the winter and summer campaigns were 133 ± 53 pg m−3 and 32 ± 27 pg m−3, respectively. Throughout the campaigns, diurnal variations of total ClPAHs concentrations did not have periodic fluctuation such as decreasing in daytime and increasing in nighttime, observed in PAHs. However, the mean concentrations of particulate ClPAHs trended to be slightly higher in nighttime than in daytime, but not for gaseous ClPAHs. Significant correlations were observed between the concentrations of total ClPAHs and total PAHs in particulate phase, but not in gaseous phase. In addition, for particulate phase, there were significant correlations between the concentrations of individual ClPAHs and corresponding parent PAHs, nitrate, and chlorine in summer, but not in winter. Considering these behaviors of ClPAHs in the air, the emission sources could have features of as follows: (i) specific emission sources emitted both ClPAHs and PAHs in particulate phase could be present in the area; (ii) particulate ClPAHs could be more strongly influenced by local sources and photochemical reactions rather than by transboundary air pollution; (iii) the possible sources could be combustion processes included biomass and fossil fuels.

Airborne PM2.5/PM10-Associated Chlorinated Polycyclic Aromatic Hydrocarbons and their Parent Compounds in a Suburban Area in Shanghai, China

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) have been reported to be formed during incineration processes. Despite dioxin-like toxicities of ClPAHs, little is known on the occurrence of these chemicals in the environment. In this study, concentrations of 24-h airborne PM10 and PM2.5-associated ClPAHs and their corresponding parent PAHs were monitored from October 2011 to March 2012 in a suburban area in Shanghai, China. In addition, daytime and nighttime particle samples were collected for 7 days in April from the same sampling site. Twelve of twenty ClPAH congeners were found in PM10 and PM2.5 at concentrations ranging from 2.45 to 47.7 pg/m(3) with an average value of 12.3 pg/m(3) for PM10, and from 1.34 to 22.3 pg/m(3) with an average value of 9.06 pg/m(3) for PM2.5. Our results indicate that ClPAHs are ubiquitous in inhalable fine particles. The concentrations of ∑ClPAHs and specific congeners such as 9-ClPhe, 3-ClFlu, 1-ClPyr, 7-ClBaA, and 6-ClBaP in particles collected during nighttime were higher than those collected during daytime, which suggests not only diffusion of ClPAHs in air by atmospheric mixing but also photochemical degradation during daylight hours. Among the individual ClPAHs determined, 6-ClBaP, 1-ClPyr, and 9-ClPhe were the dominant compounds in PM10 and PM2.5. The percent composition of 6-ClBaP, 1-ClPyr, 7-ClBaA, and 3-ClFlu between PM10 and PM2.5 was similar. Significant positive correlations were found between concentrations of ClPAHs and their corresponding parent PAHs, particle mass, and total organic carbon (organic carbon plus elemental carbon), indicating that ClPAHs are sorbed onto carbonaceous matter of PM. Concentrations of parent PAHs predicted by multiple linear regression models with PM mass, total organic carbon, temperature, and relative humidity as variables reflected the measured concentrations with a strong coefficient of determination of 0.917 and 0.946 for PM10 and PM2.5, respectively. However, the models generated to predict ClPAH concentrations in PM did not yield satisfactory results, which suggested the differences in physical-chemical properties and formation processes between ClPAHs and their corresponding parent PAHs. 7-ClBaA and 6-ClBaP collectively accounted for the preponderance of the total dioxin-like TEQ concentrations of ClPAHs (TEQClPAH) in PM samples. Exposure to toxic compounds such as ClPAHs and PAHs present in PM2.5 can be related to adverse health outcomes in people.

Occurrence of chlorinated and brominated polycyclic aromatic hydrocarbons in surface sediments in Shenzhen, South China and its relationship to urbanization

One hundred and fourteen surface sediments were collected from the Maozhou River Watershed in Shenzhen, China from December 2009 to January 2010. Three individual chlorinated polycyclic aromatic hydrocarbons (ClPAHs), six individual brominated polycyclic aromatic hydrocarbons (BrPAHs), and five corresponding parent polycyclic aromatic hydrocarbons (PAHs) were determined. The concentration of 9-chlorophenanthrene was the highest ranging from 0.51-289 ng g(-1) (average, 16.5 ng g(-1)). For BrPAHs, the concentration of 2-bromofluorene was the highest ranging from 0.31-266 ng g(-1) (average, 35.3 ng g(-1)). No correlation was observed between the concentrations of ClPAHs and parent PAHs in surface sediments. In addition, there was no correlation between 1-bromopyrene, 7-bromobenz(a)anthracene and 9,10-dibromoanthracene, and corresponding parent PAHs. However, a significant correlation was found between 9-bromophenanthrene and phenanthrene (p < 0.01), between 9-bromoanthracene and anthracene (p < 0.05), and between 2-bromofluorene and fluorene (p < 0.05). Six fly ash samples collected from one of the municipal domestic waste incineration plants in Shenzhen were also analyzed for source identification. The concentration of 7-bromobenz(a)anthracene was the highest, ranging from 3.21-4.08 ng g(-1). In addition, 2-bromofluorene was not detected in all the fly ash samples. No correlation was found between the concentrations of Cl-/BrPAHs and corresponding parent PAHs in fly ashes. We also examined the relationship between the levels of Cl-/BrPAHs in surface sediments and the urbanization process. Our results suggested the levels of individual Cl-/BrPAHs congeners presented a similar increasing trend with the increasing urbanization level.

Chlorinated and Parent Polycyclic Aromatic Hydrocarbons in Environmental Samples from an Electronic Waste Recycling Facility and a Chemical Industrial Complex in China

Chlorinated polycyclic aromatic hydrocarbons (CIPAHs) are a class of halogenated contaminants found in the urban atmosphere; they have toxic potential similar to that of dioxins. Information on the sources of CIPAHs is limited. In this study, concentrations of 20 CIPAHs and 16 parent PAHs were measured in electronic wastes, workshop-floor dust, vegetation, and surface soil collected from the vicinity of an electronic waste (e-waste) recycling facility and in surface soil from a chemical industrial complex (comprising a coke-oven plant, a coal-fired power plant, and a chlor-alkali plant), and agricultural areas in central and eastern China. High concentrations of SigmaCIPAHs were found in floor dust (mean, 103 ng/g dry wt), followed in order of decreasing concentration by leaves (87.5 ng/g drywt), electronic shredder waste (59.1 ng/g dry wt), and soil (26.8 ng/g dry wt) from an e-waste recycling facility in Taizhou. The mean concentration of SigmaCIPAHs in soil from the chemical industrial complex (88 ng/g dry wt) was approximately 3-fold higher than the concentration in soil from e-waste recycling facilities. The soils from e-waste sites and industrial areas contained mean concentrations of SigmaCIPAHs 2 to 3 orders of magnitude higher than the concentrations in agricultural soils (ND-0.76 ng/g), suggesting that e-waste recycling and chlorine-chemical industries are potential emission sources of CIPAHs. The profiles of CIPAHs in soil and dust were similar to a profile that has been reported previously for fly ash from municipal solid waste incinerators (6-CIBaP was the predominant compound), but the profiles in vegetation and electronic shredder waste were different from those found in fly ash. Concentrations of 16 parent PAHs were high (150-49,700 ng/g) in samples collected from the e-waste recycling facility. Significant correlation between SigmaCIPAH and SigmaPAH concentrations suggests that direct chlorination of parent PAHs is the major pathway of formation of CIPAHs during e-waste recycling operations. Dioxin-like toxic equivalency quotients (TEQs) for CIPAHs and PAHs in samples were calculated on the basis of relative potencies reported for CIPAHs and PAHs. The highest mean TEQ concentrations of CIPAHs (518 pg-TEQ/g) were found for workshop-floor dust, followed by leaves (361 pg-TEQ/g), electronic shredder waste (308 pg-TEQ/g), soil from the chemical industrial complex (146 pg-TEQ/g), and soil from the sites of the e-waste recycling facility (92.3 pg-TEQ/g). With one exception, the floor dust samples, the TEQ concentrations of CIPAHs found in multiple environmental matrices in this study were higher than the TEQ concentrations of PCDD/Fs in the same samples reported in our earlier study.

Chlorinated Polycyclic Aromatic Hydrocarbons in the Atmosphere: Seasonal Levels, Gas-Particle Partitioning, and Origin

Ambient concentrations of 26 chlorinated polycyclic aromatic hydrocarbons (CIPAHs) with 2- to 5-rings were investigated in a Japanese urban city from December 2004 to December 2005. All the targeted CIPAHs were detected in either the gaseous or particulate phase. During the study, the ambient (gaseous + particulate) concentration of total CIPAH ranged from 18 to 330 pg m(-3). The concentrations of gaseous CIPAHs tended to be 2 approximately 100 times higher than those of particulate CIPAHs. A seasonal variability of both gaseous and particulate CIPAH concentrations was observed, with higher concentrations in winter than in summer. A compositional analysis also showed a characteristic trend: relatively low molecular weight CIPAHs dominated in warmer seasons, and high molecular weight CIPAHs dominated in colder seasons. For some CIPAHs, temperature dependence of gas-phase concentrations was statistically significant (p < 0.05), and temperature accounted for 27-63% of the variability in their concentrations. The natural logarithm of total concentrations of particulate CIPAHs were significantly correlated (p < 0.05) with the reciprocal mean temperatures, but not for gaseous CIPAHs, suggesting that there are differences of the sources and ambient fates between gaseous and particulate CIPAHs. Back trajectory analyses suggested that air masses, originating from China, were associated with the highest CIPAH concentrations.