Volume 17(2), 376- 379, 2013 JOURNAL of Horticulture, Forestry and Biotechnology www.journal-hfb.usab-tm.ro Galls most used for tanning in Romania - Andricus hungaricus and Andricus quercuscalicis: tannin level comparison

Hac, P.A.1*, Borlea Gh. F.1, Popescu Iuliana1

1Banat’s University of Agricultural Sciences and Veterinary Medicine – Timişoara

*Corresponding author. Email: [email protected]

Abstract Galls of Andricus hungaricus and Andricus quercuscalicis were Key words the most used in Romanian tanerries. Austrian-Hungarian Empire, at the end of XIXth century, exported these galls and the forestry industry substantially gall, tanning, Andricus profited financially. Because of the high level of tannin, compared with other hungaricus, Andricus natural plant or product components, galls were used to tan the thickest oxen quercuscalicis hide parts utilized for shoe making. It was generally known that such methods were used no later than the middle XXth century. However, it was later discovered that gall tanneries used galls up the the year 2000 in the Pancota area of Arad County, Romania. Previously, people from Ineu region collected forest galls and brought them to Pancota’s open market for sale. Tanners bought galls at the same price as acorn and then used their attics to dry them. Subsequently, they milled and boiled the galls together with leather. People, it was discovered, brought to market galls of Andricus quercuscalicis. Also, as mentioned in literature, galls of Andricus hungaricus were used in tannery. The question is, if the people sold only galls of Andricus quercuscalicis because these were the only galls found, or that only these galls were useful for tanneries. Research focused on analyzing the level of tannin in both gall types and concluded by identifying which one is preferred for tanning.

For many years, galls were considered harmful to host Andricus quercuscalicis galls, in that area called plant in a way that represented a tangible threat for „cobii”, and, by carts were transported to Pancota forests. After more detailed studies of these formations, (about 20 km away). And, sold the galls to tanners with it was concluded that the negative impact of the galls a price equivalent to corn. Galls were then attic dried was more minimal than originally thought. and ground into a powder utilizing a stone-grinding Subsequently, galls were then commonly used by mill-process. The flour obtained was placed in water, humans for many purposes. For example, in 1861, boiled, and mixed with animal hides. The tanned hides England imported over 800 tons of Cynips were used especially in the making of shoes, gallaetinctoriae gall (today Andricus gallaetinctoriae) specifically shoe soles. from Turkey for commercial purposes, especially for It is with high certainty that such historic use of galls medicinal use (4). The United States has imported galls for commercial purposes will sooner or later find their from Turkey since 1945. Ink obtained from European place amongst natural treatments used in the tanning oak galls was used for centuries. Monks used this gall- industry and not only. Thereby, such gall-use could based ink for translations and municipal documentation create a large potential for studying such processes and for 1000 years. In recent history the 1945 U.S. treaty for gall formation research. with Japan, ending WWII, was signed with oak gall ink (8). G. Csoka (Gubacsok, 1997) states that the Material and Methods exportation of Andricus hungaricus and Andricus quercuscalicis galls generated significant revenue for There were used 10 galls of Andricus quercuscalicis the Austrian-Hungarian Empire during the late 19th and 10 galls of Andricus hungaricus. All of them were century (4). The most important use of galls was for collected from Mures Floodplain Natural Park, Arad tanneries, because of its high level of tannin. It was County. recently found that in Pancota city, from Arad County, Tannin content analysis was performed according to one of the important tannery centers in western the International Pharmacopoeia and AOAC method. Romania, galls were used in skin processing until the Tannins are dosed on the basis of its reducing, by year 2000. The villagers around Ineu city collected titration with potassium permanganate. Tannins were

376 extracted from finely ground product with hot water, to be determined during the research. Also, in some with subsequent extraction for one hour. The extracts certain areas, it was assumed that Andricus were combined, and an aliquot was titrated with quercuscalicis galls were preferred rather than potassium permanganate in the presence of indigo. In Andricus hungaricus ones. It was supposed that is order to eliminate the effect of reducing other because of the higher level of tannin contained by the substances solubilized in the extract along with tannins, first one comparing with the second one. another portion of the extract was treated with Tannin content in the sample was calculated using the activated charcoal, and the filtrate obtained was titrated formula: with potassium permanganate in the presence of indigo. Extracts treated with activated charcoal adsorb % tannin = (V – V ) xFx0,04157xV/m (1) tannins, and the filtrate remains only reducing 1 2 substances leached. Three grams finely ground material was extracted with V - total volume of extract; 250 ml of hot distilled water, added five successive V1 - volume of 0.1 N KMnO4 solution used in fractions of 50 ml. Extracts were measured together titration of 10 ml of extract containing tannins and total score. 10 ml of the extract was measured extract other reductants; then added 750 ml of distilled water and 25 ml of V2 - volume of 0.1 N KMnO4 solution used in indigo. Titrate with 0.1 N KMnO4 solution until the titration of 10 ml of the extract were adsorbed on indicator to turn golden yellow (1). activated carbon tannins; Results F - factor 0.1 N KMnO4 solution used in titration = 0.9856 In order to verify why the two galls were used in tanning instead other products, the level of tannin had

Table 1 Andricus hungaricus galls - level of tannin Sample mass No. The total amount of extract, V (ml) V1 V2 % tannin (g)

1 3,0675 235 14,2 10,6 11,30

2 2,9982 235 14,3 10,8 11,24

3 3,0220 235 14,8 11,3 11,15

Average content of tannin, % 11,23

377 Table 2 Andricus quercuscalicis galls – level of tannin Sample mass No. The total amount of extract, V (ml) V1 V2 % tannin (g)

Nr. Masa probei Volumul total de extract V1 V2 % tanin crt (g) V (ml)

1’ 2,9704 240 10,5 7,6 9,60

2’ 3,1052 240 11,1 8,1 9,50

3’ 3,1820 240 11,4 8,3 9,58

Average content of tannin, % 9,56

The results above invalidate the assumption that did not differ significantly and the reason for Andricus Andricus quercuscalicis galls contain more tannin quercuscalicis being more used should have a different comparing with Andricus hungaricus galls. Actually, factual or practical basis. For example, such a reason the results show the opposite; Andricus hungaricus could be the fact that Andricus hungaricus develops galls contain 11,23% tannin comparing with the dry only on Quercus robur, but Andricus quercuscalicis mass and Andricus quercuscalicis galls contain 9,56% develops on Quercus petraea and Quercus robur. And of tannin. It is important to mention that such as a practical matter, it’s easier, obviously, to find one determinations cannot be found very often in the or both two host plant within a certain area. literature. The very few found are quite old and they don’t mention the scientific names of the species, but The research within this paper is financed through the the common names and it is not sure what exact grand “STUDII DOCTORALE PENTRU FORMARE species is about (1). Anyway, such research should ÎN CERCETARE (FOR-CE), ID 80127”Proiect continue in order to verify if the level of tannin differ cofinanţat din Fondul Social European prin Programul depending on the area that galls develop, or other Operaţional Sectorial Dezvoltarea Resurselor Umane factors, within the same species. It was mentioned 2007-2013, prin OI POS DRU, Axa prioritară 1. above that galls of Andricus quercuscalicis were used Educaţia şi formarea profesională în sprijinul creşterii for tanning in Pancota area even until the year of 2000. economice şi dezvoltării societăţii bazate pe It was assumed that these galls were preferred for such cunoaştere, Domeniul major de intervenț ie 1.5. purposes. Based on the results, we can state that Programe doctorale şi post-doctorale în sprijinul Andricus hungaricus galls could also be used for cercetării tanning and the reason for not being so is not the level of tannin. References

Conclusions 1.Andreescu, V., Amzica A., 1959: Exploatarea pădurilor. Litografia Învăţământului, Oraşul Stalin, The following research on Andricus hungaricus and România Andricus quercuscalicis galls most used in Romanian 2.Atanassova, M., Christova-Bagdassarian V.: tanneries revealed the following: the level of tannin Determination Of Tannins Content By Titrimetric was 11,23% for the first species and 9,56% for the Method For Comparison Of Different Plant Species. second, comparing with the dry mass. According to Journal of the University of Chemical Technology and these results, the level of tannin in these two galls is Metallurgy, 44, 4, pp 413-415, 2009 quite similar, both having been used in tanneries for a 3.Cook, M., Rokas, A., Pagel, M., Stone, G., 2002: long period of time in Romania. It was recently Evolutionary shifts between host oak sections and host- discovered that Andricus quercuscalicis galls were plant organs in Andricus gallwasps. UK, Evolution, used in tanneries up to the year of 2000 in Pancota 56(9), pp 1821-1830 area, Arad County. And it was assumed that this 4.Crawley, M.J., Akhteruzzaman, M., 1988: Individual certain gall species is preferred rather than Andricus variation in the phenology of oak trees and its hungaricus galls, because of its higher level of tannin. consequences for herbivorous insects. British The truth is that the level of tannin in these two galls

378 Ecological Society. Functional Ecology, vol.2, no.3, pp 7.Ionescu, A.M.,: Biologia galelor. Editura Academiei 409-415 R.S. România, Bucureşti, 178 p., 1973 5.Csóka, G.: Plant galls, Agroinform, Budapesta, 160 8.Ionescu, A.M.: Fauna Republicii Populare Române. p., 1997 Insecta. Cynipinae. Editura Academiei Republicii 6.Hac, P.A.: Aspecte privind prezenţa galelor pe Populare Române, 237 p., 1957. plantele lemnoase în Parcul Natural Lunca Mureşului. 9.Russo, R.: Field guide to plant galls of California and Revista Pădurilor nr. 4/2009, Bucureşti, pp 33-39., other Western State. University of California Press, 2009 Londra, 397 p., 2006.

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