Hazardous implications of halogenated polycyclic aromatic hydrocarbons in feedstuff: Congener specificity and toxic levels in feed ingredients and feeds.

Studies have shown that halogenated polycyclic aromatic hydrocarbons (HPAHs), including chlorinated (ClPAHs) and brominated PAHs (BrPAHs), could be hazardous pollutants due to their pervasive occurrence in the environment. However, their accumulation properties and toxic potentials in animal feedstuffs remain unclear. This study investigated 75 congeners of parent PAHs, ClPAHs, and BrPAHs in animal-based feed ingredients and fish and swine feeds in Japan using a GC/Orbitrap MS system. The total parent PAHs ranged from below the method detection limit (

Voyaging of halogenated polycyclic aromatic hydrocarbons, an emerging group of pollutants, on micro-mesoplastics in the marine environment.

The limited existing research on the accumulation of hazardous chlorinated and brominated polycyclic aromatic hydrocarbons (ClPAHs and BrPAHs) in micro-mesoplastics (mMPs) motivated this investigation. We collected mMPs from the coastal environments of Sri Lanka and Japan. Out of 75 target compounds analyzed, 61 were detected, with total parent PAH concentrations reaching 16,300 and 1770 ng/g plastic in Sri Lanka and Japan, respectively. The total parent PAH concentrations in mMPs from the southern Sri Lankan coastline were relatively higher than those from the eastern coastline. Phenanthrene and naphthalene were the dominant parent PAH congeners in most mMP samples. Chlorinated pyrenes and brominated naphthalene were predominant among halogenated PAHs. The estimated toxic equivalency quotient (TEQ) ranged from 0.67 to 1057 ng-TEQ/g plastic, with the highest levels observed in polystyrene (PS) particles from the southern Sri Lankan coast. Benzo[a]pyrene and dibenzo[a,h]anthracene exhibited elevated TEQ for parent PAHs, whereas dichloropyrene, and dibromopyrene represented the highest TEQs for ClPAHs and BrPAHs, respectively. The data evidenced that several HPAH congeners can increase the PAH-like toxicity (∼86%) in mMPs. This study provides insights into the accumulation of parent and halogenated PAHs in mMPs, highlighting their potential combined implications in marine and terrestrial ecosystems.

Approaches to the source evaluation of chlorinated polycyclic aromatic hydrocarbons in fine particles.

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) have been recognized as novel hazardous pollutants; however, the dominant sources remain unclear. This study investigates the occurrences of ClPAHs in five stages of size-segregated particles collected from an urban site and evaluates the sources and factors affecting the concentrations using organic and inorganic source tracers. ClPAHs are the most frequently detected in the finest particle fraction (less than 1.1 µm; PM1.1), similar to polycyclic aromatic hydrocarbons (PAHs), hopanes, and levoglucosan (LEV). The concentrations of total ClPAHs in PM1.1 shows a significant correlation (p < 0.05) with those of total PAHs and specific hopanes but not to LEV and biogenic fatty acids; this suggests that ClPAHs dominantly originate from industrial activities and vehicular emissions. Heatmap analysis, including source tracers, is used to categorize the possible sources of ClPAHs into three types: ClPAH-specific sources, local industrial activities and vehicular emissions, and remote industrial activities. Furthermore, correlation network analysis is used to clarify the relationships between the pollutants.

Comparative Study on the Distribution of Essential, Non-Essential Toxic, and Other Elements across Trophic Levels in Various Edible Aquatic Organisms in Sri Lanka and Dietary Human Risk Assessment.

Thirty-six elements are categorized as essential but toxic in excess amount (EBTEs), non-essential toxic (NETs), and Other in 29 different edible aquatic species dwelling in offshore pelagic, and coastal and estuarine (CE) ecosystems were investigated in Sri Lanka. Elements were analyzed using an energy-dispersive X-ray fluorescence (EDXRF) spectrometer, and an NIC MA-3000 Mercury Analyzer. EBTEs showed a negative relationship, whereas NETs showed a positive relationship between the concentration (mg/kg wet weight) and trophic levels in both ecosystems. EBTEs showed trophic dilution, whereas NETs showed trophic magnification. Some elements in a few organisms exceeded the maximum allowable limit which is safe for human consumption. There was a positive relationship (R2 = 0.85) between the concentration of mercury and body weight of yellowfin tuna (YFT). For the widely consumed YFT, the calculated hazard index (HI) for the non-carcinogenic health and exposure daily intake of NETs for adults were 0.27 and 9.38 × 10-5 mg/kg bw/day, respectively. The estimated provisional tolerable weekly intake (PTWI) (µg/kg bw/w) was 0.47 for arsenic and 0.05 for antimony, cadmium, mercury, and lead. The HI and PTWI values were below the recommended limits; thus, consumption of YFT does not pose any health risk for Sri Lankan adults.

Presence of Halogenated Polycyclic Aromatic Hydrocarbons in Milk Powder and the Consequence to Human Health.

Recent reports of the presence of halogenated derivatives of polycyclic aromatic hydrocarbons (PAHs) in human foods of animal origin, such as chlorinated (ClPAHs) and brominated (BrPAHs) PAHs, suggest that their contamination in dairy products may also pose a human health risk. This study used GC/Orbitrap-MS to analyze 75 congeners of halogenated PAHs and parent PAHs in milk and creaming powder samples commonly found in grocery stores in Sri Lanka and Japan. Our investigation revealed a total of 31 halogenated PAHs (HPAHs) in the samples. The concentrations of total parent PAHs in the samples from Sri Lanka and Japan ranged from not detected (n.d.)−0.13 and <0.001−16 ng/g dry weight (d.w.). Total ClPAHs and BrPAHs in the samples ranged from 0.01−3.35 and 1.20−5.15 ng/g (d.w.) for Sri Lanka, and 0.04−2.54 and n.d.−2.03 ng/g d.w. for Japan, respectively. The ClPAHs were dominated by chlorinated-pyrene, -fluoranthene, and -benzo[a]pyrene congeners, whereas the BrPAHs were dominated by brominated-naphthalene and -pyrene congeners. The toxic assessment estimated based on the intake of toxic equivalency quotients (TEQs) for target compounds in milk powders revealed that HPAHs might contribute additively to the PAHs-associated health risk to humans, indicating that more research is needed.

Occurrences and Potential Sources of Halogenated Polycyclic Aromatic Hydrocarbons Associated with PM2.5 in Mumbai, India.

Occurrences of chlorinated and brominated polycyclic aromatic hydrocarbons (ClPAHs and BrPAHs, respectively) in fine aerosol particulate matter <2.5 µm in diameter were investigated in urban and suburban sites in Mumbai, India; and the possible sources from association with indicators, such as hopanes, steranes, and trace elements are discussed. The mean concentrations of total ClPAHs and BrPAHs were 0.54 and 0.25 ng/m3 in the urban site and 0.16 and 0.02 ng/m3 in the suburban site during the campaign, respectively. The variations in total Cl-/BrPAH concentrations showed a similar trend between the urban and suburban sites, whereas the composition profiles varied in each air sample. The relationships between the concentrations among individual compounds in the urban site suggest that dominant sources of Cl-/BrPAHs could be common to PAHs but not in the suburban site. Principal component analysis using the data set of certain compounds showed that Cl-/BrPAH concentrations in urban and suburban sites are occasionally driven by specific sources of either coal combustion or traffic emissions. In contrast, most air samples during the campaign could be attributed to a mix of those sources. Environ Toxicol Chem 2022;41:312-320. © 2021 SETAC.

Application of gas chromatographic retention times to determine physicochemical properties of nitrated, oxygenated, and parent polycyclic aromatic hydrocarbons.

Nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs) are receiving attention because of their high toxicity compared with parent PAHs. However, the experimental data of their physicochemical properties has been limited. This study proposed the gas chromatographic retention time (GC-RT) technique as an effective alternative one to determine octanol-air partition coefficients (KOA) and sub-cooled liquid vapor pressures (PL) for 11 NPAHs, 10 OPAHs, and 19 parent PAHs. The slopes and intercepts of the linear regressions between temperature versus KOA and PL were provided and can be used to estimate KOA and PL for the 40 targeted compounds at any temperature. The internal energies of phase transfer (ΔUOA) and enthalpies of vaporization (ΔHL) for all targeted compounds were also calculated using the GC-RT technique. High-molecular-weight compounds may release or absorb higher heat energy to transform between different phases. NPAHs and OPAHs had a non-ideal solution behavior with activity in octanol (γoct) in the range of 19-53 and 18-1,078, respectively, which is larger than the unity threshold. A comparison among four groups of PAH derivatives showed that a functional group (nitro-, oxygen-, chloro-, and bromo-) in PAH derivatives increased γoct for corresponding parent PAHs by tens (mono-group) to hundreds of times (di-group). This study suggests that the GC-RT method is applicable for indirectly measuring the physicochemical properties of various groups of organic compounds.

Halogenated polycyclic aromatic hydrocarbons in edible aquatic species of two Asian countries: Congener profiles, biomagnification, and human risk assessment.

Seventy-five contaminants including chlorinated/brominated/parent polycyclic aromatic hydrocarbons (Cl/Br/PAHs) were investigated in 29 edible aquatic species from the Indian Ocean near Sri Lanka and 10 species from the Pacific Ocean near Japan. Concentrations of total ClPAHs and BrPAHs in the samples were 2.6-57 and 0.30-9.5 ng/g-dry weight from the Indian Ocean, and 0.35-18 and 0.03-3.3 ng/g-dry weight from the Pacific Ocean, respectively. Comparing the profiles of Cl/BrPAHs among the samples, congeners of chlorinated and brominated pyrene were predominant components and enhanced the potential for biomagnification in the sample from the off-shore pelagic environment in the Indian Ocean. The incremental lifetime cancer risks estimated by intake of the targets in consuming aquatic organisms showed that approximately one-third of studied organisms exceeded the acceptable risk level for Sri Lankans.

The association between antimicrobials and the antimicrobial-resistant phenotypes and resistance genes of Escherichia coli isolated from hospital wastewaters and adjacent surface waters in Sri Lanka.

The presence of antimicrobials, antimicrobial-resistant bacteria (ARB), and the associated antimicrobial resistance genes (ARGs) in the environment is a global health concern. In this study, the concentrations of 25 antimicrobials, the resistance of Escherichia coli (E. coli) strains in response to the selection pressure imposed by 15 antimicrobials, and enrichment of 20 ARGs in E. coli isolated from hospital wastewaters and surface waters were investigated from 2016 to 2018. In hospital wastewaters, clarithromycin was detected at the highest concentration followed by sulfamethoxazole and sulfapyridine. Approximately 80% of the E. coli isolates were resistant, while 14% of the isolates exhibited intermediate resistance against the tested antimicrobial agents. Approximately 61% of the examined isolates were categorized as multidrug-resistant bacteria. The overall abundance of phenotypes that were resistant toward drugs was in the following order: ß-lactams, tetracycline, quinolones, sulfamethoxazole/trimethoprim, aminoglycosides, and chloramphenicol. The data showed that the E. coli isolates frequently harbored blaTEM, blaCTX-M, tetA, qnrS, and sul2. These results indicated that personal care products were significantly associated with the presence of several resistant phenotypes and resistance genes, implying their role in co-association with multidrug resistance. Statistical analysis also indicated a disparity specific to the site, treatment, and year in the data describing the prevalence of ARB and ARGs and their release into downstream waters. This study provides novel insights into the abundance of antimicrobial, ARB and ARGs in Sri Lanka, and could further offer invaluable information that can be integrated into global antimicrobial resistance databases.

Seasonal variation and gas/particle partitioning of atmospheric halogenated polycyclic aromatic hydrocarbons and the effects of meteorological conditions in Ulsan, South Korea.

Atmospheric halogenated polycyclic aromatic hydrocarbons (Halo-PAHs) and parent PAHs were monitored in Ulsan, South Korea for one year (January‒December 2015) to investigate their seasonal patterns, gas/particle partitioning behavior, and the impact of meteorological conditions. The mean concentrations of 24 chlorinated PAHs, 11 brominated PAHs, and 13 parent PAHs in the gaseous and particulate phases were 8.64 and 9.64 pg/m3, 11.6 and 1.62 pg/m3, and 2.17 and 2.40 ng/m3, respectively. Winter had the highest ClPAH and PAH levels, with significant contributions from poly-chlorine groups and high-molecular-weight compounds. However, BrPAHs showed reverse patterns with the highest concentration in summer and the dominant gaseous fraction throughout the year. This finding could be explained by the strong local sources of BrPAHs, related to automobile and petrochemical industries. In contrast, the effects of the temperature inversion layer and atmospheric transport from the outside of Ulsan were more apparent for ClPAHs and PAHs, particularly in winter and spring. Regarding gas/particle partitioning, Halo-PAHs exhibited different seasonal behaviors from those of parent PAHs. The sorption pathway of Halo-PAHs seemed to shift from absorption as the sole dominant mechanism in winter and spring to both adsorption and absorption in summer and fall, while both partitioning mechanisms contributed equally for parent PAHs during the entire year. This study implies that Halo-PAHs and parent PAHs might not share the same atmospheric behavior, possibly due to different characteristics in atmospheric reactions with other chemicals and particle-size distribution. However, there have been limited studies about the formation of Halo-PAHs and their physicochemical properties; hence, further in-depth investigations are of vital importance.

Accumulation of halogenated polycyclic aromatic hydrocarbons by different tuna species, determined by high-resolution gas chromatography Orbitrap mass spectrometry.

Halogenated polycyclic aromatic hydrocarbon (HPAH) concentrations in tissues from three tuna species Thunnus albacares (yellowfin tuna), Katsuwonus pelamis (skipjack tuna), and Auxis thazard (frigate tuna) were determined by high-resolution gas chromatography Orbitrap mass spectrometry. The tuna samples were collected from the Indian Ocean. The instrument conditions gave high mass accuracy at 0.9 m/z isolation width of the mass filter and a mass error of <±1.0 ppm for many HPAHs. A total of 29 of the 30 targets chlorinated PAHs (ClPAHs) and 20 of the 21 targets brominated PAHs (BrPAHs) were detected in the tuna muscle samples. The mean total ClPAH, BrPAH and PAH concentrations for tuna were 127.2, 156.6 and 682.8 ng/g lipid weight, respectively. The mean total ClPAH and BrPAH concentrations (ng/g lipid weight) in the tuna were considerably lower than that of PAH concentrations. The mean total ClPAH, BrPAH and PAH concentrations in T. albacares respectively were 185.8, 249.2 and 784.1 ng/g lipid weight, irrespective of the body sizes. The mean total ClPAH, BrPAH and PAH concentrations in K. pelamis respectively were 45.1, 24.8 and 555.6 ng/g lipid weight. The mean total ClPAH, BrPAH and PAH concentrations in A. thazard respectively were 34.09, 4.73 and 433.24 ng/g lipid weight. The total ClPAH concentrations and body weights significantly positively correlated for T. albacares. The mean total ClPAH concentration in white muscles was significantly higher (p < 0.05) for large than for small T. albacares. This suggests ClPAHs could bioaccumulate in T. albacares, possibly because they are poorly metabolized. The chlorinated phenanthrene and pyrene concentrations indicated tuna accumulate these compounds increasingly effectively as the tuna grow. This was the first time large numbers of HPAHs were found in biological samples. HPAHs may adversely affect the health of humans consuming tuna.

Passive air sampling of halogenated polycyclic aromatic hydrocarbons in the largest industrial city in Korea: Spatial distributions and source identification.

Some halogenated polycyclic aromatic hydrocarbons (Halo-PAHs) are known to be more toxic than their corresponding parent PAHs, but studies on Halo-PAHs have been somewhat limited. In this study, passive air samplers were used to monitor Halo-PAH and PAH contamination at 20 sampling sites in Ulsan, one of the largest industrial cities in South Korea. The mean concentrations of Σ24 ClPAHs, Σ11 BrPAHs, and Σ13 PAHs were 207 pg/m3, 84 pg/m3, and 26 ng/m3, respectively. Industrial areas displayed higher concentrations of both Halo-PAHs and PAHs than urban and rural areas. Strong correlations between energetically unfavorable Halo-PAHs and their corresponding parent PAHs suggest that the main formation mechanism of Halo-PAHs is not direct halogenation of PAHs. Low molecular weight Halo-PAHs with one halogen atom and their parent PAHs were dominant. The profiles of ClPAHs and BrPAHs in petrochemical, automobile, shipbuilding, and non-ferrous industrial complexes were distinguished. The toxicity equivalency quantities (TEQs) of ClPAHs, BrPAHs, and PAHs at the industrial sites also showed the highest values of 4.2, 0.5, and 18.3 pg-TEQ/m3, respectively, reflecting the high toxicity of Halo-PAHs. To the best of our knowledge, this is the first study reporting atmospheric levels of both ClPAHs and BrPAHs using passive air samplers.

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.

Spatial distribution and exposure risks of ambient chlorinated polycyclic aromatic hydrocarbons in Tokyo Bay area and network approach to source impacts.

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) receive increasing attention as hazardous pollutants in terms of the high environmental persistence and toxicities. Ambient concentrations of 24 ClPAHs and 24 PAHs were investigated at 14 sites in the Tokyo Bay area of Japan. Twelve of 18 ClPAH species were detected in air samples, in spite of small sampling volumes. Mean concentrations of total PAHs in gas and particle phases were 5400 and 1400 pg/m3, and mean concentrations of total ClPAHs in gas and particle phases were 40 and 14 pg/m3, respectively. The spatial distributions of both total ClPAH and PAH concentrations indicated heavy pollution at sites in industrial activity areas. Principal component analysis suggested that the dominant sources of gaseous and particulate ClPAHs differed substantially from each other. In particular, gaseous ClPAHs could be produced by specific sources different from those of particulate ClPAHs. However, the dominant sources of particulate ClPAHs could be the same as those of particulate PAHs, including industrial activities such as steel and gas-production plants and natural gas-fired power plants. The influences of spatial relationships among sampling sites were represented using a network analysis. The constructed network showed that ambient ClPAHs and PAHs were dominated by local rather than regional pollution, because there were weaker relationships among nearby sites. Finally, exposure risks for ClPAHs were dominated by 7-chlorobenz[a]anthracene, followed by 9-chlorophenanthrene and 6-chlorobenzo[a]pyrene, and total risk was ∼1/200 that of PAHs.

Chlorinated polycyclic aromatic hydrocarbons in surface sediment from Maowei Sea, Guangxi, China: occurrence, distribution, and source apportionment.

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) with three to five aromatic rings have been documented to ubiquitously occur in environmental matrices. In this study, residual concentrations and profiles of 20 individual ClPAHs were determined in 35 surface sediment samples from Maowei Sea, a semi-enclosed shallow inland bay located in the northwestern part of South China Sea. The concentrations of ΣClPAHs in sediment ranged from 313 to 9650 pg/g dw with a detection rate of 43-100%. Of the individual ClPAH congeners, 9-ClPhe was the most abundant in Maowei Sea with the concentrations that ranged from 99.9 to 3610 pg/g dw (mean 1120 pg/g dw). High-molecular-weight ClPAH congeners (four to five rings) were predominant in sediments from sampling locations near a petrochemical industrial complex, whereas low-molecular-weight ClPAH congeners (three rings) were predominant in sediments from estuarine and mangrove locations. A positive matrix factorization (PMF) model in combination with dioxin-like toxic equivalency quotient (TEQ) results was used to apportion sources of ClPAHs. Vehicular emission, combustion/chemical industrial processes, and two other unknown sources accounted for 40.1, 25.5, 20.8, and 13.6%, respectively, of ClPAH sources in sediment; their contribution to TEQs in sediments were 24.2, 40.5, 19.3, and 16.0%, respectively. Further investigations are needed to elucidate potential sources and ecological risks of ClPAHs in sediments.

Size Distribution of Chlorinated Polycyclic Aromatic Hydrocarbons in Atmospheric Particles.

The particle size distribution of chlorinated polycyclic aromatic hydrocarbons (ClPAHs) in particulate matter (PM) in Japan is examined for the first time. PM was collected using a PM0.1 air sampler with a six-stage filter. PM was collected in October 2014 and January 2015 to observe potential seasonal variation in the atmospheric behavior and size of PM, including polycyclic aromatic hydrocarbons (PAHs) and ClPAHs. We found that the concentration of PAHs and ClPAHs between 0.5-1.0 µm and 1.0-2.5 µm markedly increase in January (i.e., the winter season). Among the ClPAHs, 1-ClPyrene and 6-ClBenzo[a]Pyrene were the most commonly occurring compounds; further, approximately 15% of ClPAHs were in the nanoparticle phase (<0.1 µm). The relatively high presence of nanoparticles is a potential human health concern because these particles can easily be deposited in the lung periphery. Lastly, we evaluated the aryl hydrocarbon receptor (AhR) ligand activity of PM extracts in each size fraction. The result indicates that PM < 2.5 µm has the strong AhR ligand activity.

Source apportionment of chlorinated polycyclic aromatic hydrocarbons associated with ambient particles in a Japanese megacity.

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) are novel species of environmental contaminants whose possible sources remain unclear. The occurrence of ClPAHs within total suspended particles (TSP) is compared with weekly air samples at two sites of differing characteristics (industrial and residential) in the megacity of Nagoya, Japan. Samples were collected over 12 months during 2011-2012. All 24 species of targeted ClPAHs were detected at both industrial and residential sites, where mean concentrations of total ClPAHs in TSP were 20.7 and 14.1 pg/m3, respectively. High concentrations at the industrial site were frequently observed during winter, suggesting potent seasonal ClPAH sources there. Positive matrix factorization modeling of particulate ClPAH source identification and apportioning were conducted for datasets including ClPAHs, PAHs, elements and ions, plus elemental carbons in TSP. Eight factors were identified as possible ClPAH sources, with estimates that the dominant one was a specific source of ClPAH emission (31%), followed by traffic (23%), photodegradable and semi-volatile species (18%), long-range transport (11%), and industry and oil combustion (10%). Source contributions of ClPAHs differed substantially from those of PAHs. This suggests specific and/or potent ClPAH sources in the local area, and that the production mechanisms between ClPAHs and PAHs are substantially different.

Spatio-temporal distribution, source, and genotoxic potential of polycyclic aromatic hydrocarbons in estuarine and riverine sediments from southern India.

In order to categorize the distribution, source, and effects of polycyclic aromatic hydrocarbons (PAHs) in aquatic systems of southern India, chemical and toxicological analyses were performed on surface and core sediments, collected from Adyar river, Cooum river, Ennore estuary, and Pulicat lake near Chennai city. The total PAH concentration in surface sediment ranged from 13 to 31,425ng/g with a mean value of 4320ng/g; the concentration was markedly higher in Cooum river compared to that at other sites. The historical PAH dissemination in core samples in the Cooum river, Ennore estuary, and Pulicat lake ranged from 30 to 31,425ng/g, from 8.6 to 910ng/g, and from 62 to 546ng/g, respectively. Surface sediments were predominantly contaminated with low molecular weight (LMW) PAHs. Historical profiles suggest that PAH contamination in the area is now greater than it had been in the past. PAH accumulation in Pulicat lake was distinct from that at other locations where high molecular weight (HMW) PAHs were predominant. DNA damage in HepG2 cells treated with sediment extracts from different locations showed a good correlation with their respective total PAH levels. Statistical analysis revealed that 3-ring and 4-ring PAHs may synergistically contribute to the genotoxic potency compared to others in sediments. The study also showed that a majority of PAHs in the study area indicated a petrogenic origin. Based on the enrichment and toxicological assessment of PAHs in sediments, Cooum river was shown to suffer the highest biological impairment among the studied water bodies.

Local and seasonal variations in concentrations of chlorinated polycyclic aromatic hydrocarbons associated with particles in a Japanese megacity.

Concentrations of particle-bound polycyclic aromatic hydrocarbons (PAHs) and chlorinated PAHs (ClPAHs) were measured in different seasons at five sampling stations in Nagoya, a Japanese megacity. The annual mean total ClPAH and total PAH concentrations were 43.3-92.6pg/m(3) and 5200-8570pg/m(3), respectively. The concentrations of total ClPAHs were significantly variable than those of total PAHs, and both total concentrations through the seasons did not significantly correlate at any of the stations. Principal component analysis was used to characterize the ClPAH sources, resulted that ClPAHs were found to be associated with the sources of high-molecular-weight PAHs in the warmer seasons and of low-molecular-weight PAHs in the colder seasons. These findings suggest that principal sources of particle-bound ClPAHs are present in the local area, and change in the seasons. Toxic equivalent (TEQ) concentrations were estimated to assess the risks associated with exposure to ClPAHs in air. The TEQ concentrations in the samples were 0.05-0.32pg-TEQ/m(3). The TEQ concentrations in summer were approximately half the TEQ concentrations in the other seasons at all of the stations.

Photochlorination of Polycyclic Aromatic Hydrocarbons in Acidic Brine Solution.

The potential for the formation of chlorinated polycyclic aromatic hydrocarbons via photochlorination of PAHs has been investigated in milli-Q water/synthetic water containing NaCl and PAHs with either UV or visible light. The photochlorination of pyrene occurred under acidic conditions in the presence of both UV and visible light, resulting in 1-chloropyrene as the main product. Benzo[a]pyrene yielded 6-chlorobenzo[a]pyrene following visible light irradiation; however the reaction was dependent upon solution pH. The photochlorination of PAHs was proposed to proceed via a consecutive reaction model. The rate constants associated with the photochlorination and photodecay processes were determined with the observed and theoretical values displaying similar trends, whereas the observed values were approximately 50-1000 times lower than the theoretical values. The lower observed values could be due to undergo photodecay rather than photochlorination of PAHs. Therefore, as photochlorination of PAHs appears to be significantly affected by solution pH, this information may allow for minimizing the impact on the environment.