Avumrx Vol. a2, Part 2, Jaly 1975, ‘THE PRODUCTION OF SALTPETRE IN THE MIDDLE AGES By A. R, Winniaust Guwrownen is first described in the thirteenth century in manuscripts ascribed to Roger Bacon, Albertus Magnus and Mark the Greek" although none of them say how the necessary saltpetre is to be obtained, The first printed accounts of its preparation describe its extraction from suitable “nitrous earth”, but are vague about where this earth comes from inthe first place, If suitable “nitrous earth” can be deliberately generated in a chosen site then a much more efficient means of large-scale saltpetre production becomes available. ‘The first description of such an artificial “nitre-bed” appearsin Conrad Kyeser’s Bellifortis (2405), @ book on military technology which contains the following rather obscure descrip- tion:? “The aforesaid things being placed in contact, sprinkle each layer with salt water, urine, or wine, and afterwards deposit another layer of ground quick-lime—again watering ‘with the aforesaid substances, Thus make layer upon layer until the hole is fall’. The nitre-bed depends on the bacterial oxidation of nitrogenous organic matter to nitrates, which can then be extracted by solution. BBy the second quarter of the fourteenth century the propellant properties of gunpowder were being exploited in guns, and the English Public Records show increasingly lange ‘purchases of gunpowder throughout the next two centuries, e.g.* (@) In from Wiliam of Stanes 1600 Ib, at 284 the Ib {) fas pom Wag indvad n 28 the In 1490 from John Nicol 00 I. at 8d the (2358 om Je Cavan poo ae ihe {In 1838 etmated by Over (the Royal Agent 0 cost in Antwerp: 200. 20o,000 Ib at 8}d_s0}4. the Tb (f) Inagpy estimated by Hoddesdon to cost in Hamburg: 500,000 Ib. at zed. the ib. In 3599 Evelyn Brothers contracted to deliver 240,00 Ib: Ooeitem ‘The steady fallin price of gunpowder, particularly during a period of rapid inflation, suggests the mass-production of saltpetre to mect a growing demand, since the other ingredients of gunpowder were relatively cheap: LLevethulme Unit for the Study of Ancient and Medioval Technology, UMIST, Manchest * Saltpets fs mentioned ia Michael Soot, De Aickomi, (ca. 1230); see SH. Thomson, 23, 1936. Thoecipes in Bacon, Albertus and Mark ate laoused at lenge ia J. Pareagton, A History of Gash Fie and Gnpornder, Cambridge, 198, chap. 2. * Conrad Keyeser, Ballots, facsimile elition, ed. Quar 2 vols, Disseldrt, 1967. * (ah and (ited by T. F. Tost, Bvglich History Revie, 26, 05, 19% (6) ttre and Papers stato of he Waren France the eign of Henry VE, Role Seis No.2, Vol. soa, (a) Letios and Papers of Henry WITT, Vol, Pt. 2, 1456-80. (e) Later and Papers of Henry VILL, Vol. XIV, PL 3 335 () Calendar of Sate Papers (Foreign) (Elzabeth 1), 1577 (g) Calendar of Stale Papers (Domest) (Elizabeth 1), 226, « Ghaceoa eect bout as, ton in thesixtonthcentary. Salphur cost about 6 ab. in the fourteenth century but only half that pic inthe eoventounth century. W. Beveridge, Prices and Wages in England, 938.126 ALR, WILLIAMS, ‘The first reference to the manufacture of saltpetre in England is in 1490, when a com- mission was issued to John Stok, Clerk of the Ordnance, “to provide houses, land, vessels, ‘wood, coals, etc. for the manufacture of saltpetze for the King’s ordnance”.® This seems to beappropriate equipment for the boiling of “nitrous earth” and the erystallsing of saltpetre, Henry VIII encouraged further attempts in this feld, to relieve himself of the necessity of importing saltpetre, and in 1515 he hired one Hans Wolf “to go from shire to shire to find a place where there is stuff to make saltpetre of”.* All the saltpetre in England seems to have been made on an itinerant basis, for in 1545, one Stephanus de Haschenpergk wrote to Henry from Lobeck, asking for financial support and claiming to have invented ‘a way of ‘making saltpetre ... in one place, without going about searching for it”.” Henry's death, shortly after, seems to have prevented this offer being followed up, if it was ever taken seriously, for Haschenpergk had previously been discharged from Henry's service Queen Mary's alliance with the Spanish rulers of the Netherlands enabled her agent Gresham to ‘import all the saltpetre required from there. With the accession of Elizabeth, the changed attitude of the Spanish forced Gresham to resort to bribery and subterfuge and it is not surprising that he wrote in 1560 “the Queen .. . should do well to macke, out of hande, ii or vi mylles for the macking of powdyr ...if the wares contynew . .. or a breach of amytie shuld chaunce betwixt her Majestic & King Phillipe” Infact, the next year in 1561, an attempt was made to establish an independent source of saltpetre in England. Two merchants, Phillip Cockeram and John Barnes, were given a license for 10 years to make saltpetre by a method that they were to parchase from a German, called Gerard Honricke or Honrick for £300.%° With the note ofthis agreement in the State Papers is a copy of Honrick’s recipe (and itis noted again in 1643) which is for the produc. tion of saltpetre in artificial nitre-beds. Quantities of saltpetre were purchased in Hamburg (1577) and as far afield as Morocco (2572)" but England seems to have become self-sufficient in saltpetre by the end of Eliza. beth’s reign, for both gunpowder and saltpetze were being exported to the Netherlands, Venice and even Turkey.?® A contemporary map shows a ““Donghill” on the land of a gunpowder manufacturer, one Hugh Sheale of Ipswich, in 2593.42 It would seem then, that Honrick’s recipe put the manufacture of saltpetre in England on a more systematic basis, ‘The necessary information had to be paid for, because the details of the nitre-bed effectively. remained a trade secret, * Materiats for a Mistry of the reign of Honey VET, Role Series, Pat. Rol. 2848) ‘ Letlrs and Papers of Henry VII, Nol. I, Pt. x, 1, 1 Leters and Papers of Henry VIIL, Vol. XX, Bt 2, yp ‘1 am indebted to Dr. A. G. Keller for pointing cut this fact about Haschenpergk. His earoer is Seserbed by D. HE. St. J. O'Nel, “Stefan von Haschenporg, an engines to King Henry VII, and his work". Avehacloga, 91, #37. 1945 "J. W. Burgon, Life of ir Thomas Gresham, 2 Vols, London, 183 |, 294. 2 Calendar of Patent Rails, (Elizabeth 1, 1360-63, 1,98, x04, ad Calendar of State Papers (Domestic) (Charles 1), 64, 75,487 '¥ E. W, Bovil, “Queen Elizabeth's Ganpowder”, Mariner's Mievr, 88, 79, London, 1047. Holiand, 1608, Calendar of State Papers (Domestic (Eeabcth I, 1601-3, 284, 10 189; Venice 1603, Calendar of State Papers (Vensdian) 9, 1155: Constantinople r605, Calonar of State Papers (Pena 1 4 grant of and to hie shows this on the accompanying map (Hast Sol Record Office, A 1X13, 439. ua‘THE PRODUCTION OF SALTPETRE 18 THE MIDDLE AGES 127 ‘Three printed technical treatises of the sixteenth century deal with the manufacture of saltpetre by means of nitre-beds, viz." Nitrebed Estraction of eltpet (@) 3540. -mtmixcuccio Pig-dung kept Layers of this “earth” Pyrotechnia for long time placed in a tub with, ina dry place. _oakcashes and quicklime and extracted with water. (3556 scricona Earth and Probably copied from Deve metallica branches Biringuccio, exposed to the sky for years (9 a574 Exc Earth from old —Textracted “earth” with Treatise on ores sheep-pens, water and poured into and assaying stables and ‘tub of wood ashes, ‘mortar from old vvalls, ‘These anthors describe the extraction of saltpetre from nitrous earth, using wood-ash (potassium carbonate) to convert the calcium nitrate present into insoluble calcium carbon- ate; followed by careful crystallization of the filtrate to remove most of the sodium chloride, Which remains in the supernatant liguid, None of them, however, describe how this “nitrous earth” may be prepared artificially. Indeed, if they had done so, the techniques would have been available to Henry VIII and Elizabeth 1, whereas in fact, the Germans ‘managed to keep them a trade secret for a considerable time. Tt will be noticed that the three writers mentioned above all state that saltpetre can be ‘made from manures of various sorts. They omit any mention of the urine employed in Kyeser's or Honrick’s MS recipes (which doubtless did not have a very wide circulation). In fact, piles of dung alone will not produce any saltpetre (see below); the addition of urine is necessary as well, Tt may seem exceedingly odd that the performance of such a process ever occurred to anybody. But Ereker's mention of “wall saltpetre” gives a clue to its origin. A mixture of earth and manure was used in building in the Middle Ages as it solidified to a hard mass ‘on standing and provided a cheap method for constructing walls¥ Where a wall or for 2% Alt have boon reprintad in English transation: (a) C.. Smith and MT. Gnu, New York, 1958; (H.C. and L. H. Hoover, New York, 19505 (¢ AG. Sisco and C, 8 Suit, Chicago, 1951. ‘Turrano in his "Book of Machines (a. 1460) deserves types of nitrous earth: "There ae two Kinds ‘one of whichis the nara altpetrs. There another mado arta, much of which x made for gun power. ‘The enethtsod fr saltpoteraecumsiate in two forme, One cart eto be found in the lds +t may be recognized very easly In sumer because where this cath i, the gronnd tarns white ‘Another earth. a places under the ground, sl in old hows, and on walls and whtre there ie 618 ‘of men or animals .."- Tulane "XXI Libros de Maguinas” Madrid N.S 3572-6 (4. G. Keller translation). He goes onto desribe bow saltpote may be extracted from these nitouscarths with water, but he doesnot scribe how nittons earth may be made articialy ‘For instance, 1387 Yarmouth waa frtifed by moans of embankments 4o foe thick made of = mixture ofearth and manure, By IL. St, J.O'Nell and W, E. Stephens, "The forlication of Vrtaouth Norfth Arehacslgy, 28,2, 1043, quoting fom HL, Manship, "History ot Gt. Yarmouth" (x10) ed ©. J. Palmer, Grae Yarmouth, 183428 ‘A. R, WILLIAMS made with such material stood near stables or latrines, the conditions for a “nitre-bed’ ‘would be failed since the earth would be absorbing urine daily. Eventually, it must have ‘occurred to some observant ‘sltpeterer” that it was the ingredients of the wall that were responsible for the saltpetre and that they would work just a8 well without the wall, [Modern writers have found it dificult to understand how saltpetre could be produced simply from an old wall. Tn fact, walls of stone or brick would be most unlikely to pro- duce nitrates. But the walls of bams, stables and outhouses would be made of cheaper ‘materials and might well incorporate quantities of dried dung. I is walls ofthis sort which ‘would be more likely tobe periodically soaked with urine, so that such walls and lor formed hatural deposits of nitrous earth. The duplication of this process in artificial nitre-beds as Fecorded by Kyeser was probably frst achieved in Germany. The nitre-beds established in England in the siteenth century were eventually made redundant by the importation of Tndian saltpetre, but they remained important in France at least until the Revolution.” ‘The eatiest unambiguous description is probably that given in the unpublished MS recipe of Gerard Hontick, which describes how “fresh horsedung” and earth "the blacker the better" are to be mixed with lime “best made of oyster shells” and moistened with MONRICK’S RECIPE Tite: “rgb making of saltpeter” ‘THE TREW and perfect arte of the making of SALTPETER to growe in Cellars, Barnes, or in Lyme or Stone quarries, The nature of SALTPETER is to growe in placis, could, and drye, where neither sonne nor rayne entrithe, nor springe resort, for the dryer fand coulder the place be, the [soner] and better do they bring forthe saltpeter. ‘And to MAKE the MOTHER OF SALTPETER these things following be requisite. FYRST black earthe the blacker the better. Thenext is URINE, namely of those ‘hiche drink either wyne or strong bears. ‘Then DONG specially of those horses, which be Fed with ootes, and be alwaye kept in the stables. ‘The fourth is LYME made of plaster of Parys. The LYMEE whiche is made of OYSTER SHELLIS is the best, and better than. tirother if it be kept from Rayne and water. ‘The LYME whiche is made withe other ‘« Partington (t) 319 analysed an efforescence from a rice wal and found i o be sodium sulphate Dot Kidd sraped an eferacence fom the wal ofthe basement laboratory beneath the (present) Oxford ‘Museum for the History of Seieace, aud found this tbe potasium nitrate. The building ofthe Ash- frotean was made of limestone and it posible that alatine drained near the laboratory wall Sie ‘John Kidd," Observations especting the natsral production of saltpetreon the walls of subterranean and iter buildings", PA Trans, (814), 598 ‘Partington (}. 314, As ateas 163, an ealier proclamation af 1625 was revived giving the slt- petremalers permission to dig up the foo of daveeots, stables, et. TE Publ Rooord Office, unpublished MS RefNo. SP 12/16/29. Words in brackets are doubtfal nadings The parchase ofthis recipe ie mentioned in the Clindar of Patent Rll of Elcabth I 1960-65, Ir tog, and copy is noted in 1641 inthe State Papers (Domest) of Charles, 487,75. 10.3578, Howick NO; + 2H,0+ + 28 Hee found that these bacteria needed free calcium or magnesium carbonate on which to ‘grow and were stimulated by some organic compounds such as a decoction of horse-dung. ‘These two kinds of bacteria have been found by all other workers who have looked for nitrifying bacteria in soils and they are wswally the only bacteria regularly found. It will be remembered that Honriek’s recipe contained lime (which would form caleium carbonate on standing), urine (which would supply ammonium ions), dung (which might supply some bacteria) and earth (which would supply some nitrifying bacteria, and might also increase the available surface area). ‘These experiments were later resumed (June 1972). A further quantity of fresh cow- ‘dung was divided into two piles of approximately 50 Ib. each, which were mixed with equal weights of soil and placed on the tray. One pile again had 8 Ibs. of ime added. Samples were taken periodically from Sample A The top layer of the pile with lime B The top layer of the pile without lime " Winogradshy’s workin discussed by (inter alia) E. J, Rassll, Phe World ofthe Soil, London, 1957, 65.332 ALR, WILLIAMS © The bottom layer of the pile with lime D_ The bottom layer of the pile without lime The nitrate concentration in the aqueous extracts was determined by means of an Orion ion-selective electrode. This method of analysis proved to be very rapid and consistent. The following results were obtained (Sigures being parts per million of nitrate (as KNO,) in original sample: Date A B 6 D 306.72 - = - = 30.173 5 382 = - 23.73 1,850 5230 = a 94.73, 1.930 3530 = - 105.73 7.950 13,600 71230 2,560 256.73 6,120 3310 10,010 5,650 25.97.73 10,400 12,100 2,080 6.770 2.9.73" 7210 12670 38,150 9740 ¥7.12.73° 14,900 16,550 9,170 10,360 The two asterisked samples produced crystals of potassium nitrate from the aqueous cextracts when these had been mixed with potassium carbonate, filtered, and slowiy evapor- ated. Ifthe concentration of nitrate in the samples is plotted against time, then after a lengthy induction period (during the winter) the concentrations of nitrate slowly start to increase Pa nitrate 36 KNO © (8) Top layer— pile without time + (0) Bottom ayer — ple without time JOT SETA WONT GANT WARY WAVE JULY) G&A NOVT ANA 1912 1973 1974‘TM PRODUCTION OF SALTPETRE IN THE MIDDLE AGES 133 but at diferent rates. ‘Those of B and D (graph 1) increase steadily and then fatten out at similar levels, reached frst by B. Those of A and C (graph 2) are more erate but A i the fist to form appreciable nitrate, These two contain the lime. (Honrick's recipe specifies quickie but it wll not have remained “quick” for long.) Initially the strongly basic calcium hydroxide may havo reduced the available nitrogen content by diving off ammonia ‘rom the urine; on weathering it would be converted to the milder ealeiam carbonate which ‘might favour the necessary bacteria by preventing the development of acidity. (A Top layer — pie with ime ++ (C) Bottom layer — ple wit ine LUT SPT NOV TANT WARY WAY RLY SEPT NOVI AN 1972 1973 1974 ‘Three conclusions may be drawn x, Traces of nitrate form frst in the tops of the piles, then percolate downwards so that the concentration is similar throughout each pile, This would explain why Honrick’s recipe ‘contains elaborate instructions for spreading the materials into thin layers. The same ‘effect would be obtained by turning over the piles frequently 12, Both urine and dung are essential (omething the early printed recipes purposely da not ‘make clear) and the admixture of earth is also necessary to obtain an appreciable yield. ‘Traces of calcium carbonate are also desirable, but the quicklime specified probably reduces the initial yield. 3. Alter xf years, the maximum yield is still only of the order of one per cent (the experi= ‘meats are stil being continued). , Even allowing for an increase in reaction velocity if thin layers were employed, it can never have been a very rapid or efficient process. Tt is remark able that it was ever devised at all, and the author, for one, has acquired a considerable respect for the powers of observation and experimental skill of the fourteenth-century chemists who discovered how to operate the artificial nitre-bed.