A new analytical approach for the detection of palm oil in vegetable oil blends

The new Food Information Regulation (1169/2011), dictates that in a refined vegetable oil blend, the type of oil must be clearly identified in the package in contract with current practice where is labelled under the generic and often misleading term “vegetable oil”. With increase consumer awareness in food authenticity, as shown in the recent food scandal with horsemeat in beef products, the identification of the origin of species in food products becomes increasingly relevant. Palm oil is used extensively in food manufacturing and as global demand increases, producing countries suffer from the aftermath of intensive agriculture. Even if only a small portion of global production, sustainable palm oil comes in great demand from consumers and industry. It is therefore of interest to detect the presence of palm oil in food products as consumers have the right to know if it is present in the product or not, mainly from an ethical point of view. Apart from palm oil and its derivatives, rapeseed oil and sunflower oil are also included. With DNA-based methods, the gold standard for the detection of food authenticity and species recognition deemed not suitable in this analytical problem, the focus is inevitably drawn to the chromatographic and spectroscopic methods. Both chromatographic (such as GC-FID and LC-MS) and spectroscopic methods (FT-IR, Raman, NIR) are relevant. Previous attempts have not shown promising results due to oils’ natural variation in composition and complex chemical signals but the suggested two-step analytical procedure is a promising approach with very good initial results.

Identifying oil species in oil mixtures

Detection of adulteration of non-processed vegetable oil with lesser value seed oils (classic example is hazelnut in virgin olive oil) has been in the centre of scientific attention for many years and several chemical methods were proposed. The recent EC Regulation 1169/2011, however, introduces necessity for different analytical method in a more complicated matrix. From the end of 2014, food businesses required to declare the composition of the refined oil mixture in the food product label. This creates a gap since there is no analytical method currently available to perform such analysis. In the first phase the work focused on 100% oil blends of various oil species of palm oil (and derivatives), sunflower and rapeseed oil before expanding to foodstuffs. Chromatographic methods remain highly relevant although suffer from various limitations which derive from natural compositional variation. Modern multivariate techniques based on machine learning algorithms, however, when applied in FTIR, Raman spectroscopic data have a strong potential in tackling the problem.

Virgin Olive Oil: Losses of Antioxidant Polar Phenolic Compounds due to Storage, Packaging, and Culinary Uses

Virgin olive oil is a high quality natural product obtained only by physical means. In addition to triacylglycerols it contains nutritionally important polar and non-polar antioxidant phenols and other bioactive ingredients. The polar fraction is a complex mixture of phenolic acids, simple phenols, derivatives of the glycosides oleuropein and ligstroside, lignans, and flavonoids. These compounds contribute significantly to the stability, flavor, and biological value of virgin olive. In the various stages of production, during storage and in the culinary uses, polar phenols and other valuable bioactive ingredients may be damaged. Oxidation, photo-oxidation, enzymic hydrolysis and heating at frying temperatures have a serious adverse effect. Due to the biological importance of the oil and its unique character, analytical methods have been developed to evaluate antioxidant activity or analyse complex phenol mixtures. These are based on radical scavenging assays and chromatographic techniques. Hyphenated methods are also used including liquid chromatography-mass spectrometry and liquid chromatography-nuclear magnetic resonance spectroscopy.

The application of TiO2 photocatalysis for disinfection of water contaminated with pathogenic micro-organisms: a review

The use of semiconductor photocatalysis for treatment of water and air has been the topic of intense research activity over the past 20 years. This powerful process has also been extended to the disinfection of environments contaminated with pathogenic micro-organisms. This review summarizes recent developments concerned with the photocatalytic treatment of water contaminated with pathogenic micro-organisms presenting a potential hazard to animals and human beings.

An analysis of implied volatility jump dynamics: Novel functional data representation in crude oil markets

The predominant fear in capital markets is that of a price spike. Commodity markets differ in that there is a fear of both upward and down jumps, this results in implied volatility curves displaying distinct shapes when compared to equity markets. The use of a novel functional data analysis (FDA) approach, provides a framework to produce and interpret functional objects that characterise the underlying dynamics of oil future options. We use the FDA framework to examine implied volatility, jump risk, and pricing dynamics within crude oil markets. Examining a WTI crude oil sample for the 2007–2013 period, which includes the global financial crisis and the Arab Spring, strong evidence is found of converse jump dynamics during periods of demand and supply side weakness. This is used as a basis for an FDA-derived Merton (1976) jump diffusion optimised delta hedging strategy, which exhibits superior portfolio management results over traditional methods.

Hydroprocessing of waste cooking oil over a dispersed nano catalyst: Kinetics study and temperature effect

The kinetics of hydrodeoxygenation of waste cooking oil (WCO) is investigated with unsupported CoMoS catalysts. A kinetic model is established and a comprehensive analysis of each reaction pathway is carried out. The results show that hydrodecarbonylation/decarboxylation (HDC) routes are the predominant reaction pathways in the elimination of oxygen, with the rate constant three times as high as that of hydrodeoxygenation (HDO). However, the HDC activity of the CoMoS catalyst deactivates due to gradual loss of sulfur from the catalyst. HDO process is insensitive to the sulfur deficiency. The kinetic modeling shows that direct hydrodecarbonylation of fatty acids dominates the HDC routes and, in the HDO route, fatty acids are transferred to aldehydes/alcohols and then to C-18 hydrocarbons, a final product, and the reduction of acids is the rate limiting step. The HDO route via alcohols is dominant over aldehydes due to a significantly higher reaction rate constant. The difference of C-18/C-17 ratio in unsupported and supported catalysts show that a support with Lewis acid sites may play an important role in the selectivity for the hydrodeoxygenation pathways and promoting the final product quality

Phytoremediation assessment of Gomphrena globosa and Zinnia elegans grown in arsenic-contaminated hydroponic conditions as a safe and feasible alternative to be applied in arsenic-contaminated soils of the Bengal Delta

Several agricultural fields show high contents of arsenic because of irrigation with arsenic- contaminated groundwater. Vegetables accumulate arse- nic in their edible parts when grown in contaminated soils. Polluted vegetables are one of the main sources of arsenic in the food chain, especially for people living in rural arsenic endemic villages of India and Bangladesh. The aim of this study was to assess the feasibility of floriculture in the crop rotation system of arsenic en- demic areas of the Bengal Delta. The effects of different arsenic concentrations (0, 0.5, 1.0, and 2.0 mg As L−1) and types of flowering plant (Gomphrena globosa and Zinnia elegans) on plant growth and arsenic accumula- tion were studied under hydroponic conditions. Total arsenic was quantified using atomic absorption spec- trometer with hydride generation (HG-AAS). Arsenic was mainly accumulated in the roots (72 %), followed by leaves (12 %), stems (10 %), and flowers (<1 %). The flowering plants studied did not show as high phytoremediation capacities as other wild species, suchas ferns. However, they behaved as arsenic tolerant plants and grew and bloomed well, without showing any phytotoxic signs. This study proves that floriculture could be included within the crop rotation system in arsenic-contaminated agricultural soils, in order to im- prove food safety and also food security by increasing farmer’s revenue.

New insights into the causes of human illness due to consumption of azaspiracid contaminated shellfish

Azaspiracid (AZA) poisoning was unknown until 1995 when shellfish harvested in Ireland caused illness manifesting by vomiting and diarrhoea. Further in vivo/vitro studies showed neurotoxicity linked with AZA exposure. However, the biological target of the toxin which will help explain such potent neurological activity is still unknown. A region of Irish coastline was selected and shellfish were sampled and tested for AZA using mass spectrometry. An outbreak was identified in 2010 and samples collected before and after the contamination episode were compared for their metabolite profile using high resolution mass spectrometry. Twenty eight ions were identified at higher concentration in the contaminated samples. Stringent bioinformatic analysis revealed putative identifications for seven compounds including, glutarylcarnitine, a glutaric acid metabolite. Glutaric acid, the parent compound linked with human neurological manifestations was subjected to toxicological investigations but was found to have no specific effect on the sodium channel (as was the case with AZA). However in combination, glutaric acid (1mM) and azaspiracid (50nM) inhibited the activity of the sodium channel by over 50%. Glutaric acid was subsequently detected in all shellfish employed in the study. For the first time a viable mechanism for how AZA manifests itself as a toxin is presented.

Quality Assurance for GCxGC-FID, Accreditation for TPH CWG Protocol

A new technological approach in the analysis and forensic interpretation of Total Hydrocarbons in soils and waters using 2D Gas Chromatography method (GC-GC) was developed alongside environmental forensic and the assessment models to provide better customer products for the environmental industry.
The objective was to develop an analytical methodology for TPH CWG. Raw data from this method is then to be evaluated for forensic interpretation and risk assessment modelling. Access will be made available to the expertise in methods of forensic tracing contaminant sources, transport modelling, human health risk modelling and detailed quantitative risk assessment.
The quantification of internal standards was key to the development of this method. As the laboratory does not test for TPH in 1D, it was requested during INAB ISO 17025 audit to individually map out where each compound falls chromatographically in the 2D. This was done through comparing carbon equivalent numbers to the n-alkane carbons. This proved e.g. 2-methylnaphthalene has 11 carbons in its structure; its carbon equivalent is 12.84 , the result of which falls within the band of Aromatic eC12-eC16 as opposed to expected eC10-eC12. This was carried out for all 16 PAH (polyaromatic hydrocarbons) and BTEX (benzene, toluene, ethylbenzene and o, m and p-xylenes). The n-alkanes were also assigned to their corresponding aliphatic bands e.g. nC8 would be expected to be in nC8-nC10.
The method was validated through a designated systematic experimental protocol and was challenged with spikes of known concentration of hydrocarbon parameters such as recoveries, precision, bias and linearity. The method was verified by testing a certified reference material which was used as a proficiency round of testing for numerous laboratories.
It is hoped that the method will be used in conjunction with the analysis through Bonn Agreement with their OSINet group. This is a panel of experts and laboratories (including CLS) who forensically identify oil spill contamination from a water source.
This method can prove itself to be a robust method and benefit the industry for contaminated land and water but the method needs to be seen as separate from the regular 1D chromatography. It will help identify contaminants and assist consultants, regulators, clients and scientists valuable information not seen in 1D

Naphthenic acid extraction and speciation from Doba crude oil using carbonate-based ionic liquids

A number of tetraalkylammonium methylcarbonate and hydrogencarbonate based ionic liquids are shown to be capable of reacting with the naphthenic acids contained in Doba crude oil via a neutralisation reaction. Spectral studies show that the ionic liquids neutralisation mechanism involves the formation of an ionic liquid-naphthenate complex, liberating methanol and carbon dioxide. Extraction of the neutralised complex into a separate methanol phase and subsequent regeneration using aqueous carbonic acid results in ∼70% of the ionic liquid being recovered for recycle. Isolation of the naphthenic acids shows that these make up to 0.85 wt% of the crude oil. Speciation of the naphthenic acids shows a mixture of monocyclic, through to tetracyclic structures with carbon numbers in the range C₁₂-C₄₀.