Graphical abstract
Keywords: Archaeological soils, Ash, Ash Deposits, Fuel, Pedoarchaeology, Geoarchaeology, Geochemistry
Abstract
As a special type of parent rock associated with human activities both in antiquity and nowadays, ash widely occurs in the settlements’ functional zones and their cultural layers. Soils developed on ash deposits of various genesis can be presented as soil chronosequences, which forms an information basis for determining the time at which settlements and their economic zones went out of use (“Archaeological ash deposits and soils formed on ash in the south of the East European Plain. Quaternary International” [1]). Studies of ash deposits and soils formed on ash were conducted in three regions of the East European Plain which differ in extent of forest cover. Geochemical associations of accumulated and dispersed elements in the upper horizon of soils of different age in relation to the original ash were determined. This makes it possible to calculate the time of biogeochemical transformation of ash in the course of pedogenesis, thus offering a new dating technique for archaeologists.
Specifications Table
| Subject | Soil Science |
| Specific subject area | Pedoarchaeology, Geochemistry |
| Type of data | Table Image Figure |
| How data were acquired | XRF spectrometer (Spectroscan Max-GV, ‘SPECTRON’, Ltd). Emission spectrometer ICPE–9000 with induction-bound plasma (Zn, Cu, Mn and Co), atomic absorption spectrometer Quant–2AT (Pb and C), spectrometer Quant–Z (Hg), photocolorimeter KFK–3–01 (As). Method of cluster analysis (hierarchic classification, unification by Ward's method). STATISTICA Advanced + QC for Windows v.10 Ru. |
| Data format | Raw |
| Parameters for data collection | The data derives from our study of 14 archaeological sites in the south of the East European Plain. The chemical composition of sampled ash deposits and soils formed on ash, as well as of plant samples (fossil and modern oak and grass plants), was analysed by 22 chemical elements, including 10 macroelements and 12 trace elements. |
| Description of data collection | The dataset includes the information on specific features of archaeological ash in relation to three other types of principal parent materials, on chemical properties of soils formed on ash, biogeochemical properties of soil formed on ash in the region with significant proportion of oak forests both in antiquity and today, and on the values of informative geochemical indicators for ash groups of different genesis for the regional reconstruction of palaeogeographic conditions. |
| Data source location | Belgorod region, Russian Federation: Borisovka, mid-5th c. BC (50°37′15.50"N; 36°0′13.40"E). Crimean Peninsula, Russian Federation: Kalos Limen, 4th c. BC – 2nd c. AD (45°31′2.90"N; 32°42′56.90"E); former village of Saya, before 1944 (45°31′7.95"N; 32°49′14.48"E); Chernomorskoe/Settlement S11-022, Bronze Age and Early Iron Age (45°29′21.10"N; 32°43′17.49"E); ancient Greek farmhouse of Kunan, 2nd c. BC (45°25′49.62"N; 32°41′35.52"E); former village of Ojrat, before 1944 (45°19′36.18"N; 32°40′14.52"E); Vitino, 4th – 3rd c. BC (45°14′10.07"N; 33°8′13.20"E); Airchi, 2nd c. BC – 1st c. AD (45°12′6.28"N; 33° 9′8.45"E). Ak-Kaya, 225–250 AD (45°7′20.04"N; 34°36′11.58"E); Borut-Khane, 1st c. BC – 1st c. AD (45°6′7.56"N; 34°18′32.76"E); Kermen-Kyr, 2nd – 3rd c. AD (44°58′39.48"N; 34°3′29.34"E); Zayachye, 2nd – 3rd c. AD (44°51′30.90"N; 33°48′50.28"E); settlement of Mysovka (Mysovoe II), 4th c. BC – 3rd c. AD (45°26′56.39"N; 35°49′16.69"E); Kazantip Vostochny 1, 3rd c. BC – 3rd c. AD (45°26′57.69"N; 35°50′29.94"E). |
| Data accessibility Related research articles |
Data provided within this article F.N. Lisetskii, V.F. Stolba. Archaeological ash deposits and soils formed on ash in the south of the East European Plain. Quaternary International (2021). 10.1016/j.quaint.2020.11.030 |
Value of the Data
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Geochemical differences in soils formed on ash, which is reflected in an increased concentrations of Cu, As, SiO2, Al2O3 and Pb and decreased concentrations of Sr, Ca, Co, Mg and Na2O, form the information basis for dating the termination of activities at archaeological sites and their economic zones.
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In regions with different sources of available fuel (wood in the forest-steppe and dung in the steppe zone), fossil ash can aid the reconstructions of paleoclimate and living conditions, using the ensemble of chemical elements (P, K, Mn, Zn, Co, Pb, Sr and Zr) as an indicator.
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Comparison of the chemical composition of experimentally ashed fossil oak wood and forb-cereal hay made it possible to determine the elements indicative of wood ash and of ash resulting from the combustion of other fuels available in the steppe conditions, which makes it possible to ascertain the genesis of archaeological ash deposits.
1. Data Description
Geochemical differences between the main parent rocks and ash and soils formed on ash (by 6 macroelements and 6 trace elements, as well as by the SiO2/(RO+R2O) ratio) reflect the specificity of ash as a parent material [1]. The hierarchical classification of ash and soils formed on ash by 12 most informative chemical elements (Sr, Ca, Co, Mg, Na, Cu, As, Si, Al, Pb, K, P) has made it possible to observe the geochemical transformation of ash in ashy deposits in the course of pedogenesis. Geochemical features of ash deposits and soils formed on ash for three regions that differ in shares of forest cover are presented in the form of input data and calculated coefficients. Oak wood was obtained from the excavations of burial mound Ak-Kaya 9, where 2325-2350 years ago, at a depth of 9.5 m, it has been used in the floor construction. As various plants and other fuels differ in their elemental composition, chemical analysis of ash is an important tool for identifying different ancient fuels [2]. In addition, experimental ashing of fossil wood (Quercus pubescens) and hay from steppe grasses with subsequent chemical analysis has been carried out to identify archaeological ashes obtained from various types of fuel.
Fig. 1 shows location of research objects (ashy soil and ash deposits) in the continental forest-steppe, Belgorod Oblast, and the Plain (steppe) and Piedmont (forest-steppe) Crimea. Table 1 lists objects of study at archaeological sites within three research regions (soils formed on ash and ash from cultural strata). Fig. 2 provides examples of the location of ash deposits on positive and negative relief elements in archaeological landscapes. Table 2 shows geochemical features of the main parent rocks, ash and soils formed on ash. Table 3 displays chemical properties of soils of archaeological sites in the south of the Kazantip Peninsula. Table 4 shows geochemical transformation of soil formed on ash (Borisovka settlement) over 24 centuries. Table 5 comprises the chemical composition of soils and ash of different ages at archaeological sites of the North-West Crimea. Table 6 contains the chemical composition of soils and ash at archaeological sites of the Piedmont Crimea. Fig. 3 features a dendrogram for the classification of ash and soils formed on ash deposits. Table 7 shows colouring and chemical composition of ash in groups classified by cluster analysis. Table 8 reports the main geochemical indicators of group objects (soils and ash), resulted from the cluster analysis. Table 9 compares the chemical composition of oak wood ash (OWA) and ash from hay of mixed grasses (GMA), using two ranked lists. Fig. 4 shows correlation of the content of chemical elements in archaeological ash from the forest area and poorly forested foothill zone. Fig. 5 shows regression dependences in the contents of Zn, Cu, Mn, Cd, Pb, As, Hg, Mo, and Co in the ash datable to the 1st c. AD and in experimentally ashed organic samples (modern oak; fossil oak; feather grass; cow dung and horse dung).
Fig. 1.
Location of research objects (ashy soil and ash deposits) within the continental forest-steppe, Belgorod Oblast (A) and within the Plain (steppe) and Piedmont (forest-steppe) Crimea (B). Archaeological sites: Borisovka, mid-5th c. BC (1); Kalos Limen, 4th c. BC – 2nd c. AD (2); former village of Saya, before 1944 (3); Chernomorskoe/Settlement S11-022, Bronze Age and Early Iron Age (4); Kunan, 2nd c. BC (5); Former village of Oirat, before 1944 (6); Vitino 4th – 3rd c. BC (7); Airchi, 2nd c. BC – 1st c. AD (8); Ak-Kaya, c. 225–250 AD (9); Borut-Khane, 1st c. BC – 1st c. AD (10); Kermen-Kyr, 2nd – 3rd c. AD (11); Zayachye, 2nd – 3rd c. AD (12); Settlement of Mysovka (Mysovoe II), 4th-2nd c. BC – 3rd c. AD (13); Kazantip Vostochny 1, 3rd – 2nd c. BC – 3rd c. AD (14). Natural areas (A): A – Typical forest-steppe; B – Southern forest-steppe; C – Steppe. Natural areas (B): A – North Crimean Lowland steppe; B – Tarkhankut elevated plain; C – Central Crimean Plain steppe; D – Kerch hilly-ridged steppe; E – Foothill forest-steppe; F – Main ridge, mountainous meadows and forests; G – Southern Coast. A screenshot of the Relief map was downloaded from the site: https://maps-for-free.com/
Table 1.
Objects of study at archaeological sites from three research regions (soils formed on ash and ash from cultural strata).
| No. | Soil/Ash | Depth (cm) | Soil colour (Munsell) | RCIE | |
|---|---|---|---|---|---|
| moist | dry | (dry) | |||
| 1 | Ash | 100 | 10YR 5/2.5 | 10YR 6/2 | 0.442 |
| 2 | Hor. А | 0-22 | 10YR 5/2.5 | 10YR 6/2 | 0.442 |
| 2 | cultural layer | >20 | 10YR 5/3 | 10YR 7/2 | 0.150 |
| 3 | Hor. А | 20 | 10YR 3/3 | 10YR 5/2.5 | 1.956 |
| cultural layer | 50 | 10YR 4/3 | 10YR 5/3 | 2.393 | |
| 4 | Hor. А | 0-18 | 10YR 3/3 | 10YR 5/2 | 1.519 |
| Hor. АВ | 18-50 | 10YR 3/2 | 10YR 6/2 | 0.442 | |
| Ash | >50 | 10YR 5/4 | 10YR 7/2 | 0.150 | |
| 4 | Hor. А | 5-26 | 10YR 3/3 | 10YR 5/3 | 2.393 |
| Hor. АВ | 26-55.5 | 10YR 3/3 | 10YR 5/2 | 1.519 | |
| Hor. В1 | 47-55.5 | 10YR 3/3 | 10YR 5/2.5 | 1.956 | |
| Ash | 55.5-60.5 | 10YR 4/3 | 10YR 6/2.5 | 0.572 | |
| 4 | Hor. C | 60–70 | 10YR 3/3 | 10YR 6/2 | 0.442 |
| Hor. С | 80–90 | 10YR 4/3 | 10YR 6/2 | 0.442 | |
| 5 | 39–41 | 39–41 | 10YR 3/2 | 10YR 5/1.5 | 1.139 |
| 5 | Ash | >41 | 10YR 4/3 | 10YR 5/3 | 2.393 |
| 6 | Hor. А | 0–16 | 10YR 3/2 | 10YR 6/2 | 0.442 |
| Hor. АВ | 16–28 | 10YR 4/3 | 10YR 6/2 | 0.442 | |
| 7 | Ash | > 30 | 10YR 4/2 | 10YR 6/2 | 0.442 |
| 8 | 235 | 235 | 10YR 5/2 | 10YR 7/1 | 0.075 |
| 8 | cultural layer | 200 | 10YR 5/3 | 10YR 6/2 | 0.442 |
| 8 | ash on the hearth stone | 152 | 10YR 4/4 | 10YR 6/4 | 0.924 |
| 9 | Hor. В1 | > 33.5 | 10YR 4/2 | 10YR 6/2 | 0.442 |
| 10 | Hor. В1 | > 37 | 10YR 5/3 | 10YR 6/2 | 0.442 |
| 10 | Ash | 63-73 | 10YR 5/3 | 10YR 7/1 | 0.075 |
| 11 | Hor. В1 | 30-35 | 10YR 4/3 | 10YR 6/1 | 0.240 |
| 12 | Hor. В1 | > 32 | 10YR 5/3 | 10YR 6/1 | 0.240 |
Fig. 2.
Location examples s of ash deposits on positive and negative relief elements in archaeological landscapes: Ash hill near the Tatar settlement of Oirat (A) 1784-1944 AD (A1 – panorama (center), A2 – hilltop, A3 – hilltop soil profile); Ash horizon at a depth of 180-213 cm in the fill of a 1st c. BC defensive ditch at the Airchi (B) settlement (B1 – ditch, B2 – ash horizon).
Table 2.
Initial geochemical data, their mean values and errors (Sx) for main parent rocks, ash and soils formed on it.
| Point no. | Macro-elements (%) | Trace elements (ppm) | SiO2 / R2O3* | ||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| CaO | P2O5 | SiO2 | Al2O3 | Fe | MgO | Co | Cu | Pb | Sr | Zn | Ni | ||
| Carbonate light brown loams (North-Western Crimea) | |||||||||||||
| 1 | 27.9 | 0.2 | 24.6 | 7.0 | 1.9 | 2.8 | 4.8 | 11.5 | 9.1 | 243.5 | 56.6 | 28.8 | 2.7 |
| 2 | 22.5 | 0.2 | 20.4 | 7.1 | 1.8 | 2.3 | 7.1 | 19.1 | 10.9 | 157.7 | 61.4 | 29.2 | 2.3 |
| 3 | 23.9 | 0.2 | 18.1 | 6.8 | 1.8 | 2.5 | 6.3 | 21.2 | 8.7 | 160.9 | 57.3 | 30.2 | 2.1 |
| 4 | 23.1 | 0.2 | 40.0 | 9.2 | 2.4 | 2.7 | 8.1 | 26.9 | 13.5 | 182.9 | 74.9 | 39.9 | 3.4 |
| 5 | 26.0 | 0.3 | 26.9 | 9.3 | 2.5 | 2.6 | 5.5 | 28.0 | 16.5 | 109.2 | 67.5 | 35.4 | 2.3 |
| 6 | 24.4 | 0.3 | 21.2 | 7.5 | 2.5 | 2.6 | 5.7 | 17.4 | 17.3 | 135.1 | 70.2 | 32.6 | 2.1 |
| 7 | 26.9 | 0.2 | 26.5 | 9.4 | 2.3 | 2.9 | 7.8 | 23.2 | 10.7 | 242.1 | 73.8 | 37.2 | 2.3 |
| 8 | 28.0 | 0.1 | 31.0 | 8.7 | 2.0 | 3.0 | 6.2 | 15.0 | 8.8 | 212.4 | 65.3 | 33.3 | 2.9 |
| 9 | 22.2 | 0.1 | 33.3 | 8.3 | 2.2 | 2.7 | 8.6 | 18.0 | 12.1 | 251.5 | 65.1 | 33.9 | 3.2 |
| 10 | 22.7 | 0.1 | 35.9 | 8.6 | 2.1 | 2.4 | 8.0 | 25.0 | 6.9 | 221.8 | 65.2 | 37.0 | 3.4 |
| 11 | 21.4 | 0.2 | 31.4 | 7.9 | 2.2 | 2.2 | 11.4 | 22.6 | 11.7 | 227.7 | 61.4 | 36.0 | 3.1 |
| Mean | 24.5 | 0.2 | 28.1 | 8.2 | 2.2 | 2.6 | 7.2 | 20.7 | 11.5 | 195.0 | 65.3 | 34.0 | 2.7 |
| Sx | 0.72 | 0.02 | 2.07 | 0.29 | 0.07 | 0.08 | 0.55 | 1.53 | 0.99 | 14.61 | 1.82 | 1.08 | 0.15 |
| Carbonate brown and grayish-brown loams, underlain by limestone (North-Western Crimea) | |||||||||||||
| 1 | 10.6 | 0.1 | 44.4 | 10.2 | 2.9 | 1.9 | 16.4 | 44.3 | 17.5 | 234.9 | 76.1 | 51.2 | 3.4 |
| 2 | 11.7 | 0.2 | 46.3 | 10.9 | 3.0 | 2.1 | 12.9 | 42.3 | 19.2 | 318.9 | 74.3 | 48.8 | 3.3 |
| 3 | 13.8 | 0.5 | 36.9 | 10.4 | 2.8 | 2.1 | 11.3 | 37.3 | 19.9 | 202.0 | 81.6 | 43.5 | 2.8 |
| 4 | 13.8 | 0.6 | 36.9 | 10.4 | 2.8 | 2.0 | 12.4 | 31.8 | 16.6 | 202.4 | 91.3 | 43.1 | 2.8 |
| 5 | 8.4 | 0.1 | 40.3 | 9.3 | 3.0 | 1.2 | 16.4 | 51.3 | 20.4 | 127.9 | 72.4 | 51.8 | 3.2 |
| 6 | 14.1 | 0.2 | 40.7 | 8.8 | 2.6 | 2.0 | 14.2 | 33.5 | 16.8 | 232.6 | 65.0 | 42.2 | 3.5 |
| 7 | 9.9 | 0.1 | 46.6 | 9.3 | 2.8 | 1.4 | 13.5 | 37.1 | 19.0 | 181.9 | 64.0 | 43.2 | 3.8 |
| 8 | 11.5 | 0.4 | 35.7 | 9.1 | 3.1 | 1.8 | 8.7 | 36.4 | 17.0 | 121.3 | 72.9 | 39.7 | 2.9 |
| 9 | 11.2 | 0.3 | 48.1 | 9.3 | 2.6 | 1.7 | 10.9 | 33.9 | 17.3 | 207.8 | 74.4 | 40.5 | 4.0 |
| Mean | 11.7 | 0.3 | 41.8 | 9.7 | 2.8 | 1.8 | 13.0 | 38.7 | 18.2 | 203.3 | 74.7 | 44.9 | 3.3 |
| Sx | 0.65 | 0.06 | 1.58 | 0.25 | 0.06 | 0.11 | 0.84 | 2.08 | 0.48 | 19.75 | 2.75 | 1.51 | 0.15 |
| Ash from the cultural layer of the archaeological sites of Crimea | |||||||||||||
| 1 | 15.6 | 1.2 | 28.0 | 5.7 | 2.0 | 2.3 | 19.1 | 18.2 | 13.1 | 349.6 | 123.4 | 34.7 | 3.6 |
| 2 | 18.0 | 1.3 | 39.2 | 8.9 | 2.7 | 2.4 | 16.4 | 27.0 | 19.9 | 359.9 | 147.5 | 44.8 | 3.3 |
| 3 | 20.4 | 1.2 | 24.1 | 6.3 | 2.3 | 2.6 | 15.3 | 18.1 | 28.2 | 367.4 | 119.4 | 33.6 | 2.8 |
| 4 | 16.5 | 1.1 | 46.6 | 7.2 | 2.3 | 2.6 | 17.7 | 20.7 | 18.6 | 338.9 | 124.8 | 45.4 | 4.8 |
| 5 | 17.7 | 1.4 | 35.9 | 7.6 | 2.2 | 2.3 | 10.4 | 19.2 | 16.1 | 304.4 | 133.2 | 36.7 | 3.6 |
| 6 | 19.0 | 1.2 | 36.2 | 7.4 | 2.3 | 2.2 | 17.5 | 19.0 | 19.8 | 376.3 | 145.6 | 36.8 | 3.7 |
| 7 | 16.4 | 0.7 | 40.2 | 6.9 | 2.3 | 1.7 | 15.7 | 17.2 | 16.6 | 275.5 | 106.4 | 37.9 | 4.3 |
| 8 | 15.3 | 0.4 | 45.0 | 9.3 | 2.3 | 2.1 | 20.0 | 48.2 | 14.0 | 683.8 | 52.2 | 48.6 | 3.8 |
| 9 | 13.1 | 0.4 | 51.8 | 10.2 | 2.4 | 2.0 | 16.5 | 42.6 | 13.7 | 563.7 | 71.0 | 48.8 | 4.1 |
| 10 | 25.1 | 1.2 | 38.7 | 7.3 | 1.5 | 2.6 | 7.1 | 46.4 | 20.1 | 289.4 | 60.4 | 41.4 | 4.4 |
| 11 | 10.2 | 0.6 | 54.4 | 9.0 | 2.4 | 1.7 | 15.7 | 35.0 | 12.5 | 149.9 | 105.7 | 44.7 | 4.7 |
| 12 | 13.6 | 0.7 | 47.0 | 8.6 | 2.2 | 1.6 | 15.3 | 46.8 | 11.5 | 175.3 | 82.8 | 47.6 | 4.3 |
| Mean | 16.7 | 0.96 | 40.6 | 7.9 | 2.2 | 2.2 | 15.6 | 29.9 | 17.0 | 352.8 | 106.0 | 41.7 | 4.0 |
| Sx | 1.10 | 0.10 | 2.60 | 0.39 | 0.08 | 0.10 | 1.03 | 3.74 | 1.35 | 42.65 | 9.38 | 1.62 | 0.17 |
| Soils formed on ash | |||||||||||||
| 1 | 9.1 | 1.0 | 52.9 | 9.0 | 2.7 | 1.4 | 15.1 | 49.4 | 20.8 | 176.4 | 174.6 | 57.6 | 4.5 |
| 2 | 11.9 | 1.1 | 51.9 | 8.8 | 2.7 | 1.7 | 16.4 | 34.8 | 18.9 | 207.4 | 166.4 | 48.5 | 4.5 |
| 3 | 6.0 | 0.6 | 53.5 | 8.9 | 2.8 | 1.2 | 16.5 | 40.0 | 24.5 | 162.2 | 116.4 | 46.2 | 4.5 |
| 4 | 8.9 | 0.6 | 55.0 | 9.1 | 2.8 | 1.5 | 16.5 | 34.7 | 21.6 | 176.9 | 167.1 | 44.8 | 4.6 |
| 5 | 13.8 | 1.1 | 30.6 | 6.6 | 2.2 | 1.9 | 13.4 | 29.8 | 17.2 | 234.7 | 126.6 | 37.1 | 3.5 |
| 6 | 17.9 | 1.2 | 36.8 | 5.9 | 2.1 | 3.3 | 18.0 | 11.7 | 33.4 | 531.3 | 113.6 | 39.5 | 4.5 |
| 7 | 16.9 | 1.3 | 45.8 | 7.6 | 2.2 | 2.5 | 8.6 | 20.8 | 38.1 | 402.2 | 143.8 | 36.3 | 4.7 |
| 8 | 7.0 | 0.5 | 55.2 | 10.3 | 2.6 | 1.6 | 20.5 | 49.6 | 13.8 | 132.2 | 80.3 | 52.3 | 4.3 |
| 9 | 8.3 | 0.6 | 42.0 | 7.6 | 2.9 | 1.3 | 14.2 | 45.0 | 17.8 | 202.6 | 106.1 | 48.9 | 3.9 |
| Mean | 11.1 | 0.89 | 47.1 | 8.2 | 2.5 | 1.8 | 15.5 | 35.1 | 22.9 | 247.3 | 132.8 | 45.7 | 4.3 |
| Sx | 1.44 | 0.11 | 2.96 | 0.46 | 0.11 | 0.23 | 1.11 | 4.28 | 2.65 | 43.92 | 10.75 | 2.37 | 0.13 |
SiO2 / R2O3 = SiO2 / ∑(Al2O3+ Fe2O3+ MnO).
Table 3.
Chemical properties of soils of archaeological sites in the south of the Kazantip Peninsula.
| Object of study | Data | Horizon, depth (cm) | Chemical indicators | |||
|---|---|---|---|---|---|---|
| CaCO3*, % | Corg, % | Total N, % | С:N* | |||
| Settlement of Kazantip Vostochny 1 | 3rd-2nd c. BC – 3rd c. AD | А, 3-21 | 14.89 | 4.17 | 0.487 | 8.6 |
| АВ, 21-40 | 17.59 | 2.11 | 0.330 | 6.4 | ||
| С, >40 | 18.61 | 1.88 | 0.182 | 10.3 | ||
| Ash deposit 150 m west of the settlement of Kazantip Vostochny 1 | 3rd-2nd c. BC – 3rd c. AD | А, 6-17 | 11.50 | 3.91 | 0.448 | 8.7 |
| С, >45 | 18.61 | 2.14 | 0.226 | 9.5 | ||
| Settlement of Mysovka (Mysovoe II) | 4th-2nd c. BC – 3rd c. AD | А, 0-22 | 13.68 | 3.52 | 0.400 | 8.8 |
| С, 28-32 | 20.22 | 1.67 | 0.204 | 8.2 | ||
The scale [8] suggests that degree of humus enrichment with nitrogen (C:N) is high (C:N is 5–8), and medium (C:N is 8–11).
Table 4.
24-century long geochemical transformation of soil formed on ash (Borisovka settlement).
| Newly formed soil | Ash | |||
|---|---|---|---|---|
| Layer, cm | A, 0-23 | AB, 23-41 | B, 41-57 | C, 62-72 |
| Soil color (dry) | 10YR 5/2.5 | 10YR 5/2 | 10YR 6/1.5 | 10YR 6/2 |
| Macroelements, % | ||||
| SiO2 | 59.57 | 61.24 | 55.48 | 32.05 |
| Al2O3 | 7.09 | 7.85 | 7.53 | 4.51 |
| CaO | 2.69 | 7.01 | 14.85 | 11.74 |
| Fe | 2.05 | 1.97 | 1.82 | 2.51 |
| TiO2 | 0.89 | 0.84 | 0.65 | 0.60 |
| P2O5 | 0.80 | 1.90 | 3.26 | 2.18 |
| K2O | 1.68 | 1.70 | 1.51 | 1.10 |
| MnO | 0.19 | 0.22 | 0.17 | 0.21 |
| MgO | 0.90 | 1.36 | 2.15 | 2.28 |
| Na2O | 1.14 | 1.31 | 1.96 | 2.81 |
| Trace elements, mg kg−1 | ||||
| As | 6.12 | 3.49 | 4.08 | 2.78 |
| Ba | 631.85 | 640.68 | 652.06 | 692.97 |
| Co | 11.91 | 11.78 | 19.33 | 15.76 |
| Cu | 32.26 | 18.48 | 2.32 | 12.70 |
| Cr | 95.61 | 72.45 | 69.92 | 88.94 |
| Ni | 35.39 | 27.34 | 28.38 | 44.98 |
| V | 69.49 | 58.54 | 53.94 | 48.52 |
| Pb | 20.19 | 19.83 | 12.32 | 27.37 |
| Rb | 78.47 | 66.51 | 58.43 | 68.32 |
| Sr | 236.22 | 326.22 | 593.16 | 783.79 |
| Zn | 143.84 | 175.44 | 190.18 | 272.84 |
| Zr | 505.59 | 409.81 | 353.61 | 444.15 |
Table 5.
The geochemical composition of soils and ash of different age at archaeological sites of North-West Crimea.
| Objects* | Depth, cm | Sr | CaO | Co | MgO | Na2O | Cu | As | SiO2 | Al2O3 | Pb | K2O | P2O5 | SiO2/(RO+R2O)⁎⁎ |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| ppm | % | ppm | % | % | ppm | ppm | % | % | ppm | % | % | dimensionless | ||
| Soils of different age on ash substrate | ||||||||||||||
| 4/2 | 5-26 | 132.16 | 6.97 | 20.52 | 1.58 | 1.17 | 49.65 | 7.57 | 55.20 | 10.25 | 13.81 | 1.90 | 0.52 | 4.75 |
| 26-55.5 | 202.63 | 8.32 | 14.16 | 1.27 | 1.07 | 44.96 | 4.39 | 42.00 | 7.63 | 17.82 | 1.69 | 0.55 | 3.40 | |
| 47-55.5 | 174.61 | 10.78 | 13.52 | 1.55 | 1.32 | 32.06 | 6.59 | 48.93 | 8.77 | 15.91 | 1.82 | 0.64 | 3.16 | |
| 4/1 | 0-18 | 162.22 | 5.99 | 16.52 | 1.18 | 0.83 | 40.02 | 4.70 | 53.54 | 8.90 | 24.54 | 1.84 | 0.56 | 5.44 |
| 18-50 | 176.88 | 8.85 | 16.50 | 1.45 | 1.12 | 34.69 | 4.64 | 55.02 | 9.08 | 21.60 | 1.86 | 0.61 | 4.14 | |
| 5/1 | 0-19 | 176.43 | 9.05 | 15.10 | 1.38 | 1.12 | 49.38 | 5.13 | 52.90 | 8.99 | 20.76 | 1.94 | 1.04 | 3.92 |
| 19-38 | 207.42 | 11.86 | 16.41 | 1.65 | 1.42 | 34.84 | 5.25 | 51.85 | 8.80 | 18.91 | 1.85 | 1.11 | 3.09 | |
| 2/1 | 0-22 | 531.26 | 17.91 | 17.99 | 3.28 | 2.27 | 11.72 | 10.17 | 36.81 | 5.86 | 33.39 | 2.32 | 1.15 | 1.43 |
| 6 | 0-28 | 402.24 | 16.94 | 8.56 | 2.50 | 1.32 | 20.82 | 7.74 | 45.80 | 7.57 | 38.05 | 3.00 | 1.33 | 1.93 |
| 3 | 20 | 162.07 | 16.48 | 8.10 | 1.92 | 1.19 | 42.10 | 7.43 | 34.01 | 8.14 | < LOQ | 1.83 | 0.49 | 1.59 |
| 50 | 178.75 | 14.35 | 10.32 | 1.55 | 1.36 | 33.83 | 6.17 | 36.39 | 7.73 | 14.99 | 1.77 | 0.53 | 1.91 | |
| Ash from cultural strata of archaeological sites | ||||||||||||||
| 5/1 | 39-40 | 338.90 | 16.49 | 17.65 | 2.56 | 2.19 | 20.65 | 5.07 | 46.63 | 7.19 | 18.55 | 2.02 | 1.10 | 2.00 |
| 4/1 | >50 | 275.45 | 16.38 | 15.67 | 1.71 | 1.47 | 17.15 | 5.63 | 40.23 | 6.87 | 16.56 | 1.67 | 0.69 | 1.89 |
| 2/2 | >20 | 289.39 | 25.08 | 7.13 | 2.57 | 2.19 | 46.41 | 4.77 | 38.68 | 7.28 | 20.15 | 1.56 | 1.20 | 1.23 |
| 4/2 | 55.5-60.5 | 231.66 | 14.06 | 13.49 | 1.90 | 1.51 | 22.21 | 6.79 | 47.26 | 8.03 | 6.45 | 1.78 | 0.73 | 2.45 |
| 4/3 | 70-80 | 149.86 | 10.25 | 15.69 | 1.67 | 1.39 | 35.02 | 5.52 | 54.42 | 9.01 | 12.45 | 1.99 | 0.65 | 3.56 |
| 4/3 | 90-100 | 175.32 | 13.64 | 15.34 | 1.59 | 1.47 | 46.81 | 5.81 | 46.96 | 8.64 | 11.46 | 1.83 | 0.70 | 2.53 |
| 8/1 | 235 | 683.84 | 15.33 | 19.99 | 2.15 | 1.64 | 48.18 | 4.25 | 44.95 | 9.34 | 13.95 | 1.67 | 0.44 | 2.16 |
| 8/2 | 200 | 563.74 | 13.13 | 16.53 | 2.03 | 1.64 | 42.62 | 4.95 | 51.81 | 10.21 | 13.66 | 1.90 | 0.43 | 2.77 |
| 8/2 | 152 | 916.93 | 24.43 | 8.40 | 2.80 | 2.06 | 15.42 | 5.19 | 37.22 | 8.51 | 13.54 | 1.53 | 0.54 | 1.21 |
| 7 | 0-22 | 465.65 | 15.54 | 16.20 | 3.05 | 2.39 | 26.15 | 30.74 | 44.55 | 7.85 | 68.57 | 3.16 | 1.18 | 1.85 |
| Soil average (S) | ||||||||||||||
| Average | 227.88 | 11.59 | 14.34 | 1.76 | 1.29 | 35.82 | 6.34 | 46.59 | 8.34 | 21.98 | 1.98 | 0.78 | 3.16 | |
| Ash average (A) | ||||||||||||||
| Average⁎⁎ | 409.07 | 16.43 | 14.61 | 2.20 | 1.80 | 32.06 | 7.87 | 45.27 | 8.29 | 19.53 | 1.91 | 0.77 | 2.17 | |
| Percentage of soil differences in relation to ash (100•[(S/A)-1]) | ||||||||||||||
| % | -44.29 | -29.47 | -1.87 | -20.32 | -28.13 | 11.74 | -19.42 | 2.91 | 0.54 | 12.51 | 3.80 | 1.23 | 45.96 | |
Archaeological sites: 4/1, 4/2, 4/3 – Chernomorskoe/S11-022 (Bronze Age); 5/1 - Kunan, ancient Greek farmhouse; 2/1 - Kalos Limen, ash deposit; 6 - ash deposit near the village of Oirat; 3 - ash deposit near the village of Saya; 2/2 - Kalos Limen, the citadel; 8/1 - Archi, defensive ditch; 8/2 - Archi, pit at the settlement; 8/2 - Archi, late Scythian furnace.
RO = CaO+MgO; R2O = K2O + Na2O. ** Average calculated without the Airchi furnace.
Table 6.
Geochemical composition of soils and ash at archaeological sites of the Piedmont Crimea.
| Depth, cm | Sr | CaO | Co | MgO | Na2O | Cu | As | SiO2 | Al2O3 | Pb | K2O | P2O5 | SiO2/(RO+R2O)* |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| ppm | % | ppm | % | % | ppm | ppm | % | % | ppm | % | % | dimensionless | |
| Borut-Khane, ancient settlement (1st c. BC - 1st c. AD) | |||||||||||||
| 0-19 | 234.71 | 13.84 | 13.44 | 1.88 | 1.89 | 29.80 | 5.21 | 30.63 | 6.59 | 17.21 | 1.56 | 1.12 | 1.60 |
| 19-37 | 310.30 | 17.49 | 14.59 | 2.26 | 2.20 | 20.86 | 5.27 | 27.43 | 5.68 | 16.84 | 1.55 | 1.20 | 1.17 |
| >37 | 349.58 | 15.57 | 19.07 | 2.28 | 2.04 | 18.23 | 6.10 | 28.02 | 5.72 | 13.07 | 1.81 | 1.22 | 1.29 |
| Borut-Khane, ash deposit (1st c. BC - 1st c. AD) | |||||||||||||
| 63-73 | 304.39 | 17.71 | 10.42 | 2.27 | 2.03 | 19.22 | 4.66 | 35.87 | 7.56 | 16.07 | 1.95 | 1.41 | 1.50 |
| Ak-Kaya (Vishennoe), ancient settlement (3rd century AD) | |||||||||||||
| 0-22.5 | 253.45 | 11.65 | 15.51 | 1.97 | 1.76 | 38.97 | 4.94 | 39.58 | 8.80 | 21.13 | 1.89 | 1.19 | 2.29 |
| 22.5-33.5 | 338.66 | 15.56 | 16.55 | 2.28 | 2.42 | 28.90 | 4.92 | 37.60 | 8.68 | 18.59 | 1.75 | 1.26 | 1.71 |
| >33.5 | 359.92 | 17.96 | 16.43 | 2.35 | 2.47 | 26.97 | 3.51 | 39.17 | 8.93 | 19.94 | 1.79 | 1.30 | 1.59 |
| Kermen-Kyr, ancient settlement (3rd century AD) | |||||||||||||
| 0-12.5 | 233.53 | 11.21 | 16.04 | 1.68 | 1.71 | 27.06 | 6.48 | 42.17 | 8.52 | 26.83 | 1.66 | 1.05 | 2.59 |
| 12.5-21 | 296.11 | 14.67 | 17.44 | 2.16 | 2.12 | 23.97 | 5.76 | 39.15 | 8.14 | 19.16 | 1.65 | 1.14 | 1.90 |
| 30-35 | 376.31 | 19.00 | 17.54 | 2.18 | 2.21 | 18.95 | 4.10 | 36.21 | 7.37 | 19.84 | 1.73 | 1.23 | 1.44 |
| Zayachye, eastern settlement (3rd century AD) | |||||||||||||
| 0-22 | 202.15 | 10.45 | 11.44 | 1.74 | 2.02 | 27.40 | 8.21 | 40.47 | 8.56 | 29.13 | 1.64 | 1.17 | 2.55 |
| 22-30 | 288.39 | 18.23 | 10.14 | 2.17 | 2.30 | 18.21 | 8.20 | 32.61 | 7.30 | 24.87 | 1.58 | 1.24 | 1.34 |
| >32 | 367.43 | 20.44 | 15.27 | 2.57 | 2.46 | 18.09 | 7.50 | 24.12 | 6.27 | 28.15 | 1.55 | 1.21 | 0.89 |
| Soil average (0-35(37) cm) (S) | |||||||||||||
| 269.66 | 14.14 | 14.39 | 2.02 | 2.05 | 26.90 | 6.12 | 36.20 | 7.79 | 21.72 | 1.66 | 1.17 | 1.82 | |
| Ash average (A) | |||||||||||||
| 351.53 | 18.14 | 15.75 | 2.33 | 2.24 | 20.29 | 5.17 | 32.68 | 7.17 | 19.41 | 1.76 | 1.27 | 1.34 | |
| The percentage of soil differences in relation to ash (100•[(S/A)-1]) | |||||||||||||
| % | -23.3 | -22.1 | -8.6 | -13.6 | -8.4 | 32.6 | 18.3 | 10.8 | 8.6 | 11.9 | -6.0 | -7.8 | 35.8 |
For each archaeological site, the termination date is indicated according to [9], as well as the dating of ceramics found when was the pit laying.
Fig. 3.
Dendrogram of the ash (right) and soil-on-ash (left) sample distribution. D - Threshold distance. *Archaeological sites: 5, 5/1, 5/2 – Kunan, ancient Greek farmhouse, 2nd c. BC; 4/1, 4/2, 4/3 – Chernomorskoe/Settlement S11-022 (Bronze Age and Early Iron Age); 2 – Kalos Limen (4th c. BC – 2nd c. AD), ash deposit; 11 – Kermen-Kyr, 2nd – 3rd c. AD; 10/2 – Borut-Khane (1st c. BC – 1st c. AD), ash deposit; 6 – ash deposit near the village of Oirat (before 1944).
Table 7.
Colour and chemical composition of ash in the groups identified by the cluster analysis.
| Objects |
Group А | x±Sx | Group В | x±Sx | |||||||||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1 | 4/1 | 5/2 | 4/2 | 4/2 | 4/2 | 8/1 | 8/2 | 10/1 | 9 | 12 | 5/1 | 10/2 | 11 | ||||||||
| depth (cm) | 62–72 | >50 | >41 | 60–70 | 80–90 | 55.5-60.5 | 200 | 152 | >37 | >33.5 | >32 | 39-40 | 63-73 | 30-35 | |||||||
| Soil color (dry) | 10 YR 6/2 | 10 YR 7/2 | 10 YR 5/3 | 10 YR 6/2 | 10 YR 6/2 | 10 YR 6/2.5 | 10 YR 7/1 | 10 YR 6/2 | 10 YR 6/2 | 10 YR 6/2 | 10 YR 6/1 | 10 YR 5/1.5 | 10 YR 7/1 | 10 YR 6/1 | |||||||
| TiO2 | % | 0.60 | 0.59 | 0.77 | 0.65 | 0.55 | 0.57 | 0.59 | 0.62 | 0.62 | ± | 0.02 | 0.41 | 0.50 | 0.42 | 0.51 | 0.45 | 0.45 | 0.46 | ± | 0.02 |
| CaO | % | 11.74 | 13.69 | 8.55 | 10.25 | 13.64 | 14.06 | 15.33 | 13.13 | 12.55 | ± | 0.79 | 15.57 | 17.96 | 20.44 | 16.49 | 17.71 | 19.00 | 17.86 | ± | 0.71 |
| Al2O3 | % | 4.51 | 6.15 | 11.91 | 9.01 | 8.64 | 8.03 | 9.34 | 10.21 | 8.48 | ± | 0.81 | 5.72 | 8.93 | 6.27 | 7.19 | 7.56 | 7.37 | 7.17 | ± | 0.45 |
| MnO | % | 0.21 | 0.13 | 0.11 | 0.11 | 0.09 | 0.10 | 0.11 | 0.10 | 0.12 | ± | 0.01 | 0.09 | 0.08 | 0.08 | 0.11 | 0.09 | 0.09 | 0.09 | ± | 0.00 |
| Fe | % | 2.51 | 3.02 | 2.89 | 2.44 | 2.16 | 2.40 | 2.25 | 2.41 | 2.51 | ± | 0.11 | 2.00 | 2.69 | 2.25 | 2.33 | 2.18 | 2.30 | 2.29 | ± | 0.09 |
| SiO2 | % | 32.05 | 33.89 | 57.66 | 54.42 | 46.96 | 47.26 | 44.95 | 51.81 | 46.13 | ± | 3.23 | 28.02 | 39.17 | 24.12 | 46.63 | 35.87 | 36.21 | 35.00 | ± | 3.28 |
| P2O5 | % | 2.18 | 0.65 | 0.58 | 0.65 | 0.70 | 0.73 | 0.44 | 0.43 | 0.80 | ± | 0.20 | 1.22 | 1.30 | 1.21 | 1.10 | 1.41 | 1.23 | 1.25 | ± | 0.04 |
| K2O | % | 1.10 | 1.50 | 2.06 | 1.99 | 1.83 | 1.78 | 1.67 | 1.90 | 1.73 | ± | 0.11 | 1.81 | 1.79 | 1.55 | 2.02 | 1.95 | 1.73 | 1.81 | ± | 0.07 |
| MgO | % | 2.28 | 2.50 | 2.18 | 1.67 | 1.59 | 1.90 | 2.15 | 2.03 | 2.04 | ± | 0.11 | 2.28 | 2.35 | 2.57 | 2.56 | 2.27 | 2.18 | 2.37 | ± | 0.07 |
| Na2O | % | 2.81 | 2.89 | 1.90 | 1.39 | 1.47 | 1.51 | 1.64 | 1.64 | 1.91 | ± | 0.21 | 2.04 | 2.47 | 2.46 | 2.19 | 2.03 | 2.21 | 2.23 | ± | 0.08 |
| Co | ppm | 15.76 | 34.15 | 20.02 | 15.69 | 15.34 | 13.49 | 19.99 | 16.53 | 18.87 | ± | 2.33 | 19.07 | 16.43 | 15.27 | 17.65 | 10.42 | 17.54 | 16.06 | ± | 1.24 |
| Ni | ppm | 44.98 | 53.92 | 48.63 | 44.66 | 47.58 | 39.12 | 48.64 | 48.84 | 47.05 | ± | 1.52 | 34.67 | 44.81 | 33.62 | 45.39 | 36.65 | 36.82 | 38.66 | ± | 2.10 |
| Cu | ppm | 12.70 | 23.87 | 35.13 | 35.02 | 46.81 | 22.21 | 48.18 | 42.62 | 33.32 | ± | 4.50 | 18.23 | 26.97 | 18.09 | 20.65 | 19.22 | 18.95 | 20.35 | ± | 1.38 |
| Zn | ppm | 272.84 | 157.73 | 120.83 | 105.68 | 82.84 | 106.08 | 52.18 | 70.98 | 121.15 | ± | 24.48 | 123.39 | 147.45 | 119.44 | 124.75 | 133.22 | 145.58 | 132.31 | ± | 4.86 |
| Sr | ppm | 783.79 | 431.63 | 170.78 | 149.86 | 175.32 | 231.66 | 683.84 | 563.74 | 398.83 | ± | 89.60 | 349.58 | 359.92 | 367.43 | 338.90 | 304.39 | 376.31 | 349.42 | ± | 10.48 |
| Pb | ppm | 27.37 | 35.05 | 22.09 | 12.45 | 11.46 | 6.45 | 13.95 | 13.66 | 17.81 | ± | 3.37 | 13.07 | 19.94 | 28.15 | 18.55 | 16.07 | 19.84 | 19.27 | ± | 2.07 |
| As | ppm | 2.78 | 5.27 | 7.12 | 5.52 | 5.81 | 6.79 | 4.25 | 4.95 | 5.31 | ± | 0.49 | 6.10 | 3.51 | 7.50 | 5.07 | 4.66 | 4.10 | 5.16 | ± | 0.59 |
| V | ppm | 48.52 | 86.65 | 70.86 | 62.16 | 67.32 | 68.30 | 50.89 | 67.57 | 65.28 | ± | 4.23 | 59.09 | 81.89 | 60.72 | 71.46 | 63.80 | 60.03 | 66.17 | ± | 3.64 |
| Ba | ppm | 692.97 | 611.73 | 496.74 | 491.84 | 507.08 | 501.92 | 375.46 | 518.86 | 524.58 | ± | 32.97 | 421.37 | 435.94 | 368.54 | 571.39 | 505.56 | 430.23 | 455.51 | ± | 29.26 |
| Cr | ppm | 88.94 | 108.26 | 86.70 | 81.25 | 78.43 | 77.76 | 79.09 | 79.96 | 85.05 | ± | 3.61 | 77.29 | 89.20 | 114.24 | 77.88 | 73.04 | 76.83 | 84.75 | ± | 6.30 |
| Zr | ppm | 444.15 | 281.69 | 298.44 | 274.54 | 251.89 | 258.93 | 167.88 | 185.04 | 270.32 | ± | 29.70 | 159.62 | 145.01 | 142.35 | 254.11 | 161.99 | 152.43 | 169.25 | ± | 17.26 |
| Rb | ppm | 68.32 | 70.98 | 72.88 | 63.71 | 61.11 | 68.25 | 40.77 | 46.28 | 61.54 | ± | 4.18 | 58.13 | 60.89 | 49.13 | 62.57 | 62.21 | 53.19 | 57.69 | ± | 2.22 |
Table 8.
Main geochemical indicators of the groups of objects (soils and ash) identified by the cluster analysis.
| Object | Depth (cm) | CIA | (Ca+Mg+10•P)/Al | Ke | (Ca+Mg)/Al | Na/Al | Ca+Mg+K | Km | (Fe+Al)/ (Ca+Na+Mg) | Σ HM | SQ |
|---|---|---|---|---|---|---|---|---|---|---|---|
| 1 | 100 | 18.54 | 7.94 | 1.77 | 3.11 | 0.62 | 15.12 | 8.71 | 0.42 | 420.39 | 7.15 |
| 4/1 | >50 | 21.42 | 3.69 | 1.64 | 2.63 | 0.47 | 17.69 | 4.86 | 0.48 | 364.33 | 7.82 |
| 5/2 | >41 | 45.58 | 1.39 | 3.90 | 0.90 | 0.16 | 12.79 | 2.20 | 1.17 | 291.89 | 8.39 |
| 4/2 | 60–70 | 36.31 | 2.04 | 3.53 | 1.32 | 0.15 | 13.91 | 2.03 | 0.86 | 255.61 | 7.71 |
| 4/2 | 80–90 | 29.65 | 2.57 | 2.52 | 1.76 | 0.17 | 17.06 | 1.87 | 0.65 | 240.69 | 7.52 |
| 4/2 | 55.5-60.5 | 27.55 | 2.90 | 2.44 | 1.99 | 0.19 | 17.74 | 2.35 | 0.60 | 232.78 | 7.25 |
| 8/1 | 200 | 28.86 | 2.34 | 2.15 | 1.87 | 0.18 | 19.15 | 1.28 | 0.61 | 217.64 | 7.66 |
| 8/2 | 152 | 33.74 | 1.91 | 2.76 | 1.48 | 0.16 | 17.06 | 1.48 | 0.75 | 228.70 | 7.91 |
| 10/1 | >37 | 19.31 | 5.25 | 1.29 | 3.12 | 0.36 | 19.66 | 4.62 | 0.39 | 257.15 | 6.55 |
| 9 | >33.5 | 24.35 | 3.73 | 1.59 | 2.27 | 0.28 | 22.10 | 3.93 | 0.51 | 303.50 | 7.95 |
| 12 | >32 | 16.79 | 5.60 | 0.89 | 3.67 | 0.39 | 24.56 | 5.22 | 0.33 | 302.69 | 6.62 |
| 5/1 | 39-40 | 22.09 | 4.18 | 2.00 | 2.65 | 0.30 | 21.07 | 2.82 | 0.45 | 264.55 | 7.82 |
| 10/2 | 63-73 | 22.01 | 4.51 | 1.49 | 2.64 | 0.27 | 21.93 | 3.89 | 0.44 | 256.63 | 7.23 |
| 11 | 30-35 | 20.39 | 4.54 | 1.44 | 2.87 | 0.30 | 22.91 | 4.19 | 0.41 | 282.84 | 7.25 |
| Average | 26.19 | 3.76 | 2.10 | 2.31 | 0.29 | 18.77 | 3.53 | 0.58 | 279.96 | 7.49 | |
| Dispersion | 60.33 | 2.90 | 0.68 | 0.57 | 0.02 | 11.34 | 3.66 | 0.05 | 2873.91 | 0.25 | |
| V. % | 30 | 45 | 39 | 33 | 47 | 18 | 54 | 38 | 19 | 7 |
Table 9.
Comparison of the chemical composition of oak wood ash (OWA) and ash from hay of mixed grasses (GMA) using two ranked lists.
| Elements | Units | OWA | GMA | OWA / GMA | Elements | Units | GMA | OWA | GMA / OWA | |
|---|---|---|---|---|---|---|---|---|---|---|
| As | ppm | 3.96 | < LOD | – | SiO2 | % | 75.84 | < LOD | – | |
| CaO | % | 37.07 | 4.74 | 7.8 | MnO | % | 1.41 | 0.27 | 5.3 | |
| MgO | % | 7.40 | 1.86 | 4.0 | Zn | ppm | 354.17 | 99.68 | 3.6 | |
| Sr | ppm | 1571.57 | 516.41 | 3.0 | Co | ppm | 52.63 | 16.69 | 3.2 | |
| Na | % | 4.71 | 1.64 | 2.9 | P2O5 | % | 2.25 | 1.27 | 1.8 | |
| Zr | ppm | 141.76 | 51.62 | 2.7 | Ni | ppm | 37.34 | 26.41 | 1.4 | |
| Al2O3 | % | 2.39 | 0.92 | 2.6 | Pb | ppm | 21.96 | 16.02 | 1.4 | |
| Fe | % | 1.10 | 0.56 | 1.9 | ||||||
| Rb | ppm | 28.60 | 15.15 | 1.9 | ||||||
| V | ppm | 34.97 | 19.40 | 1.8 | ||||||
| Ba | ppm | 805.92 | 541.31 | 1.5 | ||||||
| K2O | % | 7.25 | 4.71 | 1.5 |
*LOD is limit of detection.
Fig. 4.
Correlation of the content of chemical elements in ash from archaeological sites of the forest area (No. 1) and sparse foothill zone (No. 10). Figure reflects К=Ci(1) / Ci(10) with differences greater than or less than 20%.
Fig. 5.
Regression dependences of the contents of Zn, Cu, Mn, Cd, Pb, As, Hg, Mo, and Co in the ash from the soil section at the settlement of Borut-Khane, 1st c. BC – 1st c. AD (Y) and in ash from samples of organic matter: modern oak (Quercus pubescens) (1); fossil oak (2); feather grass (Stipa capillata) (3); cow dung (4); horse manure (5).
2. Experimental Design, Materials, and Methods
2.1. Research objects
Objects of study (ashy soil and ash deposits) include 14 archaeological sites located within three research regions in the south of the East European Plain (Fig. 1, Table 1). Ash deposits can be found both on positive landforms (ash hills from a few meters to 10–13 m high) (Fig. 2, A) and in subordinate positions, such as defensive ditches of archaeological sites (Fig. 2, B). The soil section made in the periphery of the Borisovka site has revealed the ashy profile to a depth of 1 m, which corresponds to the mid-5th c. BC phase of the settlement. The archaeological sites of the North-West Crimea, in whose cultural strata ash has been sampled, range in date from the Late Bronze Age (second half of the 10th c. BC) to the Early Iron Age (3rd c. AD). In addition, at the two Tatarian settlements abandoned in 1944 (former villages of Saya and Ojrat) ash pits were studied. In the foothill Crimea, among the Late Scythian settlements (Ak-Kaya, Kermen-Kyr, and the village of Zayachye), Borut-Khane stands out with the ash hills ranging in height from 0.5 to 2.0 m. The earliest phase of this site dates to the 3rd–2nd c. BC, while its termination date does not exceed the 1st century AD. For the sake of ash identification, the purest layer of ash at a depth of 46–98 cm in the profile of the site's defensive earthwork was selected, which then has been sampled at a depth of 63–73 cm for chemical analyses. At present, the nearest oak woodlands are located at a distance of 4.3 km from the settlement of Borut-Khane.
Colours (dry and moist) were described using the Munsell system [3]. This system uses cylindrical coordinates, which hinders its use for statistical calculations [4]. The conversion of Munsell soil colour values into the RCIE redness index of the CIE-L*a*b* system based on a universal colour space in Cartesian coordinates was carried out using the formula [5]: RCIE = [1010 × a(a2 + b2)0.5]/(bL6). The values of parameters L, a, b were obtained from the Munsell/CIE-L*a*b* system conversion table [4]. RCIE values shown in Table 1 are for dry soil.
2.2. Dating of archaeological sites
The age of each site was established archaeologically (coins, amphora stamps or other narrowly datable pottery) or based on historical record [6]. Based on archaeological date of each site, the age of soils was determined. The date at which human activity at settlements ceased and pedogenesis began was controlled by the method of pedogenetic chronology, which is based on the chronosequence showing the dependence of the humus horizon thickness on soil age [7]. Ash layer from the Bronze Age and Early Iron Age site of Chernomorskoe/S11-022 (No 4) has been radiocarbon dated. A sheep/goat bone, collected for this purpose at a depth of 62 cm from the top surface, inside a 60–90 cm-thick layer of ash, has been dated to 1130–760 ВС (95.4%) (Kyiv Radiocarbon Laboratory, Ki-19342).
2.3. Comparison of main parent rocks and ash
The chemical composition of main parent rocks (carbonate loam and limestone eluvium) was compared with that of archaeological ash and soils formed on it (Table 2). Concentration of macro and microelements within ash deposits and soils was determined by technique of measuring metals mass fraction and oxides in powder samples using an XRF spectrometer (Spectroscan Max-GV).
As a special type of parent material, ash differs significantly in its chemical composition from the more widely distributed rocks (loam and eluvium of carbonate rocks): it has a higher content (> 30%) of P, Ca, Sr (as compared to loam) and P, Co, Sr, Zn, Pb, Cu (as compared to eluvium) and smaller concentrations of Cu, Pb, Fe, Ni (as compared to loam) and Ca (as compared to eluvium).
2.4. Chemical properties of soils of archaeological sites in the dry steppe
Ash pits and soils formed on ashy cultural strata were studied on the Kazantip Peninsula (Table 3), which is an area completely devoid of forests due to climatic conditions (annual precipitation 329 mm). The ash accumulation in this area stops in the 3rd century AD but the life here continued also later (7th–9th centuries AD).
The titrimetric version of the determination of Corg after I. V. Tyurin was carried out by oxidation of the organic substance with a solution K2Cr2O7 in sulphuric acid in a thermostat (at Т = 140 °С)), which is accompanied by the reduction of Cr (VI) to Сг3+. Nitrogen total (N) was determined using the Kjeldahl method (GOST 26107–84, Last Modified: 09.12.2018) “Soils. Methods for determination of total nitrogen". In titration method, nitrogen is calculated from the amount of sulphuric acid spent for titrating ammonium borate. The data obtained for Corg and N were used to assess the degree of enrichment of humus with nitrogen (C:N) according to the scale [8]. Acidimetric method used to determine the content of carbonates (СО2) in the soil is based on their destruction with hydrochloric acid solution followed by titration of its residue with sodium hydroxide solution.
2.5. Soil formed on ash in the forest region and in the steppe zone
A soil section on the periphery of the Borisovka settlement (forest-steppe) revealed a 1 m thick ash deposit associated with the mid-5th century BC phase of the site (Table 4). Grouping of soils and ash from archaeological sites is based on the most informative associations of chemical elements, using cluster analysis (unification by Ward's method) normalized by mean-square deviation. The chemical composition of the ash of different age from archaeological sites of North-West Crimea and of related soils is presented as an ensemble of the 12 most informative macro- and trace elements (Table 5). Data on the geochemical composition of soils and ash from the Piedmont Crimea, which are similar to objects from North-West Crimea, are presented in Table 6. Dendrogram of the ash and soil-on-ash sample distribution clearly shows two clusters of objects (Fig. 3). Table 7 summarizes the data on the geochemical composition of ash in the groups identified by the cluster analysis.
2.6. Main geochemical indicators of soils and ash
Table 8 shows the main geochemical indicators of the groups of objects (soils and ash) identified by the cluster analysis. The justification of the used ratios and coefficients was performed according to [10], [11], [12]. The palaeogeographic potential has an interpretation of the biogeochemical features of all soils both on defensive structures (ramparts and ditches) [13], and on the territory of settlements and in their surroundings. Using the determinations of the bulk composition of soils and ash deposits, the most informative geochemical indicators were calculated: SiO2/(RO + R2O), where RO = CaO + MgO; R2O = K2O + Na2O. The informative coefficient group includes the eluviation coefficient (Ke= Si/(Ca+K+Mn+Mg+Na)); coefficient of mobility (Km = (Na+K+Mg+Zn)/SiO2); amount of heavy metals (Σ HM = Σ (As, Co, Cr, Cu, Pb, Zn); and quality assessment for a group of chemical elements useful for plants (SQ= ∏(Ca, Al, Mn, Fe, Si, K, Mg, Ni, Cu, Zn)1/10). We provide a comparison of weathering coefficient (CIA values [14]) in horizon A of virgin soils so that we can compare with CIA values for soils formed on ash (Table 8). CIA values in horizon A of virgin soils vary from 26.99 (meadow steppe of the Piedmont Crimea) and 32.52 (reserved steppe of North-West Crimea) to 48.11 (coastal steppe of the Kerch Peninsula) and 59.93 (protected oak forest with an age of 250 years in Belgorod Oblast).
2.7. Justification of the genesis of ash deposits
The chemical composition of ash prepared from plant samples was investigated using a variety of techniques, including emission spectrometry (Zn, Cu, Mn and Co: spectrometer ICPE–9000 with induction-bound plasma), atomic absorption spectroscopy (Pb and Cd: spectrometer Quant–2AT; Hg: spectrometer Quant–Z) and photocolorimetry (As: photocolorimeter KFK–3–01). Ashing of samples was carried out in a muffle furnace at 450 °C. Comparison of the geochemical composition of oak wood ash and ash from hay of mixed grass using two ranked lists presented in Table 9. Fig. 4 shows the ratio of chemical elements in ash from archaeological sites in the forest area and sparse foothill zone. A comparison of 22 chemical elements contained in the ash from archaeological sites of the forest area (No 1) and the sparsely wooded foothill zone (No 10) has shown that these two regions used fuel of different genesis (Fig. 4). The ash obtained from the combustion of oak mixed with some other hardwoods (Borisovka settlement, mid-5th c. BC) has a higher content (> 20%) of 11 chemical elements and a lower content (<20%) of 5 chemical elements than the ash from the settlement of Borut-Khane, 1st c. BC – 1st c. AD, which is located in the region with a shortage of wood (Piedmont (forest-steppe) Crimea) and also in the arid conditions of the Roman times. Regression relationships of Zn, Cu, Mn, Cd, Pb, As, Hg, Mo, Co content in the ash from the soil section at the settlement of Borut-Khane and in the ash from various organic matter samples have made it possible to determine differences in the genesis of ash deposits.
As judged by regression lines in relation to complete junction, the ash from the settlement of Borut-Khane, 1st c. BC – 1st c. AD (Fig. 5), situated in the region which in antiquity and nowadays was short of firewood (red arrow), differs significantly from oak ash (in excess of As, Hg, Mn, Co), being most similar to the ash of feather grass (the main steppe grass) and cow dung, i.e. in composition it is close to kizyak which was probably the main fuel at that time.
2.8. Data analysis
Macro-elements and trace elements were determined by wavelength-dispersion (XRF analyser Spectroscan Max-GV). The results were quantitatively calibrated using a set of state (GOST) standard samples of soil composition. The geochemical composition of each soil sample was determined by two repeats. In case of unacceptable discrepancies between the measurements, which were detected using the spectrometer software, additional replicates were performed until an acceptable result was achieved (usually in the third repeat).
CO2, Corg, total N (data presented in Table 3). Corg in soils was determined by the titrimetric version of Tyurin's method with oxidation in a thermostat at 140 ˚С, СО2 by acidometry [15]. Total nitrogen (N) was estimated by Kjeldahl's procedure. For the accuracy control, every tenth sample was measured in two repeats. In addition, after each ten measurements, a device control was carried out by measuring standard reference samples.
CRediT Author Statement
Fedor N. Lisetskii: Conceptualization, Investigation, Writing–original draft, Funding acquisition; Arseniy O. Poletaev: Visualization; Vladimir F. Stolba: Archaeological dating, Writing–review and editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships which have, or could be perceived to have, influenced the work reported in this article.
Acknowledgments
This work was funded by the Russian Science Foundation, project no. 20-67-46017.
Footnotes
Supplementary material associated with this article can be found in the online version at doi:10.1016/j.dib.2020.106691.
Appendix. Supplementary materials
Data for Reference
Archaeological ash deposits and soils formed on ash in the south of the East European Plain (Original data) (Mendeley Data).
References
- 1.Lisetskii F.N., Stolba V.F. Archaeological ash deposits and soils formed on ash in the south of the East European Plain. Quatern. Int. 2021 doi: 10.1016/j.quaint.2020.11.030. [DOI] [Google Scholar]
- 2.Canti M.G. Aspects of the chemical and microscopic characteristics of plant ashes found in archaeological soils. Catena. 2003;54:339–361. [Google Scholar]
- 3.Munsell soil color charts: year . Gretag Macbeth Grand Rapids; MI, New Windsor: 2000. Revised Washable Edition. [Google Scholar]
- 4.Vodyanitskii Y.N., Kirillova N.P. Conversion of Munsell color coordinates to Cie-L*a*b* system: tables and calculation examples. Moscow Univ. Soil Sci. 2016;71:139–146. doi: 10.3103/S0147687416040074. [DOI] [Google Scholar]
- 5.Barron V., Torrent J. Use of the Kubelka–Munk theory to study the influence of iron oxides on soil color. J. Soil Sci. 1986;4:499–510. doi: 10.1111/j.1365-2389.1986.tb00382.x. [DOI] [Google Scholar]
- 6.Lisetskii F.N., Stolba V.F., Pichura V.I. Late-Holocene palaeoenvironments of Southern Crimea: soils, soil-climate relationship and human impact. Holocene. 2017;12:1859–1875. 10.1177/0959683617708448. [Google Scholar]
- 7.Lisetskii F.N., Stolba V.F., Goleusov P.V. Modeling of the evolution of steppe Chernozems and development of the method of pedogenetic chronology. Eurasian Soil Sci. 2016;8:846–858. doi: 10.1134/S1064229316080056. [DOI] [Google Scholar]
- 8.Orlov D.S., Biryukova O.N., Rozanova M.S. Revised system of the humus status parameters of soils and their genetic horizons. Eurasian Soil Sci. 2004;8:798–805. [Google Scholar]
- 9.Smekalova T.N., Koltukhov S.G., Zaitsev Ju.P. Saint Petersburg; Aletheia: 2015. Atlas of Late Scythian fortresses in the Crimean foothills. ISBN 978–5–9906154–7–2. [Google Scholar]
- 10.Alekseev A., Alekseeva T., Kalinin P., Hajnos M. Soils response to the land use and soil climatic gradients at ecosystem scale: mineralogical and geochemical data. Soil Tillage Res. 2018;180:38–47. doi: 10.1016/j.still.2018.02.008. [DOI] [Google Scholar]
- 11.Lisetskii F.N., Smekalova T.N., Marinina O.A. Biogeochemical features of fallow lands in the steppe zone. Contemp. Probl. Ecol. 2016;9:366–375. 10.1134/S1995425516030094. [Google Scholar]
- 12.Prikhodko V.E., Azarenko Y.A., Shayakhmetov M.R., Tishkin A.A., Gorbunov V.V., Pivovarova E.G. Reconstruction of the climate of the Medieval Epoch based on soil and geochemical studies of kurgans of the Srostki Culture in the South of Western Siberia. Eurasian Soil Sci. 2020;3:267–282. doi: 10.1134/S1064229320030059. [DOI] [Google Scholar]
- 13.Lisetskii F., Poletaev A., Zelenskaya E., Pichura V. Associated data on the physicochemical properties of pedosediments, climatic and dendrochronological indicators for palaeogeographic reconstructions. Data Brief. 2020;28 doi: 10.1016/j.dib.2019.104829. 10.1016/j.dib.2019.104829. [DOI] [PMC free article] [PubMed] [Google Scholar]
- 14.Nesbitt H.W., Young G.M. Early Proterozoic climates and plate motions inferred from major element chemistry of lutites. Nature. 1982;299:715–717. [Google Scholar]
- 15.Theory and Practice of Chemical Analysis of Soils. Ed. L.A. Vorobeva. Moscow: GEOS, 2006. 400 p.
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Data Availability Statement
Archaeological ash deposits and soils formed on ash in the south of the East European Plain (Original data) (Mendeley Data).