Indian Journal of History of Science, 32(1), 1997 USE OF METALS IN AYURVEDIC MEDICINE BHANU PrakasH* (Received 16 August 1994; after revision 14 May 1996) The study of ancient Ayurvedic literature indicates the use of minerals, gems and metals to have begun in 7th century BC and before this treatment of diseases was done mainly with herbal medicines, worships and prayers or chanting of mantras etc. Siddha Nagarjuna has been considered to be the father of Indian alchemy and Rasa Sastra. The metals used for the preparation of Ayurvedic drugs are gold, silver, copper, lead, tin, zinc. iron, and some of their alloys. Mercury and sulphur have been extensively used in the alchemical process of conversion of these metals into bhasma. ‘A large number of processes have been described for the preparation of metallic bhasma in the Ayurvedic text but no scientific process control has been discussed. In the present paper it has been endeavoured to understand the physico- chemical nature of the changes occurring during various stages of the preparation of metallic hasma. The process of preparation of bhasma can be classified into two main groups, viz, metal extraction (satvapatana) and conversion of the purified metal or its alloy into nontoxic bhasma. During the processing of these metals, they have to pass through the steps viz. (i) Selection and control of raw-material, Gi) Sodhana (iii) Marana (iv) Mardana or Bhavana and (v) Jirana. In this paper the processing details of copper, iron.winc and lead bhasma have been described and the physico-chemical and microstructural changes occurring have been discussed 80 as to evaluate the technology of this ancient process. At the end, the paper describes some of the equipment and techniques used for the preparation of Bhasma. Key Words : Kupi Pika, Marana, Metallic Bhasma, Puta Pika, Sodhana INTRODUCTION The Ayurvedic medicinal system has been in vogue since the vedic period or even earlier. In principle this system advocates a holistic approach to the human health care i.e. a balance between the physical, mental and spiritual functions of the human body. As Rao (1993) has quoted from Atharvaveda ancient Indians had already a deep understanding about the role of natural environment viz. vegetation, oxygen, hydrogen, nitrogen, carbon and the products formed by their synthesis in sunlight, in the maintenance of human health and increasing the *Department of Metallurgical Engg., Banaras Hindu University, Varanasi2 INDIAN JOURNAL OF HISTORY OF SCIENCE longevity. In the early period the treatment of diseases was done mainly by chanting prayers, hymns and the use of single herbal decoctions but with time and experience more complex and durable herbal drugs like dsavas, arista, kalpanas, oils and ghritas were prepared for the internal as well as external uses. The earliest systematic approach to the development of ayurvedic medicine and surgery begins with the valuable contributions made by Caraka and Susrutz around c.7 BC. While Caraka Samhita records a detailed account of the properties of vegetable plants, herbs and their effect on the diseases prevalent in those days, Susruta samhit& deals with the pioneeing work done by Maharsi Susruta on surgery.These samhitas indicate the use of some primary metals like gold, silver, copper and iron and their alloys including bronze and brass. Joshi (1993) and Dixit (1993) have quoted the selective use of these metals even for serving food, vegetables and fruits and the recommendations for the storage of cooked food etc. to avoid their surface interactions. In Rasaratnasamuccaya, gold, silver, copper and iron have been mentioned as pure metals, lead and tin as puti Jauha ie, of lower grade and brass and bronze as mixed metal or alloys. In a recent study conducted by World Health Organization (WHO) during 1991-92 and published in Copper topic, it has been concluded that a daily consumption of about 3.5 to 4.5 mg. of copper is essential for healthy functioning of vital organs like heart and lungs etc. Ever since the discovery of metals viz. Au, Ag, Cu Fe and Pb and their alloys, one of their main use was to produce cooking and serving utensils. Thus the food cooked in copper, bronze, brass or iron utensils assimilated small doses of these elements and helped in the maintenance of health. From 7th century BC to 7 century AD, their use as medicine was restricted to their metallic foil, powder or naturally occurring minerals and gems. Mitra and Sayakhara (1993) have published a detailed account of Metals and Minerals available in ancient India. Fig. (1) shows few of the surgical tools designed by Susruta. He has given a detailed description of the process of manufacture of these tools and their desirable properties. For example, while describing the method of shaping the surgical knife from ‘Tikspa Loha’ (high carbon steel) he has given a detailed account of the hardening and tempering treatments so that the knife obtains razor sharp edge capable of dividing human hair into two halves longitudinally.USE OF METALS {N AYURVEDIC MEDICINE. 3 Fig. I Sketch of some of the surgical instruments designed by Susruta. Having observed the effect of pure metals and their minerals on the human health, the refinement of the medical preparation had already begun around 7 century AD. Some of the minerals or the associated metallic chemicals might have shown toxic effect and lead to the elaborate processing details described in the ancient ayurvedic text regarding the metal extraction and preparation of their bhasra. Siddha Nagarjuna has been called the father of the preparation of bhasma ug alchemical knowledge developed in (8-9) century AD. The methodology « preparation of 4yurvedic medicines is known as ‘Rasa Sastra’ and it includes the extraction of metals from their minerals, their purification and conversion into digestible metallic bhasma. The word Rasa connotes numerous things including mercury, which has been extensively used in the preparation of ayurvedic drugs and bhasma. By the end of 15th century the technology of Preparation of potent metallic bhasma was fully developed and the use of other metals i.e. zinc, tin, arsenic, antimony had also begun. The details of these processes have been recorded and published in many books viz. Rasaratnasamuccaya (8-15 century AD), Rasdmnava, Rasendracidamani (12-13 century AD), Ayurvedprakash (17 century AD) and Rasatarangini (20 century AD). The process of manufacturing metallic bhasma consists of three main operations viz.4 INDIAN JOURNAL OF HISTORY OF SCIENCE (1) satvapatana (metal extraction) (2) bhasmikarana (conversion to nontoxic chemical form) (3) other processes i.e. conversion to metallic chemicals using sublimation, distillation etc. The processing of minerals, metals and gems can be classified into the following steps; (i) selection and control of raw material. (ii) sodhana or purification. (iii) marana or conversion to nontoxic fine powder. (iv) mardan or bhavana-preparation of intermediate mixture or paste. (v) Irana or putapak-alchemical reactions at high temperature. These processes are common to all the above mentioned manufacturing processes viz, satvapatana, bhasmikarana and other process like preparation of medicinal compound by sublimation and condensation etc. The specific operations carried out at cach steps for few metals are given below and the details of the process varies from metal to metal and the type of the medicine to be prepared. SeLection aND Convrot or Raw MATERIAL This involves the choice of proper starting materials or metal and other organic, inorganic substances and herbs required for the production of the desired drug. In ancient times mostly pure metals like copper, iron, zinc and lead etc. were produced from their rich minerals following the commercial procesess or special method of satvaoatana. Today mostly commercially available metals and alloys are used, but for the preparation of high quality drugs, metals extracted from some particular mineral using savapalana process is used. Extraction of iron from Biotite is one such example. In many cases the collection of herbs is specified at particular time of the year when its specific part ie. leaves, trunk, bark or root is supposed to contain special elements and organic compound. Similar precaution is taken in the selection of rich minerals and other ingredients.USE OF METALS IN AYURVEDIC MEDICINE 3 SopHana The process of purification of the‘starting metal consists of either treatment of the metal pieces with specific organic juice mixture (herbal extract) at room temperature or in Sun, or by thermal cycling of heating the metal to a specified temperature and quenching it in one or more liquids such as lime water, urine, oil, herbal extract etc. One of the major changes taking place during this process is development of thermal cracks in the metal pieces which make it amenable to grinding into fine powder. The second change is that the metallic surface reacts with the ingredients of the quenching liquid and get converted into organometallic or inorganic compounds. The process efficiency is increased by intermediate trituration after each thermal cycle. Thus an intermediate product is formed in the form of fine powder which can be easily processed further to produce metallic bhasma. Also some of the unwanted elements may be forming volatile compound and getting removed or forming some other compound to get removed during subsequent treatment. This processing is called Sodhana because it is supposed to produce nontoxic metallic compound is not yet known. MARANA This process mainly consists of the conversion of nontoxic metallic compound into inorganic or organometallic forms which could improve the rate of reaction during pufa or jardna. This is achieved by mixing with herbal drugs and slow heating like bhavana or carrying out high temperature treatment like calcination and roasting with lemon juice etc. This also helps in the formation of nontoxic metal powder or its compound. MarDAN During this treatment the metallic powder or compound (produced after aforementioned treatment) is mixed with more herbal drugs or elements like sulphur, mercury etc. or inorganic compounds like borax, lime etc. and triturated to mix it thoroughly and prepare final charge for /arana or pufapak. Some times this process is associated with slow chemical reaction of S to convert Hg into HgS or Ag into Ag,S to enhance the process of formation of red HgS compound (Makarddhvaja). The process also includes conversion of the charge mix into pellet or briquettes and their drying in Sun rays.6 INDIAN JOURNAL OF HISTORY OF SCIENCE JARaNA Or Putapak This process consists of giving final heating to extract the metal during Satvapdtana ot the conversion of the metal into final product or bhasma. Many a times the process is repeated after mixing some organic extracts, trituration and formation of pellets. One thermal cycling of drug is known as ‘puta’ and the process as ‘pufapaka, and the number of such putas to be given are mentioned for each drug Some of the case studies to show the efficacy of these processing steps are described below for all the three processes viz. Satvapatana, Bhasmikdrana and manufacture of some drugs by sublimation. 1. SaTVAPATANA The meaning of this terms is separation of safva or pure metal during smelting process. The examples described here are extraction of iron from Biotite and copper from chalcopyrite. (i) Extraction of Iron from Biotite-Biotite or black mica contains about 19.8% Fe, 37.8% A1,O,, 34.5% SiO., 6.4% MgO, 0.9% CaO and 0.4% TiO,. From this mineral about 50% of the iron is extracted and it is considered to be the best for the product of /oha bhasma. In Rasaratnasamuccaya the process has been described as :- padamsa tankanopetam musli rasa marditam rundhyat kosthyam drdham dhamatam satvapatanam bhavedyahanam (RR. 5.2/26) Jha (1990) has studied and investigated this process in great detail and successfully extracted iron following the process mentioned in the aforementioned sloka. The flowsheet of the process developed by him is given in Fig. 2. In principle, calcined and ground Biotite powder was mixed with Musi (herbal root) and borax in the ratio of 4:1:1 and made into pellet, which was dried in Sun and then smelted in a crucible raising the temperature first to 1000'C for three hours and then to 1450°C to separate liquid iron from FeO rich molten slag. Fig. 3 shows different stages of the preparation of Biotite for melting. The determination of the first stage heating temperature was done on the basis of the thermogravimetric study and the curves obtained at 900 to 1000°C are shown in Fig. 4. During the smelting studies the proportion of Mus/i (reductant) and Borax (flux) were varied but maximum metal extraction was obtained only with the proportion mentioned in the literature (i.e. 4:1:1). Rasaratnasamuccaya has also mentioned the classification of Fe-C alloys, as shown in Fig. 5, into three major groups viz. kanta loha, tiksna loha and munda loha. This afd itsUSE OF METALS IN AYURVEDIC MEDICINE 7 subclassification are based on the magnetic properties and the end use. The details of the process of extraction of iron from Biotite has been published by Jha et al. (1989). SATVAPATANA OF IRON FROM BIOTITE (C.B. JHA 1990) Raw Material = - 4 Sodhan - 1 Tirturation - 4 Pellctisation - Satvapatana = - L Product Biotite, Musli & Borax Calcination of Biotite & quenching in cow's urine -150p with 25% Musli & 25% Borax with water & Sun drying smelting in a crucible at 1450-1500 C (i) Satva Fe-Calloy Gi) FeO rich slag Fig. 2 Flowsheet for the extraction of iron from Biotite ay per process mentioned in Rasa Samucca, Fig. 3 Different stages of treatment of Biotite during extraction of iron.8 INDIAN JOURNAL OF HISTORY OF SCIENCE 30 SAMPLE — BIOTITE MIXTURE PELLET PELLET SIZE - 15mm 25 1.W.= INITIAL WEIGHT Ww, 950°C (2.5859) _ 900°C (2.8059) “1000 (2.4909) ~ x a ° ‘%e WEIGHT LOSS s 10 20 30 40 50 60 Fig. 4 Weight loss during isothermal reduction of Biotite mixture pellet at 900, 950 and 1000°C Kinds of Iron Proportion (Loha) Bhrimaka Very soft magnetic iron '- Cumbaka Mildly magnetic, stricks to iron pieces Kanta Loha- + Karsaka It oan attract iron objects {Soft tron) - Dravaka Very strong magnetic iron Romaka Permanent magnet, develops strong magnetic field arround it. It may be Ele mukh, or Sarva Mukh Khara Develops good cutting edge breaks on bending - Sara Softor iron and it has fibrous fracture - Hrnnata Hard and tough has fibrous fracture Tikshna Loa - Travaratta Develops good cutting edge. (Carbon Steel) ~ Vajra Has good hardening and tempering property has bluish colour and hard cutting edge Kala Developes hard cutting edge after blue tempering, Mrdu Soft britle iron may be grey cast iron. Has low melting point. Munda Loha —- Kunda Mottled grey iron (Cast Iron) Kadara White cast iron Fig. 5 Classification of Fe-C alloys and their properties as given in Rasa Ratna Samucca. (8-12 C.A.D.)USE OF METALS IN AYURVEDIC MEDICINE 9 (ii) Extraction of Copper from Chalcopyrite-Chalcopyrite is a mixed ore of CuS and FeS, and the process of extraction of copper from this mineral has been known since the early copper age. But in the Ayurvedic text a very simple method has been mentioned and this process has also been studied by Jha (1990), taking the help of thermogravimetric studies. In principle the process consists of roasting the rich sulphide mineral to remove sulphur and convert copper sulphide into copper oxide (CuO) and subsequently into copper citrate by the addition of lemon juice during the roasting operation. During this process, copper and iron both get converted into citrates and on heating to 900°C, copper citrate gets decomposed and copper sponge mixed with the slag. In this process also borax is used as flux. On further heating to 1200 to 1250"C the gangue material form iron rich slag and pure copper metal separates into a button. The complete flowsheet of this process is given in Fig. 6 EXTRACTION OF COPPER FROM CHALCOPYRITE (C.B. JHA 1990) Chalcopyrite L Crashing & Grinding L Sodhan (with lime juice at 750 C) 4 Griding in red hot condition (-150p ) 4 Roasting (Fe, Cu Oxides & Citrates) 4 Trituration (with lemon juice & Borax) 4 Pelletisation (15mm), Sun drying L Smelting (1200-1250 C) 4 Satva (Copper Alloy) Slag (Iron rich) Fig. 6 Flowsheet for the extraction of copper from chalcopyrite.10 INDIAN JOURNAL OF HISTORY OF SCIENCE By controlling the reduction parameters it is also possible to produce Cu-Fe alloy, which is considered an excellent material for the production of bhasma, Similar very simple mineral processing techniques have been mentioned in the Ayurvedic text to extract metals suitable for the preparation of bhasma 2, BHASMIKARANA For the preparation of metallic bhasma the processing technology is much more complex than those used for satvapatana. The metal pieces have to go through a number of steps and processes by cyclic heating and quenching in different liquids to obtain purified and nontoxic metal powder. During the thermal cycling microcracks have been found to be developed at the grain boundaries and on certain lattice plains, and the intermittent trituration helps in the formation of fine powder and bringing its surface in intimate contact with the herbal drug ctc. Thus a large surface area in exposed to interact and to produce organometallic solid compounds as the intermittent product and final production of the bhasma. This microfine medicinal product has easy digestive power and quick reaction with the bile juices. In one case microfine Fe,O,, Fe,O, mixed mincral could be processed into lauha bhasma by giving only one puta. (i) Svarna bhasma - During the process of production of gold bhasma this highly ductile metal is converted into fine powder as seen from the microstructure given in Fig. 7. Since gold is a noble metal it does not get converted into any inorganic compound but when taken as a medicine the fine gold particles react with the organic bile juices and form organometallic compounds. Parish (1992) has published the structure of some of the gold compounds used in medicine (ii) Lauha bhasma - In ancient times cither naturally occurring iron oxide or bhasma prepared from wrought iron i.e. iron produced by satvapatana, was used for medicinal purposes. In recent years many compounds of iron have been used in modern medicine to develop body strength but, in ayurveda lauha bhasma is still in use, but the starting material i.e. wrought iron has been replaced by steel scrap. Recently Thirutharu (1991) has conducted a systematic study on the preparation of /auha bhasma starting from mild stecl turnings. The flowsheet of the process is given in Fig. 8. It consists of an elaborate process of sodhana by quenching the raw material in six different liquids from a temperature of 850°C and repeated each process seven times. Due to quenching, microcracks were developed in the iron pieces and it could be easily converted into fine powder by itermittent trituration after each quenching. During repeated heating, the iron surface got oxidized and the layer of this chemical compound was removed during trituration, thus exposing fresh surface for the chemical reaction.USE OF METALS IN AYURVEDIC MEDICINE iW Fig. 7 Microstructure of gold bhasma. It shows microfine particles of gold without any formation of surface compound. (Polished and unetched. Mag X 100) PREPARATION OF LOH BHASMA (G.A. THIRUTHARU 1991) Raw Material L Sodhan | Tirturation Marana Sthalipaka L Putapaka Product Mild steel tumings Heated to 850 C & quenched 7 times in olium Sesam, Butter Milk, Cow’s Urine, Sour Gruel, Black gram decoction and triphala respectively -Intermidiate grinding to convert into black powder Bhanu Pak-Reacted with Triphala 21 times in Sun rays Boiling in Triphala till dry (pink coloured powder) @ — Ardhagajaputa-4 times at 600 C Gi) Trituration-cach time in Triphala kasiya (iii) Kapotputa-at 550 to 600 C Iron Oxide containing Fe, Fe,0,, Fe,0, Fig. 8 Flowsheet for the preparation of Loha bhasma from mild steel turnings.12 INDIAN JOURNAL OF HISTORY OF SCIENCE, This was followed by m4rana i.e. slow reaction between iron powder and alkaline extract of friphala in Sun rays, This takes about one to two months or more: to convert almost all the iron into black coloured organometallic compounds. Finally the iron compound was boiled in iriphala extract 10 produce ‘a pink coloured compound, This was subjected to a number of puta at 600°C to produce a mixture of Fe-Fe,O, and Fe,O,, Fig. 9 gives a microphotograph of the oxidized iron particle. This shows iron core at the centre which gradually gels oxidized to Fe,O, on the surface following the topochemical process of oxidation of iron via Fe ~> FeO + Fe, 0, > Fe,0,. Fig. 9 Show the topochemical nature of oxidati , (outer layer) - os is® ie Fig. 10 Microstructure of Loha bhasma after 9th puta. This shows the presence of metallic iron particles coated with oxide layer. The large circular particle is scmifused mass formed duc to the fusion of ash from organic herbs and iron oxide.USE OF METALS IN AYURVEDIC MEDICINE 13 Before giving the next pusa every time about 250 grams of the friphala was added to the lauha bhasma during trituration. The microstructure of the product after ninth pufa is shown in Fig. 10. In this figure the presence of Fe metal can be easily seen at the core of the bhasma particle and this was confirmed by the spectrophotometric studies.In the ayurvedic literature lauha bhasma prepared after 1000 puta has been said to be more potent and it may be expected to be consisting of almost pure iron particles resulting due to the reduction of the oxides by carbon from triphala extract. The large spherical particles scen in this picture is the fused particles formed due to the interaction of iron oxide and the ashes, (iii) Copper bhasma - Copper bhasma was produced by Das (1989) following the flowsheet given in Fig. 11 and the progress of the conversion of metallic copper into bhasma was studied under metallurgical microscope. After sodhana by repeated quenching into various liquids from 850°C and trituration, an intermediate product was prepared by trituration with Hg.S and lemon juice. During this process first black HgS is produced by interaction between purificd He and S and then it is reacted with copper particle in presence of lemon juice. This mixture was pelletised. Sun dried and then given pufa in Damaruyantra for 8 hours. During this process copper was probably converted into sulphide and He metal was collected as distillate. Ths CuS residue was taken out from the yantra and repelletised and then subjected to gradual oxidation by giving 20 “Kapota puta’. In this case also the progressive information of copper oxide on the metallic copper particle was seen. (iv) Zine bhasma - Rath (1991) has prepared zine bhasma following the conventional procedure given in the flowsheet shown in Fig. 12 and he has compared the results obtained by giving conventional Varahuputa and heating in electric muffle furnace. In this process the zinc metal was melted (450°C) and then poured in lime water for sodhana. This quenching treatment caused development of microcracks at the grain boundary of the metal pieces and also separation of some compound or pin hole porisity at certain structural planes (may be widmdinnstatten planes) as seen in Fig. 13. This helped in the fragmentization of the metal pieces during trituration, For jaraga hot grinding was done at 600°C along with the addition of apamarga paftcanga and the fine powder was sieved to 150- size. This powder was given Bhavana (low temperature heating with Ghytakumari extract and pelletised. After Sun drying of the pellets one half was given seven puta in Varahaputa furnace and the other half was heated inan aerated muffle furnace at 650°C. On visual examination it was found that while the colour of the pellets fired in vardhapufa was brownish, the pellets fired in mufle furnace resulted into white zine oxide. This difference may14 INDIAN JOURNAL OF HISTORY OF SCIENCE PRODUCTION OF COPPER BHASMA (B. DAS 1989) Pure Copper + Sodhana (Heated to 850C & quenched 7 times in Til oil, Takra, cows urine, kanji and kulattha Kasaya) L Marana (-180p triturated with Hg, S & lemon juice) 1 Pelletisation (kajjali-HgS with herbs, and Sun dried) 4 Puja Paka (8 hours in Damaru Yantra) L eee Copper Intermediate Product Hg Concentratic L Pelletised (CuS with lemon juice and Sun Dried) L Kukut Puta (20 times) L Tamra Bhasma (Copper Oxide) Fig. 11 Flowsheet for the preparation of copper bhasma, be because during Varahapufa the maximum temperature attained is approximately 850°C, which may cause oxidation of any iron present in the pellets and give brownish colour. In this case also the metallographic examination of the particles showed increase in metallic zinc with increase in the oumber of putas. This effect may be due to the intermittent addition on the organic extract of Ghrtakumari. The Ayurvedic text is not very clear about the presence of inetallic particles in the bhasma and its therapeutic effect, but a number of visual and alchemicalUSE OF METALS IN AYURVEDIC MEDICINE. 15 PRODUCTION OF ZINC BHASMA (C. RATH 1991) Zine Pieces Lt Sodhana (7 times melting at 450°C and quenching in lime water) Jarana (Grinding with apamarse Panchanga at 600°C) ae (-150p) Bhavana (Trituration with Ghritakumari extract) ao (Sun drying) Puta Paka aaa 7 times) Yashada Bhasma (An oxide of Zinc) Fig. 12 Flowsheet for the preparation of zinc bhasmna.'” Fig. 13 microstructure of zinc metal after Shodhan. It shows formation of intergranular cracks and precipitation of some compound on cleavage planes. (etched, Mag X 200).16 INDIAN JOURNAL OF HISTORY OF SCIENCE tests have been mentioned to test the quality of the bhasma before its use. The most common test is known as Nirutha test. During the present studies the quality of the drug produced was tested using modern chemical analysis techniques, such as spectrophotometer, Atomic absorption spectrophotometer, XRD, XRF and Auger. This helped in the identification of the chemical compound formed during the preparation of bhasma as well as determined the presence of trace elements getting added from the organic sources. 3. SUBLIMATION AND DISTILLATION METHODS In preparation of bhasma using sublimation and distillation method Hg, $ and As are gencrally mixed with the metal to be converted in bhasma and then either Damaru or Kupipaka yantra is used for further processing of the mixture. By these methods Makaradhvaja and Nagabhasma have been prepared and tested. Naga bhasma - Nagaraja (1993) has done detailed studies on the preparation bhasma (PbS) and clinical studies on its effect in the management of es Mellitus. Fig. 14 gives the flowsheet for the preparation of lead bhasma using Kupipaka yantra. In this process purified lead was melted and mixed with purified mercury and immediately triturated in Kha/wa yantra. This was followed by trituration with purified sulphur and realgar for a week, daily for three hours. This powder was filled in the Kupi bottle and subjected to programmed heating in a muffle furnace instead of the conventional Va/uka yantra (Sand bath). Fig. 15 shows a typical time-temperature curve for heating of the Kupipaka yantra and (eevra (fast) reaching a maximum temperature of 600-650°C. The details of this yantra is given later. The total time taken in Kupipaka was 48 hours. On cooling the Kupi (bottle), Manikya rasa (AgS. As,S,) was found deposited at the neck and Naga bhasma (PbS) was formed as bottom residue. In the other Naga bhasma was prepared using Varahaputa and Fig. 16 shows the microstructure of lead bhasma obtained after sixty puta. This confirms that during this process mainly lead sulphide is produced as final bhasma. The production of PbS compound has been confirmed by Auger analysis. EQuipMENT AND TECHNOLOGY In order to carry out the above mentioned extraction and bhasmikarana processes the ancient Ayurvedacharyas had designed a number of equipments and furnaces ete. known as ‘yantras’ and also developed many refined techniquesUSE OF METALS IN AYURVEDIC MEDICINE 17 PREPARATION OF NAGA BHASMA BY KUPIPAKA TECHNIQUE (T.N. NAGARAJA 1993) Lead Metal 4 Sodhana - (With Cumodaka) 4 1. Trituration (Molten Lead With Hg) 4 2. Trituration - (in Solid State With sulphur & Realgar) 4 Putapaka (In kupipaka yantra, programmed Heating for 48 Hrs.) Product 1. Concentratre (Manikya-Rasa, HgS. As,S,) 2. Residue (Naga Bhasma, Pbs) Fig. 14 Flowsheet for the preparation of Naga (lead) bhasma by Kupipaka method Temperature in °C 800; 69 600 600 Tivragni 400) madhyamagni 300 300300 300 200 180/" 150 150 150 150 150 150 150 150 a a Se Mriduagni 0 100 200 300 400 500 Duration in minutes Fig. 15 Heating schedule for the electric kupipaka furnace.18 INDIAN JOURNAL OF HISTORY OF SCIENCE lo produce nontoxic end-product suitable for therapeutic use. Some of the iwchnological skills and equipment are described below : (i) Mineral identification and processing - In ancient times as the process of chemical analysis and other sophisticated equipment for the mineral identification were not developed the minerals and gems were identified by visual examination of their physical properties like, colour, lustre, light refraction and streak ete These minerals and gems were collected from specific places as identified by the skilled workers. Fig. 16 Shows microstructure of lead bhasma (PbS) ‘after 60 puta (etched 5% Nital, Mag. X 500). In the absence of mineral processing technology mostly hand picked pure minerals and gems were used for the preparation of medicine. Some of the mineral processing methods known were washing, crushing, grinding and heavy media separation using panning process. Metals found in native forms such as gold and copper were either hand picked as nuggets or separated from the associated sand and clay by panning process which is prevalent even today in some form or other. For mining of minerals the use of fire setting and quenching technique i.e. thermal cracking has becn mentioned in many texts. The same principle has been used for fragmentization and grinding the minerals and metals into fine powder. For the purpose of crushing and grinding a variety of mortars and pestles made from agate, granite, porcelain and iron have been usedUSE OF METALS IN AYURVEDIC MEDICINE 19 Thermal cracks are generally developed during the processes of sodhana or marana by heating the material to a specific temperature (300 to 800°C) and then quenching into a number of liquids and/or herbal extracts etc. In some cases like lead or zinc the metal is heated to the molten state and then poured carefully in the liquid bath. This helped in purification of the minerals and metals by chemical reaction with the solution and at the same time granulated the material by developing intergranular and cleavaged cracks. The microphotograph shown in Fig. 13 clearly shows the intergranular cracks and pre same compound or pinhole gas porosity developed on Widmiinnstitten planes of zinc metal. This is followeti by grinding to separate the cracked particles This process has been found effective even to convert highly ductile metals like gold, silver or lead into microfine particles. By the process of intermittent grinding any chemical layer formed on the particle surface is exposed for further chemical reaction during the next heating and quenching cycle. As seen from the flowsheets given in Figs. 12 and 14 some time these processes are to be repeated 30 to 50 times and in a number of solutions to produce the product of the desired fineness. (ii) Heating System - The ancient energy source could be divided into two major groups viz. Sun rays and heat obtained by combustion of dried cowdung cakes or wood and charcoal. For slow rate of heating and drying below 50°C, generally Sun rays were used, but for faster heating to higher temperature furnaces using combustion of cowdung ‘cakes or wood and charcoal with natural or forced draft were used. In the absence of temperature measuring devices the desired heating rate, the maximum temperature attained and maintained as well as the subsequent cooling rate of the material were achieved by the judicious selection of the fuel and control of its combustion intensity. Thus most of these ancient furnaces worked on total energy control system as it will become obvious from the study of the furnaces using cowdung cakes as fuel. These are known as ‘pufa’ furnaces and their classification as well as approximate weight of the dried cowdung cakes used in each furnace is given in Table I. Fig. 17 shows a photograph of Gajaputa and Argdhagajaputa furnaces and time-temperature curves measured by thermocouple for some of these puta furnaces is given in Fig. 18. From this figure it can be seen that the initial rate of heating of material in a}l the furnaces is almost same i.e. 30°C/min., and the maximum temperature attained (650+30°C) is also consistent. In the case of ‘Kapotapuja” where the firing is done in open space, the duration for which the temperature remained constant is 30 minutes and in other cases it increases upto 60 minutes. The maximum temperature recorded in a refractory lined furnace is 1000°C. The cooling rate of the material in all the cases is also constant except in the20 INDIAN JOURNAL OF HISTORY OF SCIENCE case of Kapotaputa. Thus we find that the rate of energy transfer and the total energy input per ‘pufa’ (heating cycle) is constant for cach furnace and it is repetitive within certain range. The total heat energy required for the preparation of any medicine is specified in terms of the type of puta furnace to be used and the number of puta to be given. For example, for the preparation of sas pula Nagabhasma (lead bhasma) about 20 Ardhagajaputa and 40 Varahpula have been specified, and during its preparation Nagaraja (1993) has found that even after 55 pufa the complete conversion of lead into its bhasma was not complete and only after 60 puta the desired medicine could be produced. Table-I Classification of Puta Furnaces Using Dried Cowdung Cakes As Fuel S.N. Type of Furnace Size In mm Number of Approx. Cowdung Cakes Weight kg 1. Mahaputa 11250x11250x11250 2000 45 2. Gajaputa 5625x5625x5625 1000 22 3. Varhaputa _ 800 18 4. Ardhagajaputa 2812x2812x2812 500 ul 5. Kukutputa - 32-40 4 6. Kapotputa — 8 tl Fig. 17 Photograph of Gajaputa and Ardhagajaputa furnace fitted with thermocoupleUSE OF METALS IN AYURVEDIC MEDICINE 2 800 700 1- MAHA PUTA | 600 2- GAJA PUTA @ & 3~ VARAHA PUTA © ° uy 500} 4 — KAPOTA PUTA & « = & 400 uo a = a * 300 200] ® 100 20 60 100 160 200 240 280 TIME IN) MINGITE® ———m Fig. 18 Time-temperature curves for the heating rate in various puta furnaces fired on cowdung cakes Another furnace capable of attaining 1500°C ie. Arigara Kosthi or crucible furnace is shown in Fig. 19. The line diagram of this furnace has been prepared as per its description in Rasaratnasamuccaya. In this furnace charcoal is burnt under forced draft ie. air supplied by two foot operated bellows. In a similar manner a number of other heating furnaces and systems like Ba/uka yantra or sand bath, etc. have been described in the ayurvedic text (iii) Crucibles and other apparatus - In order to heat the metals and other materials to high temperature in ‘the above mentioned furnaces and heating Systems a varicty of earthen pots, saucers etc. and crucibles made from refractoryn INDIAN JOURNAL OF HISTORY OF SCIENCE FURNACE WALL i fi Poy ch CSG C74 i Fig. 19 Schematic diagram of ‘Angara Kosthi’ i.e, Charcoal fired crucible furnace capable of attaining 1500°C.USE OF METALS IN AYURVEDIC MEDICINE, 33 clay are used. Rao (1989) and Bronson (1986) have described in detail the material and method of manufacturing a variety of crucibles used for sarvapatan, phasmikarana and other alchemical processes. Lowe et al. (1990) have examined the mineralogical constituent of crucibles used for melting ‘wootz’ steel, which could be heated to 1500°C. These fired crucibles have been found to be made of graphitised mullite containing some small prills of iron embedded in the crucible wall. These iron prills might have got formed by the in situ reduction of iron oxide, present in the clay or due {o the penetration of molten steel in the wall. Fig. 20 shows a picture of the ancient crucible preserved in Madras National Mricenm Fig, 20 Photograph of two shapes of ancient crucibles preserved ut Madras National Museum. Some of the special apparatus used in the manufacture of ayurvedic medicines are : (a) Damaru yantra (b) Patala yantra (c) Kupipaka yantra Fig. 21 shows a picture of the Damaru yantra and Patala yantra. The use of these has been described in detail by Ray (1956). Damaru yantra is heated from the bottom to sublime or evaporate the volatile product formed in the24 INDIAN JOURNAL OF HISTORY OF SCIENCE. charge kept in the bottom pot which is deposited on the inner side of the top cover of this closed system, maintained at low temperature by covering it with wet cloth. The product is taken out after separating the two pots and then scrapping the product deposited inside the upper pot. In Pata/a yantra the heating is done from the top and the liquified product is collected in the bottom pot maintained at lower temperature. The zinc extraction retorts used at Zawar around 200 BC to 1100 AD and described by Craddock (1985) et al. has been designed on the same principle. Fig. 21 Schematic drawing of Damaru and Patal yantra, Kupipika yantra, shown in Fig. 22 is a modern version od Damaru yantra and it is made by wrapping cloth on a glass bottle (beer bottle), coating it with yellow refractory clay and drying in Sun. This apparatus is also used for collecting volatile products formed by interaction of metals with Hg, As or Sulphur. In this yantra the charge is put in the bottom of the refractory lined bottle and then the bottle is either heated in a sand bath (Baluka yantra) as shown in Fig. 22 or using a vertical muffle furnace. In both the cases the top 1/3 part of the bottle is kept outside the heating source. When the- charge begins to get heated at first water vapour and other volatile materials present in the herbs come out from the bottle and then, if sulphur has been used, SO, begins to come out. At this stage the bottle mouth is closed tightly with a refractory plug. Now the volatile sulphide such as As,S, or HgS get volatilisedUSE OF METALS IN AYURVEDIC MEDICINE: 25 STOPPER CLOTH +CLAY LINING GLASS BOTTLE ee SRND BATH. 8300 - 600°C. ; ae METAL CONTAINER: ‘ KUPI PAKA YANTRA Fig. 22 Schematic drawing of Kupipaka yantra fixed in Baluka yantra (sand bath).26 INDIAN JOURNAL OF HISTORY OF SCIENCE and condensed at the bottle’s neck and the other product such as lead sulphide (refer Fig. 15) remain at the bottom. After the processing is over, the bottle is carefully cut from the centre taking precaution for not disturbing the deposits or contaminating them with glass particles. In this case both the top as well as bottom products are used as medicine. Processes IN PHysicaL CHEMISTRY The process of satvapajana and bhasmikarana employs many of the alchemical principles and observations. In these processes Hg has been used extensively to bring about the desired chemical changes in the metals. This metal has been called Rasa in the Ayurvedic text and the treatise of medical preparation is known as Rasa sastra. The other element used freely is sulphur. Today high chemical reactivity of both these elements is known and from the study of the processes reported in this paper as well as those mentioned in the ayurvedic text it seems that the Ayurvedic doctors were conscious of their properties. In many processes mercury alone has been used to amalgamate with the metals and form an intermediate product, which could increase the surface reactivity of the metal with other chemicals and herbs. It has been also used along with sulphur to facilitate formation of respective sulphide. In these cases mercury and sulphur have acted as promoters for the final chemical reaction. Mercury itself being in liquid state, it does not readily react with sulphur powder to form HgS (black oxide) but when Hg is amalgamated with gold or silver it gets converted into semisolid mass and easily reacts with sulphur to form black sulphide HgS as well as Ag,S (kajja/i) and thus it promotes the high temperature reaction with other metals. During the manufacture of Makaradhavaja (red HgS) by distillation in Kupi yantra HgS gets deposited at the neck of the bottle and all the gold and silver remain at the bottom and used as gold or silver bhasma. In other cases mercury is obtained as distillate and the metal sulphide is converted into oxide during subsequent treatment. Most of the other chemical reactions involve heterogencous kinetics i.e. reaction betwen solid-gas or solid-liquid and it is known that the rate of such reactions is proportional to the interfacial area. During such reactions, at first a surface layer of the chemical is readily formed (chemical rate controlled) and afterwards the rate of reaction becomes diffusion, rate controlled and slow. The ancient ayurvedic drug manufacturers were conscious of these facts and overcame this problem firstly by increasing the primary surface area and secondly by removing the chemical layer formed on the metal particles and thus exposingUSE OF METALS IN AYURVEDIC MEDICINE 27 new metallic surface. These conditions were achieved by thermal cracking of the metal particles and intermittent grinding or trituration with some drugs required for further processing. In solid-solid reaction as explained earlier, extensive trituration increased the chemical rate kinetics. The exact control of the drug composition was achieved by controlling the proportion of various drugs and minerals added to the charge during processing and the type as well as number of pufas given to the mixture. The final product was judged by visual examination, taste and special tests described for each case. During the modern studies of metallic drug preparation extensive use’ of chemical analysis, XRF and XRD analysis. Auger study and optical as well as scanning electron microscopic studies have made it possible to gain better understanding of the ancient processes identify the nature of the metallic compound formed and used as drug and also improve their quality control procedures. ConcLusions In conclusion it can be said that : 1. The necessity and effect of metals on human health was recognised as early as 7th century BC. 2. Around 7th century AD, the manufacture of nontoxic drugs from the metals like gold, silver, copper, iron had begun and the processes were improved with the increasing understanding of the alchemical processes. 3. Between 8th and 16th century AD many new processes of Satvdpatana and bhasma preparation were developed by their own tools, yantras and puta furnaces for the conversion of metals into drugs. 4. The modern analysis of these processes confirm the high level of understanding of the physico-chemical principles and the skill achieved at an early date. REFERENCES AND Notes Ayurveda Prakash, Madhava Upadhyay, Chaukhamba Vidya Bhawa, Vara Bronson B. Archacomateriels, 1, 1, p. 14 1986. Caraka Sambith, Sahitya Pandurange Hiranya Sager Press, Bombay. 1941.28 INDIAN JOURNAL OF HISTORY OF SCIENCE, Journal of Indian Copper Development Centre, Calcutta 16, (4) and 17(3), 1991 & 1992, Craddock P.T., Freestone C, Gurjar L.K., Hegde K.T.M. and Sonowane V.H- The Mining Magazines, p. 45. Jan, 1985 Dax B. Metallographic study of metallic bhasma, M.D. Thesis, B.H.U., Varanasi, 1989. Dixit S.K. Use of Metals in Ancient Medicine, Swadeshi Vigyan Karyashala, Varanasi, 1-3 Oct. 1993. Jha, C.8., Joshi D, Prakash B. ‘Metal extraction in Ayurvedic System of Medicine’, Bul. Metals Museum 14, p. 17. Dee. 1989. Jha C.B. Study of Satvapatana with spectal reference to Abharaka and Makshika, Ph.D thesis, B.H.U., Varanasi, 1990. Joshi D. ‘Metals and their Pharmaceuticals Processing Techniques as mentioned in Ayurveda’- Congress on Traditional Sciences and Technologies of India, Bombay, 3rd Dec. 1993. Lowe T., Merk N and Thomas G. Symp. on Materials in issues in Art and Archaeology, U.S.A. April 1990, Mitra S and Sayakhare, ‘Metals and Minerals in Ancient India." Soyvenir Volume of First National Workshop on Rasa Sastra, Varanasi 19-21 Feb. 1993. Nagaraja T.N. Phurmaceutical Study on Naga (Lewd) and its role in the Management of Madbumeha (Diabetes Mellitus), Ph.D. thesis, B.H.U., Varanasi, 1993, Parish RV. Gold Bulletin 17 (3), p. 221, 1992. Rath CR. Metallographic ani! Clinical Studies on Yasad Bhasma, M.D. thesis, B.H.U. Varanasi, 1991 Rao K.N.P. Metts News, 103), p 1. 1989. Rao, T.S. ‘Atharva Veda : An Ulterior Modern Science’. ‘Congress on Traditional Sciences and Technologies of ladia’, ® Nov, 3 Dec., Bombay, 1993 Rasdrnava Chaukhamba Amar Bharati Prakash, Varanasi, 1978. Rasaratnasamuecaya, D.A. Kulkarni Meharchand Lakshmandas, Delhi, 1969. Rasendra Cagamani, Motilal Banarsidass, Sanskrit Press, Lahore, 1932. Rasatarangini- 8. Sharma, Motilal Banarsidass, Varanasi, 1979. Ray, Priyadaranjan (Ed) ‘History of Chemistry in Ancient and Medieval India’, Indian Chem. Soc, Calcutta, 1956 “Susrute Sambita’, Chaukhumba Orientalia, Varanasi, 1980, Thirutharu GA. Determination of Free Metals in Ayurvedic Bhasma, M.D. thesis, B.H.U., Varanasi, 1991