Photolysis of polycyclic aromatic hydrocarbons in water

We have studied the photochemical reactions of eight polycyclic aromatics and heteroatom analogs (PAHs). Quantum yields and rate constants in sunlight and at single wavelengths were measured and half-lives of the PAHs as a function of the time of year were calculated. Product studies and the effect of humic acid and oxygen on rates are reported.     

Comparison of drinking water mutagenicity with leaching of polycyclic aromatic hydrocarbons from water distribution pipes

The primary objectives of this study were to examine the changes in concentration of six polycyclic aromatic hydrocarbons (PAH) and the possibility of changes in mutagenic potential of treated waters as a result of their passage through commonly used distribution pipes. With the exception of the finished water taken at one treatment plant in which the total concentration of the six PAH was 138.5 parts per trillion (ppt), the total initial concentration in all other treated water ranged from 0 to 13.4 ppt. The corresponding total PAH concentration in water after passage through the distribution pipes varied from 0 to 61.6 ppt. This demonstrated that PAH concentration in water can increase as a result of their passage through coated distribution pipes. Mutagenic activity was also detected in many of the treated water samples, however, the levels of this activity did not correlate with either the transit of water through the distribution system or the levels of PAH in the water. There was some evidence to indicate that the water treatment process itself may have contributed to the mutagenicity observed in the finished water.     

Volatilization of polycyclic aromatic hydrocarbons from coal-tar-sealed pavement

The effects of the herbicide atrazine on the gill of the freshwater fish Prochilodus lineatus were evaluated after exposure of fish to 2, 10 and 25 μg L⁻¹ atrazine during 48 h (acute exposure) and 14 d (subchronic exposure). Ions and osmolality were measured in plasma and gill samples were taken to determine the Na⁺/K⁺-ATPase (NKA) and carbonic anhydrase (CA) activities and for morphological analysis. Plasma osmolality and Na⁺ and Cl⁻ ions changed depending on atrazine concentration, but atrazine exposure had no effect on the Na⁺/Cl⁻ ratio. NKA activity did not change after atrazine exposure, but CA activity decreased in fish exposed to 25 μg L⁻¹ for 14 d. Gill MRC density decreased after acute exposure but did not change in fish exposed to the subchronic treatment. The MRC density at the epithelial surface increased in fish exposed to 25 μg L⁻¹, and the MRC fractional area (MRCFA) increased in fish exposed to 10 μg L⁻¹. The changes in MRCs provide evidence of morphological adjustments to maintain ionic homeostasis in spite of the inhibition of CA activity at the highest atrazine concentration.     

Desorption of polycyclic aromatic hydrocarbons from field-contaminated soil to a two-dimensional hydrophobic surface before and after bioremediation

This study investigated environmental distributions and production mechanisms of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) in the sediments from some tidal flats located in Asia. Cl-PAHs were found in sediments taken from Arao tidal flat, Kikuchigawa River and Shirakawa River. The range of ∑Cl-PAHs was from 25.5 to 483 pg g⁻¹ for Kikuchigawa River and Arao tidal flat, respectively.Concentrations of PAHs and Cl-PAHs showed no significant correlations (r = 0.134). This result suggests that the origins of these compounds differ. In the identified Cl-PAH isomers, the most abundant Cl-PAH isomer was 9,10-dichloroanthracene (9,10-di-Cl-ANT) in the three sites. In general, concentrations of Cl-ANTs in the coastal environment are about 3-5 orders of magnitude lower than those of anthracene (ANT). However, concentration ratios between Cl-ANTs and ANT (Cl-ANTs/ANT) in the sediments ranged from 4.1% to 24.6%. This result indicated that Cl-PAHs were not generated under industrial processes but the high concentration ratios have resulted from the contribution of photochemical production of Cl-ANTs in the sediments because ANT is known to have high photochemical reactivity.For examining this phenomenon, ANT adsorbed onto glass beads was irradiated with UV under the mimicked field conditions of tidal flats. As a result, it was noticed that, while chlorinated derivatives were negligible in a light-controlled group, production of 2-Cl-ANT, 9-Cl-ANT and 9,10-diCl-ANT on the irradiated surface were found in this study. These results suggest that photochemical reaction of PAHs can be a potential source of the occurrence of Cl-PAHs in the coastal environment.     

Distribution of polycyclic aromatic hydrocarbons in water and surface sediments from Daya Bay,China

Marine culture is thriving in China and represents a major component of the regional economy in coastal zones, yet the environmental quality of many of those areas has never been studied. This paper attempts to investigate the quality status of Daya Bay, a key aquaculture area in China. The levels of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in water and sediment samples of the bay. The total concentrations of 16 PAHs varied from 4228 to 29325 ng l(-1) in water, and from 115 to 1134 ng g(-1) dry weight in sediments. In comparison to many other marine systems studied, the PAH levels in Daya Bay waters were relatively high, and at six sites they were sufficiently high (> 10 microg l (-1)) to cause acute toxicity. The PAH composition pattern in sediments suggest dominance by medium to high molecular weight compounds, and the ratio of certain related PAHs indicate important pyrolytic and petrogenic sources. Further analysis showed that the distribution coefficient (KD) increased with the particular organic carbon content of sediments, consistent with the PAH partition theory. The organic carbon normalised distribution coefficient (K(oc)) also increased with the compounds' octanol/water partition coefficient (K(ow)), confirming the potential applicability of the linear free energy relationships in the modelling and prediction of PAH behaviour in marine environments.     

紫外光(UV)光解油田采出水中多环芳烃

为了探讨紫外光光解人工模拟油田采出水中多环芳烃的降解效率,利用自制反应装置对油田采出水中多环芳烃(PAHs)的紫外光光解做了一个初步研究。研究结果证明,紫外光光解对油田采出水中的多环芳烃萘和芴有显著的降解能力。实验室的测试表明,与紫外UVA(365 nm)、UVB(308 nm)的光照相比,紫外UVC(254 nm)在光照60 min的条件下,2种多环芳烃各自的去除率都近似达到了99%。可见,在光解效力和暴露时间两方面,紫外UVC对采出水中萘和芴的去除具有相对稳定和比较高的效率。     

Characterizing the interactions between polycyclic aromatic hydrocarbons and fulvic acids in water

Polycyclic aromatic hydrocarbons (PAHs) are persistent, bioaccumulative, and toxic chemicals and are listed as priority pollutants by the US EPA. Although they are sparsely soluble in water, their solubility can be increased by binding to dissolved organic matter in natural waters, which will further increase their environmental risk as toxic pollutants. In this study, the interaction between PAHs, exemplified by fluorene and anthracene, and fulvic acid (FA) was studied using fluorescence quenching titration method with fluorescence emission spectra, respectively. The association of FA with the mixture of fluorene and anthracene was also evaluated by excitation–emission matrix (EEM) fluorescence spectrometry combined with parallel factor (PARAFAC) analysis. Results demonstrate that EEM fluorescence spectrometry with PARAFAC analysis was sensitive and reliable to determine the binding properties of PAHs with FA in a mixed aqueous solution. The conditional stability constants and binding capacities show that both PAHs bind to FA tightly.     

Halogenated polycyclic aromatic hydrocarbons in the environment

Halogenated polycyclic aromatic hydrocarbons (HPAHs) have been reported to occur in air, sediment, fly ash, and biota samples. This review summarized current existing data on the environmental occurrence, behavior, physicochemical properties, emission sources, and toxic equivalents of HPAHs. Firstly, the physicochemical properties of HPAHs were summarized. Then, an overview of environmental occurrence of HPAHs in ambient matrices including biological samples was reviewed. Meanwhile, the emission sources and possible formation mechanisms of HPAHs were discussed. Apart from that, the aryl hydrocarbon receptor (AhR)-mediated activities were summarized, which indicated that the position and number of halogen atoms on the parent PAHs molecule were important determinant factors affecting the AhR-mediated activity of individual HPAHs congeners. Finally, some research recommendations on HPAHs were given.     

Pollution survey of polycyclic aromatic hydrocarbons in surface water of Hangzhou, China

The concentrations of 10 polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured for five times (July and November 1999–2002) in four water bodies of Hangzhou, China. To investigate possible sources of PAH contamination, sediments, soils, runoff water and atmospheric particles of the region were also analyzed for their PAH contents. The maximum levels of PAHs in the water bodies (34.4–67.7 μg/l) were found in July, while significantly lower PAH concentrations (4.7–15.3 μg/l) were measured in November. The contamination is substantial and it may have resulted in acute toxic effects on aquatic organisms. The measured PAH concentrations in sediments and soils (224–4222 ng/g), runoff water (8.3 μg/l) and air particles (2.3 μg/m³) are discussed in relation to concentrations and patterns found in the surface water bodies. Comparison of PAH levels in sediments and soils led to the conclusion that the erosion of soil material does not contribute significantly to the contamination of sediments. The atmospheric PAH deposition to water bodies in the city area of Hangzhou was estimated to be 530 tons/a, while the contribution of surface runoff water was estimated to be 30.7 tons/a. The ratios of selected PAH were then used to illuminate the possible origin of PAHs in the examined samples (petrogenic, pyrogenic).     

Long-range transport of polycyclic aromatic hydrocarbons from China to Japan

Airborne particulate matter was collected at Wajima, on the Noto Peninsula, Ishikawa, Japan by a high-volume air sampler with a quartz filter every week from 17 September 2004 to 16 September 2005. Polycyclic aromatic hydrocarbons (PAHs) extracted from filters were analyzed by HPLC with fluorescence detection. The atmospheric concentrations of PAHs at Wajima were higher during the heating period of China (when coal is burned for heat) than during the no-heating period. A meteorological analysis indicated that the air samples collected in that heating period at Wajima were transported mainly from Northeast China over the Japan Sea. Principal component analysis of nine PAHs indicated a Chinese origin of the PAHs. These results strongly suggest that the high-level PAHs detected at Wajima were the result of long-range transport from China.     

Eisenia fetida increased removal of polycyclic aromatic hydrocarbons from soil

The removal of phenanthrene, anthracene and benzo(a)pyrene added at three different concentrations was investigated with or without earthworms (Eisenia fetida) within 11 weeks. Average anthracene removal by the autochthonous micro-organisms was 23%, 77% for phenanthrene and 13% for benzo(a)pyrene, while it was 51% for anthracene, 47% for benzo(a)pyrene and 100% for phenanthrene in soil with earthworms. At 50 and 100mg phenanthrene kg(-1)E. fetida survival was 91% and 83%, but at 150 mg kg(-1) all died within 15 days. Survival of E. fetida in soil amended with anthracene < or = 1000 mg kg(-1) and benzo(a)pyrene < or = 150 mg kg(-1) was higher than 80% and without weight loss compared to the untreated soil. Only small amounts of PAHs were detected in the earthworms. It was concluded that E. fetida has the potential to remove large amounts of PAHs from soil, but more work is necessary to elucidate the mechanisms involved.     

Emission of polycyclic aromatic hydrocarbons from gasohol and ethanol vehicles

The exhaust emission of the polycyclic aromatic hydrocarbons (PAHs) considered toxic to human health were investigated on two spark ignition light duty vehicles, one being gasohol (Gasohol, in Brazil, is the generic denomination for mixtures of pure gasoline plus 20–25% of anhydrous ethyl alcohol fuel (AEAF).)-fuelled and the other a flexible-fuel vehicle fuelled with hydrated ethanol. The influence of fuel type and quality, aged lubricant oil type and use of fuel additives on the formation of these compounds was tested using standardized tests identical to US FTP-75 cycle. PAH sampling and chemical analysis followed the basic recommendations of method TO-13 (United States. Environmental Protection Agency, 1999. Compendium Method TO-13A – Determination of polycyclic Aromatic hydrocarbons (PAH) in Ambient Air Using Gas Chromatography/Mass Spectrometry (CG/MS). Center for environmental research information, Cincinnati, p. 78), with the necessary modification for this particular application.Results showed that the total PAH emission factor varied from 41.9 μg km^?1 to 612 μg km^?1 in the gasohol vehicle, and from 11.7 μg km^?1 to 27.4 μg km^?1 in the ethanol-fuelled vehicle, a significant difference in favor of the ethanol vehicle. Generally, emission of light molecular weight PAHs was predominant, while high molecular weights PAHs were not detected. In terms of benzo(a)pyrene toxicity equivalence, emission factors varied from 0.00984 μg TEQ km^?1 to 4.61 μg TEQ km^?1 for the gasohol vehicle and from 0.0117 μg TEQ km^?1 to 0.0218 μg TEQ km^?1 in the ethanol vehicle.For the gasohol vehicle, results showed that the use of fuel additive causes a significant increase in the emission of naphthalene and phenanthrene at a confidence level of 90% or higher; the use of rubber solvent on gasohol showed a reduction in the emission of naphthalene and phenanthrene at the same confidence level; the use of synthetic oil instead of mineral oil also contributed significantly to a decrease in the emission of naphthalene and fluorene. In relation to the ethanol vehicle, the same factors were tested and showed no statistically significant influence on PAH emission.     

Formation rates of polychlorinated dibenzofurans and dibenzo-p-dioxins from polycyclic aromatic hydrocarbons, activated carbon and phenol

The formation rates of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from polycyclic aromatic hydrocarbons (PAHs), activated carbon, and phenol were compared. The heat treatment at 300°C of all tested PAH on silica in the presence of CUCl₂ Preferred PCDDs over PCDDs. Perylene reproducibly gave a higher yield of PCDDs than activated carbon gave under the same conditions. The formation rate of PCDDs from perylene could be higher than the values in this study because the residence time of perylene in the reactor is shorter than that of activated carbon. PCDDs were mainly formed from phenol.     

Determination of polycyclic aromatic hydrocarbons in dry tea

Twenty-eight different tea samples sold in the United States were evaluated using high-performance liquid chromatography (HPLC) with fluorescence detection (FLD) for their contamination with polycyclic aromatic hydrocarbons (PAHs). Many PAHs exhibit carcinogenic, mutagenic, and teratogenic properties and have been related to several kinds of cancer in man and experimental animals. The presence of PAHs in environmental samples such as water, sediments, and particulate air has been extensively studied, but food samples have received little attention. Eighteen PAHs congeners were analyzed, with percentage recovery higher than 85%. Contamination expressed as the sum of the 18 analyzed PAHs was between 101 and 1337 μg/kg on dry mass and the average contents in all of the 28 examined samples was 300 μg/kg on dry mass. Seven of the congeners were found in all samples with wide ranges of concentrations as follows: fluorene (7–48 μg/kg), anthracene (1–31 μg/kg), pyrene (1–970 μg/kg), benzo(a)anthracene (1–18 μg/kg) chrysene (17–365 μg/kg), benzo(a)pyrene (1–29 μg/kg), and indeno(1,2,3-cd)pyrene (4–119 μg/kg). The two most toxic congeners benzo(a)pyrene and dibenzo(a,h)anthracene were found at high concentrations only in Earl Grey Twinnings, Earl Grey Harney& Sons Fine Teas, and Chai Ultra Spice Black Tea Twinnings. Six PAH congeners are considered as suspected carcinogens (U.S.EPA), formed the basis of the estimation of the toxic equivalent (TEQ), Chai Ultra-Spice Black Tea Twinnings had the highest TEQ (110.9) followed by two grey tea samples, Earl Grey Harney & Sons Fine Tea (57.7) and Earl Grey Twinnings (54.5). Decaffeinated grey teas had the lowest TEQs, decaffeinated Earl Grey Bigelow (9.4) and Green Tea Honey Lemon Decaffeinated Lipton (9.6).     

Absorption of polycyclic aromatic hydrocarbons to cellulose

Polycyclic aromatic hydrocarbons (PAHs) are widespread toxic chemicals. The environmental fate of these chemicals is in part controlled by sorption to (organic matter in) sediments and soils. One of the most abundant organic matter compounds on earth is cellulose. Remarkably, sorption of PAHs to cellulose has hardly been studied; only two reports on the binding of some low-molecular-weight PAHs exist in the literature. In this study, sorption of PAHs to cellulose was investigated in more detail, by measuring isotherms for a series of 13 PAHs, covering a wide hydrophobicity range. The results indicated that sorption of PAHs to cellulose is a linear partition process for all PAHs investigated (phenanthrene-indeno[1,2,3-cd]pyrene). The affinity of PAHs for cellulose appeared to be about 400 times lower than for octanol and even up to 300000 times lower than for black carbon or coal. Linked to the estimated yearly production of cellulose and black carbon, these results suggest that cellulose is probably not a major environmental sorption domain for PAHs.     

Lability of polycyclic aromatic hydrocarbons in the rhizosphere

Remediation of soils containing high concentrations of polycyclic aromatic hydrocarbons (PAHs) seldom results in complete removal of contaminants, but residual toxicity often is reduced. In this study, soil from a former manufactured gas plant site was treated for 12 months by phytoremediation and then tested for total PAHs, Tenax-TA extractable ("labile") PAHs, aqueous soluble PAHs (PAH(wp)) , and biotoxicity assessed by earthworms survival, nematode mortality, emergence of lettuce seedlings, and microbial respiration. Prior to phytoremediation, the soil had toxic impacts on all bioassays (except the nematodes), and 12 months of remediation decreased this response. Change in labile PAHs was a predictor for change in total PAH for 3- and 4-ring compounds but not for the 5- and 6-ring. Decreases in labile PAHs were correlated (r(2)>or=0.80) with toxicity in the bioassays except microbial respiration. PAH(wp) was correlated only with nematode toxicity prior to remediation but with none of the tests after remediation. Total PAHs were not correlated with any of the bioassay tests. Tenax-TA appears to have potential for predicting residual toxicity in remediated soils and is superior to total concentrations for that application.     

Determination of polycyclic aromatic hydrocarbons in roasted coffee

Polycyclic aromatic hydrocarbons (PAHs) are suspected to be carcinogenic and mutagenic. This study describes the presence of PAHs in light, medium and dark roasted coffee including instant and decaffeinated brands. Total PAHs concentration was related to the degree of roasting with light roasted coffee showing the least and dark roasted coffee showing the highest level. Both instant and decaffeinated coffee brand showed lower levels of PAHs. Naphthalene, acenaphthylene, pyrene and chrysene were the most abundant individual isomers. The concentrations ranged from 0 to 561 ng g^?1 for naphthalene, 0 to 512 ng g^?1 for acenaphthylene, 60 to 459 ng g^?1 for pyrene and 56 to 371 ng g^?1 for chrysene. Thus, roasting conditions should be controlled to avoid the formation of PAHs due to their suspected carcinogenic and mutagenic properties.     

Accumulation of polycyclic aromatic hydrocarbons in crankcase oil

The concentrations of polycyclic aromatic hydrocarbons (PAHs) were measured in automotive crankcase oils. PAHs were not detected in the new oil; however, concentrations increased rapidly with usage in the gasoline engine of an automobile. The PAH distributions found were dominated by alkylated two- and three-ring compounds. The concentrations of these compounds increased until about 4000 miles and then levelled out. Four-ring compounds continually increased with miles driven, and the five-ring benzopyrenes were only detected in the oil used for the longest distance (about 5800 miles).     

Ionic liquid-containing semipermeable membrane devices for monitoring the polycyclic aromatic hydrocarbons in water

Ionic liquid-containing semipermeable membrane devices (IL-SPMDs) were developed to monitor the polycyclic aromatic hydrocarbons in water. Uptake kinetics of naphthalene, 1-methylnaphthalene, phenanthrene, pyrene, chrysene by layflat low-density polyethylene tubing (15 cm x 2 cm) filled with 0.5 ml 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid were studied in a laboratory continuous-flow system for the duration of 16 days. The device concentration factors were in the range of 830-7800 for the studied PAHs. The kinetic parameters of IL/water partition coefficients, analytes uptake rate constants and sampling rates were estimated using mathematical models. These parameters were used in the field experiment to estimate the concentrations of the PAHs in Lanzhou section of Yellow River in China, with the result in comparison with that obtained by triolein-SPMD.     

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

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