Introduction
Ayurveda is a Sanskrit term, made up of the words
"ayus" and "veda. "meaning life and science; together
translating to 'science of life'. A blend of several herbs
and spices make up the powdered mixture known as
"churna". Depending on its intended use for medicinal,
beauty, or culinary purpose, the recipe varies. Avipittakara
"churna" is a traditional Ayurvedic formula used
widely and almost daily to control vitiated pitta dosha,
remove heat in the digestive system, control indigestion,
constipation, vomiting and anorexia. A major analytical
challenge for these types of samples is mainly addition
of multiple herbs with sugar and the natural color of
herbs
[1]
.
The dried leaves result in highly complex extracts from
the sample preparation due to the rich content of active
ingredients, essential oils and the typical high boiling
natural polymer compounds. Due to the use of pesticides
in the fresh herbs, the "churna" may contain residual
pesticides. Analysis of pesticide residues is thus important
and governmentally regulated
[2]
. Strict quality parameters
have been mented to preserve the quality and efficacy of
these "churnas".
Sample Preparation
In brief, the QuEChERS sample preparation (see Figure
1) involved the extraction of 15 g of a powder sample
of Avipittakara "churna" with 15 mL acetonitrile
(containing 1% acetic acid) in the presence of 3 g
magnesium sulfate, 1.5 g sodium acetate and 1 g NaCl.
The supernatant (1 mL) was collected after centrifugation,
and dispersive cleanup was performed using 200 mg
PSA and 10 mg GCB. The extract was centrifuged at
10 000 rpm for 5 min, and 3 µL of supernatant was
Figure 1. Sample preparation for extraction of pesticides from
ayurvedic churnas
Analysis of Multi-Residue Pesticides Present in
Ayurvedic Churna by GC-MS/MS
Manoj Surwade
1
, Sunil T Kumar
1
, Aarti Karkhanis
1
, Manish Kumar
1
, Soma Dasgupta
1
, Hans-Joachim Huebschmann
2
,
1
Thermo Fisher Scientific, Mumbai, India;
2
Thermo Fisher Scientific, Singapore
Keywords:
Traditional herbal medicine, fast liquid/liquid extraction,
QuEChERS, timed-SRM, retention time synchronization, MRM, ion
ratio confirmation, TraceFinder data processing
Technical Support Note-000
Detection, Identification, and Quantitation of
zo Dyes in Leather and Textiles by GC/MS
Adi Purwanto
1
, Alex Chen
2
, Kuok Shien
3
, Hans-Joachim Huebschmann
3
PT Alpha Analyti al Indonesia, J karta,
2
Alp a Analytical Pte., Singapore,
3
Th rmo Fisher Scientific,
Singapore
tr duction
zo dyes are compounds charact rized by their vivid
color and provi e exc llent colori g properties. They
a e important and widely used as coloring agents in the
textile and le ther industries. The risk in the use of zo
dyes arises mainly from the break own pr ducts that can
created
in vivo
by reductive cl avage of the azo group
into aromatic amines. Due to th toxicity, c rcinogenicity
an pote ti l utagenici y of thus forme aromatic
amines, the use of certain azo dy s as textile and l ather
lorants, a d the exposure of consumers using the extile
and ather colored with azo compounds causes a serious
health concern
[1]
. The two m i routes of consumer
expo ure are the skin absorption of the azo compounds
from the dyed clothes worn, and potential oral ingestion,
mainly referring to the sucking of textil s by b bies and
young children. The man facturing workers can also b
exposed via the i h lation route.
The EU Commis ion classified 22 amines as p oven
or uspected human carcinogens. “Azo dyes which, by
reducti cleavage of one or more azo groups, m y release
one or more of hese aromatic amines in detectable
conc ntratio s, i e. above 30 ppm in the finished articles or
in the dyed parts thereof … may not be used in textile and
le ther articles which may come into direct and prolonged
contact with the human skin or oral cavity”
[2]
. The EU
Directive 2002/61/EC has banned the use of dangerous
azo colorants, placing textiles and leather articles colored
with such substances on the market, and requested the
development of a validated analytical methodology for
control. Since the azo dyes are one of the longest known
synthetic dyes, simple and inexpensive in preparation,
available easily in bulk and in great variety, and rarely
cause acute symptoms, the textile manufactures can be
persuaded to use them despite the regulations — if the
strict and reliable analytical control is not imposed.
Experimental Conditions
Sample Preparation
The sample preparation for the analysis of textile samples
depends on the nature of the textile. The textiles made of
cellulose and protein fibers, for example cotton, viscose,
wool, or silk
[3]
make the azo dyes accessible to a reducing
agent without prior extraction. The EN ISO 17234-1
standard method for the analysis of such textiles is based
on the chemical reduction of azo dyes followed by solid
phase extraction (SPE) with ethyl acetate providing a
ready-to-inject extract after solvent concentration.
The analysis of synthetic fibers like polyester, polyamide,
polypropylene, acrylic or polyurethane materials requires
prior extraction of the azo dyes and is described in the
EN 14362-2 standard method. The analysis of leather
samples follows the EN ISO 17234 standard meth d.
The azo group of most azo dyes can be reduced in the
presence of sodium dithionite (Na
2
S
2
O
4
) under mild
conditions (pH = 6, T = 70 °C), resulting in the cleavage
of the diazo group and formation of two aromatic amines
as the reaction products. The amines are extracted by
liquid-liquid extraction with t-butyl methyl ether (MTBE),
concentrated, adjusted to a certain volume with MTBE,
then analyzed by GC/MS. The quantitation is performed
:
azo yes, canc rogenic am s, tex iles, leather, EN ISO
standard method, ISQ Series GC/MS, fast full scan detection, quantitation,
confirmation, library se rch
.
Application No e 10329
A
o
0361
Weigh 15 g of
Churna
15 mL acetonitrile (with 1% acetic acid) was added, shaken
well.Further 3 g MgSO
4
+1.5 g NaOAc+1 g NaCl was added
and homogenized using a Vortex mixer
After centrifugation (5000 rpm, 5 min), cleanup of 1 mL
up rnatant performed by dispersive SPE using 200 mg PSA
and 10 mg GCB
Centrifuge t 1000 rpm f r 5 min, 3 μL of supernatant
inj cted to GC-MS/MS
