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THE PHYSICIAN-SURGEON AL-ZAHRAWI AND THE NATURAL ORIGINS AND MANUFACTURE OF DRUGS

Prof. Dr. Sami Khalaf Hamarneh
and Mrs. Nazha Tawfiq Hamarneh.
U.S.A.

PART TWO: DISCUSSION AND EVALUATION OF THE 28th TREATISE

The book of al-Zahrawi al-Tasrif Uman Ajiza an al-Talif was considered as a medico-pharmaceutical encyclopedia, and one of the greatest of its time. In spite of its popularity as a whole, however, historians of the healing arts did not give due credit to the twentyeighth treatise, nor the evaluation it deserves. This is, therefore, an attempt to discuss its content and remedial virtues, as relevant to manufacturing and therapy. Indeed the treatise, in three sections, discusses the three natural kingdoms of Materia medica: minerals, vegetables and animals and their products. Because of lack of space, only ligh lights and important examples will be reviewed briefly, hoping for a more comprehensive study at a ater date. It is sufficient now to state, the author's approach, methodology and

procedures will be followed, beginning with examples on preparing, washing, roasting, burning and storing of some mineral products.  Quotations, and exposition, as well as free interline translations of the original texts will be done, in keeping up the meaning clear, but not necessarily verbose or redundant.

Litharge and the Lead Compounds: In the first section of the twenty-eighth treatise, we begin by considering the litharge and the procedures of its isolation, washing and the physical and chemical treatment. The fused, semi crystalline or amorphous lead monoxide = Pbo, is the result of incomplete fusing of the oxide (mainly orange-yellow in color) known in al-Andalus as the golden (al-dhahabi).

If mixed with ointment it turns whitish, and if "silvery litharge", it turns dark black. For washing it white, "take the best, heavy and pure litharge, pound in a mortar and put in a new pot, cover with water and add a handful of wheat and barley. Transfer all into a fine, thin clean wollen rag, and lay inside near the edge of a casserole, and cook until the grains become tendor. Then lift all in a large vessel, throwaway the grains, wash well, and repeatedly with strong rubbing. Take out and dry; transfer and grind into a mortar. Add hot water with continuing grinding, until the resulting powder smoothed out,dissolving in the water. Leave aside until clear, decant for a long while. At evening, repeat grinding, covering with hot water, and leave another while and decant. This is done for several days. Mix with manna and salt, cover with hot water again for the last time. Leave until it becomes white, and dries out as a powder."

For explanation, in fusing the lead by roasting the monoxide, it is thus converted into powder which is insoluble in water. By treating it with an organic matter, such as grains or sugar, it can easily dissolve. The resulting CO2, react to form the basic lead carbonate.

Galena, which is native lead sulphide = Pb S, is the principal ore of lead and it occurs in grayish black crystals. It can be prepared by using high temperature, heating in an oven or furnace with the lead.2 Indeed galena is widely distributed as an ore in many lands and often mixed with zinc sulphide. It produces considerable amount of lead. When galena is roasted, the sulphide of lead converts into lead oxide in this manner:

 2 Pb S + 3 02  ------  2 Pb 02 + S 02 then
Pb S + 2 02  Pb S O 4

The roasted ore is then mixed with coke and limestone in a blasting furnace, for the purpose of melting the lead. The formula follows:
2 Pb O + Pb S ----------- 3 Pb + S 02

Litharge is finally used in the reduction of silver, and in industry it is employed for making varnish and paints.3

Another lead salt that played an important part in the history of alchemy, pharmacy and industry is the white lead = the basic lead carbonate, 2 Pb C03 Pb (OH)2 a pigment also known as ceruse or cerussa. The author recommends the following: place one or more wide-mouthed vats or cisterns, wider at top than at bottom, into a cell or dark shed undisturbed by wind, bringing on in it manure or goats dung. Place the manure up to about half way around the vats. Inside the vats put vinegar and dregs or lees. Over to the top add some fully riped white grapes, and tightly cover with rounded sack or pack-cloth or wool. At vat's top, pierce 20 to 30 holes through which strings are suspending to hold plates of lead tied to each, measuring about 6 inches long and one digit (or finger) thick. The plates suspends 3 digits above, then have another covering sack, shut tightly, and close the door real well for about ten days. Thereafter, open and take out the plates carefully to find them covered with black ceruse in color. Return the plates, leave for similar period until all the lead transformed. Put in another batch, and so on, all winter long. Early in spring, gather all the ceruse in a vessel or pot with water, wash and recant, again and again until all turn into white, clean precipitate. Then tablets can be molded by hand, or like a cone or kneaded over a marble top or slate, and dry completely in the sun, undisturbed by wind or dust until result in a very white, bright powder that rubs soft".4

When the ceruse is roasted or burnt and powdered, it is put in a deep saucepan or earthenware, heated by fire with continuing stirring, until the powder is completely burned. Take off, leave to cool and store.

To explain, lead acetate reacts with C02 produce soft powder of ceruse. In another method, lead salt such as carbonate, reacts with ammonium carbonate to form the ceruse. The procedure was known since Theophrastup (d. 285 B.C.), followed by Dioscorides and Pliny in the first century. Al-Zahrawi and others elaborated influencing the West again. Suspending lead plates in earthenware pots with vinegar, causing fermentation. Lead acetate turns into carbonate with the aid of organic matter, resulting into white powder of ceruse, also used in paint.

Similarly cadmia (Greek Kadmeia or calamine which is native zinc carbonate, the best being from Cyprus) can be burned in a furnace, while smoke clings to the walls and are collected. "It is, therefore, known as yellow tuttie. It is formed by burned copper (the scoria). It is known in al-Andalus".

To form red lead, which is lead peroxide, Pb304, or minium, al-Zahrawi recommends the following: 'take thin plates of lead within new casserole boiler (or earthenware cooking pot) and sprinkle with sulphur one plate after another, until full. Put on fire, burn with flames, stir with an iron handle, until ashes, take off and cool".5

Verdigris: A green or greenish blue pigment resulting from the action of acetic acid on copper is known as basic copper acetate, or oxyacetate [green blue needles or scales as Cu (C2 H3 02)2, Cu (OH) 2.5 H20]. In the same manner that cerusa is described above, the author recommends the procedure for verdigris. "Take one or more vats, the top being wider than the bottom, and put in a cell filled with dung. The plates are of red copper about 1 1/2 inches wide, and 6 in. long. Mix grapes with vinegar, and close the vat tight, for ten days", the plates are then taken out, scraped and return until all copper changes into verdigris. Start a new batch once again.6

For burning the verdigris, it is recommended that some powder is put into an earthenware on fire with constant stirring. The color changes into yellow. Take down and cool. Dioscorides describes it in the Fifth Book. Al-Zahrawi improved on it, then was carried on to the West and thus continued until the modern times. The acetous fermentation by C02, precipitate and scraped gently.7

Now we turn to trioxide arsenic, As2 03. The author recommends subliming, by grinding well together with common salt, and putting in two retorts tightly closed and installed on fire for hours. "Sublimation takes place from the lower retort to the top one, take down and cool off". Collect the precipitate and fire again, until the upper retort fills the arsenic carbonate and turns into white powder. Burn in a vat, close tightly to roast over oven for five hours, changing into the red arsenic8.

Mercuric Salts: "For calcination of mercury", the author recommends "that live, pure mercury free from lead be ground with vitriol, moisten with vinegar and continue to pound until all the mercury integrated. Transfer to the two retorts, close and heat over fire". When reaction is complete, take down and cool. Open the retorts to find the powder in the upper one. Repeat until calcinated that resulted into yellow mercuric oxide.

It can also be made from mercuric chloride with sodium hydroxide giving odorless, yellow-orange precipitate, which dissolves readily in acid. By fire, it turns to red mercuric oxide. In Islam, calomel was widely known and used as non-corrosive, mercurous chloride (Hg CI) by treatment of mercurous sulphate and common salt.9

Cinnabur or vermillion was another mercuric salt known and found abundantly in al-Andalus, as red mercuric sulphide = Hg S. It is found pure in nature as an ore thus become a source for preparing mercury. "It is recommended to take one part of mercury and one part yellow sulphur put in a glazed vessel' close and place over fire, one-third full. Submerge in square-shaped oven and suspend so that two-thirds above the level". Heat gently for 12 hours, take down to cool. When the vessel is broken, vermilion is found.10

In relation to this, the author describes the lime, as a natural product found in abundance: in white marbles, egg shells, and shells or marine animals. "To wash lime, one first ground and pass it through sieve, transfer into a clean pot, cover it with water, leave for hours with occasional stirring. After set for a while and decant. Do seven times as such until well washed (calx, lime or quicklime)", with equal
 parts:

Ca O + 2H2 O ------------  Ca (OH)2 (greyish-white masses or soft, white powder, when exposed absorbes CO2). Used also as precipitated chalk, which is calcium carbonate a remedial agent!

The Caustic Medicine: A chemical recipe as "A caustic distillate", was recommended by the author, and known in Persian as al-dik bardik, meaning an earthenware or urn on top of another (boiler over boiler). Take yellow arsenic and mix with quicklime, verdigris, mercury and al-fali (or kili) one half a pound of each. Add one-fourth pound of sal ammoniac". Grind together with water till the Hg mix thoroughly. Dry and grind again, and put in a special distilling apparatus (al-uthal). Take a new urn with mouth up fitted on its top another and close firmly sealed. Put both over a furnace with the "caustic mixture in", heating for six hours. Distilling takes place and the powder collects in two urns. It seems possible that the resulting caustic "medicine" contains corrosive sublimate, and one or two inorganic acids.12

Section Two of Uber Servitor: In the second discourse of the 28th treatise of al-Tasrif, the author discusses the preparing, correcting and curing of natural substances and materia medica from the plant kingdom. Therefore, briefly here mention will be made for the extracting of juices such as aloes (Aloe vera Linn. and other species), absinthium (wormwood), fumitory, Lycium, galbanum, sarcocol and liquorice (roots of glycyrrhizae).13 Described also, the methods of washing plant products such as acacia (gum arabic), whitening of vinegar, distilling of camphor for aromatic water, ameliorating colocynth with other gums, burning scammony, drying squill, extracting of fleawort, spurge, and opium from the poppy (air-dried milky exudation obtained by incising the unripe capsules of Papaver somniferum Linn.), man- drake (the Mandragora officinarum L.),!4 cardomom, and lily cooked with honey for medicinal purposes. Mention, likewise, is made of the distillation of sandal and other woods, whitening of olive oil, and extracting and using of liniments (anointing extracted oils).15

Aromated Water of Roses: In many parts of the Islamic world: in Pakistan, Iran, Iraq, Syria, Morocco and al-Andalus the manufacture of rose water was well known and practiced. It is mentioned in Greek writings as in Theophrastus and Dioscorides.16 A modified and elaborated method is presented by al -Zahrawi in the following manner; giving other procedures and options. He suggested that in "a large room a cistern or water tank with plate, leaded cover be installed there. It has holes to allow passing of the distilled water leading through a row of 50 to 100 vessels. Outside the room, a large copper vat is placed full of water, and connected with a running stream. The fire oven under the cistern inside, connects with the tank beyond the wall where the smoke also keeps outside".

"Start the fire under the cistern for boiling, and immediately keep the water source running to cool the system. As soon as the water fills the cistern, it pours out through the holes to the outside, and into the distilling glass vessels."17

Molds for tablets (lozenges): It is very possible that al-Zahrawi's al- Tasrif refers to the first time in Islam, and indeed anywhere else that tablet molds are accurately described .and beautifully illustrated. Here is the explanation. .'Take a board or plate made of hard, smooth wood of suitable kind, or ebony, ivory or grindingstone about 2 inches tl:tick, 9 in. long, and 1 1/2 in. wide. Cut horizontally in two halves, and engrave or curve on each side as many as needed or circles, in the right size and shape. On one or both sides, engrave the name desired super-imposed, so that once the tablets are made, the inscription reads properly." Technically, before the mold is closed, it is anointed so that it will not stick or disintegrate. 18 Indeed Arabic pharmacy in the variation of forms and preparations, as well as in the technology it perceived, influenced the professions for several centuries.

At the close of the second section, the author describes decoctions and the stainers. The depiction of the strainers is both useful and meticulous, and executed so clearly, possibly for the first time in pharmaceutical literature. He explains how three stains, one below the other in a row, are shown: The top is the smaller and lighter in texture, such as fibers of palm-trees and wool. The next is larger, and the third still larger, yet less porous. They suspend from a special support. The decoctions are poured in the first, to the second. If it was clogged by sediments or dregs, it will be returned and strained through seive or the like, to the third. When the liquid is clear, it pours to a receiver below. Syrups or honey may be added, to make the decoction more palatable.19

The Third (Last) Section: Only few substances from the animal kingdom are reported here, and the methods for their extracting, or preparing for use in medicine and therapy. The author refers to the burning of shells and horns; cloven, split or double hoofs egg shells, various bones, crab and lobsters, scorpions, snakes and hounds. He then describes the Spanish flies (cantharides) which are reddish in colour and which collected in early spring.20 Al-though in this text reference is made to taking bloods of certain animals, and birds for dietetic values, yet it is interesting to realize, that the Muslims thought of the importance of the structure of blood, in regard to health and healing process as a whole. Several diseases were recommended for therapeutic uses, such as the extracting of bladder and kidney stones, and their importance in sanitation. In addition, other animal products are listed and explained: the extracting of gall bladders of many animals, brains of birds and vultures; the manners of preparing, washing, perfuming and storing of fats, suets and other greases; the tanning, and uses of leathers: purifying of honeys, and its mixing with syrups and other medicinal compounds: and the whitening process of wax. Many of such substances are mentioned by Dioscorides, although in a primitive way.

Finally, the author explains in detail the preparing of sal Ammoniac from the igneous, sedimentory and rubble-stones, scoria or conglomerates, especially in the porches of baths where manure and animal dungs found in plenty. It is recommended that conglomerates are first crushed, and powdered, put in a widemouthed vat, closed tightly covered by an earthenware, preferably glazed. .'Make a hole in it at the bottom and seal the mouth of the vat tight. Build an oven in such a way that the vat suspend in the middle of the oven, that is fire resistant. Then start the fire, and watch closely the hole in the bottom of the glazed earthenware. If the hole emits moisture, then the procedure and the operation is going well, for the hole is unclogged. After the emission of the moist, white sal ammoniac begin to ascend and distill. Thereupon close the hole tight, take away the fire, and leave to cool. Take off the covering plate, and the sal ammoniac will be found in layers covering the plate. Break the plate gently, and collect the sal ammoniac until the time of need".21

The author clearly explained the extracting of sal ammoniac, through personal experimentation. The resultant was ammonium chloride odorless, white powder, often in a semi-crystalline form. Al-Biruni suggested that the meaning of the word, "the gentle fire" which derived from its preparation. It is very important in the use of colouring the metals, as well as in dyeing, cleaning metal surfaces, in drug manufacturing, and as an excellent source of ammonia, and other industries. However, al-Zahrawi's method seemed to have continued almost unchanged, up to the late European Renaissance.22

This was a brief survey to identify and describe some of the procedures, technologies, and preparations of natural products required for pharmaceutical industries, as well as therapy and iat-rochemistry. In this 28th treatise of al-Tasrif, originality and ingenuity had been shown. There was in addition personal observations based on experimentation, either by the author himself, or under his own supervision.

Here indeed for the first time in medico-pharmaceutical literature, we have illustrations and depictions of equipment, apparatus and instruments of real historical value. As competent physician- -surgeon-pharmacist, the author's prestige and contributions could hardly be over exaggerated. He is worthy of high credit and compliment, as one of the greatest figures in the healing arts in Islam during the Middle Ages, as evident from his own writings.

REFERENCES

1. Index of Manuscripts of Medicine, Pharmacy and Allied Sciences in the Zahiriyah Ubrary, Damascus, Arab Academy, 1969, pp. 147-168
2. F. SHERWOOK TAYLOR AND CHARLES SINGER, "Pre-Scientific Industrial Chemistry", A History of Technology, vol. 2., Oxford, Engl., 1956, pp. 371- 72 and The British Pharmaceutical Codex, London, Engl. 1934, pp. 821-82.
3. P. DIOSCORDES, "The Materia Medica", Oxford English trans. 1934, pp. 633-636; and Abu'I-Rayhan al-Biruni, Pharmacy and Materia Medica HAKIM M. SAID ED. KARACHI, Hamdard, 1973, Arabic text p. 344.
4. White lead is mentioned in Theophrastus, Dioscorides and Pliny. See JOHN M. STILLMAN "The Story of Early Chemistry", New York-London, 1924, pp.19-20, 35; and JAMES R. PARTINGTON, A History of Chemistry, vol. 1 part 1, London MacMillan, 1970, pp. 32-33 and 66.
5. DISCORIDES, "Materia Medica", Book five, 1934 ed. Engl., pp. 623-28
6. AL-BIRUNI, "Materia Medica", 1973 edition, pp. 120-21 in Arabic text (Engl. 95) and the Medical Formulary of al-Kindi, edited and transl with annotation by M. Levey, The University of Wisconsin Press, 1966, pp. 229, 234-35 and 250.
7. STILLMAN, "Early Chemistry", Op.Cit.,1924 pp.33-34,91 and TAYLOR AND SINGER, Chemistry, Op. Cit. p. 360
8. Trioxide arsenic had a continuous history from the Greek to late Middle Ages, together with the other salts: orpiment (which is arsenic trisulfide, As 2 S3) and the other pigment, realgar (Arabic rahj al-ghar), powder of the mine and from which the trioxide is produced. In Islam, these salts were important, to the work and manipulation of the alchemists. See DIOSCORIDES,Materia Medica,Op.Cit, p.642 and ROBERT P.MULTHAUF,The Origin of Chemistry, London, Oldbourne, 1966, pp. 21, 29, 106-10 229-31.
9. Ibid., pp. 227-8, through action of mercury the corrosive sublimate of calomel result as a precipitated powder, used as a white, tasteless insoluble powder as purgative.
10. DIOSCORIDES, "Materia Medica", pp. 637-38, gives reference to the origin of the metal vermilion as a red pigment. It is known to Theophrastus in his "On Stones", treatise. See also STILLMANN, "Chemistry", pp. 18-20, as being found in Spain. In regard to the importance of sulphur in relation to the mercuric salts, see M.ULLMAN, " Al-Kibrit", The Encyclopaedia of Islam, New Edition, vol. V. 1979: 88-90.
11. DIOSCORIDES, "Materia Medica", p. 648; and al-Biruni, Op. Cit., HAKIM SAID'S edition, I: 207-8, 320 (Arabic text).
12. It does not seem clear if acid hydrochloric was formed. Because of the presence of much alkalinity in the mixture it changed immediately and discomposed. There must also be many impurities that make it hard to decide, or give precise identification. For the ingredients of the "Caustic mixture", several dictionaries and lexicons are consulted: E.A. ELIAS, "Modern Dictionary", Cairo, 1950 used or any edition; J. G. HAVA, S. J. AL-FARAID, Arabic-English Dictionary, Catholic Press, Beirut, 1964; and A.K. BEDEVIAN, "Illustrated Polyglottic Dictionary of Plant Names", Cairo, 1936
13. DIYA AL-DIN ABU MUHAMMAD IBN AL-BAYTAR (the Herbalist, d. 1248), "al-Jami li-Mufradat al-Adwiyah wa'l Aghdhiya, Bulaq edition, 1291 /1874; al-Biruni, "Materia Medica", Op. cit., 1973, HAKIM MUH. SAID'S edition, al-Antaki, "al- Tadhkirah", Cairo edition, all in alphabetical order.
14. Bedevian, Dictionary, Op. Cit., p. 382 known also as tuffah al-Majanin and siraj al-qutrub (Family Solanaceae); and al-Biruni, Op. Cit., 380-81. It is known since antiquity, see L. KEIMER, "Mandragora Office", Bulletin Instit. d'Egypte, vol. 32, 1951, p. 375.
15. HAMARNEH and GLENN SONNEDECKER, "al-Zahrawi, op. Cit., 1963; pp. 77 -80; and The Medical Formulary of al-Samarqandi, by M. LEVEY and NOURY AL-KHALEDY, University of Pennsylvania Press, 1967 (see references).
16. MAX SPETER, "zur Geschichte der Wasser -Destillation: das Berchile Albukasims, "Pharmaceutica Acta Helvetiae", 5 (L930), pp. 116-120, and R.P. MULTHAUF, Chemistry, O.P., Cit., 1966, pp. 203, 207.
17. R. JAMES FORBES, "Short History of the Art of Distillation", Leiden, Brill, 1948, 11-40, and M. LEVEY, "Evidences of ancient distillation. Sublimation and extraction in Mesopotamia". Centaurus, 4 (1955), pp. 23-33.
18. S. K. HAMARNEH, " Early Arabic pharmaceutical instruments". Journal of the American Pharmaceutical Association", Pract. Edition., Vol. 21 (1960) pp. 90-92.
19. Ibid and with PROF. GLENN SONNEDECKER, A pharmaceutical View of al-Zahrawi, Op. Cit., 1963, pp. 72-76.
20. IBN AL-BAYTAR, "al-Jami" under the letter "Dhal" gives detailed identification of the cantharides and virtues derived from it, citing many Greek and Arabic authorities. It was known in Spain, hence and beetles called Spanish flies (Cantharis vesicatoria Latr.), see The British Codex, 1934, pp. 272-3; and The Dispensatory of the U.S.A. Ed. 1950, pp. 210-13
21. F.S. TAYLOR, "The Alchemists, Founders of Modern Chemistry", New York, Henry Schuman, 1949, pp. 82-83 and 92-93 PARTINGTON, History, Op. Cit. 1: pp 204, 287
22. R. P. MULTHAUF, "Sal Ammoniac: a case history in industrialization", Technology and Culture. 4 (1965), pp. 569-270; H. LEICESTER, The Historical Background of Chemistry, New York, 1956, chap. vii; and JULIUS RUSKA, "al-Nushadirsal ammoniac" The Encyclopaedia of Islam, vol. 3, part2., Leiden E. J. Brill, 1936 p. 967