Incorporation of process integration into life cycle analysis for the production of biofuels

This article presents a new approach for incorporating process-integration tools into life cycle analysis (LCA) for biofuel production. Process synthesis techniques using mass- and energy-integration tools are employed to generate various scenarios for reducing mass and energy consumption in the process. The global implications of these changes and the associated trade-offs are assessed using the LCA tool: GREET. The developed approach enables the consideration of several levels of process integration while tracking the process economics and the reduction of the net greenhouse gas emissions. Several cases of biofuels with different processing technologies have been considered in this study, and the results show that when the process-integration tools are effectively utilized and combined with LCA, better insights are obtained and the net greenhouse gas emissions decrease drastically for different biofuels.     

Evidence of sequential lift in growth of aligned multiwalled carbon nanotube multilayers

We synthesized aligned multiwalled carbon nanotube multilayers by aerosol-assisted catalytic chemical vapor deposition through sequential injections of aerosols containing both carbon and catalyst precursors. Each sequence was traced by a specific duration or precursor mixture, with the carbon source being possibly enriched in (13)C isotope labels. We discovered that any sequence involved the growth of a new layer on the substrate surface, under any pre-existing one by lifting it up, giving definitive evidence of a base-growth mechanism.     

Study of the natural occurrence of T-2 and HT-2 toxins and their glucosyl derivatives from field barley to malt by high-resolution Orbitrap mass spectrometry

This paper reports a new method for the determination of T-2 and HT-2 toxins and their glucosylated derivatives in cereals, and some survey data aimed at obtaining more comprehensive information on the co-occurrence of T-2 and HT-2 toxins and their glucosylated derivatives in naturally contaminated cereal samples. For these purposes, barley samples originating from a Northern Italian area were analysed by LC-HRMS for the presence of T-2, HT-2 and relevant glucosyl derivatives. Quantitative analysis of T-2 and HT-2 glucosides was performed for the first time using a recently made available standard of T-2 glucoside. The glucosyl derivative of HT-2 was detected at levels up to 163 µg kg^–1 in 17 of the 18 analysed unprocessed barley grains, whereas the monoglucosyl derivative of T-2 toxin was detected in only a few samples and at low µg kg^–1 levels. The ratio between glucosylated toxins (sum of T-2 and HT-2 glucosides) and native toxins (sum of T-2 and HT-2) ranged from 2% to 283%. Moreover, taking advantage of the possibility of retrospective analysis of full-scan HRMS chromatograms, samples were also screened for the presence of other type-A trichothecenes, namely neosolaniol, diacetoxyscirpenol and their monoglucosyl derivatives, which were detected at trace levels. A subset of nine different samples was subjected to micro-maltation in order to carry out a preliminary investigation on the fate of T-2, HT-2 and relevant glucosides along the malting process. Mycotoxin reduction from cleaned barley to malt was observed at rates ranging from 4% to 87%.     

Electrochemical reduction of hexahydro-1,3,5-trinitro-1,3,5-triazine in aqueous solutions

Electrochemical reduction of RDX, hexahydro-1,3,5-trinitro-1,3,5-triazine, a commercial and military explosive, was examined as a possible remediation technology for treating RDX-contaminated groundwater. A cascade of divided flow-through cells was used, with reticulated vitreous carbon cathodes and IrO2/Ti dimensionally stable anodes, initially using acetonitrile/water solutions to increase the solubility of RDX. The major degradation pathway involved reduction of RDX to the corresponding mononitroso compound, followed by ring cleavage to yield formaldehyde and methylenedinitramine. The reaction intermediates underwent further reduction and/or hydrolysis, the net result being the complete transformation of RDX to small molecules. The rate of degradation increased with current density, but the current efficiency was highest at low current densities. The technique was extended successfully both to 100% aqueous solutions of RDX and to an undivided electrochemical cell.     

Epoxide-diol pathway in the metabolism of 5H-dibenzo[b,f]-azepine (iminostilbene)

5H-Dibenzol[b,f]azepine-10,11-epoxide and 10,11-dihydro-10,11-dihydroxy-5H-dibenzo[b,f]azepine were identified by gas chromatography-mass spectrometry in rat urine as the main biotransformation products in the metabolism of 5H-dibenzo[b,f]azepine (iminostilbene). The presence of these metabolites was confirmed in vitro by incubating iminostilbene with rat liver microsomal enzymes.     

Determination of Deoxynivalenol and Nivalenol in Wheat by Ultra-Performance Liquid Chromatography/Photodiode-Array Detector and Immunoaffinity Column Cleanup

An ultra-performance liquid chromatography (UPLC®) method has been developed for the simultaneous determination of deoxynivalenol (DON) and nivalenol (NIV) in wheat. Ground sample was extracted with water and the filtered extract was cleaned up through an immunoaffinity column containing a monoclonal antibody specific for DON and NIV. Toxins were separated and quantified by UPLC® with photodiode-array detector (λ?=?220 nm) in less than 3 min. Mean recoveries from blank wheat samples spiked with DON and NIV at levels of 100–2,000 μg/kg (each toxin) ranged from 85 to 95 % for DON and from 81 to 88 % for NIV, with relative standard deviations less than 7 %. Similar recoveries were observed from spiked samples when methanol/water (80:20, v/v) was used as extraction solvent. However, by using a wheat sample naturally contaminated with DON and NIV, the one-way analysis of variance (Student–Newman–Keuls test) between different extraction solvents and modes showed that water extraction provided a significant increase (P?<?0.001) in toxin concentrations (mean values of six replicate analyses) with respect to methanol/water (80:20, v/v). No significant difference was observed between shaking (60 min) and blending (3 min). The limit of detection (LOD) of the method was 30 μg/kg for DON and 20 μg/kg for NIV (signal-to-noise ratio 3:1). The immunoaffinity columns showed saturation of DON/NIV binding sites at levels higher than 2,000 ng in blank wheat extracts spiked with the corresponding amount of mycotoxin, as single mycotoxin or sum of DON and NIV. The range of applicability of the method was from LOD to 4,000 μg/kg, as single mycotoxin or sum of DON and NIV in wheat. The analyses of 20 naturally contaminated wheat samples showed DON contamination in all analyzed samples at level ranging from 30 to 2,700 μg/kg. NIV was detected in two samples at negligible toxin levels (up to 46 μg/kg). This is the first UPLC® method using immunoaffinity column cleanup for the simultaneous and sensitive determination of DON and NIV in wheat.     

Changes in nutritional and sensory properties of orange juice packed in PET bottles: An experimental and modelling approach

Sensitivity to oxidation of an orange juice was investigated through packaging in standard PET or active PET with oxygen scavenger bottles. The evolution of dissolved oxygen was found to be similar in all bottles, whereas ascorbic acid degradation was related to the oxygen transfer with higher losses in standard PET (53%) against active PET (31%). Moreover, when juice was exposed to high intensity light, a fold faster degradation of ascorbic acid was observed compared to total darkness. Depending also on the light intensity and regardless of the package permeability, changes in the aromatic profile of the juice were observed due to the degradation of limonene and the formation of α-terpineol, an off-flavour. A mechanistic model was developed to predict the shelf life of orange juice. This model, coupling O₂ transfer and ascorbic acid oxidation reaction in the bottled juice, confirmed that oxygen permeation through packaging material could not be neglected.     

New Environmentally Friendly Oxidative Scission of Oleic Acid into Azelaic Acid and Pelargonic Acid

Oleic acid (OA) is a renewable monounsaturated fatty acid obtained from high oleic sunflower oil. This work was focused on the oxidative scission of OA, which yields a mono-acid (pelargonic acid, PA) and a di-acid (azelaic acid, AA) through an emulsifying system. The conventional method for producing AA and PA consists of the ozonolysis of oleic acid, a process which presents numerous drawbacks. Therefore, we proposed to study a new alternative process using a green oxidant and a solvent-free system. OA was oxidized in a batch reactor with a biphasic organic-aqueous system consisting of hydrogen peroxide (H₂O₂, 30 %) as an oxidant and a peroxo–tungsten complex Q₃{PO₄[WO(O₂)₂]₄} as a phase-transfer catalyst/co-oxidant. Several phase-transfer catalysts were prepared in situ from tungstophosphoric acid, H₂O₂ and different quaternary ammonium salts (Q⁺, Cl^–). The catalyst [C₅H₅N(n-C₁₆H₃₃)]₃{PO₄[WO(O₂)₂]₄} was found to give the best results and was chosen for the optimization of the other parameters of the process. This optimization led to a complete conversion of OA into AA and PA with high yields (>80 %) using the system OA/H₂O₂/[C₅H₅N(n-C₁₆H₃₃)]₃{PO₄[WO(O₂)₂]₄} (1/5/0.02 molar ratio) at 85 °C for 5 h. In addition, a new treatment was developed in order to recover the catalyst.