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Abstract and Figures
Thermal papers (e.g. point of sale receipts, adhesive labels, tickets) significantly contribute to contamination of paper material cycles and the environment with substances of (eco-) toxicological concern. In particular, they contain color developers like endocrine disrupting bisphenols in typical concentrations of about 1–2 percent per weight (wt%). Bisphenol A (BPA) was used as the common color developer over the last decades, but it will be restricted for thermal paper application in the European Union to a limit of 0.02 wt% from 2020 onwards. Consequently, a variety of BPA substituents such as bisphenol S (BPS) and its derivatives gain importance in thermal paper application. In this study, a rapid, reliable and cost-effective method for identification and quantification of BPA, alternative color developers and related substances like sensitizers is presented based on HPLC separation coupled with diode array detection (DAD) and Corona charged aerosol detection (CAD). Quantification was performed with regard to the intended use of the substances in thermal papers. Besides traditional UV external calibration using reference standards, alternative quantification approaches, in particular UV chromophore concentration for BPS derivatives and CAD universal response technique for low-volatile color developers, were applied and compared in order to allow quantification without reference substances. A market analysis for intended used color developers and sensitizers was performed on thermal paper samples (n = 211) collected in Germany during 2018 and 2019. Pergafast 201 (in 41.7% of the samples) was the most common color developer with concentrations above 0.02 wt%, followed by BPA (36.0%), BPS (13.3%) and other BPS derivatives known as D8, D-90, BPS-MAE and TGSA, that are mainly present in adhesive labels. Sensitizers were determined in over 90% of the samples.
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... Recently, new phenol-free ink developers had been reported in the literature as alternative to BPS and its analogous compounds, such as urea urethane compound (UU), N-(p-toluenesulfonyl)-N′-(3-p-toluenesulfonyloxyphenyl) urea (Pergafast 201), 4,4′-bis(N-carbamoyl-4-methylbenzenesulfonamide) diphenylmethane (BTUM), 4-hydroxyphenyl 4isoprooxyphenylsulfone (D-8), and 4-hydroxy-4′benzyloxydiphenylsulfone (BPS-MAE) (United States Environmental Protection Agency 2014; Eckardt et al. 2020). The Pergafast 201 and UU have been considered important non-phenolic bisphenol substitutes in the European market (Björnsdotter et al. 2017b). ...
... The Pergafast 201 and UU have been considered important non-phenolic bisphenol substitutes in the European market (Björnsdotter et al. 2017b). Although Pergafast 201 can be considered to be of low toxicity (Goldinger et al. 2015), its use has not been applied on a large scale due to its higher cost of manufacture; thus, thermal papers based on phenolic ink developers, especially BPA and BPS, are still more common and accessible in several countries (Eckardt et al. 2020). ...
Concerns about human health regarding the large use of bisphenol A in thermal papers have led to its replacement by bisphenol S. Analyses of bisphenols require several sample pretreatment steps, which are laborious, expensive, and time-consuming. A paper spray ionization mass spectrometry (PSI-MS) was developed to detect and quantify bisphenol S in three different brands of thermal papers commercially available. Parameters such as paper size, and paper position relative to the mass spectrometer inlet were evaluated. The analyses were performed in selected ion monitoring mode on a linear ion trap mass spectrometer. The developed method presented absolute recovery values ranging from 92.2 to 109.04%, accuracy values from −1.2 to 9.0%, and inter assay precision from 1.8 to 5.6% and enabled LOD as low as 5 ng g−1. The concentration of bisphenol S in all of the three brands of BPA-free thermal papers evaluated ranged from 1.36 to 6.77 μg g−1, and the concentrarion of BPA ranged from 6.56 to 16.4 μg g−1 in all samples of thermal paper evaluated. The PSI-MS method described here was comparable to the conventional ones, such as liquid chromatography coupled with mass spectrometry and gas chromatography coupled with mass spectrometry described in the literature. The present study proved to be practical, fast, and efficient for the direct determination of bisphenol S in thermal papers. Furthermore, the methodology here described showed to be a promising alternative to replace the classical methods for determination of bisphenol S, due to its simplicity, and no needing of any sample pretreatment.
... Da BPA als gesundheitsschädlich gilt, darf es in Thermopapieren in der Europäischen Union ab dem Januar 2020 nur noch beschränkt einge-setzt werden. Als Folge werden heute vermehrt verschiedene alternative Entwickler verwendet . Trotzdem wird BPA heute immer noch als Entwickler eingesetzt, weshalb im experimentellen Umgang mit Thermopapieren geeignete Vorsichtsmassnahmen (Handschuhe) zu treffen sind. ...
de Fingerabdrücke sind eines der wichtigsten Beweismittel bei der Aufklärung von Kriminalfällen, ihre Sicherung zählt daher zu den Hauptaufgaben der Forensik. Beim Sichtbarmachen latenter Fingerabdrücke auf Quittungsbelegen stehen Forensiker vor einer schwierigen Aufgabe, da viele gängige Nachweismethoden die Farbreaktion im Thermopapier auslösen, womit dieses schwarz, der Aufdruck unleserlich und damit die Beweiskraft des Belegs zunichte gemacht wird. Die Zusammenhänge um thermochrome Dreikomponentengemische helfen, die Entwicklung eines Fingerabdrucks auf Thermopapier durch gezielte Wärmeeinwirkung zu verstehen. Die Schwärzung des Thermopapiers am Ort des Fingerabdrucks beruht nach unseren Ergebnissen auf Zwischenmolekularen Kräften. Neu ausgebildete Kräfte zwischen den Molekülen der hydrophoben Fingerabdrucksekrete und den Komponenten des thermochromen Gemischs im Thermopapier führen dazu, dass der im Papier eingelagerte Farbentwickler und Leukofarbstoff schon bei geringerer Hitzeeinwirkung mobilisiert werden und so den schwarzen Entwickler‐Farbstoff‐Komplex bilden können. Diese Hypothese wird durch eine neu entwickelte Methode gestützt, wonach Fingerabdrücke auch durch Eintauchen des Quittungsbelegs in heißes Wasser entwickelt werden können.
en Fingerprints are one of the most important forms of physical evidence in criminal investigations. When making latent fingerprints visible on thermal paper receipts, forensic experts face a difficult task as many common detection methods for visualizing latent fingerprints do not work without organic solvents or the use of heat. However, processing techniques often trigger the color reaction in the thermal paper, making this black, the print illegible and thus the probative value of the document is nullified. A fundamental knowledge of the design and operation of thermal papers is indispensable for understanding why damage occurs during chemical development of latent ridge detail on these papers and why fingerprints can be developed through the controlled application of heat. On our results, the blackening at the location of the fingerprint below the color change temperature of the thermal paper based on intermolecular forces. Newly formed interactions between the molecules of the hydrophobic fingerprint secretions and the components of the thermochromic mixture in the thermal paper lead to the fact that leuco dye and color developer encapsulated in the thermal coat of the paper is mobilized even at low heat and can thus form the black developer‐dye complex. A newly developed method whereby fingerprints can also be developed by immersion in hot water supports our hypothesis.
In this study, a mixed-mode strong anion-exchange (MAX) adsorbent was developed based on amine-functionalized poly(divinylbenzene) (PDVB) functionalized with polyethyleneimine (PEI) followed by quaternization with glycidyl phenyl ether (named as PDVB-QPEI). Fourier Transform Infrared spectroscopy and nitrogen adsorption-desorption experiments indicated that the PDVB-QPEI was successfully synthesized with a BET specific surface area (SBET) of 118.5 m² g⁻¹, pore volume of 0.37 cm³ g⁻¹, and pore size of 16.41 nm. High ion-exchange capacity (IEC) of 0.57 mmol g⁻¹ was achieved. The important parameters influencing SPE efficiency were optimized, including adsorbent mass, pH of the sample, type and volume of washing solvent and eluent. The practical capability of this novel PDVB-QPEI MAX adsorbent was tested for solid phase extraction and purification of bisphenol analogues and monoalkyl phthalate esters (MPEs) in urine samples. Outstanding extraction and cleanup efficiency were achieved simultaneously for urine samples due to high selectivity of the PDVB-QPEI adsorbent for bisphenol analogues and MPEs. Recovery values ranged from 80.1% to 102.4% with precision (relative standard devition, n=3) below 6% for these blank urine samples spiked at different levels. The limit of detections (LODs) obtained by HPLC-DAD were in the range of 3 − 9 ng mL⁻¹. The PDVB-QPEI is superior to commercial adsorbents (Oasis HLB, C18 and Oasis MAX). These results demonstrated the great potential application of the PDVB-QPEI adsorbent in routine analysis of bisphenol analogues and MPEs in complex samples.
The objective of this work was to evaluate thermal paper (TP) tickets used in Argentina as a potential source of bisphenol A (BPA) that could impact humans and the environment. BPA in TP was measured by HPLC ranging from 11.1 to 30.5 mg BPAg⁻¹. In order to estimate the impact on humans, dermal BPA estimated daily intake was calculated as being 79.3 ± 19.5 μgd⁻¹ for workers and 1.6 ± 0.4 μgd⁻¹ for the general population. To evaluate TP’s impact on the environment, BPA migration from TP to water and soil was studied. In the case of water, 99.6% of the BPA tickets content migrated in 30 h, while 78.0% moved into the soil in 96 h. BPA degradation kinetics in soil and water were also carried out; while in soil 61.9% of BPA degraded in 120 h, no degradation was observed up to 120 h in tap or river water.
Additionally, ecotoxicological effects of BPA on the earthworm Eisenia andrei, a representative terrestrial indicator, were studied performing bioassays on lethality, avoidance, and reproductive and enzymatic activity. BPA showed to be very toxic to E. andrei (LC50 value in contact paper test of 17 μgcm⁻², 95% confidence interval 6–46 μgcm⁻², 24 h exposure) and also caused an increase of total cocoons for earthworms exposed to 10 and 50 mg BPA kg⁻¹ soil. Evasion response was observed at a concentration of 50 mg BPA kg⁻¹ soil, while no effect was observed on cholinesterases, carboxylesterases, and glutathione S-transferases activities (1, 10, and 50 mg BPA kg⁻¹ soil). Finally, a simple BPA degradation technology using water peroxide and radish (Raphanus sativus) tissue as catalyst was explored as a simple and domestic potential treatment to avoid BPA migration to the environment.
Bisphenols (BPs) have attracted attention worldwide due to their distribution in environmental, biological fuids and food
matrices. Therefore, the monitoring of BPs is necessary for human health. Since their occurrence in such matrices at very
low concentrations diferent sample extraction and cleanup techniques mostly solid phase extraction (SPE) and microextraction followed by HPLC widely utilized for analysis of BPs. Diferent sample extraction techniques that have been used for
extraction of BPs such as liquid–liquid extraction, dispersive liquid–liquid microextraction, solid phase extraction (SPE),
molecularly imprinted polymers, magnetic solid phase extraction and quick, easy, cheap, efective, rugged and safe were
reviewed and discussed. In this review, the sample extraction techniques and HPLC methods using various detectors that
have been developed and validated so far, for analysis of BPs in biological, food and environmental samples, are overviewed
Aufgrund der Belegausgabepflicht, welche seit 01.01.2020 rechtskräftig ist, wird eine deutlich größere Menge an Thermopapier verbraucht. Das Problem hierbei sind die verwendeten Inhaltsstoffe im Thermopapier. Diese sind sowohl schädlich für die Umwelt als auch für den menschlichen Körper. Aufgrund dieser Giftstoffe ist das richtige Entsorgen von Kassenbelegen seitens der Konsumierenden ein wichtiges Thema. Zusätzlich ist vielen Konsumierenden eine digitale und somit nachhaltige Alternative nicht bekannt. Ziel des Beitrages ist es daher, nachhaltige und digitale Alternativen zu den herkömmlichen Kassenbelegen aus Thermopapier theoretisch und empirisch zu überprüfen. Im Mittelpunkt steht hierbei die Sicht der Konsumierenden, weshalb 154 Verbraucherinnen und Verbraucher im Outlet-Center Metzingen mithilfe einer digitalen Verbraucherbefragung integriert wurden. Die theoretische Einbettung des Themas erfolgt anhand folgender Wissenschaftsgebiete: Digitalisierung, Verhaltensökonomie, Nachhaltigkeitswissenschaften und Handelsrecht.
In recent years, the use of quantitative liquid chromatography (LC) coupled charged aerosol detection (CAD) for poor UV absorbing analytes in multicomponent mixtures has grown exponentially across academic and industrial sectors. The ballpark of previous LC-CAD reports is focused on practical applications, as well as optimization of critical parameters such as: response dependencies on temperature, nebulization process, analyte volatility, and mobile-phase composition. However, straightforward approaches to deal with the characteristic nonlinear response of CAD still scarce. A highly overlooked parameter is the power function value (PFV), whose optimization enables a detection signal that is more linear with higher signal-to-noise ratio (S/N) and lower relative standard deviation (RSD) of area counts. Herein, a systematic investigation of different regression models (log-log, first-and second-degree polynomial) by both interpolation and extrapolation process in conjunction with PFV optimization throughout the development of LC-CAD assays is reported. The accuracy of the results via interpolation is always good (< 5%) when operating in the vicinity of the optimum PFV regardless the regression model choice. On the contrary, extrapolation process only worked when applying log-log regression at the optimum PFV (accuracy <5%). This outcome indicates that a first-order regression via interpolation can be a safe and simple choice for quantitative LC-CAD in highly regulated laboratories (GLP, GMP, etc.). Whereas a straightforward extrapolation combined with log-log regression can enable the deployment of high-throughput LC-CAD assays, especially but not limited to laboratories where the synthetic process route is undergoing rapid change and optimization (medicinal chemistry, discovery, biocatalysis, process chemistry, etc.). This approach is crucial in developing quantitative LC-CAD assays for poor UV absorbing pharmaceuticals that are sensitive, precise, accurate and robust across early and late-stage pharmaceutical development.
Even with all the biological problems associated with bisphenol-A (BPA), this chemical is still being widely used, especially in thermal paper receipts. In this study, renewable mesoporous silica nanoparticles (MSN), obtained from sugarcane ash, functionalized with hexadecyltrimethylammonium (CTAB) were applied as an adsorbent in the removal of BPA from the aqueous solution. The versatility of this material and its BPA adsorption capacity were tested at different pH values, being practically constant at pH between 4 and 9, with a slight increase in pH 10 and a greater increase in pH 11. The removal time evaluation indicates a very fast adsorption process, removing almost 90% of BPA in the first 20 min of contact. The kinetic model indicates a monolayer formation of BPA molecules on the MSN-CTAB surface. The maximum adsorption capacity (Qmax) was 155.78 mg g−1, one of the highest found in literature, and the highest for material from a renewable source.
Bisphenol A (BPA) is an industrial chemical used as an additive in conventional point-of-sale thermal paper receipts. Due to BPA being an endocrine disruptor and a substance of very high concern, the European Union (EU) has proposed to ban its use in thermal paper from 2020. Potential similarities in toxicological profiles have raised concerns that the use of bisphenol S (BPS) as a substitute for BPA may result in yet another situation of a problematic chemical being distributed in consumer products. This study provides a comprehensive evaluation of the current knowledge of BPA and BPS use in thermal paper and, based on dynamic material and substance flow modeling, quantifies potential effects of the BPA ban on future BPA and BPS flows within the European paper cycle. Based on available data and the modeling of BPA and BPS flows, approximately 200 tonnes of BPS are estimated to be present in the current European paper cycle. The modeling further demonstrated that by substituting 50% of BPA, BPS amounts in the European paper cycle would increase more than fivefold over a modeling period of 60 years. In the same time, more than 90 tonnes of BPA would still be circulated in European paper products. BPA alternatives other than BPS should receive additional attention, as very limited quantitative data currently exist. The results of this study quantitatively demonstrate that chemical bans alone are not sufficient to ensure clean material cycles, and so the effective regulation of potential substitutes needs to be implemented in parallel.
There is growing evidence that bisphenol A (BPA) may adversely affect humans. BPA is an endocrine disruptor that has been shown to be harmful in laboratory animal studies. Until recently, there were relatively few epidemiological studies examining the relationship between BPA and health effects in humans. However, in the last year, the number of these studies has more than doubled. A comprehensive literature search found 91 studies linking BPA to human health; 53 published within the last year. This review outlines this body of literature, showing associations between BPA exposure and adverse perinatal, childhood, and adult health outcomes, including reproductive and developmental effects, metabolic disease, and other health effects. These studies encompass both prenatal and postnatal exposures, and include several study designs and population types. While it is difficult to make causal links with epidemiological studies, the growing human literature correlating environmental BPA exposure to adverse effects in humans, along with laboratory studies in many species including primates, provides increasing support that environmental BPA exposure can be harmful to humans, especially in regards to behavioral and other effects in children.
Of 13 thermal printing papers analyzed, 11 contained 8-17 g/kg bisphenol A (BPA). When taking hold of a receipt consisting of thermal printing paper for 5 s, roughly 1 microg BPA (0.2-6 microg) was transferred to the forefinger and the middle finger if the skin was rather dry and about ten times more if these fingers were wet or very greasy. This amount transferred to dry skin was neither significantly increased when taking hold of the paper at up to 10 sites, nor reduced when BPA-free paper was contacted afterwards. After 60-90 min, BPA applied to the skin as a solution in ethanol was only partially or no longer at all extractable with ethanol, whereas BPA transferred to the skin by holding thermal printer paper remained largely extractable after 2 h. This suggests that penetration of the skin depends on the conditions. Extractability experiments did not enable us to conclude whether BPA passes through the skin, but indicated that it can enter the skin to such a depth that it can no longer be washed off. If this BPA ends up in the human metabolism, exposure of a person repeatedly touching thermal printer paper for 10 h/day, such as at a cash register, could reach 71 microg/day, which is 42 times less than the present tolerable daily intake (TDI). However, if more than just the finger pads contact the BPA-containing paper or a hand cream enhances permeability of the skin, this margin might be smaller.
Coatings for cans or closures are essential to protect the metal from corrosion and the food from migration of hazardous metal ions. Since coatings are no inert materials, they can release substances of potential health concern into food. In the present study, a comprehensive analysis is presented for a complex two-layered polyester–phenol-coating commercially used for metal closures of complementary infant food in sterilised glass jars. Focussed on the identity and migration of cyclic polyester oligomers as a kind of predictable non-intentionally added substances, polyester resin raw materials (n = 3) as well as individual coating layers (n = 3) were characterised by several analytical strategies (size exclusion chromatography, high-performance liquid chromatography mass spectrometry, diode array detection, charged aerosol detection, monomer determination after alkaline hydrolysis, overall migrate). The main polyester monomers were terephthalic acid, isophthalic acid, trimellitic acid, ethylene glycol, diethylene glycol, neopentylglycol, 2-methyl-1,3-propanediol, 1,4-butanediol and tricyclodecanedimethanol. The coatings were extracted with solvents acetonitrile and ethanol (24 h, 60°C), food simulants 50% ethanol, 20% ethanol and water (1 h, 121°C) as well as homemade and commercial baby food (1 h, 121°C). The released total polyester content determined by alkaline hydrolysis ranged from 288 µg/dm² (water, 1 h, 121°C) to 6154 µg/dm² (acetonitrile, 24 h, 60°C). However, individual cyclic oligomers, mainly dimers, were released from the coating to up to about 140 µg/dm². Migration into infant food was best represented by the food simulants water (up to 1% fat) and 20% ethanol (up to 5% fat). Cyclic polyester oligomers are classified as Cramer III substances by the threshold of toxicological concern concept associated to an exposure threshold of 1.5 µg/kg body weight per day. Exposure to cyclic polyester oligomers might be a potential concern for highly exposed infants.
Thermal printing is a fast, widespread and inexpensive technology that uses a developer to produce a print on the paper, among many applications. A common developer is bisphenol A (BPA), used for this purpose in its free form. Consequently, the handling of thermal paper, as evaluated by the European Food Safety Authority, was reported to be the second largest source of external human exposure to this endocrine disrupting chemical. Recently, reports have been made on the substitution of BPA by alternative developers, which are yet less studied. In this study, 311 receipts and other thermal paper products were collected from 14 countries in Europe, Asia, North America and Oceania and analysed using liquid chromatography coupled to quadrupole time-of-flight mass spectrometry. BPA was the most frequently used main developer and was detected in 194 thermal paper samples, which represents a detection frequency of 63 %. A statistically significant difference in the detection of BPA was shown between continents. BPA was followed by bisphenol S (BPS) which was detected in 64 samples as the main developer. Pergafast 201 was the third most abundant main developer and detected in 37 samples as the main developer. Less frequently used main developers included BPS-MAE, TGSA, D-8, and D-90, many of them being BPS derivatives. Two oligomers of D-90 (n = 1 and n = 2) were also identified. The sensitizer diphenyl sulphone (DPS) was identified using high-resolution mass spectrometry for the first time and detected in combination with other developers than BPS for the first time. Despite the lack of structural, nation-wide legislation prohibiting the use of BPA in thermal paper, it is clear that alternative developers are currently globally in use for the manufacturing of thermal paper.
Bisphenol A (BPA) is a high-production-volume chemical with endocrine disrupting properties commonly used as color developer in thermal paper. Concerns about the potential hazards of human BPA exposure have led to the increasing utilization of alternatives such as bisphenol S (BPS) and bisphenol F (BPF). This study was designed to assess: (i) BPA, BPS, and BPF concentrations in 112 thermal paper receipts from Brazil, France, and Spain by liquid chromatography coupled to mass spectrometry (LC-MS); and (ii) hormone-like activities of these receipts using two receptor-specific bioassays, the E-Screen for (anti-)estrogenicity and PALM luciferase assay for (anti-)androgenicity. BPA was present in 95.3% of receipts from Spain, 90.9% of those from Brazil, and 51.1% of those from France at concentrations up to 20.27 mg/g of paper. Only two samples from Brazil, two from Spain, and ten from France had a BPS concentration ranging from 6.46 to 13.29 mg/g; no BPA or BPS was detected in 27.7% of French samples. No BPF was detected in any receipt. Estrogenic activity was observed in all samples from Brazil and Spain and in 74.5% of those from France. Anti-androgenic activity was observed in > 90% of samples from Brazil and Spain and in 53.2% of those from France. Only 25.5% of French samples were negative for both estrogenic and anti-androgenic activity. Estrogenic and anti-androgenic activities per gram of paper were up to 1.411 µM estradiol (E2) equivalent units (E2eq) and up to 359.5 mM procymidone equivalent units (Proceq), respectively. BPA but not BPS concentrations were positively correlated with both estrogenic and anti-androgenic activities. BPA still dominates the thermal paper market in Brazil and Spain, and BPS appears to be one of the main alternatives in France. There is an urgent need to evaluate the safety of alternatives proposed to replace BPA as developer in thermal printing. The large proportion of samples with hormonal activity calls for the adoption of preventive measures.
In terms of risk assessment especially for known and unknown substances migrating from food contact materials, quantification without corresponding reference substances currently poses a challenge. In the present study, the opportunity of a universal response quantification approach was evaluated by using a corona charged aerosol detector (CAD) for liquid chromatography combined with inverse gradient compensation. Characteristics of CAD detection in dependence of substance properties were analyzed with 46 randomly chosen reference substances. An almost equal CAD response (±20%) was achieved for non-volatile substances with a molecular weight of minimum 400 g/mol and a vapor pressure of maximum 10−8 Torr. We empirically defined an analytical parameter, Q50/35, the quotient of CAD peak areas at CAD evaporator temperatures of 50 °C and 35 °C, to predict the adequacy of the CAD universal response approach for quantification of known and unknown analyte substances. Exemplarily, we applied the CAD universal quantification approach for the determination of extractable oligomers below 1000 g/mol from a variety of food contact polycondensate plastic materials (e.g. polyesters like polyethylene terephthalate, polybutylene terephthalate, Tritan copolyester, polyamides 6, 6.6 and 6 T/6I and polyarylsulfones polyphenylsulfone and polyethersulfone). Quantitative results for in total 44 oligomers out of 11 materials were compared with established material-specific quantification methods using extracted oligomer mixtures as well as individual oligomers isolated from the mixtures. CAD-based quantification results were generally in accordance to published quantification approaches for polyamide oligomers and oligomers from polyarylsulfones. For oligomers extracted and isolated from polyester materials a slight underestimation was determined by CAD universal response approach. In terms of detection limits and accuracy, the universal CAD approach exhibits no advantages compared to established UV-methods, to date.
Polyphenylsulfone (PPSU) is a new material for the production of baby bottles. PPSU is a polyether plastic formally composed of bisphenol S (BPS) and 4,4ʹ-dihydroxybiphenyl (DHBP), which both have slight endocrine activities in in-vitro-tests. So far, little is known about the presence and the release of potentially hazardous substances from PPSU baby bottles. In our present study, we present a three step approach for the analysis of PPSU starting with polymer characterization in terms of chemical structure, total oligomer content and hydrolytic stability. Second is the determination of extractables focussing on monomers, monomer derivatives, linear and cyclic oligomers below 1000 dalton (Da) and residual solvent. Third is a risk assessment on migration-related substances in accordance to EU plastics regulation No 10/2011 based on triplicate consecutive migration experiments using official milk simulant 50% ethanol. We analysed five types of PPSU baby bottles from different brands as well as corresponding raw materials from different manufacturers by various analytical techniques (HPLC-DAD/FLD/Corona/ESI-MS, HPLC-SEC, GC-MS, ¹H-NMR). We found significant variations of PPSU materials from different producers with regard to polymer and oligomer chain end groups (methoxylation, chlorination), while total oligomer content below 1000 Da was similar (mean about 0.48%). BPS was not detected above 0.3 mg/kg polymer in any PPSU sample. Residual DHBP content ranged between 1.7 and 15.5 mg/kg polymer. The most common oligomer in all PPSU samples was the cyclic tetramer (about 1200 mg/kg polymer), which is the only cyclic compound below 1000 Da. Residual solvent, sulfolane, was determined to a maximum of 1300 mg/kg polymer. In migration tests, we detected exceedances of neither specific migration limits (SML) for listed substances nor of thresholds of toxicological concern (TTC) for non-listed substances (monomer derivatives, oligomers). Based on our analytical results, no concerns exist regarding migration of polymer-related substances from PPSU baby bottles.
Bisphenol A (BPA) was commonly used as color developer for thermal paper such as cash register receipts, labels or tickets. Therefore, thermal paper was considered by the European Food Safety Authority (EFSA) as the main source of human exposure to BPA beside epoxy based food contact materials. In this study, a German market analysis on the use of BPA and alternative color developers in thermal paper receipts is provided for the years 2015, 2016 and 2017.114 (2015), 98 (2016) and 99 (2017) samples were randomly collected and analyzed by HPLC-DAD. In summary, BPA was still the most frequently found color developer (48.2% in 2015, 46.9% in 2016 and 52.5% in 2017). The most commonly used alternative was the phenol-free substance Pergafast® 201 (34.2%, 33.7%, 40.4%). The bisphenol analogs bisphenol S (BPS; 11.4%, 9.2%, 6.1%) and D8 (6.1%, 7.1%, 1.0%) were less common. Another phenol-free substituent, a urea urethane compound (UU), was also detected (3.1% in 2016). Concentrations of color developers in thermal paper ranged from 1.4 to 32.4 mg/g (median values between 2.5 and 15.9 mg/g). Concentrations of BPA were found to be highest followed by BPS, UU, Pergafast® 201 and D8. In addition, two pharmacologically active substances, dapsone (6.0 mg/g) and tolbutamide (5.5 mg/g), were detected in a non-marketed thermal paper, that was supposed to use ascorbic acid as initial color developer. Different release experiments of the detected color developers were performed. Sensitizers 1,2-diphenoxy-ethane, 1-phenylmethoxy-naphthalene and diphenylsulfone, used frequently in the thermal paper processes, were quantified.
Thermal paper contains potentially toxic additives, such as bisphenol A (BPA), as a common color developer. Because of its known endocrine disrupting effects, structural analogues to BPA, such as bisphenol S (BPS), D-8 and Pergafast 201, have been used as alternatives, but little is known about the presence and toxicological effects of alternatives other than BPS. In this study, thermal paper is screened by direct probe ambient mass spectrometry (rapid pre-screening method not requiring sample preparation) and by liquid chromatography (LC) with high resolution time-of flight (TOF-MS) mass spectrometry. Cash receipts and other thermal paper products (cinema tickets, boarding passes and luggage tags) were analyzed. Besides BPA and BPS, other developers only recently reported (Pergafast 201, D-8) or to the best of our knowledge not reported before (D-90, TGSA, BPS-MAE) were frequently found as well as some related unreported impurities (2,4-BPS that is a BPS related impurity and a TGSA related impurity). To gain some insight into the potential estrogenicity of the detected developers, a selection of extracts was further analyzed using a LC-nanofractionation platform in combination with cell-based bioassay testing. These preliminary results seems to indicate very low or absence of estrogenic activity for Pergafast 201, D-8, D-90, TGSA and BPS-MAE in comparison to BPA and BPS, although further dose-response tests with authentic standards are required to confirm these results. Compounds for which standards were available were also tested for developmental toxicity and neurotoxicity using zebrafish (Danio rerio) embryos. TGSA and D-8 induced similar teratogenic effects as BPA in zebrafish embryos. BPS and 2,4-BPS did not induce any developmental effects but 2,4-BPS did alter the locomotor activity at the tested concentration. Our findings suggest that the alternatives used as alternatives to BPA (except BPS) might not be estrogenic. However, TGSA and D-8 showed abnormal developmental effects similar to BPA.
Bisphenol A (BPA), a synthetic xenoestrogen widely used in various industrial fields, can be present, in its un-reacted form, as an additive in thermal paper. BPA is virtually ubiquitous in industrialized societies and humans are exposed to this chemical via dietary and non-dietary sources. Since in 2015 European Food Safety Authority (EFSA) indicated that thermal paper, is the second source of BPA exposure after the food chain, some suppliers replaced BPA with its analogue Bisphenol S (BPS), speculatively supposed to be safer.
In this work BPA and BPS concentration levels were determined in 50 thermal paper receipts collected in Italy by liquid chromatography coupled to tandem fluorescence and ultraviolet detection. BPA was found in 44 samples at mean concentration of 107.47 µg/100 mg of paper (from below Limits of Quantification (LOQ) to 1533.733 µg/100 mg of paper). BPS was found in 31 samples at mean concentration of 41.97 µg/100 mg of paper (from below the LOQ to 357.989 µg/100 mg of paper). 26 samples were positive to both BPA and BPS. The estimate daily intake (EDI) values of BPA and BPS occurring through dermal absorption were calculated for 70 kg body weight individuals. For general population, they were 0.0625 µg/day for BPA and 0.0244 µg/day for BPS, based on the mean content of bisphenols found. For occupationally exposed individuals, they were 66.8 µg/day for BPA and 15.6 µg/day for BPS, based on the worst scenario. Such levels would produce a dermal intake below the Tolerable Day Intake established by EFSA (4 µg/kg bw/day); nevertheless, the occurrence of co-exposure to dietary and non-dietary sources should be considered in the health risk assessment, mainly for people frequently exposed to thermal paper contact, as for occupational reason.
This opinion describes the assessment of the risks to public health associated with bisphenol A (BPA) exposure. Exposure was assessed for various groups of the human population in three different ways: (1) external (by diet, drinking water, inhalation, and dermal contact to cosmetics and thermal paper); (2) internal exposure to total BPA (absorbed dose of BPA, sum of conjugated and unconjugated BPA); and (3) aggregated (from diet, dust, cosmetics and thermal paper), expressed as oral human equivalent dose (HED) referring to unconjugated BPA only. The estimated BPA dietary intake was highest in infants and toddlers (up to 0.875 µg/kg bw per day). Women of childbearing age had dietary exposures comparable to men of the same age (up to 0.388 µg/kg bw per day). The highest aggregated exposure of 1.449 µg/kg bw per day was estimated for adolescents. Biomonitoring data were in line with estimated internal exposure to total BPA from all sources. BPA toxicity was evaluated by a weight of evidence approach. “Likely” adverse effects in animals on kidney and mammary gland underwent benchmark dose (BMDL10) response modelling. A BMDL10 of 8 960 µg/kg bw per day was calculated for changes in the mean relative kidney weight in a two generation toxicity study in mice. No BMDL10 could be calculated for mammary gland effects. Using data on toxicokinetics, this BMDL10 was converted to an HED of 609 µg/kg bw per day. The CEF Panel applied a total uncertainty factor of 150 (for inter- and intra-species differences and uncertainty in mammary gland, reproductive, neurobehavioural, immune and metabolic system effects) to establish a temporary Tolerable Daily Intake (t-TDI) of 4 µg/kg bw per day. By comparing this t-TDI with the exposure estimates, the CEF Panel concluded that there is no health concern for any age group from dietary exposure and low health concern from aggregated exposure. The CEF Panel noted considerable uncertainty in the exposure estimates for non-dietary sources, whilst the uncertainty around dietary estimates was relatively low.
Bisphenol A (BPA) is widely used as a color developer in thermal paper. Thermal paper is ubiquitous in daily life due to its use in cash register receipts, so opportunities for human contact abound. For this study, 10 blank cash register receipts were obtained from businesses in suburban Boston. BPA was extracted and analysis of concentration was performed using gas chromatograph/flame ionization detector. In some receipts, BPA was not detected but in others it was as high as 19 mg for a 12-inch long receipt, which is in line with concentrations indicated in patents. This study is intended to highlight the potential for human exposure to BPA as well as the ease with which exposure may be reduced through the use of BPA-free thermal paper.
As the evidence of the toxic effects of bisphenol A (BPA) grows, its application in commercial products is gradually being replaced with other related compounds, such as bisphenol S (BPS). Nevertheless, very little is known about the occurrence of BPS in the environment. In this study, BPS was analyzed in 16 types of paper and paper products (n = 268), including thermal receipts, paper currencies, flyers, magazines, newspapers, food contact papers, airplane luggage tags, printing paper, kitchen rolls (i.e., paper towels), and toilet paper. All thermal receipt paper samples (n = 111) contained BPS at concentrations ranging from 0.0000138 to 22.0 mg/g (geometric mean: 0.181 mg/g). The overall mean concentrations of BPS in thermal receipt papers were similar to the concentrations reported earlier for BPA in the same set of samples. A significant negative correlation existed between BPS and BPA concentrations in thermal receipt paper samples (r = -0.55, p < 0.0001). BPS was detected in 87% of currency bill samples (n = 52) from 21 countries, at concentrations ranging from below the limit of quantification (LOQ) to 6.26 μg/g (geometric mean: 0.029 μg/g). BPS also was found in 14 other paper product types (n = 105), at concentrations ranging from <LOQ to 8.38 μg/g (geometric mean: 0.0036 μg/g; detection rate: 52%). The estimated daily intake (EDI) of BPS, through dermal absorption via handling of papers and currency bills, was estimated on the basis of concentrations and frequencies of the handling of papers by humans. The median and 95th percentile EDI values, respectively, were 4.18 and 11.0 ng/kg body weight (bw)/day for the general population and 312 and 821 ng/kg bw/day for occupationally exposed individuals. Among the paper types analyzed, thermal receipt papers were found to be the major sources of human exposure to BPS (>88%). To our knowledge, this is the first report on the occurrence of BPS in paper products and currency bills.
Cyclic oligomers are the major substances migrating from polyamide (PA) food contact materials. However, no commercial standards are available for the quantification of these substances. For the first time the quantification of cyclic oligomers was carried out by HPLC coupled with a chemiluminescence nitrogen detector (CLND) and single-substance calibration. Cyclic monomer (MW = 226 Da) and dimer (MW = 452 Da) of PA66 were synthesised and equimolar N detection of CLND to synthesised oligomers, caprolactam, 6-aminohexanoic acid (monomers of PA6) and caffeine (a typical nitrogen calibrant) was proven. Relative response factors (UVD at 210 nm) referring to caprolactam were determined for cyclic PA6 oligomers from dimer to nonamer, using HPLC-CLND in combination with a UVD. A method for quantification of cyclic oligomer content in PA materials was introduced using HPLC-CLND analysis and caffeine as a single nitrogen calibrant. The method was applied to the quantification of cyclic PA oligomers in several PA granulates. For two PA6 granulates from different manufacturers markedly different oligomer contents were analysed (19.5 versus 13.4 g kg⁻¹). The elution pattern of cyclic oligomers offers the possibility of identifying the PA type and differentiating between PA copolymers and blends.
Bisphenol A (BPA) is used in a variety of consumer products, including some paper products, particularly thermal receipt papers, for which it is used as a color developer. Nevertheless, little is known about the magnitude of BPA contamination or human exposure to BPA as a result of contact with paper and paper products. In this study, concentrations of BPA were determined in 15 types of paper products (n = 202), including thermal receipts, flyers, magazines, tickets, mailing envelopes, newspapers, food contact papers, food cartons, airplane boarding passes, luggage tags, printing papers, business cards, napkins, paper towels, and toilet paper, collected from several cities in the USA. Thermal receipt papers also were collected from Japan, Korea, and Vietnam. BPA was found in 94% of thermal receipt papers (n = 103) at concentrations ranging from below the limit of quantitation (LOQ, 1 ng/g) to 13.9 mg/g (geometric mean: 0.211 mg/g). The majority (81%) of other paper products (n = 99) contained BPA at concentrations ranging from below the LOQ to 14.4 μg/g (geometric mean: 0.016 μg/g). Whereas thermal receipt papers contained the highest concentrations of BPA (milligram-per-gram), some paper products, including napkins and toilet paper, made from recycled papers contained microgram-per-gram concentrations of BPA. Contamination during the paper recycling process is a source of BPA in paper products. Daily intake (DI) of BPA through dermal absorption was estimated based on the measured BPA concentrations and handling frequency of paper products. The daily intake of BPA (calculated from median concentrations) through dermal absorption from handling of papers was 17.5 and 1300 ng/day for the general population and occupationally exposed individuals, respectively; these values are minor compared with exposure through diet. Among paper products, thermal receipt papers contributed to the majority (>98%) of the exposures.
Metal cans for food use can be coated with lacquers based on polyester resins. Recent research has focussed on the identification and quantification of migrants released by coatings that are potentially absorbable (below 1000 Da). The presented method describes a procedure that was optimized to hydrolyse the polyester migrants into their monomers, polyvalent acids and polyols. The polyols were identified by gas chromatography with flame ionization detection GC-FID and the acids by high-performance liquid chromatography (HPLC) coupled with an ultraviolet and an electrospray ionization-mass selective detector (HPLC-ESI-MSD/UVD), respectively. With the knowledge of the polyester monomers, it was possible--at least tentatively--to identify the main components in the migrate as cyclic oligoesters by HPLC-ESI-MSD/UVD. A cyclic oligomer, CYCLO [3IPA (isophthalic acid) 3EG (ethylene glycol)] was synthesized and characterized by infrared, nuclear magnetic resonance and mass spectrometry as well as by elementary analysis for further confirmation. To determine the amount of migrating cyclic oligoesters, the response of the migrating substances was compared using different detectors, UVD, MSD and evaporative light scattering detector (ELSD). The response of the ELSD was dependent on the molecular weight of the analytes that reduced the accuracy of this detection type. The wavelength with the same absorption coefficient for IPA and terephthalic acid (TPA) was obtained at 232 nm. The UV(232nm) response of an oligoester is proportional to the number of its IPA/TPA moieties, which was verified for several TPA/IPA esters. The amount of the migrating oligoesters was determined using an UV(232nm) calibration of a commercially available TPA ester and the number of IPA/TPA moieties molecules gained from the ESI-MSD spectra. According to this method, the amount of migrating oligoesters below 1000 Da in the 95% ethanol migrate varied from 0.1 to 0.6 mg dm(-2) (0.6-3.6 mg kg(-1) food) in the examined coatings. The determined amounts account for about 50% of the total migrate below 1000 Da.
stated a BPA percentage of 52% in the Netherlands (29 samples), 42% in Sweden (34) and Norway (12), respectively, while Spain (25) remained highest usage of BPA in 88% of the samples
However, the situation
might be heterogeneous between different European countries.
Björnsdotter et al. (2017) stated a BPA percentage of 52% in the
Netherlands (29 samples), 42% in Sweden (34) and Norway (12),
respectively, while Spain (25) remained highest usage of BPA in 88%
of the samples . The most common substituents were BPS (28%
in the Netherlands, 30% in Sweden, 8% in Spain) and PF201 (14%
in the Netherlands, 27% in Sweden, 58% in Norway) [
US EPA, Bisphenol A Alternatives in Thermal Paper -Final Report, 2015.
Supramolecular solvent-based microextraction of emerging bisphenol A replacements (color developers) in indoor dust from public environments
M J Dueñas-Mas
M.J. Dueñas-Mas, A. Ballesteros-Gómez, S. Rubio, Supramolecular
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developers) in indoor dust from public environments, Chemosphere 222
(2019) 22-28, http://dx.doi.org/10.1016/j.chemosphere.2019.01.095.
Linear and cyclic oligomers in polybutylene terephthalate for food contact materials
F. Brenz, S. Linke, T. Simat, Linear and cyclic oligomers in polybutylene
terephthalate for food contact materials, Food Addit. Contam. Part A 35
(2018) 583-598, http://dx.doi.org/10.1080/19440049.2017.1414958.
Oligomers in polyethylene furanoateidentification and quantification approach via LC-UV LC-MS response ratio
M. Hoppe, P. De Voogt, R. Franz, Oligomers in polyethylene furanoateidentification and quantification approach via LC-UV LC-MS response ratio,
Food Addit. Contam. Part A 35 (2018) 2244-2255, http://dx.doi.org/10.1080/
Universal response in liquid chromatography using charged aerosol detection
T. Górecki, F. Lynen, R. Szucs, P. Sandra, Universal response in liquid
chromatography using charged aerosol detection, Anal. Chem. 78 (2006)
Universal response model for a corona charged aerosol detector
J CHROMATOGR A
J P Hutchinson
P R Haddad
J.P. Hutchinson, J. Li, W. Farrell, E. Groeber, R. Szucs, G. Dicinoski, P.R. Haddad,
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