Toxicity of Water- and Organic-Soluble Wood Tar Fractions from Biomass Burning in Lung Epithelial Cells.

Widespread smoke from wildfires and biomass burning contributes to air pollution and the deterioration of air quality and human health. A common and major emission of biomass burning, often found in collected smoke particles, is spherical wood tar particles, also known as "tar balls". However, the toxicity of wood tar particles and the mechanisms that govern their health impacts and the impact of their complicated chemical matrix are not fully elucidated. To address these questions, we generated wood tar material from wood pyrolysis and isolated two main subfractions: water-soluble and organic-soluble fractions. The chemical characteristics as well as the cytotoxicity, oxidative damage, and DNA damage mechanisms were investigated after exposure of A549 and BEAS-2B lung epithelial cells to wood tar. Our results suggest that both wood tar subfractions reduce cell viability in exposed lung cells; however, these fractions have different modes of action that are related to their physicochemical properties. Exposure to the water-soluble wood tar fraction increased total reactive oxygen species production in the cells, decreased mitochondrial membrane potential (MMP), and induced oxidative damage and cell death, probably through apoptosis. Exposure to the organic-soluble fraction increased superoxide anion production, with a sharp decrease in MMP. DNA damage is a significant process that may explain the course of toxicity of the organic-soluble fraction. For both subfractions, exposure caused cell cycle alterations in the G2/M phase that were induced by upregulation of p21 and p16. Collectively, both subfractions of wood tar are toxic. The water-soluble fraction contains chemicals (such as phenolic compounds) that induce a strong oxidative stress response and penetrate living cells more easily. The organic-soluble fraction contained more polycyclic aromatic hydrocarbons (PAHs) and oxygenated PAHs and induced genotoxic processes, such as DNA damage.

Analyses of Acidic Tar Dyes in High-Protein Foods and Examination of Extraction and Clean-Up Methods for Various Foods.

Extraction and clean-up methods were examined for the analysis of acidic tar dyes in various high-protein foods. 1% Aqueous ammonia followed by ethanol, 1% aqueous ammonia-ethanol (1 : 1) mixture, and 1% aqueous ammonia-tetrahydrofuran (1 : 1) mixture were used in sequence for boiled fish paste (kamaboko), pounded fish cake (hanpen), and sausage. The sausage extract was centrifuged at low temperature to solidify and remove the contained fat. Salted cod roe with red pepper was extracted twice with 1% aqueous ammonia-ethanol (1 : 1) mixture, followed by extraction with 1% aqueous ammonia-tetrahydrofuran (1 : 1) mixture. A divinylbenzene-N-vinylpyrrolidone copolymer column was used for the clean-up of xanthen dyes. In the case of clogging-prone samples, the same type of large-particle-size column was used. A polyamide column was used for clean-up of the other dyes. When each dye was added at 5 µg/g in the foods, recoveries from kamaboko, hanpen, and sausage ranged from 76 to 102%, and the average recovery from the two types of salted cold roe with red pepper ranged from 45 to 98%.

Analysis of Acidic Tar Dyes in High Protein Food: Effect of pH of Column Loading Solution for Clean-Up.

The effect of pH of the clean-up process in the analysis of 11 permitted tar dyes in high protein food was investigated by using a handmade polyamide column (PA column) and Oasis HLB. Boiled fish paste spiked with the 11 dyes was extracted with appropriate solvents and the pH of the extract was adjusted to 3.0-7.0 in increments of 0.5, followed by clean-up with the PA column. At pH 3.0-5.5, precipitate formed in the extract clogged the column, and the recoveries of R3, R104 and R105 were 26-68%. At pH 6.0-7.0, clogging was not observed and the recoveries of the 3 dyes were somewhat higher, at 38-79%. The recoveries of other dyes were more than 80% at pH 3.0-7.0. With Oasis HLB, column loading was conducted at pH 11.0, and the recoveries of the 3 dyes improved to 70-83%. In conclusion, all 11 dyes could be cleaned-up with the PA column and Oasis HLB and the recoveries exceeded 70%.

Recovery of Palm Oil and Valuable Material from Oil Palm Empty Fruit Bunch by Sub-critical Water.

Oil palm empty fruit bunch (EFB) is one of the solid wastes produced in huge volume by palm oil mill. Whilst it still contains valuable oil, approximately 22.6 million tons is generated annually and treated as solid waste. In this work, sub-critical water (sub-cw) was used to extract oil, sugar and tar from spikelet of EFB. The spikelet was treated with sub-cw between 180-280°C and a reaction time of 2 and 5 minutes. The highest yield of oil was 0.075 g-oil/g-dry EFB, obtained at 240°C and reaction time of 5 minutes. Astonishingly, oil that was extracted through this method was 84.5% of that obtained through Soxhlet method using hexane. Yield of oil extracted was strongly affected by the reaction temperature and time. Higher reaction temperature induces the dielectric constant of water towards the non-polar properties of solvent; thus increases the oil extraction capability. Meanwhile, the highest yield of sugar was 0.20 g-sugar/g-dry EFB obtained at 220°C. At this temperature, the ion product of water is high enough to enable maximum sub-critical water hydrolysis reaction. This study showed that oil and other valuable material can be recovered using water at sub-critical condition, and most attractive without the use of harmful organic solvent.

Screening method for solvent selection used in tar removal by the absorption process.

The aim of this paper is the study of the treatment of flue gas issued from a process of biomass gasification in fluidized bed. The flue gas contains tar which should be selectively removed from the fuel components of interest (e.g. H2, CO and light hydrocarbons) to avoid condensation and deposits in internal combustion engine. The chosen flue gas treatment is the gas-liquid absorption using solvents, which present specific physicochemical properties (e.g. solubility, viscosity, volatility and chemical and thermal stability) in order to optimize the unit on energetic, technico-economic and environmental criteria. The rational choice of the proper solvent is essential for solving the tar issue. The preselection of the solvents is made using a Hansen parameter in order to evaluate the tar solubility and the saturation vapour pressure of the solvent is obtained using Antoine law. Among the nine families of screened solvents (alcohols, amines, ketones, halogenates, ethers, esters, hydrocarbons, sulphured and chlorinates), acids methyl esters arise as solvents of interest. Methyl oleate has then been selected and studied furthermore. Experimental liquid-vapour equilibrium data using bubbling point and absorption cell measurements and theoretical results obtained by the UNIFAC-Dortmund model confirm the high potential of this solvent and the good agreement between experimental and theoretical results.

Aqueous extracts of cigarette tar containing the tar free radical cause DNA nicks in mammalian cells.

The ability of aqueous extracts of cigarette tar to nick DNA was investigated using viable mammalian cells. Tar extracts contain a radical with a stable electron spin resonance (ESR) signal at g = 2.0036 characteristic of a semiquinone. The association of the tar component that carries the ESR signal with DNA was demonstrated using viable rat alveolar macrophages. The formation of single-strand DNA breaks caused by cigarette tar extracts in viable rat thymocytes follows saturation kinetics, indicating a tar component associates with DNA and then nicks it. These studies support our hypothesis that tar components that contain the cigarette tar radical can enter cells, associate with, and then nick DNA.

Mutagenicity in Salmonella typhimurium TA98 of the serum extract of the organic matter derived from airborne particulates.

To investigate the interactions between mutagens and serum components, the mutagenicity of the serum extract of the organic matter derived from airborne particulates (tar) was examined by the Salmonella/mammalian microsome mutagenicity test. The mutagens in the organic matter were found to be extracted with serum but not with saline. The mutagenic activity of the serum extract of the tar, however, decreased to about 60% compared with that of the DMSO extract, when they were activated by S9 mix. On the other hand, without S9 mix, the mutagenic activities of the serum and DMSO extracts were about the same. Gel filtration of the serum extract was carried out and followed by mutagenicity testing of each fraction. It is suggested that the mutagens, which require metabolic activation, combine mainly with beta-lipoproteins and the direct mutagens with both alpha- and beta-lipoproteins in serum.

[Determination of B(a)p contents of pine tar and its extractives].

In this paper, the B(a)P contents of pine tar and its extractives A, B were determined by PC-Scanning method. After combining extraction by caffeine and formic acid with PC-Scanning method, the B(a)P contents were obtained. The results showed the B(a)P contents of pine tar and its extractives A, B were 6171.3 ppb, 2285.2 ppb, 129.6 ppb, among them, the B(a)P content of B was the lowest.

Traditional Tar Production from the Anatolian Black Pine [Pinus nigra Arn. subsp. pallasiana (Lamb.) Holmboe var. pallasiana] and its usages in Afyonkarahisar, Central Western Turkey.

BACKGROUND: Tar is one example of a plant product used in folk medicine and it is obtained from Pinus nigra Arn. subsp. pallasiana (Lamb.) Holmboe, which is very common in the West Anatolian Region. Old trees that are good for kindling and have thick trucks are preferred to obtain tar. Tar is used not only as traditional medicine but also for protection against both endoparasites and ectoparasites. The objective of this study was to record the traditional method of obtaining tar and its usages in Afyonkarahisar which is located in the Western Anatolian Region of Turkey. METHODS: In order to record the traditional methods of obtaining tar, we visited the villages of Doglat, Kürtyurdu and Çatagil in Afyonkarahisar (Turkey) June-July, 2012. Ethnobotanical data about the method of collection and traditional usages of tar were obtained through informal interviews with 26 participants (16 men and 10 women). Data concerning the method of tar collection and its traditional usages were recorded and photographed. RESULTS: The traditional method for obtaining tar from Pinus nigra subsp. pallasiana by local people was recorded and the local usages (curing ear pain in children, osteomyelitis, wounds, ulcers, eczema, acne, alopecia, fungus, foot-and-mouth disease in animals, mouth sores in sheep and goats, protection against endo- and ectoparasites, repellent for snakes, mice, flies (Tabanus bovinus) and ticks, and the prevention of water leakage from roofs) of tar are described. CONCLUSION: In this study, the traditional method for obtaining tar and the traditional usages of tar are explained. Documentation of the method of obtaining tar and its traditional usages may contribute to scientific research on the benefits and usages of tar in medicine, veterinary medicine, as well as other fields.

Fast microwave-assisted catalytic gasification of biomass for syngas production and tar removal.

In the present study, a microwave-assisted biomass gasification system was developed for syngas production. Three catalysts including Fe, Co and Ni with Al2O3 support were examined and compared for their effects on syngas production and tar removal. Experimental results showed that microwave is an effective heating method for biomass gasification. Ni/Al2O3 was found to be the most effective catalyst for syngas production and tar removal. The gas yield reached above 80% and the composition of tar was the simplest when Ni/Al2O3 catalyst was used. The optimal ratio of catalyst to biomass was determined to be 1:5-1:3. The addition of steam was found to be able to improve the gas production and syngas quality. Results of XRD analyses demonstrated that Ni/Al2O3 catalyst has good stability during gasification process. Finally, a new concept of microwave-assisted dual fluidized bed gasifier was put forward for the first time in this study.

Absorptive removal of biomass tar using water and oily materials.

Water is the most common choice of absorption medium selected in many gasification systems. Because of poor solubility of tar in water, hydrophobic absorbents (diesel fuel, biodiesel fuel, vegetable oil, and engine oil) were studied on their absorption efficiency of biomass tar and compared with water. The results showed that only 31.8% of gravimetric tar was removed by the water scrubber, whereas the highest removal of gravimetric tar was obtained by a vegetable oil scrubber with a removal efficiency of 60.4%. When focusing on light PAH tar removal, the absorption efficiency can be ranked in the following order; diesel fuel>vegetable oil>biodiesel fuel>engine oil>water. On the other hand, an increase in gravimetric tar was observed for diesel fuel and biodiesel fuel scrubbers because of their easy evaporation. Therefore, the vegetable oil is recommended as the best absorbent to be used in gasification systems.

Assessment uncertainty associated to the analysis of tar from gasification of sewage sludge.

The uncertainty evaluation associated with the quantification of tar from gasification of sewage sludge is present. Each of the sources of uncertainty associated with the wet type sampling method and GC-MS analysis was identified to determine the critical stages of the analytical methodology in order to reduce them. The study shows that major contributions to the overall uncertainty are related to extraction steps. High expanded uncertainties were found for all compounds, due to the segregation of the tar in different samples because of the sampling method. However, the analytical method used was successfully applied for the evaluation of the tar cleaning filter in a real gasification plant.

Gas cleaning, gas conditioning and tar abatement by means of a catalytic filter candle in a biomass fluidized-bed gasifier.

A bench-scale fluidized-bed biomass gasification plant, operating at atmospheric pressure and temperature within the range 800-820 degrees C, has been used to test an innovative gas cleaning device: a catalytic filter candle fitted into the bed freeboard. This housing of the gas conditioning system within the gasifier itself results in a very compact unit and greatly reduced thermal losses. Long term (22h) tests were performed on the gasifier both with and without the catalytic candle filter, under otherwise identical conditions. Analysis of the product gas for the two cases showed the catalytic filtration to give rise to notable improvements in both gas quality and gas yield: an increase in hydrogen yield of 130% and an overall increase in gas yield of 69% - with corresponding decreases in methane and tar content of 20% and 79%, respectively. HPLC/UV analysis was used to characterize the tar compounds.

Time-dependent inhibition and tetrahydrobiopterin depletion of endothelial nitric-oxide synthase caused by cigarettes.

Smoking causes a dysfunction in endothelial nitric-oxide synthase (eNOS), which is ameliorated, in part, by administration of tetrahydrobiopterin (BH(4)). The exact mechanism by which the nitric oxide deficit occurs is unknown. We have previously shown that aqueous extracts of chemicals in cigarettes (CE) cause the suicide inactivation of neuronal NO synthase (nNOS) by interacting at the substrate-binding site. In the current study, we have found that CE directly inactivates eNOS by a process that is not affected by the natural substrate l-arginine and is distinct from the mechanism of inactivation of nNOS. We discovered that CE causes a time-, concentration-, and NADPH-dependent inactivation of eNOS in an in vitro system containing the purified enzyme, indicating a metabolic component to the inactivation. The CE-treated eNOS but not nNOS was nearly fully reactivated upon incubation with excess BH(4), suggesting that BH(4) depletion is a potential mechanism of inactivation. Moreover, in the presence of CE, eNOS catalyzed the oxidation of BH(4) to dihydrobiopterin and biopterin by a process attenuated by high concentrations of superoxide dismutase but not catalase. We speculate that a redox active component in CE, perhaps a quinone compound, causes oxidative uncoupling of eNOS to form superoxide, which in turn oxidizes BH(4). The discovery of a direct inactivation of eNOS by a compound(s) present in tobacco provides a basis not only for further study of the mechanisms responsible for the biological effects of tobacco but also a search for a potentially novel inactivator of eNOS.

High-performance liquid chromatography of unmodified rosin and its applications in contact dermatology.

Rosin is a well recognised skin sensitiser and is also amongst the most common causes of occupational asthma. Due to its complex chemical composition, it is difficult to isolate its many components and this has hindered progress in the identification of the specific respiratory and contact allergens it contains. This paper reports the application of high-performance liquid chromatography and other analytical techniques to the isolation and identification of contact allergens in complex mixtures such as rosin. HPLC methods were developed in order to isolate as many rosin components as possible and these were then patch tested on rosin sensitive individuals. The structure of the most dermatologically active component was then determined using mass spectrometry, nuclear magnetic resonance and infrared techniques. An HPLC method has also been developed which will enable the identification of rosin in commercial products, providing a valuable tool for determining the cause of rosin contact allergy. Furthermore, mass spectral data for the common abieitic-type resin acids are compiled which were used to confirm the identification of the HPLC resin acid peaks and have not been reported previously.