Final Report. Administrative Arrangement 2003-20707 "Fibre Labelling - PLA - Dow"

Abstract not availableJRC.I-Institute for Health and Consumer Protection (Ispra

Report on the collaborative trial organised by the JRC on the determination of PVC and phthalates in textile products

On behalf of CEN/TC 248/WG 26 and ISO/TC 38/WG 22, the European Commission’s Joint Research Center (JRC) organised a collaborative study on the determination of PVC and phthalates in textiles products. The purpose of the study was the comparison and validation of four methods for the determination of phthalates and the validation of one method to determine the content of PVC in textile products. Methods 1, 2 and 3 were based on ultrasonic extraction of phthalates with n-hexane/acetone 80/20 v/v, n-hexane, tert-butyl methyl ether, respectively, and method 4 foresaw PVC dissolution in tetrahydrofuran and re-precipitation with acetonitrile. One method for the quantification of PVC in textile products based on the dissolution of PVC with tetrahydrofuran, followed by the washing of the residue and its gravimetric determination was also investigated (method 5). The collaborative exercise was organised, according to ISO 5725-2, as a balanced uniform-level experiment with the same number of test results in each laboratory, which each laboratory analysing the same levels of test samples. Thirteen laboratories both European and non-European participated to this study. The Italian company MP S.p.A produced both the PVC samples and the textile ones, made by cotton spread with PVC layer. Four textile and one PVC samples containing in total 7 phthalates (DEHP, DBP, BBP, DINP, DIDP, DNOP and DIBP) at 3 concentration levels and one sample, in which the PVC mass per cent had to be measured were analysed in triplicates. Levels I, II and III refer to samples containing a specific phthalate in concentrations of approximately 200, 1000 and 5000 mg/kg. In the case of DIDP and DINP, level I corresponded to approximately 500 mg/kg of PVC. These phthalate concentrations were selected in order to assess the precision of the analytical methods in the range of the current limits for toys and childcare articles. The homogeneity study was carried out by the JRC and all samples could be considered ‘sufficiently homogeneous’ according to the IUPAC harmonised protocol for proficiency testing. Results were statistically evaluated following the rules laid down in ISO 5725 parts 2 and 5. The consensus values and the precisions of the various methods, in terms of repeatability and reproducibility limits as well as repeatability and reproducibility relative standard deviations, were evaluated. Applying ISO 5725-2, the statistical outliers identified with Cochran’s and Grubbs’ tests were rejected, together with the results of LC0004 for method 4 and the ones of LC0005 for DIDP in methods 1-4, which were identified as outliers with Mandel’s h statistics. On the contrary, considering ISO 5725-5, all test results were retained and robust statistics was used. These two alternative approaches gave results that could be considered in good agreement. Generally, the differences were always lower than 35 %, except in few cases. Concerning the extraction efficiency, method 4 proved to be the best one in terms of phthalates’ recovery, whereas method 2 was the worst one. Practically the same recovery rate was shown by methods 1 and 3. Relative standard deviations of repeatability and reproducibility ranged from 3.0 to 23.5 % and from 19.4 and 189.9 % respectively. This means that both the four methods and the laboratories’ performance have to be drastically improved. Poor repeatability was observed in the case of several laboratories and the large spread in the mean values calculated in the 13 laboratories is responsible for the high observed relative standard deviation of reproducibility. Regarding method 5 for the quantification of PVC, repeatability and reproducibility relative standard deviations were 0.6 and 1.4% respectively. Considering that these values are in the same range of the values obtained with similar dissolution methods validated in the context of quantification of fibre binary mixtures, this method can be considered validated.JRC.I.1-Chemical Assessment and Testin

European Survey on the Release of Formaldehyde from Textiles

Always more frequently consumers are exposed to hundreds of potentially hazardous chemicals in their everyday life. These compounds can come into contact with their body through three different pathways: inhalation, ingestion and dermal absorption. The scope of the present work was to make a survey on the level of free and releasable formaldehyde that can be found in textile products sold on the European market and produced all over the world, to develop a method to better mimic the foreseeable conditions of use and to assess whether the detected amounts of released formaldehyde are hazardous to human health through dermal exposure.JRC.I.5-Physical and chemical exposure

European Survey on the Presence of Banned Azodyes in Textiles

Abstract A European survey on the presence of banned azodyes in textiles, in particular textile clothing, produced all over the world was performed. The selection of fabrics was planned among coloured textile products, in order to cover as many different types of fibres and type of garments as possible. The whole population was considered as target. Samples were bought in 24 Member States of the European Union, from different sources, with different compositions and various production countries or areas. Part of them was printed and some were ¿easy care¿ or Oeko-Tex labelled. A total of 116 samples were analysed with standard method EN 14362-1 (without extraction) and 72 also with standard method EN 14362-2 (with extraction). Measurements were performed in duplicate and standard deviations were calculated. In the case of the method without extraction, 2.6 % of samples (3 out of 116) intended to be in direct contact with skin contained over 30 mg/kg of some banned aromatic amines, which is the limit established by Directive 2002/61/EC. The highest concentration (434.2 mg/kg) was measured for benzidine. Other ten samples (8.6 %) contained some prohibited aromatic amines in levels lower than the limit. Comparison between method EN 14362-1 and a slightly modified version of it showed that generally the standard method gave lower results than the ones obtained with the modified one. Considering the method with extraction from fibres, only one sample T188 contained some banned aromatic amines, one of which, benzidine, in concentration of 39.0 mg/kg. Several not carcinogenic aromatic amines, different from the ones listed in Directive 2002/61/EC, were detected in 21 samples. They were quantified based on calibration curves of some banned aromatic amines of similar structure. Their concentration was often higher than 30 mg/kg and in certain cases even higher than 100 mg/kg. Colour fastness to washing, perspiration and saliva was evaluated for the samples which contained some forbidden aromatic amines, in order to estimate the tendency of dyes to migrate. Results showed a very high colour fastness in terms of colour degradation, except for some samples including the two positive ones T188 and T292. On the contrary, colour fastness in terms of staining was not high, in particular on polyamide. Staining was generally higher to washing than to saliva; the lowest staining was obtained to perspiration. Almost no differences were observed among results obtained with acid and basic saliva or with acid and basic perspiration simulants. The three positive samples T148, T188 and T292 were among the worst specimens concerning both colour degradation and staining. Following the recommendations of the Technical Guidance Document, data were used to estimate adult and child dermal exposure to carcinogenic aromatic amines. From data obtained with the EN-14362-1 standard method and the modified one, the maximum dermal uptakes evaluated in the case of a child were 8.2 and 11.8 mg/kg bw and, in the case of an adult, 3.1 and 4.4 mg/kg bw respectively.JRC.I.5-Nanobioscience

Safety of tattoos and permanent make-up: Compilation of information on legislative framework and analytical methods

This document summarises the work carried out within Working Package 1 of the Administrative Arrangement 33617 on tattoos and permanent make-up, signed with Directorate General Health and Consumers (DG SANCO), now DG Justice (DG JUST). It includes: the description of the project; the description of the recommendations contained in the Council of Europe Resolution (2008)1 on requirements and criteria for the safety of tattoos and permanent make-up; the minutes of the meeting of the Consumer Safety Network Subgroup Tattoos and Permanent Make-up (CSN-STPM), held on 11th November 2014, in Ispra (VA), Italy; a collection of analytical methods that could be useful to implement the recommendations of the Council of Europe Resolution (2008)1, as well as a review of existing legislation/guidelines frameworks for the safety of tattoo and permanent make-up products in the European countries and some other jurisdictions.JRC.I.1-Chemical Assessment and Testin

Fibre labelling. Polytrimethylene terephthalate - PTT - DuPont: Final report

In 2011 DG Enterprise and Industry requested the European Commission’s DG-JRC to technical evaluate a petition submitted by E. I. du Pont de Nemours and Company (DuPont). This petition requested the creation of a new generic fibre name under the Directive 2008/121/EC on textile names, now repealed by the EU Regulation 1007/2011. This would allow distinguishing between their fibre, polytrimethylene terephthalate (PTT) and, in particular, polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), the two most common types of polyesters. Although the three polyesters are very similar in terms of chemical composition, according to DuPont, PTT fibres have a set of improved properties that justify the petition. As identification and quantification methods are required in order to allow market surveillance of textile products, the JRC was responsible for the verification of the test methods proposed by the applicant and for the development and validation of the new required ones. Regarding identification, Fourier Transform Infrared Spectroscopy can distinguish between PTT, PET and PBT. This distinction can be achieved also using Differential Scanning Calorimetry (DSC), but only on the basis of their crystallisation peaks, since the melting peaks of PTT and PBT occur at the same temperature. The mechanical properties of PTT were studied. Tests were carried out at 25% elongation. In these conditions, PTT showed an elastic recovery and a permanent deformation ranging from 65.7 to 78.1% and from 5.4 to 8.8 %, respectively. On the basis of such results, PTT cannot be considered an elastic fibre. Regarding quantification, the usual pre-treatment protocol is applicable to PTT fibres. The correction factor b for mass loss during pre-treatment for PTT was established as 0%. The experimental value for the agreed allowance of PTT was determined (0.34%). However, for consistency with the values already adopted for polyester and elastomultiester, the value 1.50% was agreed by the members of the European Network of National Experts on Textile Labelling (ENNETL). PTT is completely soluble in method 14. The following correction factors d for PTT (mass loss due to dissolution methods) were determined: 1.00 for methods 2, 3, 7 and 11; 1.01 for methods 1, 4, 5, 9 and 10; 1.02 for method 13; 1.03 for methods 6, 8 and 16. Method 15 is not applicable to binary mixtures containing PTT. Several binary and ternary blends containing PTT were quantified using both manual separation method and chemical dissolution ones. The JRC developed a new DSC method that was proved to be adequate and accurate for the quantification of PTT in blends with PET. The method uses calibration curves prepared with yarns manually separated from the sample under analysis, thus ensuring a common thermal history. Different types of integration as well as multipoint and single point calibration curves based on PTT or PET melting peaks were evaluated. The JRC organised the validation of the optimised DSC method at European level, as a balanced uniform–level experiment with six levels and 15 laboratories. The best results were obtained using multipoint calibration curves based on the integration of PTT melting peak with a linear integration. The method was successfully validated and showed good accuracy, in terms of both trueness and precision, as proved by the following parameters: bias values (0.06 -1.30%), confidence limits at 95 % probability level (0.60 - 1.07%) and HORRAT values (0.5 – 2). Results were presented in two meetings of ENNETL, held in Ispra, Italy, on 30th November 2012 and 4th October 2013. The definition proposed by DuPont for PTT (“fibre formed of linear macromolecules comprising at least 85% (by mass) in the chain of an ester of 1,3-propane diol and terephthalic acid) was consistent with the evaluation carried out. As regards the proposed name of the fibre (triexta) there was no consensus among the experts belonging to ENNETL.JRC.I.1-Chemical Assessment and Testin

Fibre Labelling. Elastomultiester - DuPont.

In December 2003, the European Commission’s Joint Research Centre (JRC) was entrusted by DG Enterprise to verify the validity and applicability of the testing methods, proposed by DuPont, for the identification, characterisation and quantification of their new fibre (elastomultiester). This is an elastic bicomponent fibre made by a combination of two different polyesters (side-by-side structure). The elastic properties are due to crimps that are formed, after heat treatment, and due to the different shrinkage of the two components. The crimp is not mechanically induced and the yarn can be used directly, as no texturing or covering before weaving is needed. Experimental results confirmed that microscopy and differential scanning calorimetry (DSC) can identify both the multicomponent nature of the new fibre and its chemical composition, whereas Fourier Transform Infrared Spectroscopy (FT-IR) can confirm only its chemical composition. The normal pre-treatment, described in Directive 96/73/EC, was proved to be applicable to the new bicomponent fibre and the agreed allowance value of 1.50 % was adopted for the new fibre, in agreement with the European Network of National Experts on Textile Labelling (ENNETL). The solubility properties of elastomultiester were evaluated. In particular, the chemical methods 1, 2, 4, 6 – 9, 13 and 14 of Directive 96/73/EC were tested and considered suitable for the quantification of elastomultiester in binary mixtures with other fibres. With the exception of method 14, the novel fibre was insoluble in all the mentioned methods and showed correction factors d equal to the ones of polyester (1.00 for methods 1, 2, 4, 7, 9, 13 and 1.01 for methods 6 and 8, respectively). In addition, also the manual separation method described in Directive 96/73/EC was proved to be suitable for the quantification of elastomultiester in binary mixtures with other fibres. A new quantitative method based on DSC was developed and successfully applied to the quantification of binary mixtures of elastomultiester with polyester and cotton and to ternary mixtures with polyester/cotton, polyester/viscose and modal/viscose. The method is also applicable to mixtures of elastomultiester with nylon. It led to a good repeatability and results were generally as good as the ones obtained with chemical methods. The comparison with quantification based on the manual separation method showed differences usually lower than 1 %. The method shows two important advantages, the first being the rapidity of the analysis and the second being the possibility to avoid manual separation in the quantification of mixtures polyester/elastomultiester. The JRC developed a test method to measure the recoverable stretch and the permanent deformation of yarns and single filaments based on elongation. Experiments performed on single filaments of elastomultiester showed that, at 50 % elongation, the novel fibre is intrinsically elastic and proved that the elasticity is not due to the construction of yarns and to the fact that they contain several single filaments; on the contrary single filaments are as elastic as yarns. In fact, in these conditions the per cent permanent deformations were usually lower than or equal to 10 %. Based on experimental results, discussions during the 2nd, 3rd, and 4th ENNETL meetings, the name and definition agreed and proposed for the new fibre were “elastomultiester: fibre formed by interaction of two or more chemically distinct linear macromolecules in two or more distinct phases (of which none exceeds 85 % by mass) which contains ester groups as dominant functional unit (at least 85 %) and which, after suitable treatment, when stretched to one and half times its original length and released, recovers rapidly and substantially to its original length”.JRC.I.2-Chemical assessment and testin

Safety of tattoos and permanent make-up State of play and trends in tattoo practices

The European Commission launched the 18-month project "Tattoos and Permanent Make-up" with the aim of collecting data about the use, the ingredients, the EU market and possible health problems associated to tattoo and permanent make-up (PMU) inks. The report on work package 1 (2015, Piccinini P. et al.) is available at http://bookshop.europa.eu/en/safety-of-tattoos-and-permanent-make-up-compilation-of-information-on-legislative-framework-and-analytical-methods-pbLBNA27394/ The present report is the outcome of the work package 2 which aims to describe the status of tattoo and PMU practices like tattoo prevalence in the population, including the removal processes, details on service providers and ink manufacturers, tattoo and PMU market, inks' chemical composition, RAPEX notifications and national market surveillance. The information was gathered through questionnaires sent to 32 national authorities (all EU MS and EFTA countries), plus OECD Secretariat, 38 ink manufacturers/distributors/private labels and 23 tattooists/PMU professionals' associations. Replies were collected from 24 EU/EFTA national authorities, 4 non-EU/EFTA countries, 7 ink manufacturers/ distributors/private labels and 10 associations. In addition, we reviewed thoroughly data available from other sources like scientific literature, RAPEX (Rapid Alert System for dangerous non-food products) notifications and national surveillance reports, as of May 2015. The main findings show that: Tattoo and PMU inks are complex chemical mixtures containing several ingredients. The main ingredients are the colorants, pigments in particular; more than 100 of them have been identified in tattoo and PMU inks. These pigments are not produced specifically for such application and a risk assessment taking into account their injection and permanence into the human body is not carried out. An additional identified risk is the presence of impurities; in fact tattoo and PMU inks' purity is on average around 70-90 %. Azo pigments, group to which most of the organic colorants in use belong, are proved to release potentially carcinogenic aromatic amines when exposed to solar, UV or laser irradiation. It is estimated that around 12 % of the whole European population, all ages comprised, are tattooed (estimation based on available data from 14 Member States) and more than 20 % in the United States. Higher tattoo prevalence was reported in young population, including adolescents. While traditionally men were more tattooed than women, figures show that this trend in Europe, Australia and North America is changing. Nowadays in a number of cases the tattoo prevalence in women is higher than in men, particularly in young generations. Most of the tattoo inks used in Europe are imported from the United States, while PMU inks are mostly produced in Europe. The European manufacturers are mainly based in the United Kingdom, Germany, Italy and Spain. With regards to the tattoo artists performing the tattoos, the number of "non-professional tattooists" might represent up to 10 times the number of "registered/professionals" ones. Around 95 % of the 126 RAPEX alerts notified for tattoo/PMU during the last decade related to chemical risks: hazardous chemicals and/or impurities (such as carcinogenic aromatic amines, polycyclic aromatic hydrocarbons, sensitizers, preservatives and heavy metals). The remaining 5% concerned microbiological risks, which are mainly due to the lack of sterility of the inks before opening and from the use of tap water for their dilution. Two thirds of the RAPEX notifications pertain to products imported, with the highest percentages from the United States.JRC.I.1-Chemical Assessment and Testin

Migration of Polycyclic Aromatic Hydrocarbons (PAHs) from plastic and rubber articles

Polycyclic Aromatic Hydrocarbons (PAHs) constitute a large group of chemically related substances many of which are known carcinogens. To minimise human exposure there are already several pieces of EU legislation which limit their presence in certain food products, as well as in water and ambient air. Under the REACH regulation (EC 1907/2006 Annex XVII, Entry 50), eight priority PAHs have for some time been restricted in extender oils used in tyres. Although not added deliberately to consumer products, PAHs can still be present as impurities. An amendment of the above mentioned legislation (Regulation EU 1272/2013) establishes content limits for the eight PAHs of 0.5 mg kg-1 for plastic and rubber components of toys/childcare articles, and 1 mg kg-1 for all other consumer articles, in direct and prolonged, or short-term repetitive, contact with the skin or oral cavity. In May 2016 DG JRC and DG GROW signed an Administrative Arrangement (AA 34003) known as the STANPAHs project. The main objective of this contract was for the JRC to provide scientific support in the implementation and potential amendment of the restriction on polycyclic aromatic hydrocarbons, in particular concerning paragraphs 5 and 6 of entry 50 of Annex XVII to the REACH legislation. The main objectives of the project were: a) to gain a better understanding of the migration behaviour of certain PAHs in plastic and rubber components of articles, and b) to develop a reliable methodology to determine PAH migration from these matrices, under conditions simulating, to the best possible extent, dermal contact (including the oral cavity). This report presents the outcomes of the experimental studies carried out at JRC and the achievements towards fulfilling these objectives. A set of manufactured polymeric plastic and rubber matrices, to be used as test materials in the project, has been chosen based on criteria such as their frequency of use in articles within the scope of the restriction and the likelihood of the presence of high PAH contents (e.g. due to their content in carbon black or extender oils). Various grades and types of ingredients known to be PAH sources were used in the formulation of the manufactured ad-hoc materials. The test materials included low density polyethylene (LDPE), polystyrene (PS) and polyvinyl chloride (PVC) as plastic matrices, and ethylene-propylene diene monomer (EPDM), natural rubber-butadiene rubber (NR-BR) and silicone as rubber matrices. Moreover, recycled granules (coated and uncoated) originating from end-of-life tyres produced before and after 2010 as well as rubber tiles made of the recycled coated granules were also made available for this study. The content of each of the eight restricted PAHs was measured by using a method developed in-house based on Randall hot extraction, purification by Solid Phase Extraction based on Molecular Imprinted Polymers, and Gas Chromatography Mass Spectrometry determination. A number of experimental studies were undertaken to generate data and information to improve the knowledge on migration of the target PAHs. Migration parameters operated in the STANPAHs project to estimate migration rates were as follows: dynamic mode at 40°C for 24 hours using a variety of migration media including artificial aqueous simulants, modified biosimulants formulations with lipidic content such as skin surface film liquid (SSFL), and 20% ethanol in water. According to scientific literature the use of 20% ethanol as the migration medium proved to correlate well with human skin absorption. Using these conditions, migration of the target PAHs into artificial sweat (EN1811) and artificial saliva (DIN53160-1) was not detected in any of the materials studied. Moreover none of the plastic polymeric materials led to detectable release of the target PAHs in any of the migration media used in this study (i.e. artificial sweat and saliva, skin surface film liquid (SSFL), and 20% ethanol solution). Similarly the tests with silicone materials did not result in detectable migration. Only the rubber matrices containing Distillate Aromatic Extract (DAE) as extender oil showed detectable migration when using 20% ethanol as the migration solution. In addition, the release of PAHs from coated recycled rubber granules was lower than from the uncoated granules suggesting that the coating acts as a barrier to chemical migration. According to industrial partners DAE is not used by European industries for manufacturing of parts of articles intended for skin contact. The materials containing DAE, although not representative for marketed products, have been made available to facilitate migration testing method development. The migration test method using 20% ethanol has been validated in-house and shows good method performance allowing the determination of PAH at trace level. Furthermore it has been considered for an initial inter-laboratory comparison study (ILC) aiming to investigate method applicability and transferability in a variety of laboratories. The within-laboratory precision, expressed as the relative standard deviation for repeatability (RSDr), and the between-laboratory precision, expressed as the relative standard deviation for reproducibility (RSDR) were assessed. In general the RSDR ranged from 28 to 113% and the RSDr from 7 to 23%. It is worth remembering that the level of PAH migration was very close to the quantification limit of the method and therefore this variability can be expected. Similar values have been reported in a recent German study with the participation of 9 laboratories on the migration of PAHs from rubber materials in contact with aqueous ethanol. The fact that better values of RSDr and RSDR were obtained for chrysene and benzo(e)pyrene that had the highest concentrations in the final migration solutions and that the analysis of the control solution used in this exercise showed a good reproducibility (RSDR% <10%), shows the possibility to reduce the variability between laboratories with a revised operating procedure in terms of injection volume and/or elution volume. In conclusion this report makes available new data and scientific information on the migration behaviour of certain PAHs from selected plastic and rubber polymeric matrices, in support of the European Commission's legal obligation to review the PAHs restriction under REACH. Standard operating procedures for quantification of the content of each of the eight restricted PAHs as well as their migration into 20% ethanol have been developed. Moreover the information gathered in STANPAHs (e.g. literature search), the ad-hoc manufactured materials still available, as well as the JRC in-house analysis method for PAH content could be of great benefit to accelerate the work towards standardisation of PAH content analysis in consumer products that has been recently undertaken by the European Standardisation Committee following a request by DG GROW.JRC.F.2-Consumer Products Safet

Comparative Proteomic Analysis of Serum from Patients with Systemic Sclerosis and Sclerodermatous GVHD. Evidence of Defective Function of Factor H

BACKGROUND: Systemic sclerosis (SSc) is an autoimmune disease characterized by immunological and vascular abnormalities. Until now, the cause of SSc remains unclear. Sclerodermatous graft-versus-host disease (ScGVHD) is one of the most severe complications following bone marrow transplantation (BMT) for haematological disorders. Since the first cases, the similarity of ScGVHD to SSc has been reported. However, both diseases could have different etiopathogeneses. The objective of this study was to identify new serum biomarkers involved in SSc and ScGVHD. METHODOLOGY: Serum was obtained from patients with SSc and ScGVHD, patients without ScGVHD who received BMT for haematological disorders and healthy controls. Bi-dimensional electrophoresis (2D) was carried out to generate maps of serum proteins from patients and controls. The 2D maps underwent image analysis and differently expressed proteins were identified. Immuno-blot analysis and ELISA assay were used to validate the proteomic data. Hemolytic assay with sheep erythrocytes was performed to evaluate the capacity of Factor H (FH) to control complement activation on the cellular surface. FH binding to endothelial cells (ECs) was also analysed in order to assess possible dysfunctions of this protein. PRINCIPAL FINDINGS: Fourteen differentially expressed proteins were identified. We detected pneumococcal antibody cross-reacting with double stranded DNA in serum of all bone marrow transplanted patients with ScGVHD. We documented higher levels of FH in serum of SSc and ScGVHD patients compared healthy controls and increased sheep erythrocytes lysis after incubation with serum of diffuse SSc patients. In addition, we observed that FH binding to ECs was reduced when we used serum from these patients. CONCLUSIONS: The comparative proteomic analysis of serum from SSc and ScGVHD patients highlighted proteins involved in either promoting or maintaining an inflammatory state. We also found a defective function of Factor H, possibly associated with ECs damage