|Year : 2022 | Volume
| Issue : 1 | Page : 141-146
Comparative pharmaceutico analytical study of Haratala (orpiment) Shodhana (purification) using different Shodhana media
Krupali Shailesh Jani1, Prashant Bedarkar1, Vinay J Shukla2, Biswajyoti Patgiri1
1 Department of Rasa Shastra and Bhaisajya Kalpana, Institute for Teaching and Research in Ayurveda, Jamnagar, Gujarat, India
2 Department of Rasa Shastra & Bhaisajya Kalpana, Pharmaceutical Chemistry Lab, Institute for Teaching and Research in Ayurveda, Jamnagar, Gujarat, India
|Date of Submission||11-Jul-2021|
|Date of Decision||08-Mar-2022|
|Date of Acceptance||08-Mar-2022|
|Date of Web Publication||27-Jun-2022|
Krupali Shailesh Jani
Department of Rasa Shastra and Bhaisajya Kalpana, Institute for Teaching and Research in Ayurveda, Jamnagar - 361 008, Gujarat
Source of Support: None, Conflict of Interest: None
INTRODUCTION: Haratala is Uprasa mentioned since vedic period. Chemically, it is Arsenic trisulfide and also classified under schedule E1 drug. There are methods and medias used for Shodhana of Haratala. In the present study for Shodhana of Haratala, three Shodhana media have been taken, i.e., Triphala Kwatha, Tila Tail, Kanji.
AIM: The aim of the study is to standardize pharmaceutical procedure of Haratala Shodhana in different Shodhana media and developing its comparative analytical profile.
MATERIALS AND METHODS: Haratala Shodhana is done in different Shodhana Media, i.e., Triphala Kwatha, Tila Taila and Kanji. Total three batches in each Shodhana media were carried out for standardization.
RESULTS AND DISCUSSION: Three hour duration was required for 100 g of Shodhana of Haratala average 2l of liquid media used for Shodhana, analytically there was significant difference in all three samples of Haratala was found, Three media were taken, i.e., Triphala Kwatha, Tila Taila, Kanji and there analytical profile will be generated to find the probable variations in before and after Shodhana.
CONCLUSION: All three media were used for Shodhana of Haratala because all liquid medias were easily available for Shodhana and all possess different therapeutic utilities. Although there is a significant difference seen analytically after Shodhana, In X-ray diffraction, maximum number of peaks were found in Triphala Kwatha Shodhit Haratala so this could be used as differentiating factor for better comparison between all three Shodhana media.
Keywords: Haratala, Kanji, Shodhana, standardization, Tila Taila, Triphala
|How to cite this article:|
Jani KS, Bedarkar P, Shukla VJ, Patgiri B. Comparative pharmaceutico analytical study of Haratala (orpiment) Shodhana (purification) using different Shodhana media. BLDE Univ J Health Sci 2022;7:141-6
|How to cite this URL:|
Jani KS, Bedarkar P, Shukla VJ, Patgiri B. Comparative pharmaceutico analytical study of Haratala (orpiment) Shodhana (purification) using different Shodhana media. BLDE Univ J Health Sci [serial online] 2022 [cited 2022 Aug 16];7:141-6. Available from: https://www.bldeujournalhs.in/text.asp?2022/7/1/141/348277
Rasa Shastra mainly means science of mercury, however, it is a specialized branch of Ayurveda dealing with material known as Rasa Dravya; they have following three attributes; instant effect, requires small dose, and extensive therapeutic utility irrespective of constitutional variation. The word arsenic is derived from the Greek word Arsenikon, meaning “potent.” It is indicated in Vrana Shodhana (wound cleaning), Pandu Karma (coloring the skin after scars of wounds), Arsha (piles), for various skin disorders, Granthi (nodules), Upadamsa (penile and veneral diseases), Visarpa (herpes) and as a hair remover in different Yogas (formulations). In Kalpasthana, two references are available regarding Dhatu Vishas in Lutadamsa Chikitsa. Simultaneously in Uttara Tantra, seven references are available in the subject of worms, eye diseases, skin diseases, and several pediatric disorders in the form of oil, powder, and Dhumapana (fumigation). If the Haratala is used without proper purification, the toxic effects are Daha (burning sensation), Kampaka (tremors), Toda (pricking pain), Kshobha, Pida, Raktadusti (vitiates blood), Kushta (skin disease), Malinikaroti Gatram, Vata Kapha Prakopatamaka Roga, Mrtyusankakara.
Hence, for the present study, the various Shodhana procedures mentioned in Rasa Ratna Samuchaya and AFI were adopted. There are various Shodhana procedures explained for Haratala in Rasa Granthas such as Rasa Ratna Samuchaya, Ayurveda Prakasha, and Rasa Tarangini. There are two methods of Shodhana mentioned in classics for Haratala Shodhana, i.e., Bhavana and Swedana and total 14 liquid medias are mentioned. Here, the attempt has been made to develop comparative study of Haratala Shodhana in different Shodhana liquid media, i.e., Triphala Kwatha (decoction of combination of three herbal drugs), Tila Taila (Sesame oil), Kanji (sour gruel) generating their analytical profile for better establishment of scientific significance role of liquid media on purification process.
Objectives of the study
- Authentification of Patra Haratala (Orpiment)
- Standard Manufacturing Procedure (S. M. P) for Shodhana procedures of Haratala by Triphala Kwatha, Tila Taila, and Kanji
- Physicochemical analysis of Haratala and Medias, before and after Shodhana procedures.
| Materials and Methods|| |
Ashudha Haratala, Triphala Yavkuta (Amalaki-Emblica officinalis Gaertn, Haritaki-Terminalia chebula Retz., Bibhitaki-Terminalia bellerica Roxb.), and Tila Taila were procured from department of RS and BK, Gujarat Ayurved University, Jamnagar. Ashudha Haratala was selected as per Grahya Lakshana. Rice for preparation of Kanji was purchased from local market of Jamnagar. Pharmaceutical procedure for Shodhana was carried out at RS and BK department IPGT and RA Jamnagar. Different samples of Ashodhita and Shodhita Haratala were analyzed for sophisticated analysis at IIT, Bombay.
Shodhana of Haratala
Shodhana of Haratala was carried out by Swedana in Dola Yantra as shown in [Figure 1]. Triphala Yavkuta was taken and Kwatha was prepared as per the reference of Sharangdhara Samhita. Kanji was prepared as per the reference of Parada Samhita. For all the batches, the coarse powder of Ashudha Haratala was tied in four folded cotton cloth and immersed in different liquid media. Continuous heating was given for 3 h, and temperature of 90°C–100°C was maintained throughout the process and after that, Haratala was washed thrice with hot water then it was dried and stored in glass container.
Analysis of Ashodhita and Shodhita Haratala
Organoleptic and physicochemical parameters Ashuddha Haratala, all Shodhita samples of Haratala were carried out. Different medias which were used for Shodhana were analyzed before and after the purification process of Haratala. Sophisticated instrumental analysis techniques such as X-ray diffraction (XRD) and atomic absorption spectroscopy (AAS) of sample of Shodhita and Ashodhita Haratala were also carried out.
| Results and Observation|| |
After complete evaluation of all the samples of Haratala pharmaceutically (Ashudha and Shudha Haratala), it was noted that before and after Shodhana color of media and Haratala was changed which is as shown in [Table 1]. Typical smell of media was felt while doing Shodhana in all the three media intense smell was felt during Shodhana in Kanji while in case of Triphala Kwatha and Tila Taila intensity was quite less as compared to Kanji. Froth formation was seen in Kanji and Triphala Kwatha because both are aqueous media so according to boiling point of water, i.e., 100 thus similar observation were noted in these both the medias. For Shodhana of 100 g of Haratala, 2l of average media was utilized for Shodhana in each batch, Shodhana media should be used as per the quantity of the material; it should not be less or more because if its less, there would not be proper exposure to the media and proper Shodhana will not take place, more quantity of media may affect the economical factor also. Maximum amount of loss was seen in case of Tila Taila Shodhit Haratala after Shodhana because Taila Taila is sticky in nature, lipophilic substances adhered to the surface of Haratala and due to this reason, Haratala was washed 6 times as compared to the other two media Shodhita Haratala, other two Medias Shodhit Haratala was washed thrice only. After Shodhana of Haratala in Triphala Kwatha it was found that there was increase in the weight of Haratala it could be due to the total solid content of Triphala Kwatha, minute particles of Tripahla gets attached on the surface of Haratala. There was a significant change in the pH of all media Triphala Kwatha, Tila Taila, and Kanji after processing with Haratala, pH was changed.
|Table 1: Average results obtained during of Shodhana of Haratala using different media;|
Click here to view
Various analytical studies have been performed of medias used for Shodhana; also, an analytical study of before and after Shodhana of Haratala has been carried out. Organoleptic characters various samples of Haratala described in [Table 2]. Physicochemical parameters of different Shodhana media which has been used, i.e., Triphala Kwatha, Tila Taila, Kanji have been described in [Table 3]. Physicochemical parameters of various samples of Shodhita Haratala have been described in [Table 4]. XRD graph is shown in [Figure 2].
|Table 4: Results of physicochemical parameters of various samples of Shodhita Haratala|
Click here to view
| Discussion|| |
After Shodhana of Haratala in different Shodhana media, as shown in [Table 1], there was shift of pH of media toward alkalinity or reduction in acidity. pH of a sample reflects H ion concentration. Hence, reduction in acidity reflects reduction in H +. Highly toxic fumes of sulfur and arsenic are emitted when in contact with acid or acid fumes. Produced sulfur gas may form H2S which is soluble in aqueous media. As2S3 reacts with water, steam, or even moist air to produce hydrogen sulfide gas. Utilization H ions from solution might have been responsible for increase of pH of all media after Shodhana.
Analysis was carried, [Table 2] reveals that sample 1, i.e., Ashuddha Patra Haratala, is having pale yellow, peculiar slight typical garlic odor with crystalline smooth surface with free flowable powder. Sample 2, i.e., Shuddha Haratala (Triphala Kwatha Shodhita Haratala), was greenish yellow, dull color, odorless, crystalline smooth with free flowable powder. Sample 3, i.e., Shuddha Haratala (Tila TailaShodhita Haratala), was shinny yellow, more bright yellow, typical odor of Tila Taila, and crystalline smooth texture and clumps, less flowability, comparatively bigger particle size. Sample 4, i.e., Shuddha Haratala (Kanji Shodhita Haratala), was whole pieces – more yellow, slightly reddish. Powder – whitish yellow, slight typical garlic odor with odor of kanji and crystalline smooth texture with free flowable powder.
Refractive index of Tila Taila before and after Shodhana was remain same; RI of a medium gives an indication of the light-bending ability of that particular media. Specific gravity of media was slightly decreased in case of Tirphala Kwatha and Kanji before and after Shodhana in media and in case of Tila Taila was slightly increased after Shodhana process, it may be due to heating, density of media was changed, total solid content was also increased after Shodhana in media because of evaporation of water portion from the media and solid particles started settle down at the bottom of the vessel.
Loss on drying as shown in [Table 4], Triphala Kwatha Shodhit Haratala has maximum % of loss on drying as compared to other two samples of Haratala i.e. Tila Taila Shodhit Haratala and Kanji Shodhit Haratala this is due to solid material was adhered to Haratala, similarly ash value and acid insoluble ash of Triphala Kwatha Shodhit Haratala was found significantly higher in amount due to inorganic material was present i.e., tannin content of Triphala was responsible for increase in value. AAS arsenic % was found more in Tila Taila Shodhita Haratala as compared to other two Shodhit medias, but we can say that after Shodhana, there was reduction in arsenic % because in Ashudha Haratala as % was more than that in Tila Taila Shodhit Haratala.
Arsenic trisulfide reacts with water or steam to produce toxic and flammable vapors; it can react vigorously on contact with oxidizing materials. As a resultant of produced arsine gas, the concentration of arsenic in sample might have been reduced after Shodhana.
It reacts with strong acids such as HCL, H2SO4, nitric acids to for H2S, arsine gases. It may also react violently with pot chlorate and other oxidizing agents, sulfur and sodium sulfide. Part of Ashuddha Haratala during boiling in aqueous media and heating in oil might have underwent through oxidation process thus transforming to oxides such as arsenic trioxide and pentaoxide which are soluble in aqueous media thus responsible for reduction in arsenic content. Although there was least possibility of the presence of arsenic oxides in Shodhit Haratala which has been revealed by lack of matching of XRD pattern of Shodhit Haratala with that of standard oxides of arsenic [arsenic trioxides (claudetite, arsenolite) and pentaoxide]. This may be because of the formation of several organo-arsenic compounds as arsine gas is highly reactive (especially in the case of Shodhana of Haratala in tila taila) and due to its water solubility transformations at surface might have been dissolved into the liquid in aqueous medias lie Triphala and Kanji. Addition of media in the sample as mentioned earlier might be one among the reasons for the reduction of arsenic content of samples of Haratala after Shodhana.
Upon analysis of data of Arsenic content in samples of Ashuddha and Shuddha Haratala, it is observed that, arsenic percentage after Shodhana has been significantly reduced [Table 4] which is probably due to leaching of arsenic in aqueous media as it is well known fact that arsenic partially leaches in water upon heating, may release arsine gas, even humidity also helps the phenomenon. It is known that solubility of arsenic trisulfide increases in sulfide solutions and more in alkaline sulfide solutions. Released arsine gas may form several organo-arsenic compounds with liquid media (Kanji, Triphala Kwatha, Tila taila, etc.), thus reducing arsenic content. Arsenic dissolution increases in sulfide solutions and due to the formation of H2S gas while heating, sulfide solution of several trace elements, sulfurous acid in traces may get formed thus facilitating further leaching of arsenic in to the liquid media for Swedana. Similar reduction has been observed in XRD study of samples of Shodhit Haratal as that of Ashodhit Haratala which is evident from reduction of intensities of the same respective major peak indexed as arsenic trisulfide.
Comparison of XRD data of different samples with standard.,
Hanawalt analysis and Fink method of exploration of data of XRD pattern of a powder for comparison of samples were applied for the evaluation of similarities and dissimilarities among diffraction pattern of different samples.
The peak which appears at 25 corresponds to orpiment (As2S3). The peaks (2q) Ashuddha Haratala 5 peaks, Tila Taila Shodhita Haratala7 peaks, Triphala Shodhita Haratala8 peaks, and Kanji Shodhita Haratala8 peaks were compared with JCPDS data and found to be as (rhombohedral) with average intensity of 90 (arbitrary unit). The peaks (2q) observed in Ahudha Haratala were 10 peaks, Tila Taila Shodhita Haratala9 peaks, Triphala Shodhita Haratala11peaks, and Kanji Shodhita Haratala7 peaks were identified as As2S3, (monoclinic).
Similarities of diffraction data of individual sample with XRD pattern of standard XRD data of orpiment.
Observations of comparison of XRD data of samples of Ashodhita and Shodhita Haratala with that of XRD pattern of standard samples of orpiment (arsenic trisulfide) and other possible compounds of arsenic (sulfides, oxides, etc.) show that all samples of Haratala Ashodhit as well as Shodhita Haratala exhibited arsenic trisulfide as major composition from 100% relative intensity at same d spacing and theta values. It is observed from data that none of the peak of any sample (Ashuddha or Shuddha Haratala 3 samples) with 100% relative intensity or major peaks with same angle theta matched with XRD pattern of possible compounds mentioned ahead – anorpiment, realgar, pararealgar, arsenic oxides (claudetite, arsenoite), other sulfides (alacronite [AS8S9], Uzonite[As4S5]). The absence of arsenic oxides suggests safety of shodhita form even after vigorous heat treatment and treatment (boiling) in acidic media. Heating with oil can be done even at higher temperature as smoking point of sesame oil is 210°C at which due to breakdown of fatty acids several organic compounds may get formed which along with arsine, H2S gas may form several organo inorganic compounds which may adhere to surface or get into Shodhita Haratala as inclusions, doping, etc., thus leading to increase arena of therapeutic efficacy.
From Auger parameter (AP) values, it appears that the samples are As2S3. AP values for AS-O are much lower than that for sulfide. For example, AP: As203 = 1263.3 and AP: As205 = 1263.6. We tried to get at% of As and S on the surface. However, XRD can get the exact phase. Trace of oxide is found in sample 2 and sample 4. This shows the role of different media in deciding the absorption, assimilation, effect, and excretion of the drug. Hence, due to these, there may be changes in the mode of action and also disease and disease condition.
Previous published research work shows that Haratala Shodhana was carried out using Tila Kshar, Kushmanda Swarasa, and Churnodaka as liquid media analytical study was performed, i.e., organoleptic parameters, physicochemical parameters, and sophisticated instrumental analysis such as ICP-AES and XRD. ICP-AES is the advance version of AAS results shows that there is difference in arsenic percentage with change in Shodhana media. Raw Patra Haratala, Kushmanda Swarasa, Tila Kshara Jala, and Churnodaka-8.89, 8.12, 9.2, and 8.89, respectively. XRD data show from AP values, it appears that the samples are As2S3. Trace of oxide is found in Kushmanda Swarasa and Churnodaka. This shows the role of different media in deciding the absorption, assimilation, effect, and excretion of the drug.
Ayurvediya rasa shastra is a very vast branch, standardization, and validation of pharmaceutical processes and developing their analytical profile for understanding the chemistry behind the role of different principles and processes is major point of concern with calibration of instrumental techniques for reproducible results and collecting a standard database for future research works.
| Conclusion|| |
Shodhana of Haratala reveals that the importance of Shodhana media both Shodhita and Ashodhita Haratala shows different physical and chemical properties. Organoleptic characteristics of samples of Haratala possess different colors, touch, and odor, pharmaceutically also difference has been found before and after Shodhana. After Shodhana, there was increase in weight of Triphala Kwatha Shodhita Haratala as compared to other two medias, which were used for Shodhana. Analytical difference has been reported in AAS- arsenic percentage is marked greater in Tila Taila Shodhit Haratala as compared to other two Shodhana media. In XRD data, maximum peaks of monoclinic structure are identified in Triphala Kwatha Shodhit Haratala. Thus, it can be concluded that all the Shodhita samples of Haratala can be used for further processing of formulation due to the reduction arsenic percentage of Haratala in all samples after Shodhana process.
Financial support and sponsorship
Conflicts of interest
There are no conflicts of interest.
| References|| |
Savrikar SS, Ravishankar B. Introduction to 'Rasashaastra' the iatrochemistry of ayurveda. Afr J Tradit Complement Altern Med 2011;8:66-82.
De S, Maiti A. Arsenic Removal from Contaminated Ground Water. New Delhi: The Energy and Resources Institute (TERI); 2012. p. 1.
Binu Alappat A, Kamdev Das, Arun Kumar Das, Roshy Joseph C. Ayurvedic review of Haratala (Arsenictrisulphide – As2 S3) and its therapeutic importance. Int J Res Altern Med 2015;2:1-10.
Sharma S. In: Shastry K, editors. Rasa Tarangini. 11th
ed. New Delhi: Motilal Banarasidas Publication; 2004. p. 246. [11/13-15].
Vagbhata R, Samucchsya R. 3/70-72, Hindi Commentary by Dattatreya Ananta Kulkarni. Delhi: Meharchandra Lacchmandas Publications; Reprint 1998. p. 53.
Jadavji T., editor. Sushruta Samhita of Dalhana, Madhyama Khanda. Ch. 9, Ver. 3. Varanasi: Choukhamba Krishnadas Academi; 2004. p. 115.
The Ayurvedic Formulary of India, Part-1, Second Revised Edition-2003, Ministry of Health & Family Welfare Government of India, Paribhasa (Glossary of Technical Term); 2003. p. 348.
Biradar S, Rukddin G, Prajapati PK. Preclinical Safety Study of Rasamanikya Prepared by Kushmanda Shodhita Haratala”. PhD Dissertation Submitted by Department of RBK IPGT & RA, Gujarat Ayurved University, Jamnagar, in 2016.
Srimannarayan, Patgiri BJ, Prajapati PK
. “Pharmaceutical Standardization and Toxicity Study of Rasamanikya”. PhD Dissertation Submitted by Department of RBK IPGT & RA, Gujarat Ayurved University, Jamnagar, in 2012.
Cullity BD, Stock SR. Elements of X ray Diffraction. Pearson. 3rd
Impression 2016. Phase Identification by X-ray Diffraction. New York: Prentice-Hall; 2016. p. 285-7.
Sangolgi B, Shimpi P, Benne S, Rao G. Physicochemical analysis of Haratala w.s.r. to its various Shodhana procedures. J Ayurveda Integr Med Sci 2017;2:88-97.
[Figure 1], [Figure 2]
[Table 1], [Table 2], [Table 3], [Table 4]