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.

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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

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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 (ICP-

MS) 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.

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 ○ 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

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 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

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 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 Absorban
ion (ppm) ce (A)

1.5 0.16

3 0.46

4.5 0.58

6 0.66

9 1.04

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Figure III: Calibration chart for determination of formaldehyde
concentration

Table II: Formaldehyde content in test fabrics determined from calibration

chart

Green white fabric Purple fabric

Absorbance Concentration Absorbance Concentration

(A) (ppm) (A) (ppm)

0.009 0.072 0.011 0.088

0.010 0.080 0.006 0.048

0.010 0.080 0.011 0.088

Table III: Selected metal ion content determined from ICP-MS

Purpl
Green
e
white
Metal Ion Samp
Sample
le
(ppb)
(ppb)

7055.
Sodium (Na) 5236.85
8

Magnesium 119.3
708.16
(Mg) 1

5703.
Silicon (Si) 4734.74
8

8
 244.5
Potassium (K) 529.85
1

283.7
Calcium (Ca) 1312.13
4

Copper (Cu) 53.1 1.19

Strontium
6.75 14.48
(Sr)

<
Barium (Ba) 8.76
1.00

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:

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 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.
http://www.cee.vt.edu/ewr/environmental/teach/smprimer/icpms/icp
ms.htm

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