Seasonal variation, sources and gas/particle partitioning of polycyclic aromatic hydrocarbons in Guangzhou, China

Air samples were collected weekly at an urban site and a suburban site in Guangzhou City, China, from April 2005 to March 2006, to measure the concentrations of polycyclic aromatic hydrocarbons (PAHs) in the ambient air and study their seasonal variations, gas/particle partitioning, origins and sources. The concentrations of ∑ 16-PAHs (particle + gas) were 129.9 ± 73.1 ng m⁻³ at the urban site and 120.4 ± 48.5 ng m⁻³ at the suburban site, respectively. It was found that there was no significant difference in PAH concentrations between the urban and suburban sites. Seasonal variations of PAH concentrations at the two sampling sites were similar, with higher levels in the winter that gradually decreased to the lowest levels in the summer. The average concentrations of ∑ 16-PAHs in the winter samples were approximately three times higher than those of the summer samples because in the summer local emissions dominated, and in the winter the contribution from outside sources or transported PAHs is increased. The plot of logK_p versus logP_L⁰ for the data sets of summer and winter season samples had significantly different slopes at both sampling sites. The slopes for the winter samples were steeper than those for the summer samples. It was also observed that gas/particle partitioning of PAHs showed different characteristics depending on air parcel trajectories. Steeper slopes were obtained for an air parcel that traveled across the continent to the sampling site from the northern or northeastern sector, whereas shallower slopes were obtained for air masses that traveled across the sea from the southern or eastern sector. Diagnostic ratio analytical results imply that the origins of PAHs were mainly from petroleum combustion and coal/biomass burning. The anthracene/phenanthrene and benzo[a]anthracene/chrysene ratios in the winter were significantly lower than those in the summer, which indicate that there might be long-range transported PAH input to Guangzhou in the winter.     

Occurrence of polycyclic aromatic hydrocarbons in water and sediment samples from KwaZulu Natal Province,South Africa

Solid‐phase extraction (SPE) and ultrasonic extraction (UE) techniques followed by Gas Chromatography‐Mass Spectrometry (GC‐MS) have been modified for qualitative and quantitative analysis of polycyclic aromatic hydrocarbons (PAHs) in water and sediment samples. Percentage recoveries of PAHs ranged from 85 to 121% in water and 82 to 117% in sediment samples. The limits of detection (LOD) and limits of quantification (LOQ) ranged from 0.02 to 0.2 and 0.05 to 0.5 µg/L for SPE while for UE, they were between 0.008–0.09 and 0.02–0.30 µg/kg, respectively. The concentration levels of PAHs (naphthalene, acenaphthene, acenaphthylene, fluorine, anthracene, phenanthrene and pyrene) detected in water samples were 0.071–2.7, 2.0–10.4 and 2.5–3.5 µg/L in wastewater, river water, and dam water, respectively. In sediment samples, concentration levels of PAHs were between 2.8–42.0 and 2.8–3.9 µg/kg, in river and dam sediment, respectively.     

The different reaction mechanisms by which chlorine and chlorine dioxide react with polycyclic aromatic hydrocarbons (PAH) in water

The removal of PAH from surface water by disinfectants like chlorine or chlorine dioxide is important where contamination by these compounds is concerned and no other water treatment processes are available. Our particular interest in these reactions arise from the fact that PAH can be used as an excellent model for the investigation of the different mechanisms by which the two oxidants react with aquatic organics. The vast differences between the rates of Cl₂ and ClO₂ reactions with various PAH, as well as the physical and chemical factors influencing those reactions indicate that chlorine reacts with PAH by several possible mechanisms, e.g. addition, substitution and oxidation. Chlorine dioxide on the other hand reacts mainly as a pure oxidant and a one-electron acceptor. As a consequence, chlorine dioxide reacts much more specifically with those PAH that undergo facile oxidation. Therefore, some PAH that react quite easily with Cl₂, do not react at all with ClO₂, while other PAH react with ClO₂ much more rapidly than with Cl₂. The widespread and highly carcinogenic benzo(a)pyrene and benzo(a)anthracene for example react with ClO₂ much faster than with Cl₂.     

Application of multi-way models to the time-resolved fluorescence of polycyclic aromatic hydrocarbons mixtures in water

The time-resolved laser-induced fluorescence of a series of polycyclic aromatic compounds (PAHs) and mixtures of these latter in aqueous solution was measured by means of an apparatus equipped with optical fibers, which allows their real time in situ monitoring. The potential of such spectroscopic technique, yielding 4-way fluorescence data arrays, together with the application of multi-way models to the matricized data, was tested for the resolution of complex aqueous mixtures containing low concentrations of PAHs, as typical fluorescent pollutants in aquatic systems. PARAllel FACtors analysis was employed for the qualitative resolution of PAHs mixtures and for calculating the fluorescence lifetimes of single PAHs; n-way partial least squares analysis was applied for evaluating the concentration of the single PAHs in the aqueous mixtures.     

Short- and long-term sorption/desorption of polycyclic aromatic hydrocarbons onto artificial solids: effects of particle and pore sizes and organic matters

In order to elucidate the effect of nanopores and organic matters on sequestration of contaminants, short- and long-term sorption and desorption of naphthalene and pyrene in seven artificial solid-water systems were studied. Fast sorption occurred in every case; steady states were reached within 1-5h. Sorption constants varied drastically among the seven absorbents, ranging from 1.19 to 5.29 x 10(3) for naphthalene, and from 24.3 to 6.52 x 10(4) for pyrene. Slow sorption continued to take place in some cases, especially on absorbents containing humic matter. Desorption usually took place in two stages, fast and slow, on both unaged and aged absorbents. Irreversibility of desorption occurred for every absorbent except for silica particles modified with octadecyl silyl. Aging led to a reduction of fast desorption fraction due to entrapment of the chemicals into nanopores and partitioning of the chemicals into condensed areas of humic matters, and showed no effect on slow desorption and irreversibility of desorption. On the whole, entrapment into nanopores and partitioning into humic matters are considered to be important for sequestration of contaminants. Irreversibility of desorption is considered to be a more influencing factor than percentage of desorption for describing the extent of sequestration.     

Health risk assessment on dietary exposure to polycyclic aromatic hydrocarbons (PAHs) in Taiyuan, China

Twenty-five kinds of seven categories of foods were sampled in December 2008 and the concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined. The highest level of total PAHs was detected in pork (195.30 ng/g) whereas the lowest concentration was found in milk (8.73 ng/g). The median values of B[a]P equivalent (B[a]P_eq) daily exposure doses for children, adolescents, adults and seniors of male were estimated to be 392.42, 511.01, 571.56 and 532.56 ng/d, respectively, whereas those for the above population groups of female were found to be 355.16, 440.51, 487.64 and 444.85 ng/d, respectively. The incremental lifetime cancer risk (ILCR) values at the 22.1th, 26.1th, 12.7th, 24.9th, 22.7th, 27.0th, 12.9th, and 25.5th percentiles for male children, male adolescents, male adults, male seniors, female children, female adolescents, female adults and female seniors, respectively, were larger than 10^− 6, indicating high potential carcinogenic risk, and were larger than 10^− 4 at the 74.5th, 78.7th, 60.6th, 77.4th, 75.3th, 79.5th, 60.8th and 77.9th percentiles for the above groups, respectively, which implied significant cancer risk. Sensitivity analysis found that the two variables of oral cancer slope factor of benzo(a) pyrene (SF) and the daily dietary PAH exposure level (ED) had the greater impact than that of body weight (BW) on the ILCR.     

Ozonation of polycyclic aromatic hydrocarbons in oil/water-emulsions: mass transfer and reaction kinetics

The ozonation of highly condensed polycyclic aromatic hydrocarbons (PAH) was studied in oil/water-emulsions, which are comparable to poorly water-soluble PAH in industrial wastewaters and at contaminated sites. As there was a lack of knowledge about the ozonation in oil/water-emulsions, first the ozone mass transfer was studied and optimized from the gas to the water phase and from the water to the oil phase. The ratio of mass transfer and oxidation reaction was determined by the Hatta-number and revealed a slow, quasi homogeneous reaction of ozone with PAH inside the oil droplets. Because the ozone gas concentration had no influence under the optimized conditions, the selective PAH-ozonation could be described microkinetically by a direct ozone reaction of pseudo-first order regarding PAH-concentrations. The determined PAH mean reaction rate constants of 1.02 min(-1) in oil/water-emulsions are in the upper range as found for PAH dissolved in water. These results give a new insight into the ozonation in the three-phase systems and into the treatment of highly condensed, hardly biodegradable PAH.     

Inferences over the sources and processes affecting polycyclic aromatic hydrocarbons in the atmosphere derived from measured data

Data concerning atmospheric lifetime and relative source contributions of polycyclic aromatic hydrocarbons (PAH) are fragmentary and contradictory. In this study, two datasets of measurements of atmospheric PAH (sum of particulate and gaseous phases), one from a national network, the other from a more local three-site study, were analysed and used to infer processes affecting PAH in the atmosphere, and their sources. PAH congener profiles measured at urban and rural locations were remarkably similar suggesting that atmospheric decay processes are relatively slow. This allows the use of such profiles to elucidate sources. A spatial analysis of two PAH datasets showed a clear influence of industry and road traffic upon local PAH concentrations. When Principal Component Analysis (PCA) was applied to UK national network data, it showed a clear influence of steel industry emissions and of home heating emissions from coal and oil in Northern Ireland. These sites also showed different winter/summer concentration ratios to the main group of sites. In the data from Birmingham (UK), PCA identified separate factors relating to gasoline and diesel vehicles, as well as the influence of wood combustion on “Bonfire night”, and a factor related to home heating emissions which shows up only in the cold season.     

Emission of polycyclic aromatic hydrocarbons and lead during Chinese mid-autumn festival

The emission factors of total particulate polycyclic aromatic hydrocarbons (PAHs), Benzo(a)pyrene (BaP), BaP-equivalent doses (BaP(eq)) and Pb for burning three kinds of charcoal were investigated in this study: fast-lighting charcoal, Taiwanese, and Indonesian charcoal (the latter two of which are not fast-lighting). Compared to the burning of Taiwanese and Indonesian charcoal, the burning of fast-lighting charcoal can emit much larger amounts of total PAHs, BaP(eq) and Pb into the atmosphere. The emission factors of total PAHs, BaP and BaP(eq) for broiling meat were noticeably higher than those for broiling vegetables and non-fish seafood. When using Indonesian charcoal to broil meat, the total emission factors of particulate PAHs and BaP were about 15.7 and 0.39 mg/kg, respectively. The total amounts of particulate PAHs and Pb emitted from cookouts during Mid-Autumn Festival were 2881 and 120 g, respectively. Total PAHs and BaP(eq) in PM(10) aerosols on Mid-Autumn Festival nights increased about 1.6 and 1.5 times, respectively, higher than those on non-festival nights. The mean concentration of Pb on the nights of Mid-Autumn Festival increases to about 2.8 times that of non-festival nights.     

Sorption of chlorinated C1- and C2-hydrocarbons and monocyclic aromatic hydrocarbons on sea sediment

The sorption of chlorinated C₁- and C₂-hydrocarbons and monocyclic aromatic hydrocarbons on sea sediment was studied with a miscible displacement technique. Detection was done either by on-line UV-detection or off-line GC-analysis. Equilibrium partitioning coefficients between the salt water phase and the marine sediment were determined for 11 compounds by fitting their breakthrough curves to a local sorption equilibrium model. Based on the obtained partitioning coefficients and on the measurement of the organic carbon content of the sediment, the sorption into the organic carbon fraction was considered. Log K_oc data (K_oc = organic carbon-water partitioning coefficient) were calculated. A linear relationship between the log K_oc values and the log K_ow data (K_ow = octanol-water partitioning coefficient) was found (r = 0.94, n = 11). However, the sorption was lower than expected from the log K_ow data. Finally, the implications of the experimental results for the sorption behaviour of the compounds in the marine environment were evaluated. It was concluded that the sea sediment does not act as an important sink for these anthropogenic compounds.     

Biodegradation of polycyclic aromatic hydrocarbons by Sphingomonas sp. enhanced by water-extractable organic matter from manure compost

The effectiveness of in-situ bioremediation of polycyclic aromatic hydrocarbons (PAHs) may be inhibited by their low aqueous solubility and strong absorption to soil constituents. The aim of this research was to evaluate the effect of water-extractable organic matter (WEOM) from manure compost on the biodegradation of various PAHs. The aqueous solubilities of PAHs including phenanthrene, pyrene and benzo[a]pyrene under different concentrations of WEOM from cow manure compost were initially evaluated. The contribution of WEOM on the degradation of PAHs by Sphingomonas sp. was then investigated. Dissolution results confirmed the ability of WEOM to increase the apparent solubility of the 3PAHs. Time course of biodegradation also revealed its positive contribution to their removal. For example, the degradation of pyrene was 118% higher in the presence of 1000 mg-C L^− 1 WEOM as compared to the mineral salt medium (MSM) alone after 48 h incubation. In addition, degradation was 12% higher with WEOM than with Glucose-Ammonium nitrate despite the more than 6 times higher cell concentration in the latter. WEOM from other manure composts such as chicken and pig were found to have the same effect. Finally, additional tests confirmed that high molecular weight WEOM (> 1000 Da) contributed mainly to solubility and biodegradation enhancements. On the basis of these results, the increase in apparent solubility of PAHs in WEOM solutions may have a significant impact on their biodegradation. It is postulated that the application of WEOM-rich manure composts may be extended in the in-situ bioremediation of PAHs-polluted soil.     

Environmental exposure to polycyclic aromatic hydrocarbons,kitchen ventilation,fractional exhaled nitric oxide,and risk of diabetes among Chinese females

Diabetes is related to exposure to polycyclic aromatic hydrocarbons (PAHs), inflammation in the body, and housing characters. However, associations of urinary monohydroxy‐PAHs (OH‐PAHs) or fractional exhaled nitric oxide (FeNO) with diabetes risk in relation to housing characters are unclear. In this study, 2645 individuals were drawn from the baseline survey of the Wuhan‐Zhuhai Cohort Study. Associations of diabetes with urinary OH‐PAHs or FeNO among cooking participants were estimated using logistic regression models. Among women with self‐cooking meals, urinary OH‐PAH levels were positively associated with diabetes risk (P < .05); the cooking women with high FeNO (≥25 ppb) had a 59% increase in the risk of diabetes (OR: 1.59, 95% CI: 1.06, 2.38), compared with those with low FeNO (<25 ppb). The cooking women with use of kitchen exhaust fans/hoods had a 52% decrease in the risk of diabetes (OR: 0.48, 95% CI: 0.27, 0.84), compared with those with nonuse of kitchen exhaust fans/hoods. The results indicated that the cooking women had an elevated risk of diabetes, which may be partly explained by an increase in the PAH body burden and higher inflammatory responses. Use of kitchen exhaust fan/hood can be associated with a lower risk of diabetes.     

Studying associations between urinary metabolites of polycyclic aromatic hydrocarbons (PAHs) and cardiovascular diseases in the United States

The association between background, enduring environmental exposure to polycyclic aromatic hydrocarbons (PAHs) and cardiovascular diseases has not been well studied in the general population. In this study, we used the National Health and Nutrition Examination Survey (NHANES) 2001-2004 to investigate the associations between eight monohydroxy PAHs (OH-PAHs) and self-report CVD. In a logistic regression model adjusting for cigarette smoking and other covariates, phenanthrene metabolite, 2-hydroxyphennathrene (2-PHEN), was significantly associated with self-report CVD. Compared to subjects within the lowest tertile of 2-PHEN, subjects within the middle and highest tertiles had higher self-report CVD (the 2nd tertile: AOR = 1.29, 95%CI: 0.97-1.72; the 3rd tertile: AOR = 1.45, 95%CI: 1.01-2.07; p for trend = 0.04). In addition, fluorene metabolite (i.e. 2-hydroxyfluorene) also showed a marginally significant linear trend with self-report CVD (p for trend = 0.07). Further studies are necessary to explore the associations between these highly prevalent pollutants and CVD.     

Distributions of polycyclic aromatic hydrocarbons in surface waters, sediments and soils of Hangzhou City, China

Ten polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in 17 surface water samples and 11 sediments of four water bodies, and 3 soils near the water-body bank in Hangzhou, China in December 2002. It was observed that the sum of PAHs concentrations ranged from 0.989 to 9.663 microg/L in surface waters, from 132.7 to 7343 ng/g dry weight in sediments, and from 59.71 to 615.8 ng/g dry weight in soils. The composition pattern of PAHs by ring size in water, sediment and soil were surveyed. Three-ring PAHs were dominated in surface waters and soils, meanwhile sediments were mostly dominated by four-ring PAHs. Furthermore, PAHs apparent distribution coefficients (K(d)) and solid f(oc)-normalized K(d) (e.g. K(oc)= K(d) / f(oc)) were calculated. The relationship between logK(oc) and logK(ow) of PAHs for field data on sediments and predicted values were compared. The sources of PAHs in different water bodies were evaluated by comparison of K (oc) values in sediments of the river downstream with that in soils. Hangzhou section of the Great Canal was heavily polluted by PAHs released from industrial wastewater in the past and now PAHs in sediment may serve as sources of PAHs in surface water. PAHs in Qiantang River were contributed from soil runoff. Municipal road runoff was mostly contributed to West Lake PAHs.     

Fate of aromatic hydrocarbons in Italian municipal wastewater systems: An overview of wastewater treatment using conventional activated-sludge processes (CASP) and membrane bioreactors (MBRs)

We studied the occurrence, removal, and fate of 16 polycyclic aromatic hydrocarbons (PAHs) and 23 volatile organic compounds (VOCs) in Italian municipal wastewater treatment systems in terms of their common contents and forms, and their apparent and actual removal in both conventional activated-sludge processes (CASP) and membrane bioreactors (MBRs). We studied five representative full-scale CASP treatment plants (design capacities of 12 000 to 700 000 population-equivalent), three of which included MBR systems (one full-scale and two pilot-scale) operating in parallel with the conventional systems. We studied the solid-liquid partitioning and fates of these substances using both conventional samples and a novel membrane-equipped automatic sampler. Among the VOCs, toluene, ethylbenzene, xylenes, styrene, 1,2,4-trimethylbenzene, and 4-chlorotoluene were ubiquitous, whereas naphthalene, acenaphthene, fluorene, and phenanthrene were the most common PAHs. Both PAHs and aromatic VOCs had removal efficiencies of 40-60% in the headworks, even in plants without primary sedimentation. Mainly due to volatilization, aromatic VOCs had comparable removal efficiencies in CASP and MBRs, even for different sludge ages. MBRs did not enhance the retention of PAHs sorbed to suspended particulates compared with CASPs. On the other hand, the specific daily accumulation of PAHs in the MBR’s activated sludge decreased logarithmically with increasing sludge age, indicating enhanced biodegradation of PAHs. The PAH and aromatic VOC contents in the final effluent are not a major driver for widespread municipal adoption of MBRs, but MBRs may enhance the biodegradation of PAHs and their removal from the environment.     

Decomposition of polycyclic aromatic hydrocarbons in atmospheric aqueous droplets through sulfate anion radicals: an experimental and theoretical study

Polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants that have received considerable attention because of their carcinogenic and mutagenic effects. PAHs can be degraded by sulfate anion radicals in atmospheric aqueous droplets. This study was to investigate the mechanism and degradation products of sulfate anion radical reaction with anthracene (ANT) by experimental and quantum chemical approaches. From these observations of the experiments, the sulfate anion radical is capable of oxidizing ANT rapidly and three intermediates anthraquinone (ATQ), 1-hydroxyanthraquinone (1-hATQ), and 1,4-dihydroxyanthraquinone (1,4-dhATQ) were detected as degradation products by GC-MS. The proposed one-electronic transfer mechanism of sulfate anion radical reaction with ANT was modeled using hybrid density function theory (BHandHLYP) methods. Geometry optimization and vibrational frequency analysis calculation were performed for reactants, transition states, intermediates, and products. The potential energy surfaces of these reactions are explored to establish structures and relative energies of reactants, intermediates, transition states, and products. Computational results suggest that initial electron transfer step is predicted to have activation energy of -3.35 kcal/mol in water, indicating that ANT can be oxidized quickly in atmospheric aqueous droplets. The reaction pathways have been proposed on the basis of these experimental and theoretical findings. The results may provide useful information for a better understanding of the sulfate anion radical-initiated reactions in atmospheric aqueous droplets such as clouds, rains or fogs.     

HPLC determination of polycyclic aromatic hydrocarbons (PAHs) in the littoral urban sewage area of cortiou (Marseille,France)

A selective method for determining polycyclic aromatic hydrocarbons (PAHs) in sediments using solid‐phase extraction and RP‐HPLC with fluorescence and UV detection is described. The complete analytical method is used to surface sediments from the creek of Cortiou (France). Sewage from the urban area of Marseille is delivered to the creek. PAH levels in sediments (µg/g) range between 2.251 µg/g (for the benzo(a)anthracene) and 相似文献   

固相萃取/高效液相色谱法快速测定水中痕量苯并(a)芘

采用固相萃取-高效液相色谱荧光检测法快速测定水中痕量苯并(a)芘的含量.用Silicycle硅胶萃取小柱富集苯并(a)芘,优化了固相萃取条件.结果表明固相萃取效率高,萃取时间短,苯并(a)芘在5.2～46.8μg/L的浓度范围内呈现良好的线性关系,回收率(n=4)为97.5%～104.9%,相对标准偏差为0.7%～1.8%,检出限达到0.4μg/L.该方法具有简便、快速、准确的特点,尤其适用于环境水中的痕量及超痕量苯并(a)芘的测定.     

The residual dynamic of polycyclic aromatic hydrocarbons and organochlorine pesticides in fishponds of the Pearl River delta, South China

Hong Kong and South China are the most developed regions within China. The industrialization in these areas has resulted in severe environmental problems. Sediment and biotic samples including tilapia (Oreochromis mossambicus), bighead carp (Aristichthys nobilis), grass carp (Ctenopharyngodon idellus), crucian carp (Carassius auratus) and mandarin fish/fresh water grouper (Siniperca chuatsi) were collected from different fishponds in the Pearl River Delta (Tanzhou, Sanjiao, Guangzhou, Shipai, Changan and Mai Po) for the analysis of polycyclic aromatic hydrocarbons (PAHs) and organochlorine (OC) pesticides. Mandarin fish, which belongs to the highest trophic level, accumulated the highest concentrations of PAHs and DDTs among all fish species. The levels of DDTs in fish samples ranged from 1.5 to 62ng g-1 (wet wt.), with more than 30% of the fish samples exceeding the limit of 14.4ng g-1 (wet wt.) for human consumption recommended by US EPA (2000). Levels of PAHs in fish samples ranged from 1.91 to 224.03ng g-1 (wet wt.), but the potency-weighted total concentrations of PAHs in all muscle tissues were below the guideline value of 0.67ng g-1 (wet wt.) for human consumption set by US EPA (2000). The guideline value calculated was based on a tissue consumption rate of 142.2g day-1 (4-5 meals per week), which is a more protective rate for populations with a high consumption of fish, like Chinese and Asians. The effect of lipid content in PAHs and DDTs accumulation in fish tissue was not significant in general.