Plastics are known sources of chemical exposure and few, prominent plastic-associated chemicals, such as bisphenol A and phthalates, have been thoroughly studied. However, a comprehensive characterization of the complex chemical mixtures present in plastics is missing. In this study, we benchmark plastic consumer products, covering eight major polymer types, according to their toxicological and chemical signatures using in vitro bioassays and nontarget high-resolution mass spectrometry. Most (74%) of the 34 plastic extracts contained chemicals triggering at least one end point, including baseline toxicity (62%), oxidative stress (41%), cytotoxicity (32%), estrogenicity (12%), and antiandrogenicity (27%). In total, we detected 1411 features, tentatively identified 260, including monomers, additives, and nonintentionally added substances, and prioritized 27 chemicals. Extracts of polyvinyl chloride (PVC) and polyurethane (PUR) induced the highest toxicity, whereas polyethylene terephthalate (PET) and high-density polyethylene (HDPE) caused no or low toxicity. High baseline toxicity was detected in all “bioplastics” made of polylactic acid (PLA). The toxicities of low-density polyethylene (LDPE), polystyrene (PS), and polypropylene (PP) varied. Our study demonstrates that consumer plastics contain compounds that are toxic in vitro but remain largely unidentified. Since the risk of unknown compounds cannot be assessed, this poses a challenge to manufacturers, public health authorities, and researchers alike. However, we also demonstrate that products not inducing toxicity are already on the market.
An instrumental method for the evaluation of olive oil quality was developed. Twenty-one relevant aroma active compounds were quantified in 95 olive oil samples of different quality by headspace solid phase microextraction (HS-SPME) and dynamic headspace coupled to GC-MS. On the basis of these stable isotope dilution assay results, statistical evaluation by partial least-squares discriminant analysis (PLS-DA) was performed. Important variables were the odor activity values of ethyl isobutanoate, ethyl 2-methylbutanoate, 3-methylbutanol, butyric acid, E,E-2,4-decadienal, hexanoic acid, guaiacol, 2-phenylethanol, and the sum of the odor activity values of Z-3-hexenal, E-2-hexenal, Z-3-hexenyl acetate, and Z-3-hexenol. Classification performed with these variables predicted 88% of the olive oils' quality correctly. Additionally, the aroma compounds, which are characteristic for some off-flavors, were dissolved in refined plant oil. Sensory evaluation of these models demonstrated that the off-flavors rancid, fusty, and vinegary could be successfully simulated by a limited number of odorants. KEYWORDS: olive oil, sensory quality, stable isotope dilution assay, headspace solid phase microextraction, partial least-squares discriminant analysisThe rising olive oil consumption outside the Mediterranean area can be explained due to the health benefits attributed to olive oil, basically by its specific odor and taste characteristics. 1It is therefore not surprising that the quality of olive oil is determined primarily by its sensory properties. Sensory evaluation is based on the so-called "Panel Test" developed by the International Olive Council.2 This procedure, if performed by well-trained panelists, gives good and reproducible results, which are comparable with those of other panels. However, there are still disadvantages in the sensory quality evaluation. These are (i) the lack of stable and standardized reference oils for the different off-flavors and (ii) the large number of panelists that is needed for statistically confirmed results. 3Several instrumental methods have been developed as alternatives to sensory methods to evaluate the quality of olive oil. Many authors identified the important aroma active compounds in olive oil even in those with different off-flavors. Two review papers summarize the scientific findings.4,5 Headspace solid phase microextraction (HS-SPME) was found as the best method for the aroma analysis of olive oil. 6 However, this method only gives exact quantification results if recovery rates and response factors are determined for each compound, which was not carried out in most studies. These disadvantages of using external calibration can be circumvented by application of stable isotope dilution assay.7 Exact quantification data are needed for the calculation of odor activity values and therefore for the assessment how important an aroma active compound is for the overall flavor. Correlation of sensory data with quantification results was made by some authors, 8,9 but not on the b...
N-acetyl-4-aminophenol (acetaminophen/paracetamol, NA4AP) is one of the most commonly used over-the-counter analgesic and antipyretic drugs. Recent studies have reported anti-androgenic effects of NA4AP in vitro and possible associations between intrauterine exposure to NA4AP and the development of male reproductive disorders in humans. NA4AP is also a major metabolite of aniline (phenylamine), representing 75-86% of the aniline dose excreted in urine. Aniline is an important large-volume intermediate in several industrial processes. Besides individuals in various occupational settings with aniline exposure, the general population is also known to be ubiquitously exposed to aniline. In this article, we provide an overview of the recent literature concerning the intake of NA4AP during pregnancy and the possible anti-androgenic effects of NA4AP as well as literature concerning its known metabolic precursor aniline. We also present new research data, including the first human biomonitoring data on NA4AP excretion in urine, showing ubiquitous NA4AP body burdens in the general population at a wide range of concentrations. We found a small but significant impact of smoking on urinary NA4AP concentrations. We further present preliminary data on NA4AP excretion after therapeutic acetaminophen use, after aniline exposure in an occupational setting, and during a controlled fasting study (excluding oral exposure to both aniline and acetaminophen). Our findings indicate exposure to aniline (or aniline-releasing substances) as well as nutrition (next to the direct use of acetaminophen as medication) as possible sources of internal body burdens of NA4AP.Reproduction (2014) 147 R105-R117
Parabens are used as preservatives in personal care and consumer products, food and pharmaceuticals. Their use is controversial because of possible endocrine disrupting properties. In this study, we investigated metabolism and urinary excretion of methyl paraben (MeP), iso-butyl paraben (iso-BuP) and n-butyl paraben (n-BuP) after oral dosage of deuterium-labeled analogs (10 mg). Each volunteer received one dosage per investigated paraben separately and at least 2 weeks apart. Consecutive urine samples were collected over 48 h. In addition to the parent parabens (free and conjugated) which are already used as biomarkers of internal exposure and the known but non-specific metabolites, p-hydroxybenzoic acid (PHBA) and p-hydroxyhippuric acid (PHHA), we identified new, oxidized metabolites with hydroxy groups on the alkyl side chain (3OH-n-BuP and 2OH-iso-BuP) and species with oxidative modifications on the aromatic ring. MeP represented 17.4 % of the dose excreted in urine, while iso-BuP represented only 6.8 % and n-BuP 5.6 %. Additionally, for iso-BuP, about 16 % was excreted as 2OH-iso-BuP and for n-BuP about 6 % as 3OH-n-BuP. Less than 1 % was excreted as ring-hydroxylated metabolites. In all cases, PHHA was identified as the major but non-specific metabolite (57.2-63.8 %). PHBA represented 3.0-7.2 %. For all parabens, the majority of the oral dose captured by the above metabolites was excreted in the first 24 h (80.5-85.3 %). Complementary to the parent parabens excreted in urine, alkyl-chain-oxidized metabolites of the butyl parabens are introduced as valuable and contamination-free biomarkers of exposure.
Bitterness and pungency are important parameters for olive oil quality. Therefore, two instrumental methods for evaluation of these taste attributes were developed. The first one is based on the photometric measurement of total phenolic compounds content, whereas the second one is based on the semiquantitative evaluation of hydrophilic compounds by highperformance liquid chromatography−mass spectrometry (HPLC-MS). Evaluation of total phenolic compounds content was performed by a modified method for the determination of the K 225 value using a more specific detection based on the pH value dependency of absorbance coefficients of phenols at λ = 274 nm. The latter method was not suitable for correct prediction, because no significant correlation between bitterness/pungency and total phenolic compounds content could be found. For the second method, areas of 25 peaks detected in 54 olive oil samples by a HPLC-MS profiling method were correlated with the bitterness and pungency by partial least-squares regression. Six compounds (oleuropein aglycon, ligstroside aglycon, decarboxymethyl oleuropein aglycon, decarboxymethyl ligstroside aglycon, elenolic acid, and elenolic acid methyl ester) show high correlations to bitterness and pungency. The computed model using these six compounds was able to predict bitterness and pungency of olive oil in the error margin of the sensory evaluation (±0.5) for most of the samples.
Apart from being considered a potential threat to ecosystems and human health, the ubiquity of microplastics presents analytical challenges. There is a high risk of sample contamination during sampling, sample preparation, and analysis. In this study, the potential of sample contamination or misinterpretation due to substances associated with disposable laboratory gloves or reagents used during sample preparation was investigated. Leachates of 10 different types of disposable gloves were analyzed using Raman microspectroscopy (μ-Raman), Fourier-transform infrared microspectroscopy (μ-FTIR), and pyrolysis–gas chromatography/mass spectrometry (pyr–GC/MS). There appeared to be polyethylene (PE) in almost all investigated glove leachates and with all applied methods. Closer investigations revealed that the leachates contained long-chain compounds such as stearates or fatty acids, which were falsely identified as PE by the applied analytical methods. Sodium dodecyl sulfate, which is commonly applied in microplastic research during sample preparation, may also be mistaken for PE. Therefore, μ-Raman, μ-FTIR, and pyr–GC/MS were further tested for their capability to distinguish among PE, sodium dodecyl sulfate, and stearates. It became clear that stearates and sodium dodecyl sulfates can cause substantial overestimation of PE.
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