The characterisation of polycyclic aromatic hydrocarbons emissions from burning of different firewood species in Australia

Four kinds of woods used for residential heating in Australia were selected and burned under two burning conditions in a domestic wood heater installed in a laboratory. The selected wood species included pine (Pinus radiata), red gum (Eucalyptus camaldulensis), sugar gum (Eucalyptus cladocalyx) and yellow box (Eucalyptus melliodora). The two different burning conditions represented fast burning and slow burning, with the air inlet of the combustion chamber respectively ‘full open’ and ‘half open’. By sampling and analysing particulate and gaseous emissions from the burning of each load of wood under defined experimental conditions, PAHs emissions and their profiles in the particulate and gaseous phases were obtained. 16 species out of the 18 selected PAHs were detected. Of these, seven species were detected in the gaseous phase and most were lower molecular weight compounds. Similarly, more than 10 species of PAHs were detected in the particulate phase and these were mostly heavier molecular weight compounds. Under both burning conditions, emission levels for total PAHs and total genotoxic PAHs were the highest for pine and lowest for sugar gum, with red gum being the second highest, followed by yellow box. Using the specific sampling method, gaseous PAHs accounted for above 90% mass fraction of total PAHs in comparison to particulate PAHs (10%). The majority of the genotoxic PAHs were present in the particulate phase. PAHs emission levels in slow burning conditions were generally higher than those in fast burning conditions.

Study of polycyclic aromatic hydrocarbons emissions from burning of local wood species in Australia

Four kinds of Australian local wood species were burned in a domestic wood heater installed in a laboratory. The selected wood species include pine, red gum, yellow box and sugar gum, that are the most popular domestic fuel wood in Australia. Particulate matter emissions from burning of each load of wood were sampled isokinetically on filter media from the flue by standard stack emission sampling train. The particle laden filters then went for Gas Chromatography/ Mass Spectrometer (GC/MS) analysis to determine polycyclic aromatic hydrocarbons (PAHs) concentrations. The sampling was conducted under two different burning conditions – air inlet of the combustion chamber fully open and half open. Approximately 15 types of PAHs were detected. Emission factors were derived as microgram of PAHs /kg of wood burned. Total particulate emission factors were also obtained from gravimetric measurement before and after the sampling. PAH emission profiles for four species were generated from the results. Comparisons of emission factors have been conducted among different species of wood, as well as under different burning conditions, ie. fast burning and slowing burning. According to the derived emission factors, pine displayed the highest level of PAHs among the four species, followed by red gum and yellow box, whereas sugar gum showed the lowest level of PAHs. Emission factors were compared between each type of wood under two different burning conditions, the slow burning condition, which was air inlet half open, clearly showed higher PAH levels compared to the fast burning condition. Total PAH fractions on particulate matter were calculated and compared among wood types under two burning conditions. During the fast burning condition, red gum and pine have the higher percentage of PAH to total particulate matter emission than sugar gum and yellow box. When changed to slow burning, the PAH fraction on particulate matter are all increased with sugar gum having the largest increase.

Surfactant-mediated biodegradation of polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAHs) are toxic environmental pollutants that are known or suspected carcinogens or mutagens. Bioremediation has been used as a general way to eliminate them from the contaminated sites or aquifers, but their biodegradation is rather limited due to their low bioavailability because of their sparingly soluble nature. Surfactant-mediated biodegradation is a promising alternative. The presence of surfactants can increase the solubility of PAHs and hence potentially increase their bioavailability. However, inconclusive results have been reported on the effects of surfactant on the biodegradation of PAHs. In this work, surfactant-mediated biodegradation of PAHs is reviewed.

A novel cloud-point extraction process for preconcentrating selected polycyclic aromatic hydrocarbons in aqueous solution

A novel but simple cloud-point extraction (CPE) process is developed to preconcentrate the trace of selected polycyclic aromatic hydrocarbons (PAHs) with the use of the readily biodegradable nonionic surfactant Tergitol 15-S-7 as extractant. The concentrations of PAHs, mixtures of naphthalene and phenanthrene as well as pyrene, in the spiked samples were determined with the new CPE process at ambient temperature (23 °C) followed by high performance liquid chromatography (HPLC) with fluorescence detection. More than 80% of phenanthrene and pyrene, respectively, and 96% of naphthalene initially present in the aqueous solutions with concentrations near or below their aqueous solubilities were recovered using this new CPE process. Importantly Tergitol 15-S-7 does not give any fluorometric signal to interfere with fluorescence detection of PAHs in the UV range. No special washing step is, thus, required to remove surfactant before HPLC analyses. Different experimental conditions were studied. The optimum conditions for the preconcentration and determi nation of these selected PAHs at ambient temperature have been established as the following:  (1) 3 wt % surfactant; (2) addition of 0.5 M Na2SO4; (3) 10 min for equilibration time; and (4) 3000 rpm for centrifugal speed with duration of 10 min.

Polycyclic aromatic hydrocarbon emission loads and profiles from the burning of locally grown wood species in Victoria, Australia - Some pilot project results

A testing facility for combustion of biomass and sampling of emissions has been established at Deakin University. In this pilot project using this facility, four kinds of locally grown wood species were burned and the particle emissions sampled and analysed for Polycyclic Aromatic Hydrocarbons (PAHs). The selected wood species covering pine, red gum, yellow box and sugar gum, are the most popular domestic fuel wood in Australia. Particulate matter emissions from burning of each load of wood were sampled from the flue using a standard stack emission sampling train. The particle-laden filters were extracted and the .extract analysed to determine PAH concentrations by Gas Chromatographyl Mass Spectrometer (Gc/MS). The sampling was conducted under two different burning conditions with the air inlet of the combustion chamber fully open and with it half open. A suite of 15 PAHs, ranging from naphthalene (C IOHB) to dibenzolahlanthracene (C12H14), were selected for analysis. PAH profiles for the four wood species, under the different burning regimes, have been generated. Some preliminary emission factors for the different wood species have been derived as microgram of summed PAHs (rPAHs) emittedlkilogram of wood burned. Total Particulate Matter (TPM) emission factors were also obtained from gravimetric measurement of the sample filter before and after the combustion. Based on these emission factors, pine displayed the highest level of rPAHs emitted from the combustion of the four wood species, with sugar gum showing the lowest level of rPAHs emission. Emission factors associated with the slow burning condition clearly showed higher l:PAH levels compared to the faster burning condition. During the faster burning condition, red gum and pine show a higher percentage of rPAH to TPM than sugar gum or yellow box. Under the slower burning. the l:PAHlTPM ratio in every case was greater.

π-Selective stationary phases: (I) Influence of the spacer chain length of phenyl type phases on the aromatic and methylene selectivity of aromatic compounds in reversed phase high performance liquid chromatography

Phenyl type stationary phases of increasing spacer chain length (phenyl, methyl phenyl, ethyl phenyl, propyl phenyl and butyl phenyl, with 0–4 carbon atoms in the spacer chain, respectively) were synthesised and packed in house to determine the impact that the spacer chain length has on the retention process. Two trends in the aromatic selectivity, q_aromatic, were observed, depending on whether the number of carbon atoms in the spacer chain is even or odd. Linear log k′ vs ϕ plots were obtained for each stationary phase and the S coefficient was determined from the gradient of these plots. For the phenyl type phases, the S vs n_c plots of the retention factors of linear polycyclic aromatic hydrocarbons vs the number of rings exhibit a distinct discontinuity that between 3 and 4 rings, which increases with increasing spacer chain length for even phases but decreases for odd phases. Accordingly, we suggest that the retention factors depend differently on the number of carbon atoms in the spacer chain depending on whether this number is even or odd and that this effect is caused by different orientations of the aromatic ring relative to the silica surface.

Characterising vehicle emissions from the burning of biodiesel made from vegetable oil

Biodiesel manufactured from canola oil was blended with diesel and used as fuel in two diesel vehicles. This study aimed to test the emissions of diesel engines using blends of 100%, 80%, 60%, 40% , 20% biodiesel and 100% petroleum diesel, and characterise the particulate matter and gaseous emissions, with particular attention to levels of polycyclic aromatic hydrocarbons (PAHs) which are harmful to humans. A real time dust monitor was also used to monitor the continuous dust emissions during the entire testing cycle. The ECE(Euro 2) drive cycle was used for all emission tests. It was found that the particle concentration was up to 33% less when the engine burnt 100% biodiesel, compared to 100% diesel. Particle emission reduced with increased percentages of biodiesel in the fuel blends. Reductions of NOx, HC and CO were limited to about 10% when biodiesel was burned. Levels of CO2 emissions from the use of biodiesel and diesel were similar. Eighteen EPA priority PAHs were targeted, with only 6 species detected in the gaseous phase from the samples . 9 PAHs were detected in particulate phases at much lower levels than gaseous PAHs. Some marked reductions were observed for less toxic gaseous PAHs such as naphthalene when burning 100% biodiesel, but the particulate PAH emissions, which have more implications to adverse health effects, were virtually unchanged and did not show a statistically significant reduction. These findings are useful to gain an understanding of the emissions and environmental impacts of biodiesel.

Degradation of phenanthrene and pyrene in soil slurry reactors with immobilized bacteria Zoogloea sp.

The environmental fate of polycyclic aromatic hydrocarbons (PAHs) in soils is motivated by their wide distribution, high persistence, and potentially deleterious effect on human health. Polycyclic aromatic hydrocarbons constitute the largest group of environmental contaminants released in the environment. Therefore, the potential biodegradation of these compounds is of vital importance. A biocarrier suitable for the colonization by micro-organisms for the purpose of purifying soil contaminated by polycyclic aromatic hydrocarbons was developed. The optimized composition of the biocarrier was polyvinyl alcohol (PVA) 10%, sodium alginate (SA) 0.5%, and powdered activated carbon (PAC) 5%. There was no observable cytotoxicity of biocarriers on immobilized cells and a viable cell population of 1.86 × 10¹⁰ g^–1 was maintained for immobilized bacterium. Biocarriers made from chemical methods had a higher biodegradation but lower mechanical strengths. Immobilized bacterium Zoogloea sp. had an ideal capability of biodegradation for phenanthrene and pyrene over a relative wide concentration range. The study results showed that the biodegradation of phenanthrene and pyrene reached 87.0 and 75.4%, respectively, by using the optimal immobilized method of Zoogloea sp. cultivated in a sterilized soil. Immobilized Zoogloea sp. was found to be effective for biodegrading the soil contaminated with phenanthrene and pyrene. Even in "natural" (unsterilized) soil, the biodegradation of phenanthrene and pyrene using immobilized Zoogloea sp. reached 85.0 and 67.1%, respectively, after 168 h of cultivation, more than twice that achieved if the cells were not immobilized on the biocarrier. Therefore, the immobilization technology enhanced the competitive ability of introduced micro-organisms and represents an effective method for the biotreatment of soil contaminated with phenanthrene and pyrene.

Biodegradation of benzo[a]pyrene in soil by Mucor sp. SF06 and Bacillus sp. SB02 co-immobilized on vermiculite

Two indigenous microorganisms, Bacillus sp. SB02 and Mucor sp. SF06, capable of degrading polycyclic aromatic hydrocarbons (PAHs) were co-immobilized on vermiculite by physical adsorption and used to degrade benzo[a] pyrene (BaP). The characteristics of BaP degradation by both free and co-immobilized microorganism were then investigated and compared. The removal rate using the immobilized bacterial-fungal mixed consortium was higher than that of the freely mobile mixed consortium. 95.3% of BaP was degraded using the co-immobilized system within 42 d, which was remarkably higher than the removal rate of that by the free strains. The optimal amount of inoculated co-immobilized system for BaP degradation was 2%. The immobilized bacterial-fungal mixed consortium also showed better water stability than the free strains. Kinetics of BaP biodegradation by co-immobilized SF06 and SB02 were also studied. The results demonstrated that BaP degradation could be well described by a zero-order reaction rate equation when the initial BaP concentration was in the range of 10—200 mg/kg. The scanning electronic microscope (SEM) analysis showed that the co-immobilized microstructure was suitable for the growth of SF06 and SB02. The mass transmission process of co-immobilized system in soil is discussed. The results demonstrate the potential for employing the bacterial-fungal mixed consortium, co-immobilized on vermiculite, for in situ bioremediation of BaP.

Annetocin and TCTP expressions in the earthworm Eisenia fetida exposed to PAHs in artificial soil

The toxicity of sublethal polycyclic aromatic hydrocarbons (PAHs) levels in soils was assessed by testing their impact on expression of annetocin, a reproduction regulating gene, and translationally controlled tumor protein (TCTP), a tumorigenic response gene, in the earthworm Eisenia fetida cultured in artificial soil spiked with, phenanthrene (Phe), pyrene (Pyr), fluoranthene (Flu), or benzo(a)pyrene (Bap). Annetocin and TCTP were both up-regulated by 0.1 and 1.0 mg kg−1 benzo(a)pyrene and TCTP was down-regulated by 10.0 mg kg−1 phenanthrene. Weight loss and cocoon production of the worms were also analyzed. Only 10.0 mg kg−1 phenanthrene impacted earthworm weight loss significantly and no significant differences on cocoon production were observed. Our study indicated that the potential ecotoxicity of sublethal PAHs in soil should not be neglected and mRNA transcription level in earthworms was a more sensitive indicator of PAHs exposure than traditional indexes using cocoon production as endpoints and/or using the whole-organism as the test materials.