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.

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.

Solvent extraction and purification of sugars from hemicellulose hydrolysates using boronic acid carriers

Research was performed to determine whether it was technically feasible to use boronic acid extractants to purify and concentrate the sugars present in hemicellulose hydrolysates. Initially, five types of boronic acids (phenylboronic acid, 3,5-dimethylphenylboronic acid, 4-tert-butylphenylboronic acid, trans-β-styreneboronic acid or naphthalene-2-boronic acid) dissolved in an organic diluent (Shellsol® 2046 or Exxal® 10) containing the quaternary amine Aliquat® 336 were tested for their ability to extract sugars (fructose, glucose, sucrose and xylose) from a buffered, immiscible aqueous solution. Naphthalene- 2-boronic acid was found to give the greatest extraction of xylose regardless of which diluent was used. Trials were then conducted to extract xylose and glucose from solutions derived from the dilute acid hydrolysis of sugar cane bagasse and to then strip the loaded organic solutions using an aqueous solution containing hydrochloric acid. This produced a strip solution in which the xylose concentration had been increased over 7× that of the original hydrolysate while reducing the concentration of the undesirable acid-soluble lignin by over 90%. Hence, this process can be exploited to produce high concentration xylose solutions suitable for direct fermentation.

Naphthalene diimide-based non-fullerene acceptors for simple, efficient, and solution-processable bulk-heterojunction devices

Two solution processable, non-fullerene electron acceptors, 2,2′-(((2,7-dioctyl-1,3,6,8-tetraoxo-1,2,3,6,7,8-exahydrobenzo[lmn][3,8]phenanthroline-4,9-diyl)bis(thiophene-5,2-diyl))bis(methanylylidene))dimalononitrile (R1) and (2Z,2′Z)-3,3′-((2,7-dioctyl-1,3,6,8-tetraoxo-1,2,3,6,7,8-hexahydrobenzo[lmn][3,8]phenanthroline-4,9-diyl)bis(thiophene-5,2-diyl))bis(2-(4-nitrophenyl) acrylonitrile) (R2), comprised of central naphthalene diimide and two different terminal accepting functionalities, malononitrile and 2-(4-nitrophenyl)acetonitrile, respectively, were designed and synthesised. The central and terminal accepting functionalities were connected via a mild conjugated thiophene linker. Both of the new materials (R1 and R2) displayed high thermal stability and were found to have energy levels matching those of the archetypal electron donor poly(3-hexylthiophene). A simple, solution-processable bulk-heterojunction device afforded a promising power conversion efficiency of 2.24% when R2 was used as a non-fullerene electron acceptor along with the conventional donor polymer poly(3-hexylthiophene). To the best of our knowledge, the materials reported herein are the first examples in the literature where synchronous use of such accepting blocks is demonstrated for the design and development of efficient non-fullerene electron acceptors.