Comparative analysis of additive decomposition using one-dimensional and two-dimensional gas chromatography: Part I - Irganox 1010, Irganox 1076, and BHT.

Plastics incorporate diverse additives, including primary antioxidants with a typical amount between 0.05 to 3 wt.%, to enhance plastics functionality and durability, preventing their oxidation and maintaining their mechanical properties. While these antioxidants offer substantial benefits, their degradation can significantly impact plastic pyrolysis by changing the pyrolysis oil product distribution. Understanding the intricate distribution of decomposition products resulting from pyrolysis is essential yet often overlooked. This study delved into the analysis of the decomposition of common primary antioxidants, namely, Irganox 1010, Irganox 1076, and butylated hydroxytoluene (BHT), utilizing both one-dimensional gas chromatography coupled with a quadruple mass spectrometer (GC-MS) and two-dimensional gas chromatography equipped with flame ionization detector and time-of-flight mass spectrometer (GC×GC-FID/TOF-MS). This study showed that GC×GC-FID/TOF-MS provided a more detailed characterization of the pyrolysis product distribution of primary antioxidants used in plastics in comparison to GC-MS. For each of the antioxidants, using the GC×GC-FID/TOF-MS analytical approach enhanced the identification of degradation products at least fivefold. Furthermore, GC×GC-FID/TOF-MS identified products of more chemical classes than GC-MS. For instance, compounds from 14 chemical classes were identified from GC×GC-FID/TOF-MS in the pyrolysis of Irganox 1010, whereas only 9 chemical classes were identified in GC-MS. Olefins were the major chemical class for both Irganox 1010 and Irganox 1076 in the decomposition process, accounting for 23.25 wt.% and 20.76 wt.%, respectively. Ketones were the major chemical class in the case of BHT, having a 6.68 wt.% yield. This research enhanced the understanding of the decomposition of primary antioxidant and their product distribution during pyrolysis and shed light on the potential necessity for using two-dimensional gas chromatography.

Quantitative analysis of residual butylated hydroxytoluene and butylated hydroxyanisole in Salmo salar, milk, and butter by liquid chromatography-tandem mass spectrometry.

Butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA) are two commonly used antioxidants with potential health risks associated with excessive intake from multiple sources. Several countries have implemented strict regulations to curb these risks. This study presents a simple LC-MS/MS method for estimating BHT and BHA levels in Salmo salar, butter, and milk. To mitigate any potential interference from the three complex matrices with the ionisation of the target analytes, the method utilised the standard addition approach. The mobile phase used to elute the analytes consisted of 0.1 % formic acid in a mixture of water and acetonitrile (25:75 v/v). Both antioxidants were detected in negative ionisation mode. BHT was identified through single-ion monitoring at a mass-to-charge ratio (m/z) of 219.4, while BHA was detected using multiple-reaction monitoring, with a transition from m/z 164.0 to 149.0. The environmental assessment of the applied procedures verified that the approach is eco-friendly.

Optimization of antioxidant and lycopene extraction from tomato pomace using Hansen solubility parameters and its application in chicken meat preservation.

Tomato pomace, composed of peels and seeds, is often discarded or used as animal feed. However, it contains valuable phytochemicals, including lycopene. Lycopene, a natural pigment, is an antioxidant known for reducing the risk of chronic diseases like cardiovascular ailments and cancer. In this study, we aimed to study the possibility of valorizing tomato pomace by quantifying phenolic compounds, evaluating the antioxidant activity of their extracts, as well as extracting and quantifying lycopene, and studying the effect of tomato peel extract on the oxidative stability of chicken patties during storage. The effectiveness of different solvent mixtures for the extraction of lycopene was evaluated using Hansen solubility parameters (HSPs). The obtained results showed that the best solvent mixture was hexane/acetone (50/50) with a Hansen theoretical distance of 7.2, indicating its favorable solvation power. It also achieved a notable extraction yield of 3.12% and the highest lycopene yield of 20.05 mg/100 g. This combination demonstrated the highest values in terms of total phenolic (24.06 mg equivalent gallic acid/100 g dry matter) and flavonoid content (30.55 mg equivalent catechin/100 g dry matter), indicating a significant presence of these compounds. However, its 1,1-diphenyl-2-picrylhydrazyl (13.51 µg/mL) and ABTS, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid, (8.52 µg/mL) IC50 values were comparatively lower than the other mixes. The use of this fraction as a food additive and antioxidant showed significant competitiveness with the conventional preservative, 2,6-di-tert-butyl-4-methylphenol. Tomato extract can be considered a potential natural preservative in food preparations due to its high lycopene content. PRACTICAL APPLICATION: This research provides valuable insights into optimizing the extraction of antioxidants from tomato pomace, using HSPs. The findings have the potential to benefit the food industry by developing improved methods for preserving chicken meat through the application of these optimized antioxidant extracts. By enhancing the preservation process, this study may contribute to extending the shelf life and maintaining the quality of chicken meat, leading to reduced food waste and improved consumer satisfaction.

Novel macromolecular synthetic phenolic antioxidants in sludge on a national scale in China: Their distribution, potential transformation products, and ecological risk.

To fulfill the growing demand for retarding the oxidation of polymers and minimizing their migration from various products, new macromolecular synthetic phenolic antioxidants (SPAs) have emerged in the market. There is a concern that these SPAs may be released into wastewater streams during their manufacturing and use, eventually ending up in wastewater treatment plants (WWTPs). Nevertheless, information regarding the occurrence of these SPAs in sludge, particularly on a national scale, is scarce. In this study, several macromolecular SPAs and their transformation products (TPs) were investigated in sludge samples from 45 Chinese municipal WWTPs. All 14 analytes were detected in the sludge samples, among which, 12 analytes were first reported in sludge. 2,4,6-tri-tert-butylphenol (AO246) and 2 macromolecular SPAs, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (AO1010) and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (AO1076), were the most dominant SPAs, with geometric mean (GM) concentrations of 547, 212, and 35.2 ng/g dw, respectively. Two TPs, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid (fenozan) and 3,5-di-tert-butyl-4-hydroxybenzoic acid (BHT-COOH), were found in some sludge samples (48.9-71.1 %) with GM of 45.5 and 12.8 ng/g dw, respectively. By using LC-Q-TOF-MS/MS analysis, we tentatively identified previously unknown TPs of 10 macromolecular SPAs in sludge. This suggests that there are still unclear mechanisms modulating the transformation of these SPAs, which underscores the complexity of their fate. Additionally, using the freshwater photobacteria Vibrio qinghaiensis sp.-Q67 (Q67) as model organism, the acute and chronic EC50 of the 14 analytes were assessed for ecological risk assessment. By considering toxicity data obtained from algae, daphnia, and fish collected or predicted from various databases, we found that these analytes, including their mixture at low detected concentrations, pose risks to aquatic systems that should not be disregarded. Overall, the current study provides a comprehensive overview of novel SPAs and their TPs in sludge, offering valuable insights for investigating their environmental behavior, fate, and risks.

A polypyrrole-cotton pad sorbent as micro-solid phase extractor enclosed in tea bag envelope for determination of synthetic antioxidants in non-alcoholic beverage products.

A polypyrrole (PPy)-cotton pad sorbent enclosed in tea bag envelope was developed and used in micro-solid phase extraction (µ-SPE) for the determination of butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT). After extraction, the extract was qualified and quantified by a gas chromatograph equipped with a flame ionization detector (GC-FID). Parameters influencing this developed method and the efficiency of µ-SPE were studied and optimized. Under the optimal conditions, the developed method provided good linearity in a concentration range of 0.100-100 µg L-1 for BHA and 0.050-50 µg L-1 for BHT, respectively. The limits of detection were 39.27 ± 0.52 ng L-1 for BHA and 16.96 ± 0.17 ng L-1 for BHT. Satisfactory relative recoveries of BHA and BHT were achieved in the range from 86.8 ± 1.9 to 117.1 ± 2.3% with acceptable relative standard deviation (RSD) below 8.1%. Good reproducibility was obtained with RSDs < 3.1%, for n = 6. The developed adsorbent is easy to operate, low cost, eco-friendly, reusable, with high extraction efficiency, and was successfully applied in the simultaneous synthetic antioxidant determination of non-alcoholic beverage samples.

A green extraction strategy for the detection of antioxidants in food simulants and beverages migrated from plastic packaging materials.

Antioxidants, widely utilized in the food packaging field, have a risk of migrating into foodstuffs and eventually entering the human body. In this work, a novel method was established for green extraction and determination of antioxidants in food simulants migrated from plastic packaging materials. It was found that the antioxidants could be extracted directly from food simulants by in-situ formation of hydrophobic deep eutectic solvents with low toxic medium-chain fatty alcohols. Under the optimal conditions, the limit of detection was 0.15 to 0.25 µg/L, and the limit of quantification was 0.5 to 1.0 µg/L for the antioxidants. The extraction reaches equilibrium in 2 min. Importantly, butylated hydroxytoluene was detected in two types of the surveyed food contact materials. The established method shows high sensitivity, high enrichment factor, and strong anti-interference ability, and can be used for the separation and enrichment of ultra-trace antioxidants in foodstuffs.

A MWCNTs-COOH/PSS nanocomposite-modified screen-printed electrode for the determination of synthetic phenolic antioxidants by HPLC with amperometric detection.

New sensing platforms based on screen-printed carbon electrodes modified with composites based on polystyrene sulfonate and oxidized multi-walled carbon nanotubes (PSS/MWCNTs-COOH/SPCE) have been used to develop a novel HPLC method with electrochemical detection (ECD) for the determination of the most used synthetic phenolic antioxidants in cosmetics: butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), tert-butylhydroquinone (TBHQ) and propyl gallate (PG). Optimal separation conditions were achieved using methanol: 0.10 mol L-1 acetate solution at pH 6 as mobile phase with a gradient elution program from 60 to 90% of methanol percentage in 15 min. The electrochemical detection was carried out in amperometric mode using the PSS/MWCNTs-COOH/SPCE at + 0.80 V vs. Ag. Under these optimal separation and detection conditions, the limits of detection (LOD) were between 0.11 and 0.25 mg L-1. These LOD values were better, especially for BHT, than those previously published in other HPLC methods. Linear ranges from 0.37 mg L-1, 0.83 mg L-1, 0.69 mg L-1 and 0.56 mg L-1 to 10 mg L-1 were obtained for PG, TBHQ, BHA and BHT, respectively. RSD values equal or lower than 5% and 8% were achieved for repeatability and reproducibility, respectively. The HPLC-ECD method was successfully applied to analyze different cosmetic samples. Recovery values within 83-109% were obtained in the validation studies.

44-Year Retrospective Analysis of Ultraviolet Absorbents and Industrial Antioxidants in Seabird Eggs from the Canadian Arctic (1975 to 2019).

Ultraviolet (UV) absorbents and industrial antioxidants are contaminants of emerging concern (CECs), but little is known about their distribution in Arctic wildlife, as well as how these contaminants vary over time, across regions, and between species. We used archived egg samples to examine the temporal patterns of 26 UV absorbents and industrial antioxidants in three seabird species (black-legged kittiwakes Rissa tridactyla, thick-billed murres Uria lomvia, northern fulmars Fulmarus glacialis) sampled in Arctic Canada between 1975 and 2019. Various synthetic phenolic antioxidants, aromatic secondary amines, benzotriazole UV stabilizers, and organic UV filters were detected in the seabird eggs. Overall, kittiwakes had higher levels of several UV absorbents and industrial antioxidants. Most target contaminants reached their peak concentrations at different points during the 44-year study period or did not vary significantly over time. None of these contaminant concentrations have increased in recent years. The antioxidant 2-6-di-tert-butyl-4-methylphenol (BHT) was the most frequently detected contaminant in seabird eggs, and its level significantly declined over the course of the study period in kittiwake eggs but did not change in the eggs of murres and fulmars. Future research should examine the effects of these CECs on the health of avian species, the sources, and exposure pathways of these contaminants.

Improvement of methods for analysing sucrose acetate isobutyrate (SAIB) in soft drinks using GC-FID and evaluating antioxidant effects in the SAIB emulsion system.

Sucrose acetate isobutyrate SAIB (E444) is a mixture produced by the esterification of sucrose with acetic anhydride and isobutyric anhydride. It is a food additive that is used as an emulsifier in soft drinks. It is difficult to analyse SAIB quantitatively because there are 256 synthesisable structures in the mixture. This study developed an analytical method for SAIB using gas chromatography-flame ionization detection (GC-FID). The pre-treatment of SAIB in soft drinks was performed using a liquid-liquid extraction method, which demonstrated a recovery rate of 107.8 ± 7.2%. In the GC-FID analysis of SAIB, numerous peaks were observed in the chromatogram, and the content of SAIB was calculated as the sum of these peak areas. A series of analytical methods were validated according to International Conference for Harmonization (ICH) guidelines. Accordingly, the applicability of the developed analytical method was confirmed for both domestic and imported soft drinks distributed in Korea. Additionally, in the linoleic acid emulsion, SAIB exhibited better lipid oxidation stability than the natural antioxidant α-tocopherol and had similar efficacy to the synthetic antioxidant butylated hydroxytoluene (BHT). Although SAIB has excellent lipid oxidation stability, it must be used within legal standards according to consumer demand to reduce the use of synthetic materials in processed foods. The validated GC-FID analytical method will enable subsequent monitoring of the distributed products.

Colorimetric sensor array based on CoOOH nanoflakes for rapid discrimination of antioxidants in food.

The identification of synthetic antioxidants has considerable significance in food safety. Here, we described the development of a colorimetric sensor array for rapid detection of eight antioxidants in food through the redox reaction between CoOOH and antioxidants in the presence of colorimetric signal indicators. The CoOOH nanoflakes exhibited high catalytic oxidation activity and can independently catalyze oxidation signal indicators showing different colors. The color reaction was inhibited to different degrees in the presence of antioxidants, which resulted in distinct signal response patterns for their discrimination. The method showed good linearity in the range from 50 to 1000 nM for butylated hydroxytoluene (BHT), butylhydroxyanisole (BHA), propyl gallate (PG) and tert-butyl hydroquinone (TBHQ). Moreover, different proportions of antioxidants were located in the middle pattern of each single antioxidant, and showed certain linear relationships among different concentration ratios. Finally, the proposed colorimetric sensor array was used for practical applications where TBHQ and BHT were detected in biscuits and sausages, and BHA and PG were detected in fried pork kebabs, respectively. The results were further confirmed by high-performance liquid chromatography, which demonstrated the great potential of the colorimetry sensor array for practical applications.

Prenatal Exposure to Emerging Plasticizers and Synthetic Antioxidants and Their Potency to Cross Human Placenta.

Gestational exposure to environmental chemicals and subsequent permeation through the placental barrier represents potential health risks to both pregnant women and their fetuses. In the present study, we explored prenatal exposure to a suite of 46 emerging plasticizers and synthetic antioxidants (including five transformation products of 2,6-di-tert-butyl-4-hydroxytoluene, BHT) and their potency to cross human placenta based on a total of 109 maternal and cord serum pairs. Most of these chemicals have rarely or never been investigated for prenatal exposure and associated health risks. Eleven of them exhibited detection frequency greater than 50% in maternal blood, including dibutyl fumarate (DBF), 2,6-di-tert-butylphenol (2,4-DtBP), 1,3-diphenylguanidine (DPG), methyl-2-(benzoyl)benzoate (MBB), triethyl citrate (TEC), BHT, and its five metabolites, with a median concentration from 0.05 to 3.1 ng/mL. The transplacental transfer efficiency (TTE) was determined for selected chemicals with valid measurements in more than 10 maternal/cord blood pairs, and the mean TTEs exhibited a large variation (i.e., 0.29-2.14) between chemicals. The determined TTEs for some of the target chemicals were comparable to the predicted values by our previously proposed models developed from molecular descriptors, indicating that their transplacental transfer potency could be largely affected by physicochemical properties and molecular structures. However, additional biological and physiological factors may influence the potency of environmental chemicals to cross human placenta. Overall, our study findings raise concern on human exposure to an increasing list of plastic additives during critical life stages (e.g., pregnancy) and potential health risks.

Using Physical Organic Chemistry Knowledge to Predict Unusual Metabolites of Synthetic Phenolic Antioxidants by Cytochrome P450.

Biotransformation, especially by human CYP450 enzymes, plays a crucial role in regulating the toxicity of organic compounds in organisms, but is poorly understood for most emerging pollutants, as their numerous "unusual" biotransformation reactions cannot retrieve examples from the textbooks. Therefore, in order to predict the unknown metabolites with altering toxicological profiles, there is a realistic need to develop efficient methods to reveal the "unusual" metabolic mechanism of emerging pollutants. Combining experimental work with computational predictions has been widely accepted as an effective approach in studying complex metabolic reactions; however, the full quantum chemical computations may not be easily accessible for most environmentalists. Alternatively, this work practiced using the concepts from physical organic chemistry for studying the interrelationships between structure and reactivity of organic molecules, to reveal the "unusual" metabolic mechanism of synthetic phenolic antioxidants catalyzed by CYP450, for which the simple pencil-and-paper and property-computation methods based on physical organic chemistry were performed. The phenol-coupling product of butylated hydroxyanisole (BHA) (based on spin aromatic delocalization) and ipso-addition quinol metabolite of butylated hydroxytoluene (BHT) (based on hyperconjugative effect) were predicted as two "unusual" metabolites, which were further confirmed by our in vitro analysis. We hope this easily handled approach will promote environmentalists to attach importance to physical organic chemistry, with an eye to being able to use the knowledge gained to efficiently predict the fates of substantial unknown synthesized organic compounds in the future.

Neurotoxic effects of synthetic phenolic antioxidants on dopaminergic, serotoninergic, and GABAergic signaling in larval zebrafish (Danio rerio).

Synthetic phenolic antioxidants (SPAs) are an environmental concern because they are widely detected in aquatic ecosystems and can pose potential threats to organisms. Studies have reported developmental deficits and behavioral changes in response to SPAs, indicating possible neurotoxic effects. However, their neuroactive potency as well as their mode of action (MoA) remain unclear. As such, this study evaluated the potential neurotoxicity of three SPAs [butylated hydroxytoluene (BHT), 2,4-di-tert-butylphenol (2,4-DTBP), and 4-tert-octylphenol (4-t-OP)] at three concentrations (0.01, 0.1 and 1 µM) to zebrafish larvae. Both 2,4-DTBP and BHT decreased spontaneous tail coiling (STC) at 28 hpf (hours post fertilization) whereas 4-t-OP increased STC. Locomotor activity, based on the velocity and distance of larvae (144 hpf) travelled, was promoted by 2,4-DTBP while it decreased in larvae with exposure to 4-t-OP and BHT. In the light-dark preference assay, exposure to either 2,4-DTBP or BHT resulted in variability in the visiting frequency to the dark zone, and larvae (144 hpf) spent less time in the dark, suggesting anxiety-like behavior. Conversely, zebrafish exposed to 4-t-OP, especially at 1 µM concentration, were hypoactive and spent more time in dark, suggestive of anxiolytic-like responses. RNA-seq was conducted to discern mechanisms underlying behavioral responses. Transcriptomic analysis revealed that gene networks related to neuroactive ligand-receptor interaction as well as neurotransmitter-related pathways were altered by all three SPAs based on gene set and subnetwork enrichment analysis. Modulation of dopaminergic, serotoninergic, and/or GABAergic signaling at the transcript level was noted for each of the three SPAs, but different expression patterns were observed, indicating SPA- and dose-specific responses of the transcriptome. The present study provides novel insight into potential mechanisms associated with neurotoxicity of SPAs congeners.

Analysis, occurrence, toxicity and environmental health risks of synthetic phenolic antioxidants: A review.

The continuous improvement of living standards is related to higher requirements for the freshness and taste of food. For example, synthetic phenolic antioxidants (SPAs) are added to fats and fried foods as food additives to minimize the oxidative rancidity of oils and fats. Hence, the global use of SPAs is increasing year by year. Dibutyl hydroxytoluene is one of the widely used SPAs, often in combination with butyl hydroxyanisole or gallate SPAs. The extensive use of these compounds makes them and their transformation products to be widespread in various environmental matrices, including indoor dust, wastewater, river water, sewage sludge, and sediment, as well as human samples, such as nails and urine, at concentrations varying from nanogram per gram (ng/g) to microgram per gram (µg/g). Animal experiments have shown that high-dose SPA exposure is toxic, which may lead to DNA damage and mismatches and the development of cancerous tumors. Since the biosphere shares the same set of genetic codes, humans and animals have many identical or similar feedback mechanisms and information pathways. Therefore, the damage of SPAs to animals may also threaten human health. This review discusses the properties, occurrence, analysis, and environmental health risks of typical SPAs, including butyl hydroxyanisole, dibutyl hydroxytoluene, tert-butylhydroquinone, propyl gallate, octyl gallate, and lauryl gallate, used as food additives. In addition, AO2246, which is used in food packaging bags, is also considered. Future research directions on SPAs and their transformation products (TPs) are identified and discussed.

Considerations when deriving compound-specific limits for extractables and leachables from pharmaceutical products: Four case studies.

Leachables from pharmaceutical container closure systems are a subset of impurities that present in drug products and may pose a risk to patients or compromise product quality. Extractable studies can identify potential leachables, and extractables and leachables (E&Ls) should be evaluated during development of the impurity control strategy. Currently, there is a lack of specific regulatory guidance on how to risk assess E&Ls; this may lead to inconsistency across the industry. This manuscript is a cross-industry Extractables and Leachables Safety Information Exchange (ELSIE) consortium collaboration and follow-up to Broschard et al. (2016), which aims to provide further clarity and detail on the conduct of E&L risk assessments. Where sufficient data are available, a health-based exposure limit termed Permitted Daily Exposure (PDE) may be calculated and to exemplify this, case studies of four common E&Ls are described herein, namely bisphenol-A, butylated hydroxytoluene, Irgafos® 168, and Irganox® 1010. Relevant discussion points are further explored, including the value of extractable data, how to perform route-to-route extrapolations and considerations around degradation products. By presenting PDEs for common E&L substances, the aim is to encourage consistency and harmony in approaches for deriving compound-specific limits.

Effect of Frying on Physicochemical and Sensory Properties of Potato Chips Fried in Palm Oil Supplemented with Thyme and Rosemary Extracts.

Quality parameters of potato chips (flat and serrated) fried either in palm oil (PO) alone or containing natural (thyme (TPO) and rosemary (RPO) extracts) and synthetic BHT (BPO) antioxidants were evaluated during storage period. The free fatty acid and peroxide values of chips fried in PO (control) were found between 0.18 and 0.21% to 1.00 and 1.04 meqO2/kg during the first storage month, respectively. However, these values were 0.07-0.10% and 0.55-0.90 meqO2/kg for chips fried in TPO, respectively. The water contents increased when storage time increased from 1 to 7 month and their values changed between 0.49 and 1.95% (flat potato chips in BPO) and between 0.88 and 1.24% (serrated potato chips in TPO). The total trans-fat contents were 0.13% (serrated potato chips in BPO) and 0.35% (both flat and serrated potato chips in PO) at the start of storage. The total trans-fat content after 7 months were 0.13% (PO fried flat and serrated potato chips) and 0.17% (serrated potato chips fried in BPO, TPO and RPO). The acrylamide contents varied between 152 (serrated potato chips in PO) and 540 µg/kg (flat potato chips fried in RPO) at the beginning of storage. However, the acrylamide contents changed during 7th storage month and ranged from 182 (serrated potato chips in PO) to 518 µg/kg (flat potato chips in RPO). Among fatty acids, while palmitic acid are determined between 37.14 (flat chips in PO) and 41.60% (serrated chips in TPO), oleic acid varied between 30.0 (flat chips in RPO) and 33.00% (serrated chips in PO). Sensory evaluation showed that PO containing antioxidants showed better consumer preference for potato chips until the end of storage.

Synthetic Phenolic Antioxidants: A Review of Environmental Occurrence, Fate, Human Exposure, and Toxicity.

Synthetic phenolic antioxidants (SPAs) are widely used in various industrial and commercial products to retard oxidative reactions and lengthen product shelf life. In recent years, numerous studies have been conducted on the environmental occurrence, human exposure, and toxicity of SPAs. Here, we summarize the current understanding of these issues and provide recommendations for future research directions. SPAs have been detected in various environmental matrices including indoor dust, outdoor air particulates, sea sediment, and river water. Recent studies have also observed the occurrence of SPAs, such as 2,6-di-tert-butyl-4-methylphenol (BHT) and 2,4-di-tert-butyl-phenol (DBP), in humans (fat tissues, serum, urine, breast milk, and fingernails). In addition to these parent compounds, some transformation products have also been detected both in the environment and in humans. Human exposure pathways include food intake, dust ingestion, and use of personal care products. For breastfeeding infants, breast milk may be an important exposure pathway. Toxicity studies suggest some SPAs may cause hepatic toxicity, have endocrine disrupting effects, or even be carcinogenic. The toxicity effects of some transformation products are likely worse than those of the parent compound. For example, 2,6-di-tert-butyl-p-benzoquinone (BHT-Q) can cause DNA damage at low concentrations. Future studies should investigate the contamination and environmental behaviors of novel high molecular weight SPAs, toxicity effects of coexposure to several SPAs, and toxicity effects on infants. Future studies should also develop novel SPAs with low toxicity and low migration ability, decreasing the potential for environmental pollution.

Improving walnuts' preservation by using walnut phenolic extracts as natural antioxidants through a walnut protein-based edible coating.

Walnut kernels contain high amounts of polyunsaturated fatty acids that determine a limited shelf life on these nuts. The application of walnut phenolics as antioxidants through a walnut protein-based coating, obtained from walnut oil cake residue, can help to increase the shelf life of walnuts. The objective was to evaluate the preservative effect of walnut polyphenols included in a walnut-proteic edible coating on walnut kernels. Three treatments of walnuts coated with walnut flour were prepared: without the addition of antioxidants (control); with the addition of a walnut phenolic extract; and with the addition of butylated hydroxytoluene (BHT). On the last storage day, the sample with the addition of walnut phenolics presented a lower peroxide (3.64 meq 02 /kg oil) and anisidine value (1.11), conjugated diene (15.92), and hexanal content (19.67 × 106 e.c.) than the control sample (6.23, 1.81, 24.65, and 122.37 × 106 e.c., respectively). Also, on the last day, the control sample showed the highest deterioration of polyunsaturated fatty acids (from 74.83 to 71.08 g/100g), carotenoid (from 3.43 to 1.90 mg/kg), and γ-tocopherol content (from 349.66 to 298.42 mg/kg). In addition, this sample exhibited the highest oxidized (20.33) and the lowest walnut flavor intensity (64.67) on day 84. Regarding consumer acceptance, the phenolic-added sample displayed a greater flavor acceptance score. Walnut phenolics, implemented through a walnut protein-based coating, improve the preservation of walnuts. PRACTICAL APPLICATION: The combination of walnut-phenolic extracts and walnut-based edible coating applied on walnuts by food industries allows to prolong their shelf life, by preserving their nutritional, sensory, and quality properties. Considering the practical feasibility, the procedure used to prepare these products is simple and requires machineries already present in food industries. In addition, the utilization of this coating with walnut-phenolics exerts benefits like, the prevention of allergen cross-contamination in the chain of production, the utilization of an industry's residue, the replacement of synthetic antioxidants and, and the diminishment of the amount and thickness of plastic needed for walnuts' packaging.

Migration analysis, antioxidant, and mechanical characterization of polypropylene-based active food packaging films loaded with BHA, BHT, and TBHQ.

Polypropylene (PP) based active composite films were prepared by adding butylated hydroxy anisole (BHA), butylated hydroxytoluene (BHT), and tertiary butylated hydroquinone (TBHQ) antioxidants using the extrusion molding process. All concentrations of BHT, 2% to 3% BHA, and 3% TBHQ significantly increased the tensile strength (TS) of the composite films compared with control films. Increasing antioxidant concentration decreased TS values for BHT films, whereas an opposite trend was observed for BHA and TBHQ films. BHA at < 2%, BHT at > 2%, and TBHQ at all added concentrations significantly reduced elongation at break (Eb ) of the composite films compared to control films. Water vapor permeability (WVP) of 1% BHT film was not significantly different from control. However, other antioxidants especially at increased concentrations significantly increased WVP values. TBHQ films with 300% to 662% increase had the highest WVP and BHT films with 5% to 81% increase had the lowest WVP among composite films. All three antioxidants had a negative effect on the transparency of the films; however the effect of BHA at higher concentrations was greater. The antioxidants did not change the color attributes of the films. Films containing all antioxidants showed 2,2-diphenyl-1-picrylhydrazyl radical-scavenging activity, which increased with increase in their concentration, especially for those containing 3 wt.% BHT and TBHQ. Overall, incorporating BHA and BHT into a PP matrix improved mechanical, barrier, antioxidant properties, and film appearance and consequently were proposed for the development of antioxidant active PP films. TBHQ film is not recommended for food packaging because of its weak mechanical properties (lower Eb and TS values, higher WVP, and greater migration).

A biomonitoring study assessing the exposure of young German adults to butylated hydroxytoluene (BHT).

The antioxidant 2,6-di-tert-butyl-4-methylphenol (butylated hydroxytoluene, BHT) is used ubiquitously in food, cosmetics, pharmaceuticals, fuels, plastics, rubbers and many other products. Therefore, exposure of the general population to this substance is likely. We analyzed the BHT metabolite 3,5-di-tert-butyl-4-hydroxybenzoic acid ("BHT acid") in 24-h urine samples from the German Environmental Specimen Bank with the aim of gaining a better understanding of the internal burden of BHT in young nonspecifically exposed adults. The study population consisted of students between 20 and 29 years of age at the time of sampling, all from Halle/Saale in Central Germany. In total, 329 samples collected in the years 2000, 2004, 2008, 2012, 2015, and 2018 were measured by ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). BHT acid was detected above the limit of quantification (0.2 µg/L) in 98% of the samples. The median of the measured concentrations was 1.06 µg/L and 1.24 µg/g creatinine respectively, the median of the daily excretion was 1.76 µg/24 h and - additionally normalized for body weight - 26.8 ng/24 h × kg bw respectively. The corresponding 90th percentiles were 3.28 µg/L, 3.91 µg/g creatinine, 5.05 µg/24 h, and 81.9 ng/24 h × kg bw. Medians of creatinine-corrected values were slightly higher in women than in men, while the opposite situation was observed for the volume concentrations and the 24-h excretion values (not corrected for body weight). Values simultaneously normalized both for 24-h excretion and body weight did not exhibit any significant differences between males and females, probably indicating a virtually identical magnitude of exposure for both genders. The background exposure of the investigated population was found to be largely constant since the year 2000, with only weak temporal trends at most. Daily intakes were estimated from excretion values and found to be largely below the acceptable daily intake (ADI) of BHT at 0.25 mg/kg bw: our worst-case estimate is a daily BHT intake of approximately 0.1 mg/kg bw at the 95th percentile level. However, these intake assessments rely on very limited quantitative data regarding human metabolism of BHT.