Note CHIMIA 2010, 64, No. 5 315 doi:10.2533/chimia.2010.315  Chimia 64 (2010) 315–320 © Schweizerische Chemische Gesellschaft Ötzi, the Iceman and his Leather Clothes

Alois G. Püntenera and Serge Moss*

Abstract: Over 5000 years ago, a man climbed up to the icy heights of the glacier in South Tyrol, Italy and died. He was found by accident in 1991, with his clothes and equipment, mummified and frozen: an archaeological sensation and a unique snapshot of a Copper Age man. For several years highly specialised research teams have examined the mummy and all accompanying items. This paper describes how fur and leather clothes of the iceman could have been tanned. Details of the analytical tests undertaken on the 5000 year old leather samples and what they revealed are presented. Keywords: Ancient tanning method · Iceman · Infrared spectroscopy · Neolithic leather clothing

Socrates says that a state is made up of skull was determined to have been broken. four sorts of people who are absolutely Later, an arrowhead was discovered in his necessary; these are a weaver, a husband- body. He was mortally wounded upon es- man, a shoemaker, and a builder. caping over the mountains. He was moving from today’s Italian lowland in the direc- Aristotle, Politics, Book 4, IV tion of the Ötztal valley, now Austria. The name ‘Iceman’ or his nickname ‘Ötzi’ was created. 1. Introduction

On Thursday, September 19, 1991 at 2. Research on the Iceman 1.30 pm, a married couple found a dead body in the Alps on the icy heights of the For the first time in the history of medi- Schnalstal glacier, 3210 m above sea level cine and archaeology, anatomical studies could be performed on a mummy clearly and in the frontier area of Tyrol between [3] Italy and Austria.[1,2] dated to the 4th millennium BC. With the The Austrian police were informed. exception of the damaged left hip region, At first glance, the police officer found the body was practically intact. It has been strange clothes and pieces of equipment on exhibit since March 1998 at the South and concluded that the accident must have Tyrol Museum of Archaeology in Bolzano, happened 100 years ago. He also believed Italy. For several years highly specialised that the body had a head injury. Did a crime research teams examined the mummy and happen 100 years ago? The federal pros- all accompanying items. The most impres- ecutor assigned the examining magistrate sive item was the copper axe, certainly to initiate a medico-legal investigation. But used as a tool and a weapon. nobody was in a hurry. The accident was Not much was known about clothing in the Neolithic time. Spindle whorls and assumed to be an old affair, which had hap- Fig. 1. Ötzi the Iceman. Source and copyright pened years ago, and was almost forgotten. loom weights have been found as well as of the picture: South Tyrol Museum of some textile fragments of flax and other The retrieval of the body by helicopter was Archaeology. not considered since this was restricted vegetable fibres. According to archaeolog- ical excavations weaving must have been to more urgent events such as traffic and known in the region at that time. Ötzi al- mountain accidents, especially because the lows us a view of the general appearance of weekend was approaching. an alpine inhabitant more than 5000 years However, the story attracted the me- ago. The clothing found had been con- dia’s attention. They speculated that the served in a surprisingly good condition. body was a soldier from the middle ages: The clothing is composed of a fur cap, a mercenary coming home after a war- a hide coat, a grass cloak, leggings, a belt, *Correspondence: S. Moss like event in Italy. First investigations of a loincloth and a pair of shoes. It is remark- Novartis Pharma AG Forum 1 the mummy, its clothes and equipment re- able that no woven materials were used, Novartis Campus vealed that the Iceman mummy was a male only tanned leather and a grass coat. The CH-4056 Basel inhabitant of the Alps. A carbon-14 analy- fur clothing has a black/brown coloured Tel.: +41 61 324 62 12 stripe design.[3] The cap, the coat and the E-mail: [email protected] sis indicated that he was much older than aVESLIC Verein Schweizerischer Lederindustrie- so far assumed (Fig. 1). He lived during the leggings are composed of many cut pieces Chemiker und -Techniker Copper Age (Neolithic), over 5000 years sewn together. The stitching threads are c/o Dr. A.G. Püntener mainly made of animal sinews and only in Postfach 505 ago. It was speculated that he could have CH-4016 Basel been a soldier, hunter or herdsman. Dur- part of plants, primarily grasses and to a E-mail: [email protected] ing the first inspection and rescue work his lesser extent bast. 316 CHIMIA 2010, 64, No. 5 Note

Our interest was the fur and leather 3.2 Vegetable Tanning clothing. The museum curators had washed Vegetable tanning sources are woods, every sample with distilled water contain- barks, leaves, fruits, roots or growths (gall- ing 2% borax and boric acid and 20% nuts). The tanning active compounds are polyethylenglycol as well as with a fatty organic macromolecules with aromatic emulsion. This treatment could have been components. Vegetable tanning agents are somewhat inconvenient as it could inter- usually sourced locally. At that time oak, fere with the analytical investigation of the birch, chestnut or spruce or barks could conservation process. Fortunately, we did have been used as tanning agents. not detect any interference from this treat- The tanning effect of vegetable tans is ment and we therefore believe that it did based on polymeric phenol groups. An ex- not negatively impact our investigation. ample is polymeric gallic acid as ellagic We have to consider that skin material Fig. 2. Surface of the hair (grain) site of the Ötzi acid and their lactones in the form of gly- is normally subject to rapid decomposi- leather (7× magnification). coside (Fig. 3). tion after the animal is killed. The first reaction takes place on the epidermis. A fast separation of the hair occurs. There- society of farmers and ranchers rather than fore, for the fur and leather industry it is of a society of hunters. of great importance that the raw hide is Whatever kind of fur has been used, properly treated immediately after slaugh- some tanning must have been carried out ter. The best method to protect hide from otherwise the material would have not been deterioration is to remove water, either by stable in the alpine climate. In the tanning drying or salting. Raw hide is still treated trade one performs a fixation of tanning in this manner worldwide today before be- agents within the collagen matrix. The ing tanned. However, these methods alone quality of the leather is improved with in- Fig.Figure 3. Gallic3: Gallic acidacid andand ellagicellagic acid.acid cannot withstand daily usage under ad- creasing degree of fixation, which is meas- verse alpine weather conditions. ured by the so-called shrinking tempera- The fur and leather items of the iceman ture. The epidermis and the corium must were almost completely intact. That indi- be strongly connected to each other. Com- cated quite clearly that his clothes had been parative shrinking temperatures according 3.3 Smoke Tanning tanned, keeping them very stable under the to the DIN 53336 method show 46–49 °C One can also envisage the use of conditions prevailing in the glacier area. for untreated hide and 58–60 °C for the smoke, which has an antibacterial and This effective conservation allowed us to Iceman’s furs. This is a clear indication conservation effect. In addition it also has perform analytical tests, finally enabling that some tanning had been undertaken. a dehydration effect. Wood smoke compo- the investigation and discovery of the little In addition, before tanning the hypoder- nents consist of a multitude of chemical known tanning method of our alpine ances- mis (subcutus) must be removed. Studies compounds including small amounts of tors, which is of great historic interest. showed that this had been done mechani- tanning agents like phenolic and formal- The fur cape was made of a bear hide, cally as scrape marks, probably from a flint dehyde derivatives. This method cannot be not an easy animal to hunt. The clothing fur stone, were found. What technique could considered as mainstream tanning. How- was first identified as mainly chamois,[4] have been used to tan the leather clothes ever, smoke influences the smell of leather a more common hunting animal, though of the Iceman? and fur depending on the selection of fire rarely used today as the hairs are too stiff material. In our investigation we could not and readily break. The fur was kept in good find any convincing indication for smoke condition. The clothing had been repaired 3. Possible Tanning Methods tanning. Nevertheless, we have to assume reasonably skilfully on several occasions. that clothing almost certainly will have had The furs were obviously designed and used We can assume in principle four tan- intensive contact with smoke due to the for a long lifetime. ning procedures which could have been weather, housing and cooking conditions The experience that chamois fur is rigid known or may have been practised at that in the Alps during Neolithic times. For and fragile was also made by the Iceman. time: metal tanning, fat tanning, smoke instance, smoking meat for food preserva- He wore apparently hairless treated skin, tanning or vegetable tanning.[6–9] tion is an old and well known procedure. more like leather. The few remaining hairs and epidermis on the samples show that the 3.1 Metal Tanning 3.4 Fat Tanning hair had been worn off by extensive use. Metal salts like alum were known and The most obvious means for skin prep- This may also have happened to his shoes. used in ancient Egypt. The western desert aration was probably the use of fat. The The inner shoe is composed of grass net- of Egypt was a major source of alum sub- observation that fat stuffing has the char- ting. The outer part is made of leather/fur. stitutes in antiquity. These could also be acteristic to make rough and hard materials Therefore, the original material must have found in the local Alpine area, commonly soft must have been known. The fur must been fur (see light microscopy, Fig. 2). in caves. Today, potassium, simple alumin- be soft for the sewn repairs as done by Ötzi. Recently German researchers, analys- ium chlorides and aluminium sulphate tan- In addition, fat has some water-repellent . ing proteins present in the hairs of Ötzi’s ning [e.g. KAl(SO4)2 12H2O] are still used effects. It is most likely that for tanning fat clothing with a hi-tech MS method and for leather gloves. materials of slaughtered animals (booty) comparing them with those found in liv- However, these substances should be could have been used. The use of vegetable ing animals, assigned samples from the highly basic or masked, otherwise the tan- fat is very unlikely as it was and remains coat and from the leggings to sheep and ning could be easily washed out. There- very difficult to collect. the upper leather of his moccasins to cat- fore, this tanning method may not be very The composition of animal fatty com- tle.[5] These results support the theory that suitable for the Alpine region, where rain ponents varies. For land animals it consists Ötzi was a member of a more developed and snowfall prevail. of triglycerides, mainly of stearic, palmitic Note CHIMIA 2010, 64, No. 5 317

and a smaller amount unsaturated oleic titanium. It is likely that many of these was used first. This technique allows in- acid. This is in contrast to fish oil which elements derive from a contamination by frared spectra of samples to be measured contains a higher amount of unsaturated silicate impurities since silicon was also which cannot be damaged and is widely fat. Saturated fatty components are incor- detected in high concentration. In fact, an used for the analysis of paper, textile, plas- porated physically into the hide and they analysis of individual sand grains taken tic or leather samples. No sample prepa- show less tanning behaviour than chemical from the Ötzi’s leather samples resulted in ration is required. The sample is simply tanning. similar concentrations of silicon, alumin- placed in contact with a special crystal The unsaturated bonds in fish oil break ium, iron, magnesium and titanium. Iron and can be recovered after the measure- at approximately 45 °C. They create for- could also originate from dried blood as ment. For the analysis of large areas the maldehyde derivatives which lead to a real Ötzi was mortally wounded, but its pres- frustrated multiple internal reflectance tanning bond with the hide. In tanning pro- ence could also be explained by some kind (FMIR) method was used whereas small cedures in German it is called ‘Sämisch­ of tanning practice since natural pigments areas could be targeted by using the ATR gerbung’ and in English ‘Chamois tan- like iron ochre were used in ancient times, objective of an IR microscope with about nage’. We know this effect from our daily for example, to paint human bodies. 100 micron contact area. ATR microscopy life, it is basically the same type of reac- Such findings trigger the question has been also applied to the analysis of skin tion which makes butter rancid. At present, whether all of the elements found in the samples of mummified corpses, including ‘Sämischgerbung’ is still used for Tyrolean Iceman’s leather come exclusively from that of the Iceman.[11,12] trousers made from the skin of red deer, natural soil or, at least partly, arise from a For each piece of leather both the hair chamois, reindeer and elks. tanning process. This question could not be and the flesh side were investigated. Due There are different application methods answered unequivocally at this stage of the to the large heterogeneity of the samples for fat stuffing. It can be performed at high investigation. However, we consider metal and also the presence of dirt and hair, temperatures, using eggs, brains or other tanning to be rather unlikely. considerable differences were occasion- emulsifiers, gypsum, highly colloidal clay ally observed between the spectra of the or other powdery supporting materials. same sample, and even between spectra of 4.2 Search for Vegetable Tanning the same side of the same piece of leather. To detect vegetable tanning agents However, most spectra resemble the spec- 4. Analytical Findings several extractions with solvents and sol- trum shown in Fig. 4. vent mixtures like water/alcohol were per- Beside bands from skin components 4.1 Search for Metals formed and the extracts analysed by dif- (protein C=O at 1649 cm–1) and inorganic Atom absorption spectroscopy (AAS) ferent analytical methods (IR, TLC) but contaminants (probably silicate at 1011 was used to identify the presence of metals. the search was negative. Also decomposi- cm–1) the spectrum shows bands at 2920, Four different samples from the Iceman’s tion (pyrolysis-gas chromatography/mass 2850, 1465 and 720 cm–1, which can be leather were investigated and the hair spectrometry, Py-GC/MS) of a very small assigned to CH vibrations of fatty alkyl (grain) and the flesh side analysed sepa- fur sample showed no aromatic vegetable chains. Furthermore two bands at 1579 and rately (Table 1). Vegetable tanned leather tanning components.[10] 1539 cm–1 assignable to ionic carboxylate was taken as reference. The chemical ele- groups suggest that salts of fatty acids must mental distribution on the Iceman’s leather 4.3 Search for Fat Tanning be present. In some spectra (not shown is very uneven. Aluminium and iron were In order to search for fatty components here) bands at about 1740 (ester C=O found in high concentrations in all sam- the leather samples were analyzed by in- stretch) and 1710 cm–1 (acid C=O stretch) ples, beside intriguingly high amounts of frared (IR) spectroscopy. To this end the at- indicating the presence of fatty esters elements such as calcium, magnesium and tenuated total reflectance (ATR) technique (triglycerides) and fatty acids could also be detected, but they are generally weaker than the bands at 1579 and 1539 cm–1, in- Table 1. Result of AAS analysis. dicating that fatty acids are predominantly present in a salt form. Chemical Element Reference Leather [%] Iceman Leather [%] It is also worth noting that in two of Si 0.02–0.07 1.5–5.0 the four pieces of leather analysed much more protein could be found on the hair Al 0.02–0.04 1.0–3.0

Fe 0.01 1.5–4.0

S 2.0 0.2–0.7

Ca 0.1–0.2 0.1–1.0 721

Na 0.2 0.7–1.0 141 4

K 0.1–0.2 0.1–0.7 146 6 328 2 Mg 0.01–0.02 0.2–0.6 157 6 164 9 285 0 154 1

P 0.03–0.1 0.06–0.3 101 1

Cl 0.06–0.1 0.01–0.02 291 8

Cr <0.01 <0.01

3500 3000 2500 2000 1500 1000 Ti <0.001 0.03–0.1 Wavenumber cm-1

Ba <0.001 0.005–0.03 Fig. 4. ATR spectrum of the flesh side of a sample of Ötzi’s trousers. 318 CHIMIA 2010, 64, No. 5 Note

Table 2. Results of the IR investigation on natural fat or fat derivatives. Age Type Fat content

11th century Upper footwear, vegetable low

12th century Upper footwear, vegetable low

14th century Sole leather vegetable almost none

New, classical standard Glace gloving, alum low

New, classical standard German deer, chamois medium

New, rediscovered Indian, elk, smoked high (mainly fatty esters)

New, rediscovered Siberian, fish high Fig. 5. Light microscope image of fatty spew 4th millennium BC (Copper age) Iceman fur high (mainly fatty acid salts) on the Ötzi leather (20× magnification). side than on the flesh side, whereas in the We tried to confirm our findings by of various kinds and fat-containing leather other two samples both sides could not be analysing the fatty particles with other ana- in general. We especially focused on vari- clearly distinguished by their ATR spectra. lytical methods which was not easy due to ous types of historical leather treatments, Since some fatty spew could be ob- the very low solubility of the sample and excluding metal and vegetable additions, served on one of Ötzi’s leather samples un- also to the small amount of material. Some in order to assess which type of procedure der the light microscope (Fig. 5), some par- indication could be obtained from mass was used by the Iceman. ticles were removed with a metallic needle spectrometry (ESI-MS) showing the pres- To obtain reference data we investi- and then analyzed with the Fourier trans- ence of palmitic acid, stearic acid and hy- gated leather from the 11th, 12th, and 14th form infrared spectroscopy (FTIR) mi- droxystearic acid after strong acidification centuries as well as different types of vege- croscope in transmission mode. Although of a fatty particle. However, MS did not table, chamois (fat) and glace (aluminium) the IR spectra (Fig. 6) differ slightly from bring any information about the concen- leather.[15] As an additional reference we particle to particle, they confirm that the tration of the detected species since only looked into newly rediscovered techniques main fatty component found on Ötzi’s a very small part of the particle could be from ancient US/Canada Indian[16] and Si- leather is clearly a salt of a saturated fatty solubilised even after treatment with acid. berian leather[17] handicraft. Supplemen- acid, most likely a calcium salt of stearic Another clue was provided by an en- tary analytical methods were used, such acid or of a close homologue. Only a small ergy dispersive X-ray (EDX) analysis, as X-ray fluorescence, to cross-check and concentration of free acid is present (1699 which revealed that calcium was the main verify the original findings or to exclude cm–1). This result was confirmed by com- element in a fatty particle beside smaller other possibilities. Table 2 summarises the paring the spectrum of the fatty particles concentrations of aluminium, silicon and analytical results in terms of fat amount with the spectrum of pure commercial cal- sodium.[14] and nature as determined in the various cium stearate (Fig. 7), which exhibits the Surprisingly, the expected natural fatty leather sample types. same typical split carboxylate band which esters and free fatty acids were only present The Iceman’s fur proved to be very dif- is converted to one single band when the as minor components. Also, unsaturated ferent from the reference leather samples. sample is dried.[13] The absence of signifi- fat components or an indication that satu- Fat was found but a strikingly high concen- cant amounts of inorganic carbonate in the rated fat had been oxidized was not clearly tration of calcium salts of saturated fatty IR spectra almost rules out that the calcium found. Their absence exclude that the fur acids distinctly characterised the Iceman’s found on Ötzi’s leather by atom absorption had been impregnated with fish oil. Based leather sample. spectroscopy (see Table 1) could originate on these results we concentrated our further We concluded that a unique, rather un- from dolomite contamination. analytical efforts on fat tanning approaches expected lubrication procedure could have 111 3 721 111 3 335 9 332 1 721 141 8 169 9 142 0 147 0 147 1 157 7 157 7 153 9 285 0 285 0 154 1 291 8 291 7

3500 3000 2500 2000 1500 1000 3500 3000 2500 2000 1500 1000 Wavenumber cm-1 Wavenumber cm-1

Fig. 6. IR microscope spectrum of a typical fatty particle from Ötzi’s Fig. 7. IR microscope spectrum of calcium stearate. leather. Note CHIMIA 2010, 64, No. 5 319

been used. The IR spectra are different However, our ancestors may have empha- any suitable organic carrier or any organic from those obtained from leathers treated sized more the practical waterproof effect emulsifier on the Ötzi’s fur, but we cannot by modern fat liquoring methods as well as rather than the leather’s appearance. We exclude the presence of colloidal clay. completely different from the more ancient hypothesised that already in those ancient chamois tanning type applied to Tyrolean times an intelligent and resourceful indi- trousers (Fig. 8). On the Tyrolean trousers vidual could have discovered that animal 6. Conclusion there is a much lower concentration of fatty fat could be saponified with wood ash and components compared to Ötzi’s clothes. we developed a procedure based on upon In the course of investigating the tan- At this stage of our investigation some this idea. ning method used for the leather clothes of questions still needed to be answered: Ash obtained by complete incineration Ötzi, a surprisingly high concentration of “What is the origin of the salts of fatty of wood is mainly composed of oxides and calcium salts of saturated fatty acids was acids found on the Ötzi’s clothes? Was an has a pH of 10~13. The ash composition found on the surface of the leather clothes. unknown tanning method used in the Alps of deciduous trees contains approx. 3–4% As this finding cannot be explained by to- in this epoch?” potassium, 15.3–46% calcium, 1–2% mag- day’s tanning methods, we concluded that nesium and 1–2% phosphorus.[19] a unique tanning procedure could have We cooked fat with ash in water under been used. 5. Further Investigation of Possible constant stirring and we obtained a fine We developed a tanning method which Old Tanning Methods emulsion[20] after removing the ash resi- could have been employed in this early due. Such a mixture consists of soluble al- time. This method was applied to leather It is well known that long chain fatty kaline fat and dispersed alkaline earth fats, to obtain accurate reference data. The acids can be produced from natural triglyc- as well as emulsified unsaponified starting analytical results from the reference fur erides by microbial activity typically found materials (Fig. 9). The untreated fat re- sample were in good agreement with those in soil. As an example, body fat is decom- leases free fatty acids upon ageing, typi- obtained from Ötzi’s clothes. This allows posed to adipocere by bacterial enzymes cally leading to fatty spew, which should us to conclude that tanning of the Iceman’s that cleave the fatty acids from the glycerol be avoided in modern tanning techniques clothes partly consisted of saponified land molecule. In soils the cleaved fatty acids but which was surely not a problem in an- animal fats, which had been physically in- may be easily converted to their calcium cient times. corporated, mainly in the form of calcium salts.[12,18] Therefore, one could envisage In this process, the possibility of side stearate. The superior water-repellent ef- that Ötzi’s clothes could have been im- reactions with unsaturated fat can be dis- fect of this tanning procedure would have mersed deliberately in soil after impregna- carded as the amounts of these by-products been especially suitable for the rainy, tion with fat or that fat simply decomposed are too small in animal fat. Therefore, the snowy and generally wet alpine conditions slowly in the glacier flow over this long principle of this tanning method is the pro- of the region inhabited by Ötzi. This may period of time. duction of high quantities of calcium salts have been the beginning of the water-repel- These hypotheses did not satisfy us of saturated fatty acids from land animal lent treatment of leather and fur. entirely and we therefore tried to imagine fat by control of time, temperature and a possible alternative tanning technique, other reaction conditions. With this mix- Acknowledgements which, although no documentary evidence ture we were able to obtain similar tanning At the end of 1992 we received first existed, could have been used in those effects as on Ötzi’s fur. The emulsion as information of the Iceman leather findings times, to explain the presence of the high such could be much more easily incorpo- and a request for analytical help. At that time concentration of calcium salts of saturated rated into the hide than untreated fat.[21] We we were Ciba-Geigy AG employees. We obtained very small pieces of Ötzi’s leather fatty acids. did this either by immersion in a bath or clothes from Dipl. Ing. J. Lange† for analytical Calcium stearate and its homologues mechanically with stuffing auxiliaries such investigation; the work basically represented are known as water repellents, even as the remaining ash or with other support- our ‘leisure time research’, which involved stronger than fat alone. In today’s tanning ing materials and we had to carefully mon- a lot of other researchers, and survived many process lime soap is known to be poorly itor the pH because high pH destroys the personal changes (retirement and re-location) soluble and results in smudges and stains. hair and the skin. We however did not find and company developments (mergers and 103 2 723 108 2 339 3 875 161 9 308 0 133 7 292 6 140 4 111 1 123 8 117 2 145 3 285 6 330 0 174 3 154 6 141 7 146 8 285 2 157 6 163 7 292 2 153 9

3500 3000 2500 2000 1500 1000 3500 3000 2500 2000 1500 1000 Wavenumber cm-1 Wavenumber cm-1

Fig. 8. ATR spectrum of Tyrolean trousers. Fig. 9. IR spectrum of a fat saponified with wood ash. 320 CHIMIA 2010, 64, No. 5 Note

spin-offs). We conclude our work with this [7] B. Tommer, ‘Die Kollagenmatrix archäo­lo­ final report and update earlier presentations gischer Funde im Vergleich zu künstlich geal­ ­ter­ given at the XXVIII IULTCS CONGRESS, ten Ledermustern historischer Gerbverfahren’, March 9–12, 2005 in Florence, Italy and 59th Dissertation an der Technischen Universität Bergakademie Freiberg, 2005. annual meeting of VGCT, Mai 10–11, 2007 [8] J. Dewhurst, J. Soc. Leather Technol. Chem. in Bad Reichenhall, Germany. Last but not 2004, 88, 260. least we would like to say thank-you to all [9] A. Gansser, ‘Die Vor- und Frühzeit der the supporters, researchers, our supervisors Gerberei’, CIBA-Rundschau 1949, 85, 3156. and our companies for allowing us to use their [10] Private communication from J. Lange†, LGR equipment. We thank also U. Bergamin and P. Reutlingen, Germany. Acker for their technical assistance in IR work, [11] L. Küpper, H. M. Heise, F.-G. Bechara, M. C. Guenat for MS measurements, K. Pulver Stücker, J. Mol. Struct. 2001, 565–566, 497. for EDX analysis, J. Pavel and D. Heim for [12] T. Bereuter, C. Reiter, W. Mikenda, Chem. Brit. elemental analysis and H. Schroeder and R. 1999, 25. [13] J. Bagg, M. B. Abramson, M. Fichman, M. D. Falchetto for reviewing the manuscript. Finally, Haber, H. P. Gregor, J. Am. Chem. Soc. 1964, we hope that in the future others will confirm 86, 2759. or modify our assumption of early leather [14] Private communication, K. Pulver, Solvias, production with a 1:1 field trial. Basel. [15] Private collection, J. Lange, LGR Reutlingen.­ Received: March 30, 2010 [16] Private communication, N. Robert, Fort St. James, National Historic Park, Canada. [1] Recommended Website: http://www.iceman.it [17] Private communication, A. Dokan, Nanai tan­ [2] M. Egg, K. Spindler, W. Groeman-van ner, Vietach, Germany. Waateringe, ‘Die Gletschermumie vom [18] S. L. Forbes, B. H. Stuart, I. R. Dadour, B. B. Ende der Steinzeit’, Jahrbuch des Römisch- Dent, J. Forensic Sci. 2004, 49, 566. Germanischen Zentralmuseums Mainz 1992, [19] A. Zoller, N. Remler, H.-P. Dietrich, 39, Teil 1,1. ‘Eigenschaften von Holzasche und [3] K. Spindler, ‘The Man in the Ice’, Weidenfeld Möglichkeiten der Wiederverwertung im Wald’, & Nicolson, London, 1994. Landesanstalt für Wald und Forstwirtschaft, [4] F. Hopfel, W. Platzer, K. Spindler, ‘Der Mann LWF Bericht 14, 1997. im Eis’, Bericht über das Internationale [20] Small laboratory test, R. Saumweber, Basel. Symposium 1992 in Innsbruck, Eigenverlag der [21] Small field test, G. Renner, Basel. Universität Innsbruck, 1992. [5] K. Hollemeyer, W. Altmeyer, E. Heinzle, C. Pitra, Rapid Commun. Mass Spectrom. 2008, 22, 2751. [6] T. Körner, ‘Geschichte der Gerberei’, in ‘Hand­ buch der Gerbereichemie’, Springerverlag, Wien, 1944, p 1.