A directional passive air sampler for monitoring polycyclic aromatic hydrocarbons (PAHs) in air mass

A passive air sampler was developed for collecting polycyclic aromatic hydrocarbons (PAHs) in air mass from various directions. The airflow velocity within the sampler was assessed for its responses to ambient wind speed and direction. The sampler was examined for trapped particles, evaluated quantitatively for influence of airflow velocity and temperature on PAH uptake, examined for PAH uptake kinetics, calibrated against active sampling, and finally tested in the field. The airflow volume passing the sampler was linearly proportional to ambient wind speed and sensitive to wind direction. The uptake rate for an individual PAH was a function of airflow velocity, temperature and the octanol-air partitioning coefficient of the PAH. For all PAHs with more than two rings, the passive sampler operated in a linear uptake phase for three weeks. Different PAH concentrations were obtained in air masses from different directions in the field test.     

Particle size distribution of n-alkanes and polycyclic aromatic hydrocarbons (PAHS) in urban and industrial aerosol of Algiers,Algeria

The distribution of ambient air n-alkanes and polycyclic aromatic hydrocarbons (PAHs) associated to particles with aerodynamic diameters lesser than 10 μm (PM₁₀) into six fractions (five stages and a backup filter) was studied for the first time in Algeria. Investigation took place during September of 2007 at an urban and industrial site of Algiers. Size-resolved samples (<0.49, 0.49–0.95, 0.95–1.5, 1.5–3.0, 3.0–7.2, and7.2–10 μm) were concurrently collected at the two sampling sites using five-stage high-volume cascade impactors. Most of n-alkanes (~72 %) and PAHs (~90 %) were associated with fine particles ≤1.5 μm in both urban and industrial atmosphere. In both cases, the n-alkane contents exhibited bimodal or weakly bimodal distribution peaking at the 0.95–1.5-μm size range within the fine mode and at 7.3–10 μm in the coarse mode. Low molecular weight PAHs displayed bimodal patterns peaking at 0.49–0.95 and 7.3–10 μm, while high molecular weight PAHs exhibited mono-modal distribution with maximum in the <0.49-μm fraction. While the mass mean diameter of total n-alkanes in the urban and industrial sites was 0.70 and 0.84 μm, respectively, it did not exceed 0.49 μm for PAHs. Carbon preference index (~1.1), wax% (10.1–12.8), and the diagnostic ratios for PAHs all revealed that vehicular emission was the major source of these organic compounds in PM₁₀ during the study periods and that the contribution of epicuticular waxes emitted by terrestrial plants was minor. According to benzo[a]pyrene-equivalent carcinogenic power rates, ca. 90 % of overall PAH toxicity across PM₁₀ was found in particles ≤0.95 μm in diameter which could induce adverse health effects to the population living in these areas.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) on glass surfaces

Sorption of polycyclic aromatic hydrocarbons (PAHs) to glass commonly used in laboratories was studied. Sorption coefficients (K_d) of five selected PAHs to borosilicate glass surfaces were measured using column chromatography. A linear relationship between log K_d and the corresponding water solubility of the subcooled liquid (log S_w) of the investigated PAHs was observed. Based on the determined sorption coefficients our data revealed that mass loss caused by sorption on glass walls strongly depends on the ratio of solution volume to contacted surface area (V/S). The influence of solution chemistry such as ionic strength, solution pH, presence of cosolvent, and the influence of temperature on the sorption process were investigated. In the presence of ionic strength, sorption coefficients concurrently increased but less than a factor of 2 up to 0.005 M calcium chloride concentration. However, further increasing ionic strength had no influence on K_d. The cosolvent reduced sorption at a concentration of methanol in water above 0.5% (v/v); however, for benzo[a]pyrene even with 10% (v/v) methanol the mass loss would be still higher than 10% (with a V/S ratio less than 0.25). Significant effects of the solution pH and temperature were not observed. These results suggest that van der Waal’s forces dominate the sorption process. In the analysis of highly hydrophobic PAHs in aqueous samples, mass loss due to sorption on glass walls should be accounted for in the final result if untreated glass is used. The presented relationship between log K_d and log S_w may help to decide if such a correction is necessary. Furthermore, the frequently used silanization of glass surfaces may not be sufficient to suppress sorption for large PAHs.     

Biomonitoring seasonal variation of urban air polycyclic aromatic hydrocarbons (PAHs) using Ficus benghalensis leaves

Temporal and seasonal variations of polycyclic aromatic hydrocarbons (PAHs) concentrations in leaves of Ficus benghalensis were investigated in Varanasi city (India). Leaf samples were collected from six sites from urban area of Varanasi and from a control site. PAH extraction was done by sonication in dichloromethane-acetone and quantification by GC-MS. In January total leaf PAHs concentrations at all the urban sites were twice higher as compared to other season's viz. summer and rainy. In contrast, at the control site leaf PAHs concentrations showed lower values than urban sites. The maximum concentrations of total PAHs in winter were due to the medium molecular weight PAHs which increases with respect to both low and high molecular weight PAHs. The temporal variation of medium molecular weight PAHs was similar both at the urban and remote sites. These results support biomonitoring ability of Ficus benghalensis leaves to temporal variations in PAHs contamination.     

Persistence of polycyclic aromatic hydrocarbons (PAHs) in sewage sludge-amended soil

The application of sewage sludge as a fertilizer is a common method used to improve soil properties. However, sewage sludge may contain various organic pollutants including polycyclic aromatic hydrocarbons. In the present study, the persistence of PAHs in soils fertilized with different sewage sludge doses was compared in relation to the sewage sludge dose applied (30, 75, 150, 300 and 600 Mgha(-1)) and the content of the polycyclic aromatic hydrocarbons in them. The experiment was carried out in two blocks of experimental plots divided according to the type of plants grown: field plants and perennial-willow. Sewage sludge addition to soils resulted in an increase in the content of polycyclic aromatic hydrocarbons in these soils. This increase was proportional to the quantity of sewage sludge applied. The results obtained showed that during a 42/54-month period, more than half of the individual PAHs introduced into the soil with sewage sludge were degraded. The scope of dissipation depended on the sewage sludge dose and the use to which the area was put. In the experiment with the willow only in the case of the highest sludge dose was a decrease in the PAH content above 50% noted; whereas in the case of the experiment with the field plants, it was higher by 50% for all sewage sludge doses. In experiment with field plants the highest scope of individual PAH disappearance was observed in the soil with the sewage sludge dose amounting to 300 Mgha(-1). In experiment with willow a relatively high dissipation of individual PAHs (>50%) was found in the treatment with the highest sludge dose (600 Mgha(-1)). A wider PAH dissipation range in the experiment with field plants was conditioned by the more favourable conditions created as a result of the breeding treatments applied. Agrotechnical treatments clearly increased the disappearance of the PAHs in those soils fertilized with the lowest sewage sludge doses (30 and 75 Mgha(-1)). The results obtained showed that the preferred method of treating a light soil fertilised with sewage sludges should be a one-year system, with a sludge application of 75 Mgha(-1).     

Seasonal variation of polycyclic aromatic hydrocarbons (PAHs) emissions in China

A regression model based on the provincial energy consumption data was developed to calculate the monthly proportions of residential energy consumption compared to the total year volume. This model was also validated by comparing with some survey and statistical data. With this model, a PAHs emission inventory with seasonal variation was developed. The seasonal variations of different sources in different regions of China and the spatial distribution of the major sources in different seasons were also achieved. The PAHs emissions were larger in the winter than in the summer, with a difference of about 1.3-folds between the months with the largest and the smallest emissions. Residential solid fuel combustion dominated the pattern of seasonal variation with the winter-time emissions as much as 1.6 times as that in the summer, while the emissions from wild fires and open fire straw burning was mainly concentrated during the spring and summer.     

燃煤电厂多环芳烃的生成与控制

多环芳烃 (PAHs)对人体健康的危害极大。本文综述了燃煤电厂煤燃烧过程中多环芳烃的生成机理 (直接释放、热解合成和高温缩合机理 )和影响因素 (煤种、温度、锅炉负荷、过剩空气系数、停留时间、钙硫比和一次风 /二次风比 ) ,在此基础上介绍了煤燃烧过程中多环芳烃的各种控制技术和方法     

Enrichment of polycyclic aromatic hydrocarbons (PAHs) in mariculture sediments of Hong Kong

Surface and core sediments collected from six fish farms in Hong Kong and from reference sites were investigated for the enrichment and sources of polycyclic aromatic hydrocarbons (PAHs). Moderately high ∑PAH₁₆ levels (123-947 ng g⁻¹, mean: 450 ng g⁻¹) were found in the surface aquaculture sediments. In comparison with the sediments from the reference sites, the average enrichment percentage of total organic carbon (TOC) and PAHs in surface sediments were 21.4 and 43.8%, respectively, and in the core sediments, 24.6 and 73.7%, respectively. Mathematical source apportionment analyses (i.e. isomer ratios, hierarchical cluster analysis, principal components analysis with multiple linear regression analysis) suggested a higher percentage of petrogenic sources in aquaculture sediments. The fish feeds might be the main source of the enriched PAHs in the aquaculture sediments. To our knowledge, this is the first study showing that PAHs in aquaculture sediments could be attributed to human aquaculture activities.     

添加剂对堆肥降解多环芳烃的影响

为了研究多环芳烃(PAHs)污染土壤堆肥修复的加速机制,在人工控温的堆肥装置中以芘、菲和芴为研究对象,采用室内模拟实验的方式研究了添加硫酸钙、过磷酸钙、草炭、竹炭、十二烷基硫酸钠(K12)和十二烷基苯磺酸钠(SD-BS)等对锯末高温堆肥降解污染土壤PAHs的影响。研究结果表明,生物堆肥可以有效的去除土壤中PAHs,堆肥7周后所有处理下芘、菲和芴的降解率基本达到80%以上。不同添加剂处理下芘、菲和芴降解率不同,尤其是添加草炭和竹炭处理中芴和菲在第4周的时候就取得90%以上的降解率,芘在第6周也取得80%以上的降解率,而且氮素的损失率也分别下降了42.6%和36.09%,比其他处理的PAHs降解率和保氮效果都要好。分析其原因,一方面可能是添加不同添加剂对堆肥过程中pH值、有机质(SOM)、总氮(TN)和过氧化氢酶(CAT)都有一定的影响,提高了土壤微生物的活性;另一方面可能是由于草炭和竹炭对氨有良好的吸附性,具有良好的保氮效果,同时也能改善了微生物和目标化合物的接触方式,从而提高了PAHs的降解率。     

Global atmospheric emission inventory of polycyclic aromatic hydrocarbons (PAHs) for 2004

The global atmospheric emissions of the 16 polycyclic aromatic hydrocarbons (PAHs) listed as the US EPA priority pollutants were estimated using reported emission activity and emission factor data for the reference year 2004. A database for emission factors was compiled, and their geometric means and frequency distributions applied for emission calculation and uncertainty analysis, respectively. The results for 37 countries were compared with other PAH emission inventories. It was estimated that the total global atmospheric emission of these 16 PAHs in 2004 was 520 giga grams per year (Gg y^?1) with biofuel (56.7%), wildfire (17.0%) and consumer product usage (6.9%) as the major sources, and China (114 Gg y^?1), India (90 Gg y^?1) and United States (32 Gg y^?1) were the top three countries with the highest PAH emissions. The PAH sources in the individual countries varied remarkably. For example, biofuel burning was the dominant PAH source in India, wildfire emissions were the dominant PAH source in Brazil, while consumer products were the major PAH emission source in the United States. In China, in addition to biomass combustion, coke ovens were a significant source of PAHs. Globally, benzo(a)pyrene accounted for 0.05% to 2.08% of the total PAH emission, with developing countries accounting for the higher percentages. The PAH emission density varied dramatically from 0.0013 kg km^?2 y in the Falkland Islands to 360 kg km^?2 y in Singapore with a global mean value of 3.98 kg km^?2 y. The atmospheric emission of PAHs was positively correlated to the country's gross domestic product and negatively correlated with average income. Finally, a linear bivariate regression model was developed to explain the global PAH emission data.     

Accumulation of weathered polycyclic aromatic hydrocarbons (PAHs) by plant and earthworm species

Experiments were conducted to assess the bioavailability of polyclycic aromatic hydrocarbons (PAHs) in soil from a Manufactured Gas Plant site. Three plant species were cultivated for four consecutive growing cycles (28 days each) in soil contaminated with 36.3 microg/g total PAH. During the first growth period, Cucurbita pepo ssp. pepo (zucchini) tissues contained significantly greater quantities of PAHs than did Cucumis sativus (cucumber) and Cucurbita pepo ssp. ovifera (squash). During the first growth cycle, zucchini plants accumulated up to 5.47 times more total PAH than did the other plants, including up to three orders of magnitude greater levels of the six ring PAHs. Over growth cycles 2-4, PAH accumulation by zucchini decreased by 85%, whereas the uptake of the contaminants by cucumber and squash remained relatively constant. Over all four growth cycles, the removal of PAHs by zucchini was still twice that of the other species. Two earthworm species accumulated significantly different amounts of PAH from the soil; Eisenia foetida and Lumbricus terrestris contained 0.204 and 0.084 microg/g total PAH, respectively, but neither species accumulated measurable quantities 5 or 6 ring PAHs. Lastly, in abiotic desorption experiments with an aqueous phase of synthetically prepared organic acid solutions, the release of 3 and 4 ring PAHs from soil was unaffected by the treatments but the desorption of 5-6 ring constituents was increased by up to two orders of magnitude. The data show that not only is the accumulation of weathered PAHs species-specific but also that the bioavailability of individual PAH constituents is highly variable.     

Leaching characteristics of polycyclic aromatic hydrocarbons (PAHs) from spiked sandy soil

In order to evaluate the factors affecting leachability of hydrophobic organic pollutants (HOPs), we performed leaching tests under a variety of conditions using sandy soil contaminated with phenanthrene and pyrene. The results obtained were: (1) the shaking time, temperature, and dissolved humic matter (DHM, as coexisting matter) increased leachability; (2) ionic strength reduced leachability; and (3) the liquid-to-solid ratio and pH level had no effect on leaching concentration of HOPs. In DHM-added leaching tests assuming equilibrium with HOPs, DHM, and solid matrix, the partitioning (binding) coefficient of HOPs to DHM was accurately calculated with the equations proposed in this study. While we recommend taking into consideration the coexistence of DHM, it is difficult to use universally because its properties differ according to origin and extracting method. It is therefore reasonable to use an alternative reagent having an effect similar to that of DHM.     

Migration of polycyclic aromatic hydrocarbons (PAHs) in urban treatment sludge to the air during PAH removal applications

In the present study, the amounts of polycylic aromatic hydrocarbons (PAHs) penetrating into air during PAH removal applications from the urban treatment sludge were investigated. The effects of the temperature, photocatalyst type, and dose on the PAH removal efficiencies and PAH evaporation were explained. The sludge samples were taken from an urban wastewater treatment plant located in the city of Bursa, with 585,000 equivalent population. The ultraviolet C (UV-C) light of 254 nm wavelength was used within the UV applications performed on a specially designed setup. Internal air of the setup was vacuumed through polyurethane foam (PUF) columns in order to collect the evaporated PAHs from the sludge during the PAH removal applications. All experiments were performed with three repetitions. The PAH concentrations were measured by gas chromatography–mass spectrometry (GC-MS). It was observed that the amounts of PAHs penetrating into the air were increased with increase of temperature, and more than 80% of PAHs migrated to the air consisted of 3-ring compounds during the UV and UV-diethylamine (DEA) experiments at 38 and 53 °C. It was determined that 40% decrease was ensured in Σ₁₂ (total of 12) PAH amounts with UV application and 13% of PAHs in sludge penetrated into the air. In the UV-TiO₂ applications, a maximum 80% of Σ₁₂ PAH removal was obtained by adding 0.5% TiO₂ of dry weight of sludge. The quantity of PAH penetrating into air did not exceed 15%. UV-TiO₂ applications ensured high levels of PAH removal in the sludge and also reduced the quantity of PAH penetrating into the air. Within the scope of the samples added with DEA, there was no increase in PAH removal efficiencies and the penetration of PAHs into air was not decreased. In light of these data, it was concluded that UV-TiO₂ application is the most suitable PAH removal alternative that restricts the convection of PAH pollution.

Implications: Polycyclic aromatic hydrocarbon (PAH) evaporation rates from sludge samples obtained from an urban wastewater treatment plant were investigated here for the first time by employing removal applications. TiO₂ and diethylamine were used as photocatalysts in this study. A special device was designed and successfully used in this study. Treatment sludge can be a significant source of PAHs for the atmosphere. The data highlight the need for removal of PAHs in treatment sludge via methods limiting their evaporation to the air. It was observed that UV-TiO₂ application was the most suitable PAH removal alternative that restricts the convection of PAH pollution.     

Source apportionment of atmospheric polycyclic aromatic hydrocarbons (PAHs) in Palm Beach County,Florida

Due to concerns about adverse health effects associated with inhalation of atmospheric polycyclic aromatic hydrocarbons (PAHs), 30 ambient air samples were obtained at an air quality monitoring station in Palm Beach County, Florida, from March 2013 to March 2014. The ambient PAH concentration measurements and fractional emission rates of known sources were incorporated into a chemical mass balance model, CMB8.2, developed by EPA, to apportion contributions of three major PAH sources including preharvest sugarcane burning, mobile vehicles, and wildland fires. Strong association between the number of benzene rings and source contribution was found, and mobile vehicles were identified to be the prevailing source (contribution ≥56%) for the observed PAHs concentration with lower molecular weights (four or fewer benzene rings) throughout the year. Preharvest sugarcane burning was the primary contributing source for PAHs with relatively higher molecular weights (five or more benzene rings) during the sugarcane burning season (from October to May of the next year). Source contribution of wildland fires varied among PAH compounds but was consistently lower than for sugarcane burning during the sugarcane harvest season. Determining the major sources responsible for ground-level PAHs serves as a tool to improving management strategies for PAH emitting sources and a step toward better protection of the health of residents in terms of exposure to PAHs. The results obtain insight into temporal dominance of PAH polluting sources for those residential areas located near sugarcane burning facilities and have implications beyond Palm Beach County, in areas with high concerns of PAHs and their linked sources.

Implications: Source apportionment of atmospheric polycyclic hydrocarbons (PAHs) in Palm Beach County, Florida, meant to estimate contributions of major sources in PAH concentrations measured at Belle Glade City of Palm Beach County. Number of benzene rings was found to be the key parameter in determining the source with the prevailing contribution. Mobile vehicle sources showed a higher contribution for species with four or fewer benzene rings, whereas sugarcane burning contributed more for species with five or more benzene rings. Results from this study encourage more control for sugarcane burns and help to better manage authorization of the sugarcane burning incidents and more restrictive transportation plans to limit PAH emissions from mobile vehicles.     

Seasonal variation of polycyclic aromatic hydrocarbons (PAHs) in Pearl River Delta region,China

A level IV fugacity model was applied to simulate the seasonal variation of polycyclic aromatic hydrocarbons (PAHs) in various bulk media in Pearl River Delta (PRD), China. The predictions were validated against monthly observed concentrations of gaseous and particulate phase PAHs in air and annual mean concentrations of all other bulk media. The uncertainty of the predictions was evaluated using Monte Carlo simulation. The influential parameters were identified using sensitivity analysis on both media concentrations and seasonal variations. The predicted concentrations and the patterns of seasonal variation generally agreed with the field observations. Concentrations of gaseous phase PAHs in air increased in the summer and decreased in the winter while concentrations of particulate phase PAHs in summer were lower than those in the winter. The relative variations of PAHs in the other bulk media were not as profound as those in air and the variation patterns were chemical compound dependent. Temperature and precipitation were the most important parameters leading to the seasonalities of PAH concentrations. Other key parameters included dry precipitation rate, advective water flow from upstream, and solid fractions in air and water.     

Occurrence of coal and coal-derived particle-bound polycyclic aromatic hydrocarbons (PAHs) in a river floodplain soil

A PAH contaminated river floodplain soil was separated according to grain size and density. Coal and coal-derived particles from coal mining, coal industry and coal transportation activities were identified by organic petrographic analysis in our samples. Distinct concentrations of PAHs were found in different grain size and density fractions, however, similar distribution patterns of PAHs indicated similar sources. In addition, although light fractions had the mass fraction by weight of less than 5%, they contributed almost 75% of the total PAHs in the soil. PAH concentrations of all sub fractions showed positive correlation with their TOC contents. Altogether, coal and coal-derived particles that were abundant in light fractions could be the dominant geosorbents for PAHs in our samples.     

The behaviors and fate of polycyclic aromatic hydrocarbons (PAHs) in a coking wastewater treatment plant

The occurrence, behaviors and fate of 18 PAHs were investigated in a coking wastewater treatment plant in Songshan coking plant, located in Shaoguan, Guangdong Province of China. It was found that the target compounds occurred widely in raw coking wastewater, treated effluent, sludge and gas samples. In raw coking wastewater, high molecular weight (MW) PAHs were the dominant compounds, while 3-6 ring PAHs predominated in the final effluent. The dominant compounds in gas samples were phenathrene, fluoranthene and pyrene, while they were fluoranthene, pyrene, chrysene and benzo[k]fluoranthene for sludge. The process achieved over 97% removal for all the PAHs, 47-92% of eliminations of these target compounds in liquid phase were achieved in biological stage. Different behaviors of PAHs were observed in the primary tank, anaerobic tank, aerobic tank, hydrolytic tank and coagulation tank units, while heavier and lower ones were mainly removed in anaerobic tank and aerobic tanks, respectively. Regarding the fate of PAHs, calculated fractions of mass losses for low MW PAHs due to transformation and adsorption to sludge accounted for 15-50% and 24-49%, respectively, while the rest was less than 1%. For high MW PAHs, the mass losses were mainly due to adsorption to sludge and separation with tar (contributing 56-76% and 22-39%, respectively), and the removal through transformation was less.     

Characterization and source identification of polycyclic aromatic hydrocarbons (PAHs) in river bank soils

Elevated PAH concentrations were detected in bank soils along the Mosel and Saar Rivers in Germany. Information on the identification of PAH sources in this area however remains unclear. This study was able to characterize the PAH sources by application of several approaches, including consideration of the distribution patterns of 45 PAHs (including 16 EPA PAHs and some alkyl PAHs), specific PAH ratios, distribution patterns of n-alkanes and principal component analysis (PCA). In addition, the efficiency of the tested approaches was assessed. The results from the application of the various source identification methods showed that pyrogenic PAHs dominate soil samples collected upstream of the confluence of the Mosel and Saar Rivers, and petrogenic and pyrogenic PAHs dominate samples downstream of the confluence. Based on the analysis of reference materials and organic petrography, the petrogenic input was found to be dominated by coal particles. More detailed information on the petrogenic sources was provided by the n-alkane analyses. The current study concludes that to accurately determine the origin of PAHs, several identification methods must be applied.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) to carbonaceous materials in a river floodplain soil

We report on sorption isotherm of phenanthrene (Phe) for river floodplain soil associated with carbonaceous materials, with particular attention being devoted to the natural loading of Phe. Our sorption experiments with original soil samples, size, and density sub-fractions showed that the light fraction had the highest sorption capacity comparable to low rank coals. In addition, the light fraction contributed most for the sorption of Phe in total soil samples. K_oc values for all fractions were in the same range, thus indicating that coal and coal-derived particles in all samples are responsible for the enhanced sorption for Phe. Sorption was strongly nonlinear and the combined partitioning and pore-filling model gave a better fit than the Freundlich sorption model. In addition, the spiked PAHs did not show the same behavior as the naturally aged ones, therefore the accessibility of indigenous background organic contaminants was reduced when coal and coal-derived particles are associated with the soils.     

我国环境介质中多环芳烃的分布及其生态风险

持久性有机污染物多环芳烃(PAHs)在我国环境介质中广泛分布,美国EPA规定的16种.优先控制多环芳烃大多在我国大气、水体、沉积物、土壤和生物体内检出.总结了我国环境介质中PAHs污染水平及特点,分析了其存在的环境风险.我国大气中PAHs污染较重,尤其是北方.水体已普遍受PAHs污染,其中部分水体污染严重;沉积物多环芳烃污染大多处于低生态风险水平,但沉积记录研究表明有越来越严重的趋势.我国土壤和生物体PAHs含量较低,污染生态风险较小.部分区域蔬菜中PAHs含量较高,存在不可忽视的生态风险.