While use of synthetic antioxidants (such as butylated hydroxytoluene and butylated hydroxyanisole) to maintain the quality of ready-to-eat food products has become commonplace, consumer concern regarding their safety has motivated the food industry to seek natural alternatives. Phenolic antioxidants can inhibit free radical formation and/or interrupt propagation of autoxidation. Fat-soluble vitamin E (α-tocopherol) and water-soluble vitamin C (L-ascorbic acid) are both effective in the appropriate matrix. Plant extracts, generally used for their flavoring characteristics, often have strong H-donating activity thus making them extremely effective antioxidants. This antioxidant activity is most often due to phenolic acids (gallic, protocatechuic, caffeic, and rosmarinic acids), phenolic diterpenes (carnosol, carnosic acid, rosmanol, and rosmadial), flavonoids (quercetin, catechin, naringenin, and kaempferol), and volatile oils (eugenol, carvacrol, thymol, and menthol). Some plant pigments (anthocyanin and anthocyanidin) can chelate metals and donate H to oxygen radicals thus slowing oxidation via 2 mechanisms. Tea and extracts of grape seeds and skins contain catechins, epicatechins, phenolic acids, proanthocyanidins, and resveratrol, all of which contribute to their antioxidative activity. The objective of this article is to provide an overview of natural antioxidants, their mechanisms of action, and potential applications.

https://onlinelibrary.wiley.com/doi/epdf/10.1111/j.1541-4337.2011.00156.x

Natural antioxidants: sources, compounds, mechanisms of action, and potential applications

Dispersive liquid–liquid microextraction method based on solidification of floating organic drop combined with gas chromatography with electron-capture or mass spectrometry detection

Phthalates are a group of diesters of ortho-phthalic acid (dialkyl or alkyl aryl esters of 1,2-benzenedicarboxylic acid). Higher-molecular-weight phthalates, such as di-2-ethylhexyl phthalate (DEHP), are primarily used as plasticizers to soften polyvinyl chloride (PVC) products, while the lower-molecular-weight phthalates, such as diethyl phthalate (DEP), di-n-butyl phthalate (DBP), and butyl benzyl phthalate (BBzP), are widely used as solvents to hold color and scent in various consumer and personal care products. Phthalates have become ubiquitous environmental contaminants due to volatilization and leaching from their widespread applications, and thus contamination of the environment has become another important source for phthalates in foods in addition to migration from packaging materials. Human exposure to phthalates has been an increased concern due to the findings from toxicology studies in animals. DEHP, one of the important and widely used phthalates, is a rodent liver carcinogen. DEHP, DBP, BBzP, and several phthalate metabolites, such as monobutyl phthalate, monobenzyl phthalate, and mono-(2-ethylhexyl) phthalate, are teratogenic in animals. Since foods are the major source of exposure to phthalates, information on levels of phthalates in foods is important for human exposure assessment. The objective of this review is to identify the knowledge gaps for future investigations by reviewing levels of a wide range of phthalates in a variety of foods, such as bottled water, soft drinks, infant formula, human milk, total diet foods, and others, migration of phthalates from various food-packaging materials, and traditional and new methodologies for the determination of phthalates in foods.

https://onlinelibrary.wiley.com/doi/pdf/10.1111/j.1541-4337.2009.00093.x

Phthalate Esters in Foods: Sources, Occurrence, and Analytical Methods.

Di(2-ethylhexyl)phthalate (DEHP) is a widely used plasticizer to render poly(vinyl chloride) (PVC) soft and malleable. Plasticized PVC is used in hospital equipment, food wrapping, and numerous other commercial and industrial products. Unfortunately, plasticizers can migrate within the material and leach out of it over time, ending up in the environment and, frequently, the human body. DEHP has come under increased scrutiny as its breakdown products are believed to be endocrine disruptors and more toxic than DEHP itself. DEHP and its breakdown products have been identified as ubiquitous environmental contaminants, and daily human exposure is estimated to be in the microgram per kilogram level. The objective of this review is to summarize and comment on published sources of DEHP exposure and to give an overview of its environmental fate. Exposure through bottled water was examined specifically, as this concern is raised frequently, yet only little exposure to DEHP occurs through bottled water, and DEHP exposure is unlikely to stem from the packaging material itself. Packaged food was also examined and showed higher levels of DEHP contamination compared to bottled water. Exposure to DEHP also occurs in hospital environments, where DEHP leaches directly into liquids that passed through PVC/DEHP tubing and equipment. The latter exposure is at considerably higher levels compared to food and bottled water, specifically putting patients with chronic illnesses at risk. Overall, levels of DEHP in food and bottled water were below current tolerable daily intake (TDI) values. However, our understanding of the risks of DEHP exposure is still evolving. Given the prevalence of DEHP in our atmosphere and environment, and the uncertainty revolving around it, the precautionary principle would suggest its phaseout and replacement. Increased efforts to develop viable replacement compounds, which necessarily includes rigorous leaching, toxicity, and impact assessment studies, are needed before alternative plasticizers can be adopted as viable replacements.

Leaching of the plasticizer di(2-ethylhexyl)phthalate (DEHP) from plastic containers and the question of human exposure

A critical review in calibration methods for solid-phase microextraction

Determination of phthalates in wine by headspace solid-phase microextraction followed by gas chromatography-mass spectrometry: fibre comparison and selection.

Determination of volatile oak compounds in wine by headspace solid-phase microextraction and gas chromatography–mass spectrometry

Determination of phthalates in wine by headspace solid-phase microextraction followed by gas chromatography-mass spectrometry. Use of deuterated phthalates as internal standards.

Multiple solid-phase microextraction (MSPME) is a stepped procedure suitable for avoiding matrix-effect errors in quantitative analyses of complex matrix samples by SPME. It is based on calculating the amount of analyte corresponding to complete extraction using the peak areas of a few consecutive extractions from the same sample. This article reviews the state of the art in MSPME, including theory and applications. It also includes a debate on calculating the limits of detection and quantification, and the use of this methodology to determine fiber-sample distribution constant.

José David Carrillo

Papers

Determination of phthalates in wine by headspace solid-phase microextraction followed by gas chromatography-mass spectrometry: fibre comparison and selection.

Determination of volatile oak compounds in wine by headspace solid-phase microextraction and gas chromatography–mass spectrometry

Determination of phthalates in wine by headspace solid-phase microextraction followed by gas chromatography-mass spectrometry. Use of deuterated phthalates as internal standards.

Multiple solid-phase microextraction: Theory and applications

Fibre selection based on an overall analytical feature comparison for the solid-phase microextraction of trihalomethanes from drinking water.