Linear free energy relationships for dechlorination of aromatic chlorides by Pd/Fe

Reductive dechlorination rate constants for five chlorobenzenes in the presence of Pd/Fe as catalyst were determined experimentally. Linear free energy relationships (LFER) for the dechlorination rate constants of five chlorobenzenes and three chlorophenols were developed by partial least squares (PLS) regression based on quantum chemical parameters computed by PM3 Hamiltonian. The optimal LFER model obtained is

logk=−1.63+1.46×10⁻³ΔH_f−7.69×10⁻¹E_LUMO

where k stands for the dechlorination rate constants, ΔH_f is the standard heat of formation, and E_LUMO is the energy of the lowest unoccupied molecular orbital. The Q²_cum value of the model is 0.879, indicating good robustness and predictive power of the model.     

Contamination of polycyclic aromatic hydrocarbons (PAHs) in microlayer and subsurface waters along Alexandria coast,Egypt

The residues of seven polycyclic aromatic hydrocarbons (PAHs) pollutants in microlayer and subsurface seawater samples collected from Alexandria coast, Egypt, were analyzed by gas chromatography–electron-impact mass spectrometry-selected ion monitoring mode (GC–MS-SIM). The pollutants studied were, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene and benzo[a]pyrene. Total PAH levels in microlayer ranged from 103 to 523 ng/l, while it ranged in subsurface samples from 13 to 120 ng/l. The Western Harbor location recorded the highest level of PAHs pollutant over all the other location for both subsurface and microlayer waters. The two major PAHs in microlayer water at the Western Harbor were fluorene and phenanthrene, making up 27% and 20% of the total PAHs, while the two major PAHs in subsurface water at the Eastern Harbor were phenanthrene and fluoranthene recording up 21% each of the total PAHs. The total PAH levels were generally in the nano-gram per liter for microlayer and subsurface seawater samples. The dominant PAHs in both subsurface and microlayer samples were fluoranthene, pyrene and benzo[a]pyrene. The microlayer enrichment factor at Alexandria’s Mediterranean coast was ranged from 29 for fluorene to 3 for phenanthrene and benzo[a]pyrene which showed PAHs concentration in the microlayer with an average of five times more than the total PAH in the subsurface samples.     

Profiles of PAH emission from steel and iron industries

In order to characterize the polycyclic aromatic hydrocarbons (PAHs) emission from steel and iron industries, this study measured the stack emission of twelve steel and iron plants in southern Taiwan to construct a set of source fingerprints. The study sampled the emissions by the USEPA's sampling method 5 with the modification of Graseby for the gas and particulate phase PAH and, then, used Hewlett-Packard 5890 gas chromatograph equipped with mass spectrometer detector to analyze the samples. The steel and iron industries are classified into three categories on the basis of auxiliary energy source: Category I uses coal as fuel, Category II uses heavy oil as fuel and Category III uses electric arc furnace. The pollution source profiles are obtained by averaging the ratios of individual PAH concentrations to the total concentration of 21 PAHs and total particulate matter measured in this study. Results of the study show that low molecular weight PAHs are predominant in gas plus particulate phase for all three categories. For particulate phase PAHs, however, the contribution of large molecular weight compounds increases. Two-ring PAHs account for the majority of the mass, varying from 84% to 92% with an average of 89%. The mass fractions of 3-, 4-, 5-, 6-ring PAHs in Category I are found to be more than those of the other two categories. The mass of Category III is dominated by 7-ring PAHs. Large (or heavy) molecular weight PAHs (HMW PAHs) are carcinogenic. Over all categories, these compounds are less than 1% of the total-PAH mass on the average. The indicatory PAHs are benz[a]anthracene, benzo[k]fluoranthene, benzo[ghi]perylene for Category I, benzo[a]pyrene, acenaphthene, acenaphthylene for Category II and coronene, pyrene, benzo[b]chrycene for Category III. The indicatory PAHs among categories are very different. Thus, dividing steel and iron industry into categories by auxiliary fuel is to increase the precision of estimation by a receptor model. Average total-PAH emission factors for coal, heavy oil and electric arc furnace were 4050 μg/kg-coal, 5750 μg/l-oil, 2620 μg/kW h, respectively. Carcinogenic benzo[a]pyrene for gas plus particulate phase was 2.0 g/kg-coal, 2.4 μg/l-oil and 1.4 μg/kW h for Category I, II and III, respectively.     

Disappearance of polycyclic aromatic hydrocarbons sorbed on surfaces of pine [Pinua thunbergii] needles under irradiation of sunlight: Volatilization and photolysis

The solar photodegradation of 16 polycyclic aromatic hydrocarbons (PAHs), sorbed on surfaces of pine [Pinua thunbergii] needles was investigated. The PAHs were produced by combustion of polystyrene and exposed onto the surfaces of pine needles. The disappearance of PAHs sorbed on the pine needle surfaces is mainly caused by volatilization and photolysis, with photolysis playing a major role. The volatilization rates correlate with PAH molecular weight significantly. The photolysis of the 16 PAHs follows first-order kinetics and their photolysis half-lives (t_1/2,P) range from 12.9 h for naphthalene to 65.4 h for fluorene. The PAHs have similar half-lives whether they are sorbed on spruce or pine needles. Compared with water, the cuticular waxes of pine needles can stabilize photolysis of PAHs and facilitate accumulation of PAHs. t_1/2,P for selected PAHs correlate with semi-empirically calculated energy of the highest occupied orbital (E_HOMO). Photochemical behaviors of PAHs are dependent not only on their molecular structures but also the physical–chemical properties of the substrate on which they are adsorbed.     

Removal of carotene-like colored compounds by liquid-liquid extraction during polycyclic aromatic hydrocarbons analysis of plant tissue

Plants contain a wide variety of chemicals, some of which may have similar chromatographic behavior to polycyclic aromatic hydrocarbons (PAHs). During solid phase extraction (SPE) with Si-gel for instance, the co-elution of carotene-like colored compounds with PAHs has been observed. In this paper, liquid–liquid extraction was applied for the separation and subsequent analysis of PAHs from plant extracts. PAHs containing 2–6 rings, which include naphthalene, phenanthrene, pyrene, benzo[a]pyrene and benzo[ghi]perylene, were used as representative target chemicals. Carotene-like compounds extracted from Komatsuna (Brassica campestris) shoot by acetone followed by Si-gel treatment were incorporated as undesired components in the model matrix. Results showed the feasibility of employing either acetonitrile or 2% (w/v) KOH–methanol as solvents for high PAHs recovery and low extraction of colored fraction. For acetonitrile, 86.9–93.5% of each PAH could be recovered after three extraction cycles (relative standard deviation, RSD < 1.6%) with only about 10% co-extraction of colored fraction. For 2% KOH–methanol, PAHs recoveries ranging from 79.3% to 83.1% after five cycles (RSD < 1.5%) were achieved while the percent extraction of colored fraction was also low at 10%. The relatively higher selectivity of the solvents for PAHs over the colored fraction as well as the solubility of the matrix solution in the solvent may have contributed to these results. On this basis, liquid–liquid extraction is very useful for the pre-treatment of plant extracts for PAHs analysis.     

Occurrence and removal of polycyclic aromatic hydrocarbons and their derivatives in an ecological wastewater treatment plant in South China and effluent impact to the receiving river

Ecological wastewater treatment plant (EWWTP), a kind of emerging wastewater treatment plant (WWTP) in recent years, combined microbiology with botany which is efficient for the removal of nitrogen and organic matter, as well as deodorization. The occurrence and removal of micro-organic pollutants in EWWTPs were still not well known. Polycyclic aromatic hydrocarbons (PAHs) and their typical derivatives (SPAHs) including the oxygenated PAHs (OPAHs), chlorinated PAHs (ClPAHs), and methyl PAHs (MPAHs) were investigated in an EWWTP in Guangdong Province, China. The concentrations of the Σ6 OPAHs (114–384 ng/L) were higher than the Σ16 PAHs (92–250 ng/L), and much higher than the Σ4 MPAHs (13–64 ng/L) and Σ9 ClPAHs (2–3 ng/L) in the EWWTP and the effluent receiving river. The total removal efficiencies of the PAHs, OPAHs, MPAHs, and ClPAHs in the EWWTP (43?±?14%, 41?±?7%, 55?±?16%, and 18?±?4%) were lower than the traditional WWTPs, probably due to the lower concentration of the sludge in the ecological treatment. The advanced treatment process (microfiltration and UV disinfection treatment) contributed much less (0–20%) to the whole removal efficiency than the ecological treatment (80–100%). The effluent from the EWWTP slightly reduced the PAHs and SPAHs concentrations in the receiving river. The high concentrations of the PAHs and SPAHs in the receiving river were similar to the influent of the EWWTP, indicating that some untreated wastewater was directly discharged to the river, especially in the upstream.

     

Leaves of Quercus ilex L. as biomonitors of PAHs in the air of Naples (Italy)

Polycyclic aromatic hydrocarbons (PAHs) were determined by the GC-MS chromatography in the leaves of Quercus ilex L., an evergreen Mediterranean oak, to monitor the degree of pollution in the urban area of Naples compared to remote areas. Leaf samples were collected in July 1998 from four urban parks, six roadsides and two sites in remote areas. The total PAH contents in Q. ilex leaves ranged from 106.6 in a control site to 4607.5 ng/g d.w. along a road with a high traffic flow. The mean concentration factors (urban/control) were 3.8 for the parks and 15 for the roads. The contribution of carcinogenic PAHs (benz[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, indeno[1,2,3-c,d]pyrene) was higher in urban area and differed according to the site, ranging from 6.7% to 21.3%. The total PAH burden in control sites was dominated by the low molecular weight PAHs, whilst along the urban roads fluoranthene, pyrene and benz[a]anthracene among the measured PAHs showed the highest values. PAHs were positively correlated (P<0.01) to trace metals measured in a previous study.     

How accurately do semi-permeable membrane devices measure the bioavailability of polycyclic aromatic hydrocarbons to Daphnia magna?

Semi-permeable membrane devices (SPMDs) are passive samplers that have been designed to sample the bioavailable fractions of hydrophobic organic compounds in aquatic ecosystems. This study aims at evaluating the ability for SPMD to sample polycyclic aromatic hydrocarbons (fluoranthene, pyrene and benzo[a]pyrene) that are actually bioavailable to Daphnia magna. For that purpose, the SPMD-available fraction and the bioavailable fraction to D. magna are compared in controlled media with Dissolved Organic Matters (DOMs) from various origins and at different concentrations. The presence of all but one DOM reduces the accumulation of PAHs in SPMD or in D. magna. Moreover, this comparative laboratory study shows that in 10 cases on 13, the SPMD-available fraction is close to the available fraction to D. magna. When significant differences are observed between SPMD-available and bioavailable fractions, they remain less than 50% at DOM concentrations below 10 mg/l DOC, which corresponds to a maximum DOC concentration usually found in temperate rivers. This study confirms the suitability of the SPMD technique to monitor readily bioavailable hydrophobic contaminants in aquatic environments containing DOM from various origins and characteristics.     

Oxidant denuder sampling for analysis of polycyclic aromatic hydrocarbons and their oxygenated derivates in ambient aerosol: evaluation of sampling artefact

The concentrations of some polycyclic aromatic hydrocarbons (PAH) and oxygenated PAH (O-PAH) can be changed by oxidation reactions during sampling. This can lead to an over- or underestimation of the corresponding adverse health effects. The aim of this study was the evaluation of these sampling artefacts. The potential of using an oxidant denuder was shown by parallel low-volume sampling with and without MnO₂ ozone denuder. Twenty-three PAH and 11 O-PAH in ambient air were analysed, both in the vapour and particulate phase. The denuder was proven to be highly efficient for stripping ozone from air while causing no significant particle losses. In general, the concentrations of 5- to 7-ring PAH, which are predominantly associated with particles, were underestimated in non-denuded samples. The highest losses due to reaction with ozone and other atmospheric oxidants were observed for benzo[a]pyrene and perylene. Concurrently, the concentrations of most of the mainly particle-associated 4- to 5-ring O-PAH were higher in the non-denuded samples. The denuder did not only remove ozone, moreover other gaseous species such as more volatile PAH and O-PAH were partially oxidized on the catalytic surface, too. Degradation of PAH and concurrent degradation/formation reactions of O-PAH occurred. The corresponding reactivities of selected PAH and O-PAH are discussed.     

Polycyclic aromatic hydrocarbons in the sediments of the South China Sea

Sixteen sediment samples, collected from the South China Sea, were analyzed for 11 parent polycyclic aromatic hydrocarbons (PAHs) using gas chromatography and gas chromatography-mass spectrometry. Total concentrations of the 11 PAHs studied in the sediments ranged from 24.7 to 275.4 ng/g with a mean of 145.9 ng/g dry sediment. PAH concentrations displayed a consistent distribution trend with the sediment organic carbon content. The linear regression analysis showed that the total concentration of PAHs in the sediment was significantly correlated to the sediment organic carbon content with a correlation coefficient of 0.735 (n=16). Special PAH compound ratios, such as phenanthrene/anthracene and fluoranthene/pyrene, were calculated to evaluate the relative importance of different origins. The collected data showed that pyrolytic input from anthropogenic combustion processes was predominant at almost all the stations investigated. Only one station, located in the proximity of oil wells, appeared to be contaminated predominantly by petrogenic input. Three anthropogenic PAHs, i.e. pyrene, benzo[a]pyrene and benzo[e]pyrene, exhibited similar distribution patterns in the studied area, implying that these compounds possess identical sources. However, perylene did not entirely follow the distribution trend of the three PAHs, suggesting that the sediment perylene probably derived from other sources such as in situ biogenic origins. Dibenzothiophene, a sulfur heterocyclic aromatic compound, was also measured in this study.     

Removal of a cationic dye from aqueous solutions by adsorption onto bentonite clay

The ability of bentonite to remove malachite green from aqueous solutions has been studied for different adsorbate concentrations by varying the amount of adsorbent, temperature, pH and shaking time. Maximum adsorption of the dye, i.e. >90% has been achieved in aqueous solutions using 0.05 g of bentonite at a pH of 9. Thermodynamic parameters such as ΔH°, ΔS° and ΔG° were calculated from the slope and intercept of the linear plots of ln K_D against 1/T. Analysis of adsorption results obtained at 298, 308, 318 and 328 K showed that the adsorption pattern on bentonite seems to follow the Langmuir, Freundlih and D–R isotherms. The temperature increase reduces adsorption capacity by bentonite, due to the enhancement of the desorption step in the mechanism. The numerical values of sorption free energy (E_a) of 1.00–1.12 kJ mol⁻¹ indicated physical adsorption. The kinetic data indicated an intraparticle diffusion process with sorption being first order. The rate constant k was 0.526 min⁻¹. The concentration of malachite green oxalate was measured before and after adsorption by using UV–Vis spectrophotometer.     

Source apportionment of polycyclic aromatic hydrocarbons in surface sediments of the Bohai Sea, China

A total of 112 surface sediment samples covering virtually the entire Bohai Sea were analyzed for polycyclic aromatic hydrocarbons (PAHs), in order to provide the extensive information of recent occurrence levels, distribution, possible sources, and potential biological risk of these compounds in this area. Surface sediment samples were collected from the Bohai Sea using a stainless steel grab sampler. Sixteen PAHs were determined by a Finnigan TRACE DSQ gas chromatography/mass spectrometry. Diagnostic ratios, cluster analysis, and principal component analysis (PCA) with multivariate linear regression (MLR) were performed to identify and quantitatively apportion the major sources of sedimentary PAHs in the Bohai Sea. Concentrations of total PAHs in the Bohai Sea ranged widely from 97.2 to 300.7 ng/g (mean, 175.7?±?37.3 ng/g). High concentrations of PAHs were found in the vicinity of Luan River Estuary-Qinhuangdao Harbor, Cao River Estuary-Bohai Sea Center, and north of the Yellow River Estuary. The three-ring PAHs were most abundant, accounting for about 37?±?5 % of total PAHs. The four-ring and five-ring PAHs were the next dominant ones comprising approximately 29?±?7and 23?±?3 % of total PAHs, respectively. Concentrations of acenaphthylene, acenaphthene, and dibenz[a,h]anthracene are higher than Canadian interim marine sediment quality guideline values at most of the sites in the study area. Contamination levels of PAHs in the Bohai Sea were low in comparison with other coastal sediments in China and developed countries. The distribution pattern of PAHs and source identification implied that PAH contamination in the Bohai Sea mainly originates from petrogenic and pyrogenic sources. Further PCA/MLR analysis suggested that the contributions of spilled oil products (petrogenic), coal combustion, and traffic-related pollution were 39, 38, and 23 %, respectively. Pyrogenic sources (coal combustion and traffic-related pollution) contributed 61 % of anthropogenic PAHs to sediments, which indicates that energy consumption could be a dominant factor in PAH pollution in this area. Acenaphthylene, acenaphthene, and dibenz[a,h]anthracene are the three main species of PAHs with more ecotoxicological concern in the Bohai Sea.     

Transformation of PAHs during ethanol-Fenton treatment of an aged gasworks' soil

PAH-contaminated soil from a former gasworks site was treated with Fenton's reagent in a number of lab-scale slurry reactors. The degradation result obtained by traditional Fenton oxidation and Fenton oxidation preceded by ethanol treatment were compared. The ethanol pre-treatment enhanced the depletion of all PAHs in the soil by facilitating their desorption from the soil matrix. However, some PAHs, especially anthracene, benzo[a]pyrene and perylene, were more extensively depleted than other PAHs with fewer or equal numbers of fused rings, indicating that the hydroxyl radicals react faster with these PAHs than with other kinds. The ethanol present in the slurry also appeared to influence the relative reactivity of the PAHs. Furthermore, the enhanced oxidation that occurred in the ethanol pre-treated soil resulted in the accumulation of oxidation products. For example, 1-indanone, anthracene-9,10-dione, 1-methylanthracenedione, 2-methylanthracenedione, 1,8-naphthalic anhydride, benz[a]anthracene-7,12-dione and two compounds tentatively identified as hydroxy-9-fluorenones were found at higher concentrations after the treatment than before it. The accumulation was most evident for the quinones, and in many cases it could be attributed to extensive oxidation of their parent PAHs, although the total oxidation efficiency in this study was relatively poor.     

Distribution and sources of polycyclic aromatic hydrocarbons in the middle and lower reaches of the Yellow River, China

In this study, concentrations, distribution between different phases, transition along the Middle and Lower reaches of the Yellow River and possible sources of PAHs were assessed. Results demonstrated that the relative proportions of 15 PAHs in all stations of the main River were similar, with concentrations of benzo[a]pyrene all above drinking water standards in most of the stations sampled. PAHs concentrations in tributaries were higher than those in the corresponding sites in the main River. PAHs concentrations of suspended particles were mainly correlated with contents of total organic carbon. However, PAHs concentrations in sediments were mainly correlated to the volume of particles with size smaller than 0.01 mm. The distribution of PAHs in all media sampled indicated that sediments could act as a sink/source for PAHs in different sections and source analysis revealed that PAHs mainly originated from coal burning, although in some tributaries PAH inputs could come from combustion of petroleum.     

Dietary risk evaluation for 28 polycyclic aromatic hydrocarbons (PAHs) in tea preparations made of teas available on the Polish retail market

The aim of this work was to assess dietary risk resulting from consumption of polycyclic aromatic hydrocarbons (PAHs) with tea infusions. To this end, levels of 28 PAHs in black, green, red and white teas available on the Polish retail market have been assessed. Profiles and correlation between concentrations of individual PAHs have been identified. A model study on transfer of PAHs from tea leaves into tea preparations has been conducted. Relatively high concentrations of 28 evaluated PAHs have been found in 58 tested samples of black, green, red and white teas sampled on the Polish retail market. Total concentration ∑28PAH ranged from 57 to 696 µg kg^?1 with mean 258 µg kg^?1 (dry tea leaves). The most mature tea leaves fermented to a small degree contained relatively the highest PAH levels among all four tested tea types. Relatively low PAH transfer rates into tea infusions and limited volumes of the consumed tea keep the risks associated with PAH dietary intake at a safely low level.

The worst-case scenario dietary intake values were 7.62/0.82/0.097 ng kg^?1 b.w. day^?1 (estimated on the basis of the maximum found concentrations 696/113/23 µg kg^?1 and maximum observed transfer rates 24/16/9%) for ∑28PAH/∑PAH4/B[a]P, respectively. MOE values calculated using the above worst case estimates exceeded 700,000 and 400,000 (BMDL₁₀ 0.07 and 0.34 mg kg^?1 b.w. day^?1) for B[a]P and PAH4, respectively. Both B[a]P and PAH4 concentrations may be used as indicators of total PAH concentration in tea leaves; PAH4 slightly better fits low molecular weight PAHs. Several correlations between various PAHs/groups of PAHs have been identified, the strongest one (R² = 0.92) between PAH4 and EU PAH 15+1.     

Studies on polycyclic aromatic hydrocarbons in two sediment cores from the huaxi reservoir,china: Assessment of levels,sources, and ecological risk

This study investigated the levels, sources and ecological risks of 16 polycyclic aromatic hydrocarbons (PAHs) in two sediment cores that were collected along the Huaxi Reservoir. The spatial distributions and residue levels of the 16 priority PAHs in the sediments from the Huaxi Reservoir were analyzed for their potential ecological risk, source apportionment and contribution to the total PAH residue. The concentration level of the total PAHs (TPAHs) was in the range 1805 ng·g^?1 to 20023 ng·g^?1 based on dry weight, and the content of PAHs in the Huaxi Reservoir exhibited a gradual upward trend. The PAH congener ratios fluoranthene/(fluoranthene + pyrene) and indeno[1, 2, 3-cd]pyrene/(indeno[1, 2, 3-cd]pyrene + benzo[g, h, i]perylene) were used to identify the source. The main source of the low molecular weight PAHs was wood and coal combustion, whereas the high molecular weight PAHs were primarily from petroleum combustion sources. The results of an ecological risk assessment demonstrated that ACE poses a potential ecological risk, while FLU, NAP, ANT, BaP, DBA, PHEN and PYR can have serious ecological risks.     

Chemical characterization and source identification of polycyclic aromatic hydrocarbons in aerosols originating from different sources

To obtain the characteristic factors or signatures of particulate polycyclic aromatic hydrocarbons (PAHs) to help identify the sources of particulate PAHs in the atmosphere, different carbonaceous aerosols were generated by burning different fossil fuels and biomass under different conditions in the laboratory, and the chemical characteristics of 14 PAHs were studied in detail. The results showed that (1) carbonaceous aerosols derived from domestic burning of coal, diesel fuel, and gasoline have much higher concentrations of PAHs than those derived from domestic burning of biomass; (2) carbonaceous aerosols derived from domestic burning of diesel fuel/gasoline have similar PAH components as those derived from high-temperature combustion of diesel fuel/gasoline, although the former have much higher concentrations of PAHs than the latter, suggesting that the burning temperature obviously affects the emitting amount of particulate PAHs, but only slightly influences the PAHs components; and (3) the ratios of benzo[b]fluoranthene/acenaphthylene, benzo[b]fluoranthene/fluorene, dibenzo[a,h]anthracene/acenaphthylene, dibenzo[a,h]anthracene/fluorine, and benzo[b]fluoranthene/benzo[k]fluoranthene in carbonaceous aerosols are sensitively dependent on their sources, indicating that these ratios are suitable for use as characteristic factors or signatures of particulate PAHs in the atmosphere.     

Particle size distribution and PAH concentrations of incense smoke in a combustion chamber

The particle size distribution and the concentrations of polycyclic aromatic hydrocarbons (PAHs) in incense smoke were studied using a custom-designed combustion chamber. Among the nine types of incense investigated, the particle and the total PAH emission factors varied significantly. The average mass median aerodynamic diameter (MMAD) of the smoke aerosol was 262+/-49nm, which positively correlated to particle emission factor (mg/stick, p<0.05). Coagulation was a major mechanism that dictates the MMAD of the smoke. The total toxic equivalency (the sum of the benzo[a]pyrene equivalent concentration) of the solid-phase PAHs (S-PAHs) was over 40 times higher than that of the corresponding gas-phase PAHs, indicating that the S-PAHs in incense smoke may pose potential health risk. Experiments show that each lowered percentage of total carbon content in the raw incense helped decrease the particle emission factor by 2.6mg/g-incense, and the reduction of S-PAH emission factor ranged from 8.7 to 26% when the carbon content was lowered from 45 to 40%.