Progress report on the development of standard methods for the characterisation of textile fibres and yarns and for the safety of textile products and toys

There is a strong need of standardisation in the field of textile products and toys, in order to allow the enforceability of restrictions established in the EU legislation. The JRC has been actively involved in the progresses made on the development of standard methods for the characterisation of textile fibres and yarns and for the safety of textile products and toy, which are reviewed in this report. A number of standard methods published or under development are entirely or partly based on the JRC work. The work performed by Working Groups (WGs), of which the JRC is member, is described: CEN/TC 248/WG 26 (on test methods for analysis of EC restricted substances in textiles); CEN/TC 248/WG 30 (on quantitative analysis of fibre mixtures); CEN/TC/52/WG 5 (on chemical properties of toys); and ISO/TC/WG 22 (on composition and chemical testing of textiles). The need for the test methods and their principles are explained, together with their stage in the approval process. The following standard methods have been published in 2013: EN ISO 1833-22 Textiles - Quantitative chemical analysis - Part 22: Mixtures of viscose or certain types of cupro or modal or lyocell and flax fibres (method using formic acid and zinc chloride) EN ISO 1833-25 Textiles - Quantitative chemical analysis - Part 25: Mixtures of polyester and certain other fibres (method using trichloroacetic acid and chloroform) EN ISO 1833-26 Textiles - Quantitative chemical analysis - Part 26: Mixtures of melamine and cotton or aramide fibres (method using hot formic acid) EN 71-3 Safety of toys Part 3: Migration of certain elements EN 71-12 Safety of toys Part 12: N-nitrosamines and N-nitrosatable substances ISO 2076 Textiles - Man-made fibres - Generic names The following standard methods and technical reports are under development or in revision or in publication: PrEN ISO 16373-1, -2 and -3 Textile – Dyestuffs - Part 1: General principles of testing coloured textiles for dyestuff; Part 2: General method for the determination of extractable dyestuffs including allergenic and carcinogenic substances; Part 3: Method for determination of carcinogenic extractable dyestuffs (method using triethylamine/methanol) PrEN 15777:2009/prA1 Textiles - Test methods for phthalates Technical report - guidance on health and environmental issues related to the chemical content of textile products intended to clothing, interior textiles and upholstery prEN ISO 18254 - Textile – Detection and determination of APEO in textiles by HPLC-MS WI 00248537 and WI 00248536 Textile – Determination of metal content Part 1: Determination of metals using microwave digestion; Part 2: Determination of metals extracted by acidic artificial perspiration solution prEN 71-3/pr A1 Safety of toys Part 3: Migration of certain elements WD 18074 Textiles - Identification of some animal fibres by DNA analysis method - Cashmere, wool, yak and their blends ISO/CD 17751-1 and -2 Textiles - Quantitative analysis of cashmere, wool, other specialty animal fibers and their blends Part 1: Light Microscopy method; Part 2: Scanning Electron Microscopy method ISO FDIS 14389 Textiles- Determination of the content of phthalates - tetrahydrofuran WD 17881-1, -2 and -3 Textiles - Determination of certain flame retardants – Part 1: Brominated flame retardants; Part 2: Phosphorus flame retardants; Part 3: Short chain paraffin flame retardantsJRC.I.1-Chemical Assessment and Testin

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

Selenium status in the body of proliferative activity of malignant cells

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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

S wave Splitting in Central Apennines (Italy): anisotropic parameters in the crust during seismic sequences

In this work, we reviewed the main anisotropic results obtained in the last two decades along the Central Apennines. Moreover, we improved this database, with new results coming from the seismicity that occurred in the Montereale area, between 2009 and 2017, which corresponds to a spatio-temporal gap in the previously analyzed datasets. The examined papers concerned both seismic sequences (as Colfiorito in 1997, Pietralunga in 2010, L’Aquila in 2009, Amatrice in 2016) and background seismicity (as the 2000-2001 Città di Castello experiment). The whole of the collected results shows a general NW-SE fast shear wave direction consistent with both the orientation of the extensional active Quaternary and inherited compressive fault systems, focal mechanisms and local stress field. Also, we observed a more intense anisotropy strength (normalized delay time > 0.006 s/km) nearby the strongest events (M > 5), all concentrated in the hanging-wall of the activated fault systems. In fact, this area is deeply affected by the surrounding rock volume perturbations that, in turn, have altered both the local stress field and crustal fracturing network. The most common anisotropic interpretative models that could explain our results are 1) the stress-induced anisotropy according to the Extensive-Dilatancy Anisotropy (EDA) model where the anisotropic pattern is related to the local stress variation and most of the variability is visible in time; 2) the tectonic-controlled anisotropy according to the Structural-Induced Anisotropy (SIA) model where the anisotropic pattern is related to the major structural features and most of the variability is visible only in space. As reported by the examined studies in Central Apennines the possibility to discriminate between stress and structural anisotropy is quite complex in a region where the directions of the extensional regime, the in situ horizontal maximum stress, the strike of major faults, both active and inherited coincide. Generally, in this review, we noted an overlap and mixture of the two aforementioned mechanisms and, just through a temporal analysis, made in the Montereale area, we supposed a predominant stressinduced anisotropy only in rock volumes where anisotropic parameter variations have been detected

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