Analysis report of textile fabrics

Tests for presence of formaldehyde and metal content in baby fabrics
12/8/2009 [Type the author name]

Introduction: Health effects of Formaldehyde: Although formaldehyde is less toxic than most reactive compounds, certain factors make formaldehyde a particular problem to human health. Firstly, it is a gas that can spread throughout the work and living space. Secondly, most of the formaldehyde resins and their end-use products are potential to liberate formaldehyde. The risk of adverse reaction to formaldehyde depends on the sensitivity of an individual, the time of exposure, and the type of contact. On breathing formaldehyde vapor, formaldehyde can result in irritation of nerves in the eyes and nose, which may cause burning, stinging sensation, a sore throat, teary eyes, runny nose and sneezing1. Skin contact with formaldehyde can cause skin rashes and allergic skin reactions. Formaldehyde is well-known sensitizer for dermatitis and instances of dermatitis resulting from wearing clothing containing high levels of formaldehyde have been documented1. The International Agency for Research on Cancer, a World Health Organization panel of 26 scientists has concluded that the formaldehyde is a human carcinogen2. Formaldehyde Release from Textiles: The formaldehyde-containing chemicals are most effective crosslinking agents for wrinkle resistance, dimensional stability and flame retardant properties of textiles. During the finishing process, the N-methylol compounds in formaldehyde-containing reagents can react with hydroxyl groups of cellulose, resulting in the preferable crosslinking reaction; they may also react with themselves or with NH groups, which occupy the reaction places on crosslinking agents (Figure I). The formaldehyde can simply be released from the N-methylol compounds (Figure II) which come from the excess finishing agents or by hydrolysis of crosslinking agents3. The formaldehyde released from a treated fabric will depend on number of factors including the following2:  
 

The type and quantity of formaldehyde resin used Environmental temperature and relative humidity The degree that the formaldehyde resin has been cured The after-treatment of finishing such as washing

Figure I: Equilibrium reaction of N-methylol compounds with hydroxyl group of cellulose, with themselves, with NH groups.

Figure II. Equilibrium reaction of formaldehyde release from N-methylol compounds.

Health Effects of Heavy Metal in Textile: The toxicity of heavy metals on human health are well known: damages of organs, disorders in the respiratory system, dysfunction of heart and blood, disorders in nervous system, skin diseases, and abnormalities in fertility5. Unfortunately, heavy metals are often present in different textile processes and toxic heavy metal is one of the major chemical pollutants on textiles. For instance, cobalt, chromium and occasionally copper and nickel are part of the most commonly used dyes for, cotton, nylon, wool and leather materials. Antimony is used to improve wash fastness on nylon fibers. Zirconium, aluminum are also used extensively in some textile processing6. To prevent these adverse effects, different standards and regulations are enacted to limit the amount of heavy metals in textile products: Oeko Tex Standard, Clean fashion, Commitextile, EC Approach, EPG (The European Product Guarantee) and Ecomarc Scheme. Some of the azo dyes are also proven to be carcinogenic, and its usage is banned. Therefore it is important to analyze textile garments for toxic substances like formaldehyde, heavy metals and banned azo dyes to confirm their safety to users. In this project two baby garments were tested for formaldehyde and metals. Infants and young children are more sensitive towards toxic substances and these products must meet the stringent international toxicity regulations. Approach to the problem: Measurement of Formaldehyde in Textiles: Measuring the content of free formaldehyde in textiles has been subject of research for many years. AATCC Method 112 and Japanese Law Method 112 are generally accepted standards for measuring the

formaldehyde content of textiles. In the AATCC Method 1124, the specimen is suspended over an aqueous solution in a sealed jar at a given temperature for a specific period. The formaldehyde gas that is given off by the specimen is absorbed into the solution. The formaldehyde in the solution is derivatized using Nash reagent, and the color of the resulting complex is measured with UV-visible spectroscopy. The amount of formaldehyde is expressed as micrograms of formaldehyde per gram of fabric. Both free and releasable formaldehyde can be captured in this testing procedure. In contrast, the Japanese Law Method 112 procedure require the free formaldehyde from the specimen to be extracted into a cold sodium sulfite solution, which is then derivatized and measured as stated above. This procedure does not necessarily capture releasable formaldehyde. Therefore in this project AATCC Method 112 was selected. The instrument of inductively coupled plasma- mass spectrometry (ICPMS) 5 is proven to be rapid, sensitive and simple method for qualitative and quantitative determination of the trace amount of metal content in textile materials. The given advantages of this instrument prompted us to use it on our textile product. Experimental: AATCC Test method 112-1996 The basic principal for this experiment is that the amount of formaldehyde absorbed is measured using a spectrophotometer from a sample suspended in a sealed jar containing water left in an oven overnight. Materials used• Preparation of NASH Reagent○ In a 1000 ml volumetric flask, 150g of ammonium acetate was dissolved in 800 ml distilled water; 3 ml of glacial acetic acid and 2 ml of acetylacetone was added to the flask. ○ The remaining space was filled with distilled water till the mark and mixed and was stored in a brown bottle. The reagent was used in the experiment after storing it for 12 hours. ○ A calibration curve was run to correct for slight changes in the standard curve. Preparation of Standard solution and calibration○ A 1500μg/g stock solution of formaldehyde was prepared by diluting 3.8 ml of reagent grade formaldehyde solution (37%) to one liter with distilled water.

The stock solution was equilibrated for 24 hours before standardization ○ The concentration of formaldehyde in the stock solution was determined by a standard method using 1M sodium sulfite and thymolphthalein indicator. 0.02N sulfuric acid was added till the blue color of the liquid mixture disappeared. On addition of formaldehyde solution the color of the liquid in the flask changed which was then titrated with sulfuric acid until the blue color was removed. ○ The formula used to calculate the concentration of formaldehyde present in the solution was○  C=30,030A(N)/10

Where C= Wt/Vol concentration of formaldehyde (μg/ml) A= Vol of acid used (ml) N= Normality of acid ○ A 1:10 dilution of standardized formaldehyde stock solution was prepared by pipetting 25 ml of standardized stock solution into a 250 ml volumetric flask and diluted to the mark with distilled water. ○ Formaldehyde solutions of concentration 1.5, 3.0, 4.5, 6.0 and 9.0 μg/ml was prepared by diluting 5, 10, 15, 20 and 30 ml aliquots of the 1:10 dilution of the stock solution with distilled water in 500 ml volumetric flasks.

Test Specimens- Two cotton baby garments were bought from Wal Mart, one garment was printed and composed of 60% cotton and 40% polyester while the second garment was dyed and composed of 100 % cotton fiber. Three specimens of 1g weight were cut from each fabric for the test. Procedure followed○ 50 ml of distilled water was placed in bottom of the jar and the fabric was suspended above water in each jar and the jar was sealed and placed in the oven at 50 °C for 20 hours ○ The fabric was removed and the jars recapped and shaked ○ 5 ml of Nash reagent was pipetted into a suitable number of test tubes (10 ml) and 5 ml of the reagent was pipetted into an additional tube for a reagent blank. ○ 5 ml of each sample was added to the incubation jar and 5 ml of water was added to the tube used as reagent blank. The tubes

were mixed and placed in water bath for 6 minutes at 58 ± 1°C and after cooling the absorbance was recorded at 412 nm using a spectrophotometer. ○ Concentration of formaldehyde was determined using the prepared calibration curve. ○ Calculation used for determining concentration F= (C)(50)/(W) Where F- Concentration of formaldehyde (μg/g) C- Concentration of formaldehyde in solution as read from the calibration curve w- Weight of the test specimen Uses and limitations of this experiment•

Upper limit of releasable formaldehyde on the fabric is 500μg/g if a 1:1 ratio of Nash reagent to sample solution is used in the analytical portion of the test and 3500μg/g if a 10:1 ratio is used. The procedure promotes release of formaldehyde from odor-free fully cured durable press fabrics.

The metal content in sample was determined by using ICP-MS instrument7•

The samples were kept in a closed beaker containing water in an oven at 80 °C for a day and the water was then used to analyze if any harmful chemicals had leached in it. This was done by passing a sample of the leached water through ICP-MS instrument and recording the readings of the chemicals present in the sample. In ICP-MS the sample was introduced by using a nebulizer in presence of argon to form a fine mist of aerosol of the liquid sample. The aerosol was passed through a spray chamber where any large droplets were removed via a drain and about 2% of the original spray was passed through chamber. The spray was then moved into a torch chamber and was mixed with more argon gas. Argon gas was heated using radio frequency waves producing an argon plasma flame. The hot plasma removed any remaining solvent and resulted in atomization of the sample followed by ionization and also excitation of samples atoms occurred. After ionization the samples were passed through MS at high speeds. In the first stage in of mass spectrometer ions in the form of an ion

beam was passed through quadruple analyzers. The analyzer made up of four metal rods which have DC and AC electrical potential applied to the opposite rods which resulted in net negative or positive potential. Ion was passed between these rods and DC and AC voltages was set to certain values where only one particular ion was able to continue on a path between the rods while other ions are forced out of this path. The ion has a specific m/z ratio. Most common type of ion detector used in an ICP-MS is the channeltron electron multiplier. The detector has a cone shaped tube to which high voltage was applied to it opposite in charge to the ions detected. Ions leaving the quadruple were attracted to the interior cone surface. They struck the surface additionally secondary electrons are emitted which move farther into tube emitting additional secondary electrons. More electrons were formed as the process was continued and resulted production of 108 electrons. One of the great advantages of this method was extreme low detection limits for a wide variety of elements.

Results and Discussion: Table I: Concentration Vs Absorbance readings of calibration chart Concentrat ion (ppm) 1.5 3 4.5 6 9 Absorban ce (A) 0.16 0.46 0.58 0.66 1.04

Figure III: Calibration concentration






Table II: Formaldehyde content in test fabrics determined from calibration chart Green white fabric Absorbance (A) 0.009 0.010 0.010 Concentration (ppm) 0.072 0.080 0.080 Purple fabric Absorbance (A) 0.011 0.006 0.011 Concentration (ppm) 0.088 0.048 0.088

Table III: Selected metal ion content determined from ICP-MS Purpl e Metal Ion Samp le (ppb) Sodium (Na) Magnesium (Mg) Silicon (Si) 7055. 8 119.3 1 5703. 8 Green white Sample (ppb) 5236.85 708.16 4734.74


Potassium (K) Calcium (Ca) Copper (Cu) Strontium (Sr) Barium (Ba)

244.5 1 283.7 4 53.1 6.75 < 1.00

529.85 1312.13 1.19 14.48 8.76

The calibration chart was generated using the values obtained from UV visible spectrophotometer for different prepared formaldehyde concentrations (Table I). It is observed that the calibration chart follows linear relation between formaldehyde concentration and absorbance for given conditions (Figure III). This calibration chart is then used to determine formaldehyde content in test samples by extrapolating UV visible spectrophotometer value of test sample on the calibration curve. There were two different baby garments analyzed for formaldehyde content and metal ion content. It is observed from the results (Table II) that very little formaldehyde content was present in the fabrics tested and the amount was well below the formaldehyde regulation of 20 ppm (International regulation) for baby clothes. Among the range of metal ions determined by ICP-MS instrument, sodium, magnesium, silicon, potassium, calcium, copper, strontium and barium ions were found to be of significant number but their value was still below ~8000 ppb (Table III). According to Oeko Tex Standard 100, all the metal ions were found to be within the regulated amount. We believe the reported metals in the fabrics resulted from improper printing and dyeing processes of these fabrics, for example high sodium ion could be due to high Glaubers salt (Na2SO4.10H20) usage during dyeing. We also believe the fabrics were processed with hard water which contains higher magnesium, calcium, and potassium ions which were left in fabrics after treatment. Conclusion:


The selected baby garments were thoroughly analyzed for formaldehyde and metal content using well established AATCC Method 112 and ICP-MS instrument respectively. Both the garments follow the international regulations for formaldehyde and metal content and pass the tests. The detected metals are not harmful to humans due to their low content. We believe, the observed metal content is due to improper use of hard water and processing. References: 1. Formaldehyde in Clothing and Other Textile. In Existing Chemiscals Information Sheet, Australian National Industrial Chemicals Notification and Assessment Scheme: October, 2007. 2. Formaldehyde In Textile. In Technical Bulletin Cotton Incorporated: North Carolina, 2007. 3. Voncina, B.; Bezek, D.; Marechal, A. M., Eco-Friendly Durable Press Finishing of Textile Interlinings. Fibers & Textiles in Eastern Europe 2002, July/September, 68-71. 4. AATCC, Formaldhyde Release from Fabric, Determination of: Sealed Jar Mehtod. 1998; Vol. AATCC Test Method 112. 5. Pranaityte B., Padarauskas A., Naujalis E., Chemija 2007, vol 18, No 3, 16-19. 6. Lenoas, K. K.; Michael, L., Am. Dyest. Report. 1994, 3, 26. 7. ms.htm


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