Pharmaceutical - analytic study of the Ayurvedic purification of Manahshila (realgar) / Asian Journal of Traditional

Medicines, 2012, 7(4)

Regular articles

Pharmaceutical - analytic study of the Ayurvedic

purification of Manahshila (realgar)
Naveena Kodlady a*, Doddamani MS b, Patgiri BJ c
a. Department of Rasashastra and Bhaishajya Kalpana including Drug Research, Institute
for Post Graduate Teaching & Research in Ayurveda, Gujarat Ayurved University,
Jamnagar 361008, Gujarat, India
b. Department of Rasashastra, Taranath Govt. Ayurvedic College, Bellary, Karnataka,
India
c. Department of Rasashastra and Bhaishajya Kalpana including Drug Research, Institute
for Post Graduate Teaching & Research in Ayurveda, Gujarat Ayurved University,
Jamnagar 361008, Gujarat, India

Abstract
Manahshila (realgar, arsenic disulphide) has been used in Ayurvedic medicine since ancient times for the treatment of conditions
such as skin diseases, cough, asthma, certain eye diseases, and psychological disorders etc. Shodhana (purification) is an integral
part of Ayurvedic processing especially for poisonous substances before they can be used for therapeutic purposes. In the case
of Manahshila, which contains the heavy metal arsenic, it is advised that it should be purified optionally by carrying out seven
levigations (Bhavana) of Zingiber officinalis Roscoe. (Ardraka) juice. A Shodhana of Manahshila was carried out and both
Ashodhita Manahshila (AM unpurified realgar) and Ardraka Shodhita Manahshila (ASM realgar purified with ginger juice)
were investigated by examination of the relevant physico chemical parameters, quantitative elemental analysis, including the
percentage of arsenic using atomic absorption spectrometry, particle size analysis using laser diffraction, and identification of
chemical moieties using X ray diffraction. A significant change was found in the particle size distribution where 50% of the AM
particles were found to be 54.18 m. while the figure for ASM was 15.55 m. There was no change in the chemical composition
and both AM and ASM remained as arsenic disulphide.

Key words: Manahshila; arsenic; shodhana; Ayurveda; XRD; laser diffraction

1 Introduction trioxide) in a number of Ayurvedic medicinal

Manahshila is one of the three important
arsenical compounds used in Ayurveda as a
therapeutic agent (the other two being Haratala
arsenic trisulphide, and Gouripashana arsenic
* Author to whom correspondence should be addressed. Address:
Department of Rasashastra and Bhaishajya Kalpana including
Drug Research, Institute for Post Graduate Teaching & Research in
Ayurveda, Gujarat Ayurved University, Jamnagar 361008, Gujarat,
India; Mobile No.: +919723844028; E-mail: naveenkodlady@gmail.
com
Received: 2011-12-20 Accepted: 2012-06-25
formulations including those found in Brihattrayis
(Three important ancient classics of Ayurveda viz.
Caraka Samhita, Sushruta Samhita and Astanga
Sangraha/Astanga Hrudaya). The important
therapeutic areas of Manahshila use include skin
diseases, respiratory diseases, certain ailments of
eyes and psychological disorders [1]. It is also used
as an ingredient of various processing techniques
involved in Rasashastra (a wing of Ayurveda
dealing mainly with mercurial, metallic and mineral
compounds along with herbal drugs) like Shodhana
(purification), Bhasmeekarana (incineration) and
Sattvapatana (metal extraction).

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 Pharmaceutical - analytic study of the Ayurvedic purification of Manahshila (realgar) / Asian Journal of Traditional
Medicines, 2012, 7(4)
Shodhana is the process by which the external
and internal impurities of the drugs are removed.
Chemical purification is different from medicinal
purification. Chemical purification involves only the
elimination of foreign matter, whereas medicinal
purification involves the removal of harmful
matter from the drug, modification of undesirable
physical properties of the drug, alteration of some
of the characteristics of the drug and enhancement
of the therapeutic action [2]. There are various
procedures involved in the Shodhana of different
Rasashastra drugs, like levigation (Bhavana),
boiling (Swedana), sublimation (Patana), quenching
(Nirvapa), immersion (Sthapana), and dehydration
(Nirjaleekarana) [3]. Arsenic is the most hazardous
substance among the top 20 listed by the Agency for
Toxic Substances and Disease Registry (ATSDR) [4].
Since Manahshila containsit should be used only
after proper purification. Shodhana of Manahshila
involves a process called Bhavana (levigation) in
which powdered drug is triturated with certain liquid
media till the contents are completely dried [5]. The
quantity of liquid medium should be sufficient to
ensure that the powder is completely soaked [6]. The
test for proper Bhavana is described qualitatively
and characterized by the softness, and flatness
(Chipitibhuya) when pressed between the fingers,
without any cracks at periphery [7]. Although
purified Manahshila is used in several formulations
of Ayurveda, there are only few published reports
about the characterization of purified and unpurified
Manahshila. Hence, an attempt was made to study
the Ayurvedic purification of Manahshila through a
study of scientific parameters.
2 Materials and methods
Raw realgar was collected from a local market
and its authenticity was confirmed byAyurvedic
descriptions of acceptable Manahshila such as its
reddish colour which changes to orange colour on
144
powdering [8] in addition to modern analytical
parameters.
2.1 Pharmaceutical
Shodhana of Manahshila is recommended to
be carried out by seven levigations with Zingeber
officinalis Roscoe. (Ardraka ginger) juice [9].
Raw realgar was powdered using a mortar and
pestle and prepared with the sample name Ashodhita
Manahshila (AM).
AM was placed in a mortar (Khalvayantra)
and mixed with the juice of Zingeber officinalis
Roscoe root and triturated with a pestle manually
until the material in the mortar dried. In this way, a
total of seven impregnations of realgar with ginger
juice were carried out. Later it was shade dried and
powdered by trituration in the mortar, and stored in
air tight glass bottle and labeled as Ardraka Shodhita
Manahshila (ASM).
2.2 Analysis
2.2.1. Organoleptic characteristics
The colour, odour and texture of AM and ASM
were assessed.
2.2.2 Physicochemical analysis
The physicochemical analyses of both samples
included ash values, loss on drying, loss on ignition,
pH as per the standard methods prescribed in
Ayurvedic Pharmacopiea of India (API) [10]. The
particle size distribution was carried out usinglaser
diffraction [11] which relies on the fact that
particles passing through a laser beam will scatter
light at an angle that is directly related to their
size. Determination of the chemical composition
and crystal structure was carried out using X-ray
diffraction (XRD) [12]. In the quantitative elemental
analysis, the percentage of arsenic was estimated
using atomic absorption spectrometry (AAS)
[13] while sulphur was determined by the Eschka
 Pharmaceutical - analytic study of the Ayurvedic purification of Manahshila (realgar) / Asian Journal of Traditional
Medicines, 2012, 7(4)

gravimetric method [14]. The determination of
the physicochemical characteristics and elemental
analysis were conducted at the Ganesh consultancy
and Analytical Services, Mysore, India. Xray
diffraction and particle size analysis were carried out
at the Department of Materials Engineering, Indian
Institute of Science, Bengaluru, India.
3 Results and discussion
A total of 660 ml ginger juice was digested in
250 g Manahshila by manual trituration for 27 hr
and 5 min. An average of 94.28 ml ginger juice
and 3 hr 52 min of trituration were needed for each
levigation of Manahshila Shodhana. However,
for the initial levigations, slightly more juice and
a longer period of trituration were needed while
for the later levigations the opposite was the case.
The Shodhana process turned the orange powder
of Manahshila into a reddish yellow colour. There
was an increase of 31 g in the weight of Manahshila
after Shodhana. The weight of Manahshila before
Shodhana was 250 g while that of Manahshila after
Shodhana was 281 g.
The organoleptic characteristics are shown
in Table 1. The results of the physicochemical
analyses of AM and ASM are tabulated in Table
2. Regarding the particle size distribution, 50% of
the AM particles were 54.18 m (Fig. 1), while the
corresponding figure for ASM was 15.55 m (Fig.
2). The results of the quantitative elemental analyses
are shown in Table 3.
3.1 XRD Analysis
The XRD findings for AM (Fig. 3) are given in
Table 4.
Note:
A total of 60 peaks were identified in the AM
sample at different angels (2) ranging from 11.74
(1st peak) to 70.88 (60th peak).

Table 1. Organoleptic characteristics of AM and ASM

Drug Colour Texture Odour

AM Orange Smooth, fine Odorless
ASM Reddish Yellow Smooth, fine Characteristic

20 100

90

80

70
Vollume (%)

60

10 50

40

30

20

10

0
0
0.1 1.0 10.0 100.0 1000.0
Particle diameter (m)
Fig. 1. Particle size report for Ashodhita Manahshila

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Table 2. Results of the physicochemical analysis of AM and The % intensity of standard arsenic disulphide
ASM (10, 10, 100 and 10) was approximately the same as
Parameters AM ASM the % intensity of 10, 14, 100 and 11, respectively.
Ash value 6.24% 7.72%
XRD findings for ASM (Fig. 4) are given in
Acid insoluble ash 0.84% 0.42%
Table 5.
Loss on drying at 105C 0.10% 0.18%
pH 8.15 7.39 Note:
Water Soluble Ash 0.04% 0.04%
Loss on ignition at 450C 91.24% 92.04% Totally 68 peaks were identified in ASM
sample at different angels (2) ranging from 11.68
Table 3. Percentage of arsenic and sulphur in AM and ASM (1st peak) to 86.66 (68th peak).

Quantitative analysis AM ASM 6 peaks were chosen with their relative

As 61.39% 62.22% intensity and compared to standard Xray powder
S 27.94% 27.24% diffraction file (JCPDS).

6 peaks were chosen with their relative 6th peak with relative intensity of 100% was
intensity and compared with standard Xray powder considered as significant at 16.253, having a 5.453
diffraction data (JCPDS). d space value.

6th peak with a relative intensity of 100% was The d values of standard arsenic disulphide
considered as significant at 16.28, having a 5.445 (3.06, 4.67 and 5.75) are almost similar to the ASM
d- space value. values found (3.065, 4.548 and 5.453).

The d values of standard arsenic disulphide The % intensity of standard arsenic disulphide
(2.102, 4.67, 5.75 and 6.76) were almost identical to (50, 10 and 100) was close to the % intensity found
the AM sample values (1.935, 4.65, 5.445 and 6.82, (50, 11 and 100, respectively).
respectively).

20 100

90

80

70
Vollume (%)

60

10 50

40

30

20

10

0 0
0.1 1.0 10.0 100.0 1000.0

Particle diameter (m)

Fig. 2. Particle size report for Ardraka Shodhita Manahshila

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Table 4. XRD findings for AM

Standard Identified
d space Intensity D space Intensity Peak No Angle 2
6.76 10% 6.82 11% 2 12.98
5.75 100% 5.445 100% 6 16.28
4.67 10% 4.65 14% 8 19.08
4.110 30% 4.093 24% 10 21.71
3.06 50% 3.063 45% 17 29.15
2.102 10% 1.935 10% 41 46.96
Name of standard: arsenic disulphide (As2 S2), JCPDS No: 21- 0805, Crystal structure: Monoclinic crystals

Table 5. XRD findings for ASM

Standard Identified
d space Intensity D space Intensity Peak No Angle 2
6.76 10% 6.862 14% 2 12.90
5.75 100% 5.453 100% 6 16.25
4.67 10% 4.548 11% 8 19.08
4.110 30% 4.095 24% 10 21.70
3.06 50% 3.065 50% 16 29.13
2.102 10% 2.015 13% 41 44.98
Name of standard: arsenic disulphide (As2 S2), JCPDS No:73-1593, Crystal structure: Monoclinic crystals

A comparison of the values of AM and ASM the Manashila after Shodhana due to the addition of
obtained is shown in Table 6. the ginger juice. Similarly, the levigation with ginger
changed the orange colour of the Manahshila powder
In the pharmaceutical study of the purification to reddish yellow. In the physico-chemical analysis,
of Manahshila, there was an increase in the weight of the AM had a total ash value of 6.24% while the value
Counts

Degrees 2-Theta
Fig. 3. XRD of Ashodhita Manahshila (shows that the sample is similar to standard arsenic disulphide)

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Counts

Degrees 2-Theta
Fig. 4. XRD of Ardraka Shodhita Manahshila (shows that the sample is similar to standard arsenic disulphide)

for ASM was 7.72%, indicating a slight increase Shodhana offers the possibility of absorption. The
in the total ash of Manahshila after Shodhana, loss on drying at 110C is a physical test to determine
which might be due to the inorganic components of the percentage moisture content and, hence, the shelf-
the Shodhana medium. In a study of thechemical life of the sample. In the present study, Shodhita
composition of ginger root, it was reported that 100 g Manahshila was found to exhibit a loss on drying
of sample contained 3.85 g ash along with a number of only 0.18% (ASM). Because of the presence of
of minerals, namely, iron (8 mg), calcium (88.4 mg), organic material there was an increase in the loss on
phosphorous (174 mg), zinc (0.92 mg), copper (0.545 drying of ASM compared with that of AM (0.10%).
mg), chromium (70 g) and manganese (9.13 mg) Hence, this shows that it has a very low moisture
as well as vitamin C (9.33 mg) [15]. There was only content and so a very low probability of allowing
a very low amount of raw and purified Manahshila bacterial and fungal growth. Ginger juice with a
which was acid insoluble, indicating that both AM pH of 3.6 is acidic nature reduces the alkalinity of
and ASM are absorbed in the stomach with the gastric AM. Overall, ASM is weakly alkalineand will be
juice. The acid-insoluble ash content of AM was less chemically active on administration. There was
0.84% while that of ASM was 0.42% suggesting that no change in the water soluble ash content between
AM and ASM although there was a slight increase in
Table 6. Comparison of identified d values of AM and ASM the loss on ignition after Shodhana of Manahshila,
AM ASM probably due to the increased organic content. There
D space Intensity (%) D space Intensity (%) was a small change in the concentrations of arsenic
6.820 11 6.862 14 and sulphur. i.e. a slight increase in the quantity
5.445 100 5.453 100 of arsenic and slight decrease in the quantity of
4.650 14 4.548 11 sulphur, although this difference was negligible in
4.093 24 4.095 24 quantitative terms and may be due to the relative
3.063 45 3.065 50 changes in the weight of arsenic, sulphur and other
1.935 10 2.015 13 minerals after levigation with ginger juice.

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The surface area of the drug particles is one
of the parameters that influence drug dissolution
and, in turn, drug absorption. Smaller particles with
a greater surface area dissolve more rapidly than
larger particles. There was a significant decrease
in the 50% particle size distribution of AM after
undergoing Shodhana. The particle size of AM
was 54.18 m while that of ASM was 15.55 m,
indicating possibly better absorption of the drug
after purification. The powder Xray diffraction
studies help in determining the composition of the
compound. On comparing the d values of both the
samples with their respective d standard showed
that the samples were similar to standard arsenic
disulphide (As2S2). There were changes in the total
number of peaks; AM produced a total of 60 peaks at
different angles ranging from 11.7470.88 whereas
ASM produced 68 peaks at angles ranging from
11.6886.66. At 100% intensity, there was a small
increase in the d space in the ASM compared with
AM. The d space of AM at 100% was 5.445 while
that of ASM was 5.453 where the standard peak was
5.75. This indicates that ASM is more close to the
standard As2S2. This also supports the fact that the
medicinal purification can also involve chemical
purification.
There are several positive factors associated with
ginger in the mode of Shodhana of Manahshila by
Ardraka Swarasa. a) Phytochelation: Phytochelatins
are heavy metal-binding peptides that play an
important role in detoxification of heavy metals
by chelation [16]. Ginger contains two important
sulphur-based amino acids called cysteine and
methionine which can act as phytochelatins and
can render arsenic nontoxic in the Manahshila. b)
Methylation: Methylation is a process of detoxifying
arsenic in the body through accelerated excretion.
This process takes place in the liver by the addition
of a methyl group to the arsenic and transforms
it into a nontoxic form which is then excreted.
149
Cysteine, which is a methyl donor peptide in ginger,
helps in the process of methylation. c) Preservation
of Glutathione: Glutathione, a natural antioxidant
recycling enzyme is an important detoxifying
compound present in the blood, which combines
with arsenic and excretes it via the bile. Arsenic
poisoning reduces the level of glutathione in the
blood. It has been shown that, following ingestion
ginger reduces the fall in the amount of glutathione
in the blood [17]. Hence, it supports detoxification
as well as combatting its possible depletion due to
arsenic. d) Neutralization of alkalinity: Ginger is
acidic with a pH value of 3.6 and Manahshila has a
pH value of 8.15. Because of its acid-base reaction,
the alkalinity of Manahshila is reduced and is
safer to use. In a previous research study, Ardraka
Shodhita Manahshila was found to be nontoxic in
experimental animals [18].
In-depth analysis of the organic and inorganic
components of ginger juice acquired by Manahshila
after Shodhana will throw more light on the
purification which was not the part of the present
study. Thin layer chromatograpy of AM and ASM
would be helpful in standardization of the Shodhana
process of Manahshila which could provide a useful
drug fingerprint.
4 Conclusion
There are only minor changes in the preliminary
physico-chemical parameters of Manahshila
after being subjected to Shodhana by levigation
with ginger juice. Shodhana does not change the
chemical composition of Manahshila. However,
there is a marked change in the particle size due to
Shodhana and about a 12.4% increase in the weight
of Manahshila after Shodhana.
Acknowledgements
 Pharmaceutical - analytic study of the Ayurvedic purification of Manahshila (realgar) / Asian Journal of Traditional
Medicines, 2012, 7(4)
The authors express their sincere gratitude
to Prof. M.S. Baghel, Director, IPGT&RA; Prof.
P.K.Prajapati, Head and Dr. Galib, Assistant
professor, Dept. of Rasashastra and Bhaishajya
Kalpana, IPGT&RA, Gujarat Ayurved University,
Jamanagar for their technical input and constant
encouragement. Thanks are also due to the
Department of Materials Engineering, Indian
Institute of Science, Bengaluru, India, and Ganesh
consultancy and Analytical Services, Mysore, India
for providing the analytical facilities.
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