In modern museums and archives, ancient texts, manuscripts and books are stored under certain conditions, which allows them to preserve their original appearance for future generations. The Dead Sea Scrolls (Qumran Manuscripts), first found in 1947 and dating back to 408 BC, are considered the most striking representative of imperishable manuscripts. e. Some of the scrolls have survived only in fragments, but there are also virtually untouched by time. And here the obvious question arises - how did people manage to create manuscripts more than 2000 years ago that have survived to this day? This is exactly what the Massachusetts Institute of Technology decided to find out. What did scientists find in ancient scrolls and what technologies were used to create them? We learn about this from the report of the researchers. Go.
Historical information
In the relatively recent year 1947, the Bedouin shepherds Mohammed ed-Dhib, Juma Mohammed and Khalil Musa went in search of a missing sheep, which led them to the caves of Qumran. Whether the shepherds found the stray artiodactyl is silent, but they found something much more valuable from a historical point of view - several clay jugs in which ancient scrolls were hidden.
Caves of Qumran.
Muhammad took out several scrolls and brought them to his settlement to show to his fellow tribesmen. Some time later, the Bedouins decided to give the scrolls to a merchant named Ibrahim Ija in Bethlehem, but the latter considered them trash, suggesting that they were stolen from the synagogue. The Bedouins did not stop trying to sell their find and went to another market, where a Syrian Christian offered to buy scrolls from them. As a result, the sheikh, whose name remained unknown, joined the conversation and advised him to contact the antiques dealer Khalil Eskander Shahin. The result of this slightly confusing story of finding a market was the sale of the scrolls for 7 Jordanian pounds (a little over $314).
The jars in which the scrolls were found.
Perhaps the priceless scrolls would have been gathering dust on the shelves of an antiques dealer if they had not attracted the attention of Dr. John C. Trever of the American School of Oriental Research (ASOR), who compared the subjects in the scrolls with those in the Nash Papyrus, the oldest biblical manuscript known at that time, and found similarities between them.
Scroll of Isaiah, containing almost the entire text of the Book of the Prophet Isaiah. The length of the scroll is 734 cm.
In March 1948, at the height of the Arab-Israeli war, the scrolls were transported to Beirut (Lebanon). On April 11, 1948, ASOR head Millar Burrows officially announced the discovery of the scrolls. From that moment, a full-scale search began for the very cave (it was called cave No. 1), where the first scrolls were found. In 1949, the Jordanian government issued a permit to conduct searches on the territory of Qumran. And already on January 28, 1949, the cave was found by the Belgian observer of the United Nations, Captain Philip Lippens and the captain of the Arab Legion Akkash el-Zebn.
Since the discovery of the first scrolls, 972 manuscripts have been discovered, some of which were intact, and some were collected only in the form of separate fragments. The fragments were quite small, and their number exceeded 15 (we are talking about those found in cave No. 000). One of the researchers tried to put them together until his death in 4, but could not finish his work.
Scroll fragments.
In terms of content, the Dead Sea Scrolls consisted of biblical texts, apocrypha and pseudepigrapha, and literature of the Qumran people. The language of the texts was also diverse: Hebrew, Aramaic and even Greek.
The texts were written with the help of coal, and the material for the scrolls themselves was parchment from the skin of goats and sheep, and there were also manuscripts on papyrus. A small part of the found scrolls was made by the technique of embossing the text on thin sheets of copper, which were then rolled up and placed in jugs. It was impossible to unfold such scrolls without their inevitable destruction due to corrosion, therefore, archaeologists cut them into pieces, which were then compiled into a single text.
Fragments of a copper scroll.
If the copper scrolls demonstrated the impartial and even cruel nature of the passage of time, then there were those over which time seemed to have no power. One of these examples is a scroll 8 meters long, which attracts attention with its small thickness and bright ivory color. Archaeologists call it the “Temple Scroll”, due to the mention in the text of the First Temple, which Solomon was supposed to erect. The parchment of this scroll has a layered structure, consisting of a collagen base material and an atypical inorganic layer.
Temple scroll. You can better view the entire Temple Scroll by .
Scientists in the work we are considering today analyzed the chemical composition of this unusual inorganic layer using X-ray and Raman spectroscopy and discovered salt rocks (sulfate evaporites). Such a find points to some unique method of creating the analyzed scroll, capable of revealing the secrets of the preservation of ancient texts, which can be applied in our time.
Results of the analysis of the Temple Scroll
As scientists note (and as we ourselves can see from the photo), most of the Dead Sea Scrolls are quite dark in color, and only a small part of the light color. In addition to its striking appearance, the Temple Scroll has a layered structure with text written on an ivory inorganic layer that covers the skin used as the base of the scroll. On the reverse side of the scroll, you can see the presence of hairs remaining on the skin.
Image #1: А - the appearance of the scroll, B - a place where the inorganic layer and text are missing, С - text side (left) and reverse side (right), D - light indicates the presence of an area where there is no inorganic layer (lighter areas), Е - Enlarged optical micrograph of the area highlighted by the dotted line in 1C.
Tracks hair follicle*, visible on the back of the scroll (1А), say that part of the text on the scroll was written on the inside of the skin.
Hair follicle* - an organ located in the dermis of the skin and consisting of 20 different types of cells. The main function of this dynamic organ is the regulation of hair growth.
On the text side, there are "bare" areas where there is no inorganic layer (1C, left), showing a yellowish collagen base layer. Also, areas were found in places of twisting, where the text, together with the inorganic layer, was "reprinted" on the reverse side of the scroll.
µXRF and EDS scroll analysis
After a visual inspection of the scroll, scientists conducted µXRF* и EDS* analysis.
XRF* (X-ray fluorescence analysis) - spectroscopy, which allows you to find out the elemental composition of a substance by analyzing the spectrum that occurs when the material under study is irradiated with X-rays. µXRF (micro X-ray fluorescence analysis) differs from XRF in significantly lower spatial resolution.
EDS* (energy dispersive x-ray spectroscopy) is a method of elemental analysis of a solid, which is based on the analysis of the emission energy of its x-ray spectrum.
Image #2
The Temple Scroll is notable for its heterogeneity (2А) in terms of chemical composition, which is why the scientists decided to use such precise methods of analysis as µXRF and EDS on both sides of the scroll.
The total µXRF spectrum of the regions of interest (sections of the scroll where the analysis was carried out) showed a complex composition of the inorganic layer, consisting of many elements, the main of which are (2S): sodium (Na), magnesium (Mg), aluminum (Al), silicon (Si), phosphorus (P), sulfur (S) chlorine (Cl), potassium (K), calcium (Ca), manganese (Mn), iron (Fe) and bromine (Br).
The µXRF element distribution map showed that the main elements Na, Ca, S, Mg, Al, Cl, and Si are distributed throughout the fragment. It can also be assumed that aluminum is fairly evenly distributed throughout the fragment, but scientists are not ready to state this with 100% accuracy due to the strong similarity of the K-line of aluminum and the L-line of bromine. But the presence of potassium (K) and iron (Fe), the researchers explain the contamination of the scroll, and not the intentional introduction of these elements into its structure during creation. There is also an increased concentration of Mn, Fe and Br in the thicker regions of the fragment where the organic layer has not been separated.
Na and Cl show the same distribution throughout the study area, that is, the concentration of these elements is quite high in areas where the organic layer is present. However, there are differences between Na and Cl. Na is more evenly distributed, while Cl does not match the structure of cracks and small delaminations in the inorganic layer. Thus, Na-Cl distribution correlation maps may indicate the presence of sodium chloride (NaCl, i.e. salt) only within the organic layer of the skin, which is a consequence of the processing of the skin in the preparation of the parchment.
Next, the researchers carried out scanning electron microscopy (SEM-EDS) of the sections of the scroll of interest, which allows them to quantify the chemical elements on the surface of the scroll. EDS provides high lateral spatial resolution due to relatively small electron penetration depth. To achieve this effect, a low-vacuum scanning electron microscope was used, since it minimizes damage caused by vacuum and allows elemental mapping of non-conductive samples.
EDS analysis of element maps (2D) shows the presence of particles in the region of interest of the inorganic layer, which predominantly contain sodium, sulfur and calcium. Silicon was also found in the inorganic layer, but not in the Na-S-Ca particles found on the surface of the inorganic layer. Higher concentrations of aluminum and chlorine were found between particles and in organic material.
Maps of the elements sodium, sulfur and calcium (insert on 2V) show a clear correlation between these three elements, and the arrows point to particles in which sodium and sulfur were observed, but little calcium.
Image #3
µXRF and EDS analysis made it clear that the inorganic layer contains particles rich in sodium, calcium and sulfur, as well as other elements in a smaller proportion. However, these research methods do not allow a detailed study of chemical bonds and phase characteristics; therefore, Raman spectroscopy (Raman spectroscopy) was used for this.
To reduce background fluorescence, which is usually observed in Raman spectra, low-energy excitation wavelengths were used. In this case, Raman spectroscopy at a wavelength of 1064 nm allows you to collect data on fairly large (400 µm in diameter) particles (3А). Both spectra in the graph show three main elements: a double sulfate peak at 987 and 1003 cm-1, a nitrate peak at 1044 cm-1, and proteins typical of collagen or gelatin.
In order to clearly separate the organic and inorganic components of the scroll fragment under study, near infrared radiation at 785 nm was used. On the image 3V the spectra of collagen fibers (spectrum I) and inorganic particles (spectra II and III) are clearly visible.
The spectral peak of collagen fibers includes the characteristic features of nitrate at 1043 cm-1, which can be associated with the vibration of NO3− ions in NH4NO3.
The spectra of particles containing Na, S, and Ca indicate that the inorganic layer contains particles from mixtures of sulfate-containing minerals in different proportions.
For comparison, the spectral peaks of the air-dried synthetic mixture of Na2SO4 and CaSO4 fall at 450 and 630 cm-1, i.e. differ from the spectra of the studied sample (3V). However, if the same mixture is dried by rapid evaporation at 250°C, then the Raman spectra will coincide with the spectra of the Temple Scroll in its sulfate fragments.
Spectrum III is associated with very small particles in an inorganic layer about 5-15 µm in diameter (3S). These particles showed very intense Raman scattering at an excitation wavelength of 785 nm. The characteristic triplet spectral signature at 1200, 1265 and 1335 cm-1 reflects vibrational units of the "Na2-X" type. This triplet is characteristic of sulfates containing Na and is often found in minerals such as thenardite (Na2SO4) and glauberite (Na2SO4 CaSO4).
Image #4
Next, the scientists used EDS to create an elemental map of large sections of the Temple Scroll, both on the text side and on the back. In turn, backscattering of the brighter text side (4B) and a darker reverse side (4C) revealed a rather heterogeneous composition. For example, next to a large crack on the side with text (4V) one can see clear differences in electron density between the inorganic layer and the underlying collagen material.
Next, a quantitative determination of all elements present in the fragment of the scroll (Ca, Cl, Fe, K, Mg, Na, P, S, Si, C and O) was carried out in the atomic ratio format.
The triangular diagrams above show the ratio of three elements (Na, Ca and S) in a 512x512 pixel ROI. Charts on 4A и 4D show the relative density of points on the diagrams, the color gradation of which is indicated to the right of 4D.
After analyzing both diagrams, it was concluded that the ratios of calcium to sodium and sulfur in each of the pixels of the studied area (on the text and reverse sides of the scroll) correspond to glauberite and thenardite.
After that, all EDS analysis data were grouped taking into account the ratio of the main elements using the C-means fuzzy clustering algorithm. This made it possible to visualize the distributions of various phases both on the text side and on the reverse side of the scroll fragment. This data was then used to determine the most likely division of the 5122 data points of each of the datasets into a predetermined number of clusters. The data for the text side was divided into three clusters, and the data for the reverse side was divided into four. Clustering results are presented as overlapping clusters on triangular plots (4E и 4H) and as distribution maps (4F и 4G).
The clustering results show the distribution of dark organic material on the reverse side of the scroll (blue on 4K) and where cracks in the inorganic layer on the text side expose the collagen layer underneath (yellow on 4J).
The main studied elements were assigned the following color: sulfur - green, calcium - red and sodium - blue (triangular diagrams 4I и 4L, as well as distribution maps 4J и 4K). As a result of "coloring", we clearly see differences in the concentration of elements: sodium is high, sulfur is moderate and potassium is low. This trend is observed on both sides of the scroll fragment (text and reverse).
Image #5
The same method was used to display Na-Ca-S concentrations in another area of the scroll fragment under study, as well as in three other fragments from cave #4 (R-4Q1, R-4Q2 and R-4Q11).
Scientists note that only a fragment of R-4Q1 from cave No. 4, according to diagrams and maps of the distribution of elements, coincides with the Temple Scroll. In particular, the results show ratios for R-4Q1 that correspond to the theoretical Na-Ca-S ratio of glauberite.
Raman measurements of the R-4Q1 fragment, collected at an excitation wavelength of 785 nm, show the presence of sodium sulfate, calcium sulfate, and calcite. Analysis of R-4Q1 collagen fibers showed no presence of nitrate.
Consequently, the Temple Scroll and R-4Q1 are extremely similar in elemental composition, which indicates the use of the same technique for their creation, apparently associated with evaporite salts. Two other scrolls obtained from the same cave at Qumran (R-4Q2 and R-4Q11) show ratios of calcium to sodium and sulfur that differ significantly from the results of the Temple Scroll and the R-4Q1 fragment, suggesting a different production method.
Summing up, we can say that the inorganic layer on the scroll contained a number of minerals, most of which are sulfate salts. In addition to gypsum and its analogs, thenardite (Na2SO4) and glauberite (Na2SO4·CaSO4) have also been identified. Naturally, it can be assumed that some of these minerals may be the decomposition product of the main layer of the scroll, but it can be confidently stated that they were definitely not present in the caves themselves, where the scrolls were found. This conclusion is easily confirmed by the fact that the sulfate-containing layers on the surfaces of all the studied fragments found in different Qumran caves do not correspond to the mineral deposits found on the walls of these caves. The conclusion is that evaporite minerals were incorporated into the structures of the scrolls during their production.
Scientists also note the fact that the concentration of sulfates in the water of the Dead Sea is relatively low, and glauberite and thenardite are not usually found in the Dead Sea region. A quite logical question arises - where did the creators of these ancient scrolls get glauberite and thenardite from?
Regardless of the origin of the source materials for the creation of the Temple Scroll, the method of its creation is very different from that used for other manuscripts (for example, for R-4Q1 and R-4Q2 from Cave #4). Given this difference, scientists suggest that the scroll itself was created according to the then generally accepted technique, but then was modified with an inorganic layer, which allowed it to survive for more than 2000 years.
For a more detailed acquaintance with the nuances of the study, I recommend looking at и to him.
Finale
A nation that does not know its past has no future. This phrase refers not only to historically significant events and personalities, but also to technologies that were used many centuries ago. Someone may think that at the moment we no longer need to know exactly how these scrolls were created 2000 years ago, since we have our own technologies that allow us to preserve texts in their original form for many years. However, first of all, isn't it curious? Secondly, many of the current technologies, no matter how trite it may sound, were used in one form or another in antiquity. And, as we already know, even then humanity was full of brilliant minds, the ideas of which can push modern scientists to new discoveries or to improve existing ones. Learning from the example of the past cannot be considered shameful, and even more so it cannot be considered useless, because the echo of the past always resonates in the future.
Friday off-top:
A documentary (Part I) that tells the story of the Dead Sea Scrolls, one of the most important archaeological finds in human history. ().
Thanks for watching, stay curious and have a great weekend everyone! 🙂
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