Manuscripts do not burn: the secret to the longevity of the Dead Sea scrolls dating back to 250 BC

In modern museums and archives, ancient texts, manuscripts and books are stored in certain conditions, which allows you to preserve their original appearance for future generations. The most prominent representative of imperishable manuscripts are the Dead Sea scrolls (Qumran manuscripts), first found back in 1947 and dating back to 408 BC. e. Some of the scrolls are preserved only fragmentary, but there are also almost untouched by time. And here the obvious question arises - how did people manage to create manuscripts that survived to our days more than 2000 years ago? This is exactly what they decided to find out at the Massachusetts Institute of Technology. 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.

History reference

In the relatively recent 1947, the Bedouin shepherds Muhammad al-Dhib, Juma Mohammed and Khalil Musa went in search of the missing sheep, which led them to the Qumran caves. Whether the shepherds found the stray artiodactyl history 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 his fellow tribesmen. Some time later, the Bedouins decided to hand over the scrolls to a merchant named Ibrahim Ija in Bethlehem, but the latter considered them garbage, suggesting that they had been stolen from the synagogue. The Bedouins made no attempt to sell their find and went to another market, where a Syrian Christian offered to buy scrolls from them. As a result, a sheikh connected to the conversation, whose name remained unknown, and advised contacting an antique dealer, Khalil Eskander Shahin. The result of this slightly confusing story of a market search was the sale of scrolls for 7 Jordanian pounds (just over $ 314).





Pitchers in which scrolls were found.



Perhaps the priceless scrolls would have been gathering dust on the shelves of an antique dealer if they had not caught the attention of Dr. John C. Trever of the American School of Oriental Studies (ASOR), who compared the scrolls to those of the Nash papyrus, the oldest known biblical manuscript, and found a similarity between them.





The scroll of Isaiah, containing almost the full 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 Burroughs officially announced the discovery of scrolls. From that moment, a full-scale search for the very cave began (it was called cave No. 1), where the first scrolls were found. In 1949, the Jordanian government granted permission to conduct searches in Qumran. And already on January 28, 1949, the cave was found by the Belgian observer of the United Nations, captain Philip Lippens and captain of the Arab Legion Akkas el Zebn.



Since the first scrolls were found, 972 manuscripts were found, some of which were intact, and some were collected only in separate fragments. The fragments were quite small, and their number exceeded 15,000 (we are talking about those found in cave No. 4). One of the researchers tried to put them together until his death in 1979, but could not finish his work.





Fragments of scrolls.



In content, the Dead Sea Scrolls consisted of biblical texts, apocrypha and pseudo-epigraphs, 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 parchments from the skin of goats and sheep, and manuscripts were also found on papyrus. A small part of the scrolls found was made using the technique of extruding text on thin sheets of copper, which were then twisted and placed in jugs. It was impossible to expand such scrolls without their inevitable destruction due to corrosion, therefore, archaeologists cut them into pieces, which were then made into a single text.





Fragments of a copper scroll.



If the copper scrolls showed 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 items is a scroll length of 8 meters, attracting attention with its small thickness and bright ivory color. Archaeologists call it the “Temple Scroll,” in view of 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 see the entire Temple scroll at this link .



Scientists in the work we are considering today conducted an analysis of the chemical composition of this unusual inorganic layer by x-ray and Raman spectroscopy and discovered salt rocks (sulfate evaporites). Such a finding indicates a unique method for creating an analyzed scroll, which can reveal the secrets of preserving ancient texts, which can be applied in our time.

Temple Scroll Analysis Results

As scientists note (and as we 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 multi-layered structure with text written on an inorganic ivory layer that covers the skin used as the base of the scroll. On the back of the scroll, you can notice the presence of hairs remaining on the skin.





Image No. 1: A - the appearance of the scroll, B - the place where the inorganic layer and the text are absent, C - the text side (left) and the reverse side (right), D - the light indicates the presence of the area where the inorganic layer is absent (lighter areas ), E - An enlarged optical micrograph of the area indicated by a dotted line at 1C.



Traces of a hair follicle * visible on the back of the scroll ( 1A ) indicate that part of the text on the scroll was written on the inside of the skin.

The hair follicle * is 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 to regulate hair growth.

On the text side, there are “bare” areas in which there is no inorganic layer ( 1C , on the left), which makes the yellowish collagen base layer visible. Plots were also found in places of twisting, where the text, along with the inorganic layer, was "reprinted" on the back of the scroll.

µXRF and EDS Scroll Analysis

After a visual inspection of the scroll, the scientists performed µXRF * and 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 is irradiated with x-ray radiation. 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 substance, which is based on the analysis of the emission energy of its x-ray spectrum.

Image No. 2



The temple scroll is distinguished by its heterogeneity ( 2A ) in terms of chemical composition, which is why scientists decided to apply such precise analysis methods as µXRF and EDS on both sides of the scroll.



The total μXRF spectrum of areas of interest (sections of the scroll where the analysis was performed) showed a complex composition of the inorganic layer, consisting of many elements, the main of which are ( 2C ): 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 map of the distribution of elements showed that the main elements of 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 say this with 100% accuracy due to the strong similarity between the K-line of aluminum and the L-line of bromine. But the presence of potassium (K) and iron (Fe), the researchers explain the pollution of the scroll, and not the intentional introduction of these elements into its structure at the time of creation. An increased concentration of Mn, Fe, and Br is also observed in the thicker regions of the fragment, where the organic layer was not 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 distributed more evenly, while Cl does not correspond to the structure of cracks and small delaminations in the inorganic layer. Thus, correlation maps of the distribution of Na-Cl can indicate the presence of sodium chloride (NaCl, i.e. salt) only inside the organic layer of the skin, which is a consequence of processing the skin when preparing parchment.



Further, the researchers performed scanning electron microscopy (SEM – EDS) of the scroll sections of interest to them, which makes it possible to quantitatively determine the chemical elements on the scroll surface. EDS provides high lateral spatial resolution due to the 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-conducting samples.



An analysis of the EDS 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 detected 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 detected between particles and in organic material.



Maps of the elements of sodium, sulfur, and calcium (insert on 2B ) show a clear correlation between the three elements, and the arrows indicate particles in which sodium and sulfur were observed, but not enough calcium.





Image No. 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 the 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 the collection of data of sufficiently large (400 μm in diameter) particles ( 3A ). Both spectra on the graph show three main elements: a double peak of sulfate at 987 and 1003 cm ^-1 , a peak of nitrate at 1044 cm ^-1 and proteins typical of collagen or gelatin.



In order to clearly separate the organic and inorganic components of the studied fragment of the scroll, near infrared radiation at 785 nm was applied. Spectra of collagen fibers (spectrum I) and inorganic particles (spectra II and III) are clearly visible in image 3B .



The spectral peak of collagen fibers includes the characteristic features of nitrate at 1043 cm ^-1 , which can be attributed to the vibration of NO3 ^- ions in NH ₄ NO ₃ .



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 Na ₂ SO ₄ and CaSO ₄ fall at 450 and 630 cm ^-1 , i.e. differ from the spectra of the test sample ( 3B ). 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 the inorganic layer with a diameter of about 5-15 microns ( 3C ). 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 Na ₂ -X type. This triplet is characteristic of sulfates containing Na, and is often found in minerals such as tenardite (Na ₂ SO ₄ ) and glauberite (Na ₂ SO ₄ · CaSO ₄ ).





Image No. 4



Scientists then applied 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 scanning of the brighter text side ( 4B ) and the darker back side ( 4C ) revealed a rather heterogeneous composition. For example, next to a large crack on the side with the text ( 4B ), you can see clear differences in the electron density between the inorganic layer and the underlying collagen material.



Next, a quantitative determination of all the 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 the three elements (Na, Ca and S) in the study area of ​​512x512 pixels. The graphs on 4A and 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 study area (from the text and back of the scroll) correspond to glauberite and tenardite.



After that, all EDS analysis data was grouped taking into account the ratio of the main elements using the fuzzy clustering algorithm of C-means. This allowed us to visualize the distribution of various phases both on the text side and on the back side of the scroll fragment. Further, these data were used to determine the most probable separation of 5122 data points of each of the data sets into a predetermined number of clusters. Data for the text side was divided into three clusters, and data for the back side was divided into four. Clustering results are presented as overlapping clusters in triangular diagrams ( 4E and 4H ) and as distribution maps ( 4F and 4G ).



Clustering results show the distribution of dark organic material on the back of the scroll (blue on 4K ) and where cracks in the inorganic layer on the text side expose the collagen layer below it (yellow on 4J ).



The following colors were assigned to the main test elements: sulfur — green, calcium — red and sodium — blue (triangular diagrams 4I and 4L , as well as 4J and 4K distribution maps). As a result of “coloring”, we clearly see differences in the concentration of elements: sodium - high, sulfur - moderate and potassium - low. This trend is observed on both sides of the scroll fragment (text and reverse).





Image No. 5



The same method was used to display the concentration of Na-Ca-S in another area of ​​the studied fragment of the scroll, as well as in three other fragments from cave No. 4 (R-4Q1, R-4Q2 and R-4Q11).



Scientists note that only fragment R-4Q1 from cave No. 4 according to diagrams and distribution maps of elements coincides with the Temple Scroll. In particular, the results show a ratio for R-4Q1, which corresponds to the theoretical Na-Ca-S glauberite ratio.



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 collagen fibers R-4Q1 did not show the presence of nitrate.



Consequently, the Temple Scroll and R-4Q1 are extremely similar in elemental composition, which indicates the application of the same methodology for their creation, which, apparently, is associated with evaporite salts. Two other scrolls, obtained from the same cave in Qumran (R-4Q2 and R-4Q11), show ratios of calcium to sodium and sulfur, which are significantly different from the results of the Temple scroll and fragment R-4Q1, 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 analogues, tenardite (Na2SO4) and glauberite (Na2SO4 · CaSO4) were also identified. Naturally, it can be assumed that some of these minerals may be the product of decomposition 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 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. Conclusion - evaporite minerals were included in the structure of the scrolls during their production.



Scientists also note the fact that the concentration of sulfates in the Dead Sea water is relatively low, and glauberite and tenardite are usually not found in the Dead Sea region. A logical question arises - where did the creators of these ancient scrolls get glauberite and tenardite?



Regardless of the origin of the source materials for creating 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 No. 4). Given this difference, scientists suggest that the scroll itself was created according to the then generally accepted methodology, but then it 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 that you look into the report of scientists and additional materials to it.

Epilogue

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 don’t need to know exactly how these scrolls were created 2000 years ago, since we have our own technologies that allow us to save texts in their original form for many years. However, firstly, 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 mankind was full of brilliant minds, whose ideas can push modern scientists to new discoveries or to improve existing ones. Learning from the example of the past cannot be considered shameful, much less it cannot be considered useless, because the echo of the past always responds in the future.





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