The First Wine & Beer. Chemical Detection of Ancient Fermented
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The First Wine & Beer Chemical Detection of Ancient Fermented Beverages ease, and materials processing. complex mixture of water and or- Rudolph H. Michei and Under certain conditions. in either ganic compounds (Figure l), iuclud- Patrick E. McGovern very dry or waterlogged'environ- ing alcohols, aldehydes, acids, carbo- Museum Amlied Saence Center for menta where microbial activitv and hydrates, proteins, esters, and Downloaded by UNIV OF PENN on July 16, 2009 Archaeokgy (MASCA) autoxidation are reduced, some or- polyhydroxyaromatics such as tan- University Museum ganic compounds or their degrada- nins, anthocyanins, flavonols, and University of Pennsylvania tion products are preserved in an- catechins, all of which contribute Philadelphia, PA 19104 cient archaeological contexts. We significantly to its color and taste. previously demonstrated the pres- Phenolic carboxylic acids, which Published on September 22, 2008 http://pubs.acs.org | doi: 10.1021/ac00056a002 Virginia R. Badier ence of royal purple, one of the most are the degradation pmducta of poly- Department of Near Eastern Studies famous dyes of antiquity, on pottery hydroxyaromatics, are relatively sta- University of Toronto ble and are a distinguishing group of Toronto. Ontario sherds (Adchem lS86,57,1514A). Canada M5S 1Al In this article, we report our investi- compounds found in grapes that gations of another luxury item of might be sought in an analysis. Even many cultures: wine. This investiga- more specific is tartaric acid and its Organic analysis applied to archaeo- tion, in turn, has led to discoveries salts, which occur in large amounts logical remains, especially the con- about another, perhaps less presti- only in grapes. The survival of the tents of pottery vessels, has devel- gious but no less important, fer- latter compounds, however, is not as- oped rapidly over the past two mented beverage: beer. sured, especially in view of their fi- decades. Lipids, resins, dyes, per- nite water solubilities. fume ingredients, drugs, and other Wine and archaeology Once a compound such as tartaric compounds-some less than a milli- The chemical detection of a fer- acid or potassium bitartrate is iden- gram in weight and some thousands mented beverage such as wine or tified, there is still the problem of of years old-have been identitied by beer is a greater analytical and ar- how to distinguish between grape using a wide range of chemical and chaeological challenge than that of juice, grape syrup, another fruit juice physical techniques. As these meth- royal purple (6, 6'-dibromoindigotin), (e.g., from dates or pomegranates) ods are further refined, archaeologi- which occurs only in certain marine that has been adulterated with grape cal chemistry promises to open up mollusks and is stable because of its juice, and wine. If written or picto- new chapters in human and environ- resonance structures. Wine is a pro- rial evidence exists, such as inscrip- mental history, including ethnicity cessed beverage made from grape tions on the sides of vessels detailing and genetic development, diet, dis- juice or must. It is an unusually their contents, interpretation is eas- 408 A * ANALMICALCHEMISTRY, VOL. 65, NO. 8, APRIL 15,1993 W03- 2700/93/0365-408Al$04.00/0 0 1993 American Chemical Society Vintugesrenefiom the tomb of Nukht, Western lhebes, New Kingdom. (Dauies, N., lhe Tomb ofNakht at lhebes; reprinted with pennission/mm the Metmpolitun Museum ofArf,New York.) ier. For prehistoric periods, however, home to one of the oldest literate civ- graphic tablet, and other artifacts there is only the “mute” archaeologi- ilizations in the world the Sumerian were discovered within an oval com- cal record. From this-at best, only a and Elamite city-states. Here, clay plex of well-constructed symmetrical partial record-the researcher at- tablets incised with pictographic rooms enclosing a central courtyard, Downloaded by UNIV OF PENN on July 16, 2009 tempts to infer whether a pottery characters were unearthed. The the Citadel Mound complex. These vessel might have served a special growing population was supported findings, which were contemporary purpose or whether the presence of by irrigation agriculture and horti- with the earliest lowland city-states grape pips (seeds) in a certain con- culture of domesticated plants (e.g., of the Late Uruk period, can be un- text points to wine-making, con- cereals, figs, and dates). Traders and derstood within the broader cultural Published on September 22, 2008 http://pubs.acs.org | doi: 10.1021/ac00056a002 sumption of the whole fruit, or some adventurers exploited surrounding developments of the time. It is plau- other activity. areas for precious commodities such sible that Godin Tepe was an early as gold, copper, lapis lazuli, carne- Sumerian and/or Elamite trading Wine-making in the highlands of lian, and timber, which were un- post, administrative center, and/or Iran? Archaeologists under the direction of T. Cuyler Young, Jr., of the Royal Ontario Museum in Toronto were ANALYTICAL faced with a puzzling set of evidence during their excavations of Period V APPROACH remains at Godin Tepe, located in the Zagros Mountains of western available in lowland Greater Meso- military base for protecting the trade Iran. Period V, dating between ap- potamia. route. proximately 3500 B.C. and 2900 B.C. The Zagros Mountains, bordering Other finds are more difficult to (the Late Udperiod), is contempo- lowland Greater Mesopotamia, pro- understand. An unusually large fun- raneous with the beginnings of com- vided some of these raw materials nel, about half a meter in diameter, plex urban life as we know it. and were tied into the wider trading and a circular “lid” of smaller diame- Lowland Greater Mesopotamia, network. Godin Tepe is located along ter were recovered from one room of comprising the wide alluvial plains the High Road or the Great Kho- the Citadel Mound comnlex. McGuire of the lower Tigris and Euphrates rasan &ad (the famous Silk Road of Gibson of the Universiiy of Chicago’s rivers in modem Iraq and of Khuz- laler times) in the central Zagros Oriental Institute proposed that the istan in southwestern Iran, was Mountains. Pottery, an early picto- funnel, covered with a coarsely wo- ANALYTICAL CHEMISTRY, VOL. 65. NO. 8. APRIL 15.1993 e 409 A ANALYTICAL APPROACH ven cloth (long since deteriorated), appeared to have been a residence is an organic or inorganic residue. might have served as a strainer for where wine might have been con- DRIFTS has the advantage that the grape must. Such large funnels are sumed; the other room might have archaeological sample need not be known to have been used much later been used to distribute wine and damaged, and it eliminates the need in wine-making installations in the other goods to merchants, soldiers, for preparing an optically transpar- Middle East. It is possible that and others through two windows fac- ent potassium bromide wafer. The grapes were heaped into the funnel, ing the central courtyard. spectra from either technique will the lid wa8 used to apply weight and The jars with the red deposits are show the same absorption bands at measure. and the iuice was directed a unique pottery type that has a rope the same wavelengths. &to a ja;. design applied as two inverted U This was a Dlausible scenario. but shapes along opposite exterior sides it lacked har'd evidence. No &ape of each vessel. During the Late Uruk pips, which are often well preserved, period, rope designs often indicated were found in the room, 'and the fun- the placement of real rope. The nel might have been used for another shape and placement of the inverted liquid. The lid might have been just U suggested a means by which these that-a lid for a wide-mouthed ves- vessels could have been supported on sel. The wine-making hypothesis, their sides. In fact, the red deposits however, became more compelling on the interiors of one whole vessel when one of us (VRB) noted a red de- were confined to the base and the posit on the insides of several jars sidewall (Figure 3). The red residue (Figure 2) from two rooms that were was on the same side of the vessel aa directly across the courtyard from the applied rope decoration on the the room where the funnel and lid outside. The deposit was precisely were found. Could the red deposits where materials would have settled have been wine deposits? One room out from a liquid if the vessel had been stored on ita side. The inference that this jar once contained a liquid was supported by another stylistic peculiarity. These jars have relatively narrow mouths and tall necks, compared with other jars of the same period. A narrow- mouthed, tall-necked vessel would Figure 2. Godin Tepe wine jar, late be better suited for storing and pour- Period V. ing liquids. (Counesy William Pran. Royal Ontario Museum.) It also seemed likely that the jars had once been sealed, because two unfired clay stoppers-slightly smaller than the mouth and neck di- ameters of the jars-were found dis- Downloaded by UNIV OF PENN on July 16, 2009 carded in other mms of the complex. The clay could have functioned like a modern-day wine cork, absorbing liquid and expanding to keep out the oxygen, if the vessels had been laid Published on September 22, 2008 http://pubs.acs.org | doi: 10.1021/ac00056a002 on their sides. Such precautions make sense if wine were the in- tended final product. Grape juice quickly ferments to wine. The trick is to stop it from be- coming vinegar, and this could have been accomplished by a technique still used today: stoppering the ves- sel and storing it on its side. ldentiflcation of tartaric acid Clearly, hypotheses about wine pro- duction and consumption at Godin Tepe stand or fall on whether the jars did indeed contain organic com- pounds derived from grapes.