Characterization, hazard identification, and risk assessment of volatile organic compounds in Poly(butylene adipate-co-terephthalate)-based food contact articles.

The chemical safety of poly (butylene adipate-co-terephthalate) (PBAT) based food contact articles (FCAs) has aroused increasing toxicological concerns in recent years, but the chemical characterization and associated risk assessment still remain inadequate as it fails to elucidate the distribution pattern and discern the potential genotoxic and carcinogenic hazards of the identified substances. Herein, the volatile organic compounds (VOCs) in 50 batches of PBAT-based FCAs of representative categories and 10 batches of PLA and PBAT pellets were characterized, by which 237 VOCs of 10 chemical categories were identified and exhibited characteristic distribution patterns in the chemical spaces derived from their molecular descriptors. Chemical hazards associated with the identified VOCs were discerned by a hazard-driven classification scheme integrating hazard-related knowledge from multiple publicly available sources, and 34 VOCs were found to bear genotoxic or carcinogenic hazards and to feature higher average molecular weight than the other VOCs. Finally, the Risk and hazard quotient (HQ) calculated as the metrics of risk suggested that all identified VOCs posed acceptable risks (Risk<10-4 or HQ < 1), whereas oxolane, butyrolactone, N,N-dimethylacetamide, 2-butoxyethanol, benzyl alcohol, and 1,2,3-trichloropropane posed non-negligible (Risk>10-6) genotoxic or carcinogenic risk and thus should be of prioritized concern to promote the chemical safety of PBAT-based FCAs.

Potential safety concerns of volatile constituents released from coffee-ground-blended single-use biodegradable drinking straws: A chemical space perspective.

Incorporating spent coffee grounds into single-use drinking straws for enhanced biodegradability also raises safety concerns due to increased chemical complexity. Here, volatile organic compounds (VOCs) present in coffee ground straws (CGS), polylactic acid straws (PLAS), and polypropylene straws (PPS) were characterized using headspace - solid-phase microextraction and migration assays, by which 430 and 153 VOCs of 10 chemical categories were identified by gas chromatography - mass spectrometry, respectively. Further, the VOCs were assessed for potential genetic toxicity by quantitative structure-activity relationship profiling and estimated daily intake (EDI) calculation, revealing that the VOCs identified in the CGS generally triggered the most structural alerts of genetic toxicity, and the EDIs of 37.9% of which exceeded the threshold of 0.15 µg person-1 d-1, also outnumbering that of the PLAS and PPS. Finally, 14 VOCs were prioritized due to their definite hazards, and generally higher EDIs or detection frequencies in the CGS. Meanwhile, the probability of producing safer CGS was also illustrated. Moreover, it was uncovered by chemical space that the VOCs with higher risk potentials tended to gather in the region defined by the molecular descriptor related to electronegativity or octanol/water partition coefficient. Our results provided valuable references to improve the chemical safety of the CGS, to promote consumer health, and to advance the sustainable development of food contact materials.

Occurrence of volatile contaminants in recycled poly(ethylene terephthalate) by HS-SPME-GC×GC-QTOF-MS combined with chemometrics for authenticity assessment of geographical recycling regions.

A comparison was performed on various methods detecting the volatile contaminants (VCs) in recycled poly(ethylene terephthalate) (rPET) flakes, the results demonstrated that head-space solid phase micro-extraction combined with comprehensive two-dimensional gas chromatograph-tandem quadrupole-time-of-flight mass spectrometry (HS-SPME-GC×GC-QTOF-MS) was a sensitive, effective, accurate method, and successfully applied to analyze 57 rPET flakes collected from different recycling plants in China. A total of 212 VCs were tentatively identified, and the possible source were associated with plastic, food, and cosmetics. 45 VCs are classified as high-priority compounds with toxicity level IV or V and may pose a risk to human health. Combined chemometrics for further analysis revealed that significant differences among these three geographical recycling regions. 6, 7, and 6 volatile markers were chosen based on VIP values and S-plot among plant1 plant 2 and plant 3, respectively. The markers differed significantly between recycled rPET samples in three geographical recycling regions based on chemometrics analysis. The initial classification rate and cross-validation accuracy were 100% on the identified VCs. These significant differences demonstrate that a systematic study is needed to obtain a comprehensive data on the contamination of rPET for food contact applications in China.

Analysis of microplastics released from plastic take-out food containers based on thermal properties and morphology study.

Plastic take-out food containers may release microplastics (MPs) into food and pose a potential risk to food safety and human health. Here, after being subjected to hot water treatment, MPs released from three types of plastic food containers (polypropylene, PP; polyethylene, PE; expanded polystyrene, EPS) were identified by micro-Raman spectroscopy. The results showed that the size of released MPs ranged from 0.8-38 µm and over 96% MPs were smaller than 10 µm. Various MPs concentrations were found from the three types of containers, that is, 1.90 × 104, 1.01 × 105, and 2.82 × 106 particles/L on average from PP, PE, and EPS, respectively. Moreover, based on thermal and morphology analysis, we discovered that both relaxations of the polymer chains in the rubbery state and defects caused by processing techniques might contribute to the release of MPs. Thus, such release can be reduced by increasing the thermal stability of the materials and mitigating the defects generated during production.

Machine learning directed discrimination of virgin and recycled poly(ethylene terephthalate) based on non-targeted analysis of volatile organic compounds.

The use of non-decontaminated recycled poly(ethylene terephthalate) (PET) in food packages arouses consumer safety concerns, and thus is a major obstacle hindering PET bottle-to-bottle recycling in many developing regions. Herein, machine learning (ML) algorithms were employed for the discrimination of 127 batches of virgin PET and recycled PET (rPET) samples based on 1247 volatile organic compounds (VOCs) tentatively identified by headspace solid-phase microextraction comprehensive two-dimensional gas chromatography quadrupole-time-of-flight mass spectrometry. 100% prediction accuracy was achieved for PET discrimination using random forest (RF) and support vector machine (SVM) algorithms. The features of VOCs bearing high variable contributions to the RF prediction performance characterized by mean decrease Gini and variable importance were summarized as high occurrence rate, dominant appearance and distinct instrument response. Further, RF and SVM were employed for PET discrimination using the simplified input datasets composed of 62 VOCs with the highest contributions to the RF prediction performance derived by the AUCRF algorithm, by which over 99% prediction accuracy was achieved. Our results demonstrated ML algorithms were reliable and powerful to address PET adulteration and were beneficial to boost food-contact applications of rPET bottles.

Investigation of factors influencing the release of chloropropanols (3-MCPD and 1,3-DCP) from food contact paper.

Chloropropanols such as 3-monochloropropane-1,2-diol (3-MCPD) and 1,3-dichloro-2-propanol (1,3-DCP) have drawn increasing attention due to their release from food contact paper and their potential carcinogenic effects. In this study, the effects were investigated of water extraction conditions on release of chloropropanols from food contact paper, and the extraction efficiencies of chloropropanols by water extract and migration method were compared. Cold water was found to be more severe than hot water for extraction of chloropropanols, with the highest water extraction value obtained at 23°C. Two hours of extraction was sufficient as the chloropropanols can be fully extracted from food contact paper within a short period of time. Increase of temperature in the range of 10°C-60°C had little impact on release of chloropropanols, however, the extraction of chloropropanols decreased when high temperatures (80°C or above) were applied due to volatilisation losses. Hence, attention should be paid when choosing extract conditions representing the worst-case scenario. The water extraction value using EN 645 method gives higher results compared to migration test described in GB 31604.1 and GB 5009.156, suggesting that the water extract method was probably more severe. For migration test, aqueous-based simulants were found to be more conservative than oil-based simulants, suggesting the conventional experiment conditions applicable for compliance test of chloropropanols migration can be simplified and optimised.

Survey of mineral oil hydrocarbons in infant formula from the Chinese market.

Mineral oil hydrocarbon (MOH) contamination of various foods in the past few decades has raised much concern due to its potential adverse health effects. Since infant formulas (IF) is the major food source for infants, it is necessary to understand MOH contamination level in IF and consequent potential food safety risks. Data on the contamination of IF by mineral oil are lacking in China. On the other hand, the analysis of MOH in food is difficult. There is no harmonised standard analytical method for testing MOHs in IF. GC-FID/MS was chosen as the analytical tool being more convenient for surveys at a national level. Fifty-one IFs comprising dairy milk-based IFs (n = 39) and goat milk-based IFs (n = 12), including different stages (Stage 1, 2 and 3), package type (metal cans and paper boxes) were collected in China market in 2018 for this survey. 17 of 51 IFs were found positive, but trace levels MOAH were found (≤0.7 mg/kg). For the positive samples, all the MOSH and MOAH hump fell into the C16-C25 fraction. MOH humps were found in all the 12 goat milk-based IFs, even 4 samples are reported with quantifiable values which are higher than the method defined LOQ. The highest quantifiable MOH contamination level of goat milk-based IFs were MOSH = 3.5 mg/kg and MOAH = 0.7 mg/kg. Further root cause analysis of contamination is highly recommended to control the MOH contamination for goat milk-based IFs.

Non-target screening of (semi-)volatiles in food-grade polymers by comparison of atmospheric pressure gas chromatography quadrupole time-of-flight and electron ionization mass spectrometry.

Atmospheric pressure gas chromatography (APGC) coupled to quadrupole time-of-flight (QTOF) and electron ionization mass spectrometry together with commercial library search are two complementary techniques for non-target screening of volatile and semi-volatile compounds. Optimization was first conducted to achieve easier search of correspondent peaks between the two systems. Analytical strategy for the determination of volatile and semi-volatile compound with different identification confidence levels was then proposed and applied to food contact grade polypropylene (PP) samples. Identification was found to be much easier and less time-consuming especially when correspondent peak was found in the two systems with the help of library search, exact mass of precursor and fragment ions as well as Kovats Index (KI). The behavior of APGC-QTOF-MS was also further investigated. Apart from the M+. ion and the well-known adduct [M+H]+ others such as [M-3H + O]+, [M-3H+2O]+ and [M-H+3O]+ were also observed for n-alkanes. Besides, new reaction products were found, formed by diol compounds (1-Monostearoylglycerol, 2-Monostearoylglycerol and NX 8000K) and silanediol dimethyl, which would be a transformation product of the silicone base septum or the methyl 5% phenyl polysiloxane based column. These new compounds were only detected in APGC-MS-QTOF as EI-GC-MS was not enough sensitive for this purpose.

Effects of Ultraviolet (UV) on Degradation of Irgafos 168 and Migration of Its Degradation Products from Polypropylene Films.

The effects of ultraviolet (UV) irradiation on the degradation of Irgafos 168 and the migration of its two degradation products, 2,4-di-tert-butylphenol and tris(2,4-di-tert-butylphenyl)phosphate, from polypropylene (PP) were investigated. A blown film machine was used to extrude PP films containing Irgafos 168, the films were stored in the dark for 45 days, two UV treatments and sunlight exposure were applied to the films, and GC-MS was used for degradation and migration studies. Extrusion, storage, UV treatments, and sunlight exposure significantly affected concentrations of Irgafos 168 and the degradation products. 2,4-Di-tert-butylphenol was the major degradation product produced by UV irradiation, but tris(2,4-di-tert-butylphenyl)phosphate was the major degradation product produced by extrusion, storage, and sunlight exposure. The degradation products have no or little health risk, because migration study and threshold of toxicological concern (TTC) analysis show that experimental maximum migration of 2,4-di-tert-butylphenol and tris(2,4-di-tert-butylphenyl)phosphate are only 2 and 53% of the theoretical maximum migration amounts, respectively.

[Determination of organochlorine pesticide residue in nine Chinese herbs by gas chromatography].

OBJECTIVE: To determine organochlorine pesticide residue in 9 Chinese herbs. METHODS: The organochlorine pesticides were extracted from the herbs with mixed solvents of n-hexane and acetone by a solid-phase extraction cartridge Florisil. Capillary gas chromatography was used to separate the samples. RESULTS: Good linearities were obtained for 11 organochlorine pesticides. The average recoveries at two concentration levels ranged from 79.9% to 89.0%,and from 86.3% to 104.8%, with relative standard deviations of 1.8% to 7.1%, respectively and detection limit of 2 g/kg. The residues of the organic pesticides exceeded national standard in Pogostemon cablin and Panax notoginseng. CONCLUSION: Capillary gas chromatography combined with electron capture detection provides a practical means for detecting organic pesticide residue in Chinese herbal medicines, and the limits of pesticide residues should be formulated in Chinese pharmacopoeia.