Study Design and Methods to Investigate Inhalation and Dermal Exposure to Polycyclic Aromatic Compounds and Urinary Metabolites from Asphalt Paving Workers: Research Conducted through Partnership

Innovations in science may require crossing traditional boundaries between industry, unions, government, and academia. While such collaborations have the potential to be highly beneficial and productive, opportunities for such collaborations are often missed due to some of the inherent challenges. This collaborative research effort demonstrates an example of how a successful partnership can optimize the ability to answer complicated scientific questions. Specifically, these researchers collaborated to investigate inhalation and dermal exposures to polycyclic aromatic compounds and related urinary metabolites in hot-mix asphalt paving workers. Reported here are details of the partnership process used to create the study design, the review processes, and details of the analytical methodologies employed to help attain the study goals related to the identification of the nature, source, pathway, and biological relevance of exposure during hot-mix asphalt paving operations. The actual results of the study are being prepared for future publications.     

Overview of Polycyclic Aromatic Compounds (PAC)

The chemical group of polycyclic aromatic compounds (PAC), including the better-known subgroup of polycyclic aromatic hydrocarbons (PAH) and the heterocyclic aromatic compounds (NSO-PAC, heterocycles), comprise several thousand individual compounds. It is hard to find a comprehensive overview in the literature of these PACs that includes a substantial amount of relevant properties. Here an attempt is made to summarize the most studied but also some less well-known PACs. In addition to basic data such as recommended names, abbreviations, CAS numbers, molecular formulas, chemical structures, and exact mono-isotopic molecular weights, physico-chemical properties taken from the literature like boiling points, vapor pressures, water solubilities, Henry's Law constants, n-octanol-water partition coefficients (log K_OW), and pK_a are summarized. Selected toxicological data are listed indicating carcinogenic and mutagenic activity or effects on different organisms.

PAC nomenclature is a complex topic, so suggestions for practical use are made. Regarding available data, estimated (instead of measured) values should be used with caution because considerable deviations from experimentally determined values can occur. For an enhanced understanding of the behavior of single PACs in comparison with each other, some of the properties mentioned above are plotted vs. the number of rings or the degree of alkylation. Also, some physico-chemical data are correlated with different functional groups as substituents of the PAHs.

This article reveals that rather little is known about the less common PACs, e.g., higher molecular weight compounds, alkylated or otherwise substituted aromatics, for instance, keto-, oxo-, amino-, nitro-, cyano-PAHs, or some heterocyclic aromatic compounds, including their derivatives. It mirrors the limited state of knowledge about the variety of PACs that do not belong to the 16 EPA PAHs.     

Development of a 5-Layer Passive Organic Dermal (POD) Sampler

A 5-layer passive organic dermal sampler was developed to allow the collection, retention, and recovery of a variety of organic compound classes simultaneously. The 5-layers, from outside in, consisted of polypropylene, polyurethane foam, C-18 solid-phase extraction disk, ethylene tetrafluoroethylene, and activated carbon cloth. The layers were enclosed in aluminum foil and placed in a muslin envelope that had a 40.0 mm diameter opening.

Ten samplers were spiked separately with three levels of diesel oil, a 50/50 diesel oil/asphalt mixture, and asphalt binder. For the diesel oil spikes, recoveries were 69.9, 71.3, 88.8, and 95.4% for 10, 10, 50, and 100 mg of diesel oil. For the 50/50 mixture, recoveries were 105.4, 92.8, and 92.0% for 10, 50, and 100 mg of the 50/50 mixture. For the asphalt binder spikes, recoveries were 104.7, 100.2, and 100.1% for 10, 50, and 100 mg of asphalt binder. For repeatability assessment, 7 samplers were spiked with 50 mg of the 50/50 mixture and recoveries averaged 92.6% (standard deviation 8.6). Samplers tested on asphalt paving workers proved functional, comfortable, flexible, and durable.     

Focused Microwave (FMW) Extraction of Polycyclic Aromatic Hydrocarbons (PAHs) from Plant Bioindicators,Comparison with Classical Techniques

Extraction efficiencies of polycyclic aromatic compounds (PAHs) from spruce needles (Picea abies) obtained by recently introduced “focused microwave assisted (FMW) extraction” (i) and conventional methods represented by extraction enhanced by sonication (ii) and Soxhlet extraction (iii) were compared. n-Hexane:acetone (azeotropic ratio, 53.5 wt % of acetone) extraction mixture was used in all experiments. The influence of various parameters (extraction time, intensity of irradiation, moisture content) both on the recoveries of PAHs from spruce needles (Picea abies) and the amount of co-isolated matrix components potentially interfering within the determinative step was examined. The mean extraction efficiencies of PAHs obtained by FMW extraction and sonication were found to be lower (82 % and 75 %, respectively) compared the extraction in Soxhlet apparatus (equal 100 %).     

Residue Levels,Profiles, Emission Source and Daily Intake of Polycyclic Aromatic Hydrocarbons Based on Smoked Fish Consumption,An Egyptian Pilot Study

Residue levels and spectrum of polycyclic aromatic hydrocarbons (PAHs) were determined in smoked fish, and canned smoked fish, collected from grocery shops from Cairo, Giza, Menoufya, and Ismailia governorates, Egypt. Residues of PAHs were monitored using gas liquid chromatography, equipped with a flame ionization detector. The concentrations of ∑13 PAHs in the smoked fish and the canned smoked fish ranged from 36.06–547.1 μg/kg, respectively. Benzo(a)pyrene was not detected in smoked canned fish, while its mean residues in smoked fish amounted to 1.1 μg/kg, corresponding to one fifth of the maximum tolerable limit of 5 μg/kg established by EU. The congeners profile showed that the sources of PAHs in the two brands of smoked fish are mainly petrogenic. Based on smoked fish the daily intake of 13 PAHs and benzo(a)pyrene were 45.59 μg/day and 0.092 μg/day, respectively, while for canned smoked fish the intake was fifteen times lower (3 μg/day), and the intake of benzo(a) pyrene is zero μg/day. Results showed that the consumption of smoked fish would pause some risk to consumers; meanwhile canned smoked fish showed no risk to Egyptian consumers.     

Monitoring and Origin of Polycyclic Aromatic Hydrocarbons (PAHs) in Effluents from a Surface Treatment Industry

ABSTRACT

In Europe, polycyclic aromatic hydrocarbons (PAHs) are a source of concern due to their toxic effects and are considered as priority pollutants by water authorities. In this study, we reported the results of qualitative and quantitative monitoring of 16 PAHs in effluents from a surface treatment industry to determine their origin. The results indicated that PAHs were present in the discharge waters at a concentration of 500 ng L^?1 (in average for the PAH sum). However, the further we returned to the start of the industrial process, the more the PAH concentrations increased. Indeed, the highest concentrations (>20,000 ng L^?1 for the PAH sum) were found in the degreasing baths – the first step in the part treatment. The final analyses showed that the PAHs came from the oils left on the metal parts by the suppliers. The important difference in concentrations between the upstream (first baths in the production line) and the downstream (discharge water) of the effluent showed that phenomena including dilution or potentially degradation occurred but that the major part of the PAHs tended to adsorb to sludge during the settling step in the effluent treatment plant.     

Levels of Polycyclic Aromatic Hydrocarbons (PAHs) in Atmospheric Environment of Urban Areas in Latin America

Polycyclic aromatic hydrocarbons (PAHs) are chemical compounds considered as pollutants of high priority due to their carcinogenic potential. PAH can appear in water, soil or in the atmosphere as adsorbed on particulate material or in gas phase. An increased number of studies on atmospheric PAH in urban areas have been published in the last decade, especially in the last years. Anthropogenic sources are frequently mentioned to be responsible for the increased concentration of PAHs in the atmosphere of urban areas, which at the same time seems to depend on meteorological parameters. This research is focused on compiling information on PAH levels in Latin America and their relationship with typical meteorological variables from seasonal and tropical countries. Brazil is the country with the most number of bibliographies about this topic, followed by Argentina, Chile and Mexico. Scarce information was found for Colombia and Venezuela and none for the rest of Latin American countries. The majority of studies checked have evaluated the climatological parameters in relationship with the PAH concentration and their distribution, finding that it affects meaningfully their levels. The monitor campaigns in Brazil have been developed mainly in the southern cities, where PAHs are strongly influenced by the seasons and their proximity to the South Pole. Tropical countries such as Venezuela and Colombia showed moderate variation of PAH concentration through months. The main influential parameters are precipitation and direction/speed winds.     

Distribution and Sources of Polycyclic Aromatic Hydrocarbons (PAHs) in Surface Sediments from the Northern Part of the Persian Gulf (Hormuzgan Province)

Sediments from the intertidal areas of Hormuzgan province in northern part of Persian Gulf (Iran) were investigated for the levels and possible sources of 15 polycyclic aromatic hydrocarbons (PAHs). Samples of sediments were collected from twelve sampling sites and analyzed for PAHs by gas chromatography–mass spectrometry (GC-MS). The results showed that the total concentrations of PAHs ranged from 765 to 1898 ng/g dry weight. Composition pattern in the sediment samples from 12 sampling sites was dominated by 4-ring PAH compounds. Molecular indices based on ratios of PAH concentrations were used to differentiate PAHs from pyrolitic, petrogenic and mixed origins. The results of study suggested that the main sources of PAHs in the sediment were mixed with pyrolitic and petrogenic inputs. According to the US sediments quality guidelines (SQGs) (ERL/ERM) sediments of the mentioned region did not show any ecotoxicological risk for benthic organisms.     

改进索氏提取器提取土壤中多环芳烃（菲、蒽、屈）

文章用改进索氏提取器与自动索氏提取器提取土壤中加标多环芳烃（菲、蒽、屈）,采用高效液相色谱法对提取液进行分离测定,并选择了流动相最佳比例。结果表明,采用改进索氏提取器,二氯甲烷作提取剂,氧化铝柱层析法纯化,并用HPLC—UVD测定可得到很好的效果。三种多环芳烃的平均加标回收率在78.7%~111%之间,且重现性较好。     

海洋中多环芳烃生物降解与修复研究进展

在人为活动和自然活动的影响下,海洋中多环芳烃(PAHs)的污染急剧加重,引起了广泛的关注。在简要介绍PAHs的特点、来源、分布以及海洋中PAHs污染的基础上,论述了海洋中PAHs微生物降解的最新研究进展,阐述了PAHs生物降解的途径和机制,归纳了微生物修复技术在海洋PAHs污染治理方面的应用以及红树林在去除PAHs中所发挥的作用,最后对海洋中PAHs的生物降解与修复技术发展前景进行了展望。     

Biosurfactant-Assisted Bioremediation of Polycyclic Aromatic Hydrocarbons (PAHs) in Liquid Culture System and Substrate Interactions

A lipopeptide biosurfactant was produced by the bacterium Pseudomonas aeruginosa strain LBP9 isolated from petroleum-contaminated soil. Phenanthrene, fluoranthene, and pyrene were used as model polycyclic aromatic hydrocarbons (PAHs) to study the effect of the biosurfactant on the biodegradation of mixed and sole substrate PAHs, and examine substrate interactivity effects on their biodegradation in liquid culture. At 400 mg/L amendment of lipopeptide, the solubility of phenanthrene, fluoranthene, and pyrene were increased to 19, 33, and 45 times their aqueous solubility, respectively, and the extent of substrate utilization rate (q_max?) of PAHs was enhanced up to three-fold in the sole substrate studies in comparison to the unamended controls. In the ternary PAH mixture at total concentration of 300 mg/L, with equal parts of each PAH, 77%, 57%, and 33% degradation of phenanthrene, fluoranthene, and pyrene were observed, respectively, at 400 mg/L lipopeptide amendment on day 30 of incubation. Whereas in the sole substrate experiments at 300 mg/L concentration of each PAH and the same level of lipopeptide amendment more than 98% fluoranthene and 76% pyrene were degraded and phenanthrene removal was so rapid that at day 4 of incubation more than 80% was degraded. Biosurfactants at optimum amounts enhanced biodegradation of PAHs. Lipopeptide amendments of 200 mg/L and 400 mg/L were found out to be optimum amounts for statistically significant (p < 0.05) biodegradation of the PAHs in the experiments. However, despite biosurfactant-enhanced bioavailability of the PAHs, biodegradation rate was competitively inhibited in the multisubstrate microcosms.     

Novel Application of Cyclolipopeptide Amphisin: Feasibility Study as Additive to Remediate Polycyclic Aromatic Hydrocarbon (PAH) Contaminated Sediments

To decontaminate dredged harbor sediments by bioremediation or electromigration processes, adding biosurfactants could enhance the bioavailability or mobility of contaminants in an aqueous phase. Pure amphisin from Pseudomonas fluorescens DSS73 displays increased effectiveness in releasing polycyclic aromatic hydrocarbons (PAHs) strongly adsorbed to sediments when compared to a synthetic anionic surfactant. Amphisin production by the bacteria in the natural environment was also considered. DSS73's growth is weakened by three model PAHs above saturation, but amphisin is still produced. Estuarine water feeding the dredged material disposal site of a Norman harbor (France) allows both P. fluorescens DSS73 growth and amphisin production.     

Monitoring and Assessment of Polycyclic Aromatic Hydrocarbons (PAHs) in the Atmosphere of Alexandria City,Egypt

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) in the total suspended particulate (TSP) were measured simultaneously between January 30, 2015 and February 11, 2016 at urban, suburb, and rural sites at Alexandria City, Egypt, using pesticide samplers. Samples were extracted and analyzed using chromatography–mass spectrometric (GC–MS). There was a significant difference in concentrations between the three sites, and between particle- and vapor-phases. Mean total PAH concentrations were 502.48, 322.57, and 417.23 ng m^?3 for the urban, the rural, and the suburban sites in particulate-phase and were 723.49, 402.26, and 543.15 for the same sites in vapor-phase, respectively. At the three sites, the most abundant compounds determined were Benzo[k]fluoranthene (BkF), followed by Benzo[a]pyrene (BaP) and Indeno [1,2,3-cd] pyrene (IcdP). These high molecular weight compounds are carcinogenic and known to originate mainly from vehicular emissions. The diagnostic ratios indicated PAHs in urban and suburban sites were predominantly from gasoline and diesel engines, while that in rural site was from biomass burning. Characterization of the emission sources was further substantiated by significant correlation between individual PAH species.     

Multimedia and Spatial Distribution,Internal Accumulation and Source Diagnostics of Polycyclic Aromatic Hydrocarbons (PAHs) of the Luan River Basin,China

The distribution, composition, and source of 16 polycyclic aromatic hydrocarbons (PAHs) in the Luan River, China, were investigated in this study. The compositional profiles of PAHs in the three mediums represented different characteristics. In different land-use areas, compositional profiles of PAHs in water were familiar, while that in sediment and bank soil presented differences. The spatial distribution of PAHs indicated that the most polluted sites all gathered in the middle and lower reaches of the region, which was different from other rivers in China. The PAH data of bank soil were used for source identification. Both diagnostic ratios of selected PAHs and principal component analysis (PCA) with multiple linear regression (MLR) analysis were studied, suggesting mixed source of PAHs in the Luan River Basin.     

Determination of Carcinogenic Polycyclic Aromatic Hydrocarbons (PAHs), Aflatoxins,and Nitrosamines in Processed Fish from the Winam Gulf Area of Kenya and Estimated Potential Exposure in Human

PAHs, aflatoxins and nitrosamines were analyzed in fish samples obtained from various markets and locations within the Winam Gulf area and processed by various methods often used in Kenya. The mean concentrations of total PAHs (TPAHs) in the smoked, charcoal-grilled and fresh tilapia muscle samples ranged from 22.27–44.58, 20.36–28.51, and 11.43–16.53 μg/kg wet weight, respectively. The concentrations of individual PAHs decreased in the order smoked>charcoal-grilled>fresh fish. Of the USEPA 16 PAHs, benzo(a)pyrene, dibenzo(a,h)anthracene, indeno(1,2,3-cd)pyrene, and benzo(g,h,i)perylene were not detected in all samples analyzed. Fluoranthene, acenaphthene, anthracene, phenanthrene, and acenaphthylene were not detected in fresh tilapia muscles but were generated in significant amounts on the samples during smoking and charcoal-grilling. The risk of exposure to human was estimated to be 0.67 μg/day through consumption of tilapia. The TPAHs levels in fresh fish, smoked and grilled tilapia were higher than the maximum allowable concentrations as per the WHO standards. Aflatoxins were found to be generated in sun-dried Dagaa during handling and storage with total mean concentrations ranging from 0.33–1.58 μg/kg wet weight but none were detected in the fresh samples. The daily intake of aflatoxins through consumption of Dagaa was estimated to be 0.0079 μg/day during the rainy season when the drying process is less efficient. None of the nitrosamines were detected in both fresh and the deep-fried tilapia muscle samples (frying temperatures ranging from 110–170°C) after exposure to nitrites and nitrates in water, in concentrations ranging up to 10 μg/L (NO₂^?) and up to 160 μg/L (NO₃^?).     

The Effect of Local Cooking Methods on Polycyclic Aromatic Hydrocarbons (PAHs) Contents in Beef,Goat Meat,and Pork as Potential Sources of Human Exposure in Kisumu City,Kenya

Roasted meat is known to be a major source of human exposure to PAHs. The contribution of direct-heat charcoal-roasted, electric- oven grilled, and shallow-pan fried meat to human exposure in Kisumu City was not known although the three modes of cooking meat are very prevalent. This study analyzed the concentrations of the PAHs in raw beef, goat meat, and pork, investigated the effect of direct-heat charcoal roasting, electric-oven grilling, and shallow-pan frying on these concentrations, and compared their concentration levels with international standards for foods in order to assess the potential risks to consumers. Samples were taken from three popular meat-roasting hotels within Kisumu City, Kenya. Extraction of PAHs was done using liquid-liquid partition after saponification with alcoholic potassium hydroxide followed by clean-up on a silica gel column and final analysis by gas chromatography-mass spectrometry (GC-MS). Roasting and shallow-pan frying introduced new PAHs and significantly (P ≤ 0.05) increased the concentrations of those existing in raw meat. Direct-heat charcoal roast beef had 5 new PAHs and a total mean PAH content of 17.88 μg/kg, compared with a mean of 1.39 μg/kg for raw beef, with the potent dibenz(a,h)anthracene also being detected. Direct-heat charcoal roasted goat meat had three new PAHs and a total mean PAH content of 4.77 μg/kg, compared with a mean of 2.13 μg/kg in raw meat, with the potent benzo(a)pyrene concentration being 8.84% of the total mean PAH. Fried pork had 7 new PAHs and a total mean PAH content of 3.47 μg/kg, compared with a mean total of 0.17 μg/kg, detected in the raw meat. Roast beef had the highest individual PAH concentration (5.03 μg/kg) and highest total PAHs concentration (17.88 μg/kg), both being higher than acceptable EU limits. The PAHs from local raw and cooked meat were characterized and quantified for the first time in Kisumu City and the study therefore provided the needed baseline data on PAHs in raw and cooked meat.     

Mangrove Oyster (Crassostrea belcheri) as a Biomonitor Species for Bioavailability of Polycyclic Aromatic Hydrocarbons (PAHs) from Sediment of the West Coast of Peninsular Malaysia

ABSTRACT

Rapid industrialization and urbanization in the west coast of Peninsular Malaysia has caused increasing pollution particularly of petroleum and petroleum by-products. Surface sediment and mangrove oyster (Crassostrea belcheri) were collected from five mangrove ecosystems in the west coast of Peninsular Malaysia and investigated for bioavailability of polycyclic aromatic hydrocarbons (PAHs). Sampling locations were selected from both remote areas with few or no previous records of petroleum pollution such as Pulau Merambong and polluted areas that are under international attention such as Klang mangrove ecosystem. PAH fractions were obtained through soxhlet extraction and two-step column chromatography and the fractions were injected to gas chromatography-mass spectrometry (GC-MS) for analysis. The concentrations of PAHs ranged from 151 to 4973 ng g^?1 dw in the sediments, while from 309 to 2225 ng g^?1 dw in the oysters. When tested for diagnostic ratios, a predominance of pyrogenic source PAHs was detected in the sediments, whereas PAHs in the oysters had mixed petrogenic and pyrogenic sources. A significant correlation (p < 0.05) was found between high molecular weight (HMW) PAHs in the sediments and oysters and biota accumulation factors (BAFs) of PAHs were approaching or exceeding unity indicating the ability of mangrove oyster in bioaccumulation of PAHs. Overall, this study indicates that mangrove oyster (C. belcheri) can be used as a biomonitor species for PAHs in an aquatic environment.     

Ecological and Health Risk Assessment of Polycyclic Aromatic Hydrocarbons (PAHs) in Surface Water from Middle and Lower Reaches of the Yellow River

In surface water from the middle and lower reaches of the Yellow River, total equivalent concentrations of 16 US EPA priority PAHs were calculated based on the measured concentrations. Ecological risk assessment approaches, including hazard quotient and overlapping areas of probability density curves, were performed to evaluate the combined ecological risks of PAHs to the aquatic organisms. The result from hazard quotient indicated that risk quotient of mollusks and zooplankton surpassed 0.1, suggesting potential risks. The potentially affected fractions of PAHs obtained from overlapping areas of probability density curve varied from 11.2% (dry season) to 5.1% (rainy season), which implied that PAHs had been posing pressures on the ecosystem. Health risk based on the incremental lifetime risk for PAHs was conducted to evaluate human cancer risk and noncarcinogenic hazard in the studied area. The results indicated that health risks mainly came from ingestion exposure pathway. The total cancer risks were in the range of 10^?8 to 10^?7, lower than the baseline value of acceptable risk (10^?6). Moreover, non-carcinogenic hazard indices of PAHs ranging from 10^?6 to 10^?5 were much lower than the threshold values (1.0). These results indicated that the water from middle and lower reaches of Yellow River might pose no health risk on local residents as a source of drinking water.     

Source Allocation of Aliphatic and Polycyclic Aromatic Hydrocarbons in Particulate-Phase (PM10) in the City of Valdivia,Chile

The concentration and signature of n-alkanes (n-C₁₀ to n-C₃₃) and 18 PAHs were determined in air filters across a year period (2010) in an urban area of the city of Valdivia, Chile. Filter samples were extracted using sohxlet apparatus and analyzed by GC-MS techniques. Concentrations of total hydrocarbons ranged from 45–352 ng.m^?3 and total PAHs ranged from 2.93–78.01 ng.m^?3. Concentrations of hydrocarbons during the summer were high (288–352 ng.m^-3) and reduced when the autumn began (45–79 ng.m^?3) to then increase almost linearly to the next summer. The drop in concentration was attributed in part to the significant reduction of traffic when summer ends as tourists leave the city (about 9–15% of the total cars circulating). Results from the chemometric technique of Polytopic Vector Analysis (PVA) indicated three main sources for the alkanes: biogenic (terrestrial plants), signatures of oil combustion, and an unconfirmed source which is thought to come from non specific organic matter degradation. Total PAHs correlated well with total particulate matter with a R² = 0.94. Levels of PAHs in the atmosphere were higher during the winter (6.85–78.01 ng.m^?3) period than the rest of the year (2.93–36.30 ng.m^?3). PVA results indicate three key sources of PAHs and two of those sources derived from oil combustion and biomass burning.