1. ITSAPT seminar, Guimaraes, November 2005 DETERMINATION OF FREE FORMALDEHYDE ON TEXTILE SUBSTRATE BY HPLC Bojana VONCINA University of Maribor, Textile Department Smetanova 17, 2000 Maribor, Slovenia

2. ITSAPT seminar, Guimaraes, November 2005 Formaldehyde is built in the atmosphere thought photochemical processes of hydrocarbons It is produced during the uncompleted combustion of wood, oil, gas, tobacco Source of formaldehyde : - Automobiles and airplanes70-80% - Heating and incineration 13-15% - Formaldehyde in chem. prod.1%

3. ITSAPT seminar, Guimaraes, November 2005 Formaldehyde is found in human body as a building blocks for amino acids and proteins Blood2-3 mg/kg Apple 17-22 mg/kg Tomatoes6-7 mg/kg Wood4-18 mg/kg Formaldehyde is often used as a building block for a number of important chemical products, intermediates and consumer goods: - urea-formaldehyde resins (25%), - phenol- formaldehyde resins (20%), - plastics (15%), - intermediates (22%).

4. ITSAPT seminar, Guimaraes, November 2005 Toxicity Data Formaldehyde is readily absorbed through skin and is toxic by inhalation It is considered toxic, carcinogen, mutagen, corrosive Health Effects: Inhalation: formaldehide is extremely destructive to tissue of the mucous membranes and that of the upper respiratory tract. Inhalation may be fatal as a result of spasm and inflammation. Eyes/Skin: extremely destructive to the tissue of the eyes and skin. Can cause allergic skin reactions Ingestion: Can cause gastrointestinal disturbances. May alter genetic material. This is considered a carcinogen. Target Organs: eyes, kidneys, liver, heart, potential cancer agent, testis, ovaries

5. ITSAPT seminar, Guimaraes, November 2005 The most effective crosslinking reagents for durable press finishing of cellulose fibers are formaldehyde adducts of urea which release formaldehyde during the production and wearing of in such way treated clothes Formaldehyde durable press finishers are applied to the textile substrate mainly in the form of N-methylol and N-alkoxymethyl compounds

6. ITSAPT seminar, Guimaraes, November 2005 Release of formaldehyde from the textile substrate can be measured by: STANDARD TEST METHODS Japan Law 112 (EN ISO 14184-1) AATCC-112 The formaldehyde content below 20 mg/kg can not be shown to be caused by the formaldehyde which was released by the crosslinking reagent. ALTERNATIVE TEST METHODS edana recommended test method using HPLC HPLC

7. ITSAPT seminar, Guimaraes, November 2005 EN ISO 14184-1 standard test method EN ISO 14184-1 standard test method Standard solutions of formaldehyde with concentration levels of 0.3, 0.6, 0.9, 3.0, 6.0, 15.0 and 30.0 mg/L in the 3,5, - diacetyl – 1,4-dihydrolutidin forms were prepared. The formaldehyde derivative solutions were prepared in water and in matrix (extract from untreated cotton fibers). Six replicates of each concentration level were prepared From the textile substrateformaldehyde was extracted with water at 40  C, filtered and then converted by using acetyl-acetone reagent to yellow colored compound

8. ITSAPT seminar, Guimaraes, November 2005 Validation of absorbance measurements on UV/Vis With Grubbs and Beck statistical test were shown that there were no aberrant values An F – test was applied to check heteroscedasticity: standard deviation increase with the concentration Correlation coefficient for standard water and matrix solutions was greater than 0.99 Quality coefficient (QC) was lower than permitted 5% Anova test shows that the experimental error was smaller than lack of fit (LOF) for the linear calibration curve Precision of standard water and matrix solutions was better than 10% The limit of detection (LOD) was 0.628 mg/l The limit of quantification (LOQ) was 1.197 mg/l The amount of formaldehyde extracted for each sample can be calculated by: Konc (x) = 7,493 ABS - 0,06356

9. ITSAPT seminar, Guimaraes, November 2005 Free formaldehyde measured by HPLC Standard water and matrix solutions of formaldehyde with concentrations levels 0.075, 0.15, 0.3, 0.6, 0.9, 3.0, 6.0, 15.0 and 30.0 mg/L in the 3,5, - diacetyl –1,4- dihydrolutidin forms were prepared Formaldehyde was extracted from textile substrate with water at 40  C, filtered and then converted by using acetylacetone reagent to yellow colored compound HPLC Varian Prostar 210 pump, Varian Prostar 310 UV/Vis detector (at 410 nm), STAR Chromatography Workstation Varian 4.5, LiChrosorb RP-18 coloum with particle size 7  m,

10. ITSAPT seminar, Guimaraes, November 2005 Validation of the HPLC analytical method The optimisation of the method (the proper column, mobile phase, solvents, temperature of the column etc.) was done. The concentration of free formaldehyde in the aqueous solution was determined using peak areas from the standard and sample chromatograms. Mobile phase methanol-water (70:30 v/v). The retantion time for formaldehyde derivative was 2.7 min

11. ITSAPT seminar, Guimaraes, November 2005 Validation of the HPLC analytical method With Grubbs and Beck statistical test were shown that there were no aberrant values An F – test was applied to check heteroscedasticity: standard deviation increase with the concentration Correlation coefficient for standard water and matrix solutions was greater than 0.99 Quality coefficient (QC) was lower than permitted 5% Anova test shows that the experimental error was smaller than lack of fit (LOF) for the linear calibration curve Precision of standard water and matrix solutions was better than 10% The limit of detection (LOD) was 0.0199 mg/l The limit of quantification (LOQ) was 0.066 mg/l The amount of formaldehyde extracted for each sample can be calculated by: Konc (x) = 0,2055 * 10 -4 AREA – 0,222

12. ITSAPT seminar, Guimaraes, November 2005 CONCLUSIONS The results obtained by the standard test method, Japan Law112, were compared with the results obtained by HPLC method where separation was performed on RP C 18 column with water-MeOH as a mobile phase. The limit of detection (LOD) for Japan Law 112 was 0.628 mg/l and the limit of quantification (LOQ) was 1.197 mg/l The limit of detection (LOD) for HPLC method was 0.0199 mg/l and the limit of quantification (LOQ) was 0.066 mg/l Matrix has no influence on the formaldehyde content in the analysed solution.

13. ITSAPT seminar, Guimaraes, November 2005 FORMALDEHYDE IN MICROENCAPTULATED TEXTILE MATERIALS Bojana VONCINA University of Maribor, Textile Department Smetanova 17, 2000 Maribor, Slovenia

14. ITSAPT seminar, Guimaraes, November 2005 Introduction Essential oils from plants Lavandula sp. (lavender), Rosmarinus sp (rosemary) and Salvia sp. (sage) are natural fungicide and antibacterial agents. These oils were microencapsuled in melamine- formaldehyde microcapsules and cross linked on PES nonwoven textile materials. Such textile material is capable of releasing formaldehyde by decomposition of microcapsules.

15. ITSAPT seminar, Guimaraes, November 2005 Sources of the formaldehyde   Textile material (PES)   cross-linking reagent   microcapsules  wall : melamine-formaldehyde resins  core :25 % mixture of essential oils, 75 % solvent 80 % mixture of essential oils, 20 % solvent  mixture of essential oils : - lavender 70 % - rosemary 20 % - rosemary 20 % - sage 10 % - sage 10 %  solvent: isopropyl mirystate

16. ITSAPT seminar, Guimaraes, November 2005 Experimental Release of formaldehyde from the textile substrate was determined by EN ISO 14184-1 (Japan Law 112 method), AATCC test 112-1998, HPLC method, where the separation was achieved with elution using methanol-water, as eluents on a reverse phase column and was monitored at 410 nm with a UV/VIS detector. In all three methods the extracted formaldehyde was converted by using acetylacetone reagent to yellow coloured compound.

17. ITSAPT seminar, Guimaraes, November 2005 The formaldehyde contents were determined in different textile samples: a) untreated textile material (PES nonwoven) b) textile material with cross-linking reagent (suspension of latex and acrilate emulsifier) c) textile material with empty microcapsules, d) textile material with cross-linkinked empty microcapsules, e) textile material with cross-linked microcapsules filled with oils ( 25 % mixture of essential oils, 75 % solvent) f) textile material with cross-linked microcapsules filled with oils ( 80 % mixture of essential oils, 20 % solvent) The formaldehyde contents were determine also in mixture of oils and pure rosemary and sage oil.

18. ITSAPT seminar, Guimaraes, November 2005 Untreated textile material and cross-linking reagent do not contain formaldehyde (7 mg/kg). Microcapsule’s walls contribute to the amount of of the formaldehyde significantly: The average formaldehyde content for the microencaptulated textile material with empty microcapsules is 715 mg/kg and 766 mg/kg for microencaptulated textile material with microcapsules filled with oils (both results are obtained by Japan Law method). Results from AATCC test for the same samples are 5.126 mg/kg and 4.174 mg/kg respectively.. Results and conclusions

19. ITSAPT seminar, Guimaraes, November 2005 Results obtained by HPLC method: indicate that only formaldehyde is released from the textile samples microencaptulated with and without essential oil. Although some amount of formaldehyde is proved in pure essential oils, amount of essential oil which is applied on textile material with microcapsules (160 g/m 2 ) contribute very little to total amount of formaldehyde. This was proved by the measurements of released formaldehyde after the mechanical damages of microcapsules on the textile substrate

20. ITSAPT seminar, Guimaraes, November 2005  Lavender: 0,54 ml/L  Rosemary: 0,15 ml/L  Sage: 0,32 ml/L mixture of essential oils :  Average amounts of formaldehyde: 0,61 ml/L  Results: from 0,18 to 0,75 ml/L (dependent on extraction conditions) Formaldehyde measurements in essential oils:

21. ITSAPT seminar, Guimaraes, November 2005Conclusion  Results given by AATCC test 112-1978 method are expected proportionally higher as results given by EN ISO 14184-1 method.  The a verage results obtained from samles prapered in production line are lower. Those samples satisfy eco-labeling system’s requirement. The explanation for this phenomenon is found in different processes of curing and drying.   By HPLC it was proven that there are no other aldehydes or ketones present on microcapsulated textile materiale It was proven that the amount of formaldehyde in essential oils is negligible It was proven that the amount of formaldehyde in essential oils is negligible   Microcapsule’s wall contributes to the highest degree of the amount of formaldehyde  After washing of textile substrate, the results are considerable lower