Review Reports - Geochemical Features of Fallow Land in Ancient Plots in the Chora of Chersonesos

Round 1

Reviewer 1 Report

The manuscript “Geochemical features of fallow land in ancient plots in the chora of Chersonesos” can be a good contribution for the environmental studies related to vineyards.

I think that some revisions should be made by the authors before paper publication, in order to achieve an improved work. Some parts of the work are a little confused and a careful revision should be done to all the text.

In table 1 Ca, Al and Fe are represented as elements and Si, Mg and P in oxides. (?)

An improvement should be done in the discussion of the results;

Page 2 Line 44 – “ and the establishment of a correspondence…”

Page 2 Line 58 – “… but on the mineral nutrition that the grape receives….”

Page 2 Line 71 – …to the beginning of the 1st century AD; the same thing on line 92.

Page 3 Line 130-132 – some references are needed.

Page 3 Line 132 – … amounts to 3300-3500 ˚C????

Page 4 Line 167-169 – “involves the calculation the multiplication …..”. The sentence is confuse and unclear.

Page 5 Line 186-187 – in the table caption I think that the units of the chemical elements contents should be included (mg kg-1 or %)

Page 5 line 197 – from this sentence and in the all the page 6 some confusion is made by the authors with the samples references (CN3 or CH3; CN387 or CH387)…..

Page 7 Line 239 – (…) groups there is accumulation of …

Page 7 line 243 – again we have CH387..

I think that this work present interesting results, but nevertheless some major revisions should be done before publication, particularly in the results discussion.

Author Response

Reviewer 2.

We would like to thank Reviewer 1 for high estimation of our work. Our answers on your remarks are below (not italics).

Point 1: Comments and Suggestions for Authors: In table 1 Ca, Al and Fe are represented as elements and Si, Mg and P in oxides. (?)

Response 1: Corrected. The transition from oxides to elements is justified and more accurate due to the different valences of the chemical elements.

Point 2: An improvement should be done in the discussion of the results;

Response 2: Text correction: The studied soils in relation to the parent rock are characterized by the greatest accumulation of phosphorus (average S/P ratio is 2.1), as well as Si, Zn, K, Cu, Mn (1.4-1.2). However, the soil of the two cuts (plot CN 130) is especially noticeably different from all other objects in the accumulation of Si, Fe, Al, K, Ni, Cu, Co, Mn. In addition to the plot of CN 130, a significant accumulation (above average) was noted for the objects OT, OR (trenching soils of NW Crimea), CN 395 and CN 391-1. The soils of NW Crimea, if shattered from plots in the Herakleian Peninsula, have a significant participation of magnesium and sodium in the cation exchange capacity, because of which the soils are less structural. The resulting regression equation showed that with increasing carbonates content (CO₂) from 3 to 27%, the CEC value is halved. Among the studied soils, only two cinnamonic soils near Cape Fiolent (CN 387 and CN 389) have a higher soil absorption capacity.

The highest values of FI are noted in soils of NW Crimea due to the higher calcium content, as well as phosphorus, but not in all cases. The soils of this region have on average greater the CEC value (1.2 times) than the soils of the Herakleian Peninsula, which is associated with a greater participation of absorbed magnesium and sodium in the composition of the CEC.

Point 3: Page 2 Line 44 – “ and the establishment of a correspondence…”

Response 3: Corrected

Point 4: Page 2 Line 58 – “… but on the mineral nutrition that the grape receives….”

Response 4: Corrected

Point 5: Page 2 Line 71 – …to the beginning of the 1st century AD; the same thing on line 92.

Response 5: Corrected

Point 6: Page 3 Line 130-132 – some references are needed.

Response 6: Corrected. Two main types of dry forest and bush soils are located here, i.e., cinnamonic light-clayey soils (a sub-Mediterranean variation of the terra rossa) and rendzina soils [25]. Soils are generally thin, stony, and carbonate-rich. The region’s climate is very dry and moderately hot, with fairly mild winters with an average annual temperature of 10.3–12.0 °С, the sum of active temperatures (Σt > 10°) per year amounts to 3300–3500 °С and an annual precipitation of 350–475 mm [35-37].

Point 7: Page 3 Line 132 – … amounts to 3300-3500 ˚C????

Response 7: This is not an error: the sum of active temperatures = the amount of average daily temperatures Σt > 10° per year can reach 4200 °С in this area. We added: per year

Point 8: Page 4 Line 167-169 – “involves the calculation the multiplication …..”. The sentence is confuse and unclear.

Response 8: Text correction: The coefficient of accumulation of trace elements (Ka) Shaw [43] proposed to calculate as the arithmetical mean of the relationship of trace elements in the soil (S) to the parent rock (P). We used the modification of this coefficient (К_S) as a geometrical mean value S/P for the trace elements group (Ni, Zn, Mn, Pb, Cu, Co, Mg, Cr, Fe, Sr, Rb, V).

Point 9: Page 5 Line 186-187 – in the table caption I think that the units of the chemical elements contents should be included (mg kg-1 or %)

Response 9: Usually, macro- and micro- elements are expressed in different units, since mg kg-1 =ppm and 1%= 10 000 ppm. Therefore, for example in Table 1 Ca with 17.7% = 177 000 mg kg-1 (ppm). This would make the table cumbersome.

Point 10: Page 5 line 197 – from this sentence and in the all the page 6 some confusion is made by the authors with the samples references (CN3 or CH3; CN387 or CH387)…..

Thank you for careful analysis of our paper. It was our mistake.

Response 10: Corrected

Point 11: Page 7 Line 239 – (…) groups there is accumulation of …

Response 11: Corrected

Point 12: Page 7 line 243 – again we have CH387..

Response 12: Corrected

Author Response File: Author Response.doc

Reviewer 2 Report

The authors studied the ampeloecological conditions based on geochemical features of the viticulture soil in NW Crimea. This is an interesting issue that will be helpful for the understanding land suitability for ancient viticulture.

The paper is interesting. However, the manuscript requires some improvements before publication.

Please find attached the report.

Comments for author File: Comments.pdf

Author Response

Reviewer 3.

We would like to thank Reviewer 1 for high estimation of our work. Our answers on your remarks are below (not italics).

Point 1: My comments to the authors are the following: Line 52. Please add “,” between S and Mg.

Response 1: Corrected

Point 2: Line 54. What do mean by “active minerals”? Please give more explanation.

Response 2: “active minerals" is the author's term [23]. But we think that it can be exchanged for fine-dispersed minerals. We did it.

Point 3: Line 132. You have written that the sum of active temperatures (Σt > 10°) amounts to 3300–

3500 °С. Do you mean the sum of active temperatures (Σt > 10°C) amounts to 33–35 °С?

Response 3: This is not an error: the sum of active temperatures = the amount of average daily temperatures Σt > 10° per year can reach 4200 °С in this area. We added: per year

Point 4: Line 146. The Soil sampling horizon (A) was of 16 or 24 cm layers-thick? Please clarify this.

Response 4: Corrected

Point 5: Results. Line 199. Please add FI, Km and Ke values in the Table 2.

Response 5: Thank you, this is a good point. We have added two new Tables.

Point 6: The results section should be re-written and will include further description of the results, especially the IF, Km and Ke coefficients.

Response 6: Text correction L 223: Four geochemical indicators (FI, Km, Ka, KS) of seven (Table 2) showed higher values in group III (soils of NW Crimea), and the smallest values in group II, group I occupies an intermediate position (soils in the area of Cape Fiolent). The eluviation’s coefficient (Ke), which by its structure gives inverse values than the four indicators mentioned above, confirms this pattern. Thus, soils from areas of NW Crimea are characterized by a more active accumulation of trace elements, reduced migration mobility and the degree of weathering in more alkaline conditions of the soil solution.

Point 7: Discussion. Line 205. “A comparison of the soils under the vineyards of an aggregate of 17 chemical elements showed” please check your statement, here you study only 13 chemical elements.

Response 7: Concentration of 20 metals and their oxides (9 macroelements and 11 trace elements) within the soils were determined. But Table 1 does not include the chemical elements with a low coefficient of variation (V ≤ 10%): Ti, Mn, Co, K, Rb, Na, As. This is added to the text.

Therefore, 13 informative elements were left for analysis.

Text correction L 223: A comparison of the soils under the vineyards of an aggregate of 20 chemical elements…

Text correction: Based on the Table 1 (concentration of the most informative 6 macroelements and 7 trace elements), data cluster analysis (Figure 2) was performed…

Point 8: Line 207. How do you mean by “natural state”? Original not inherited?

Response 8: Previously, standards were submitted. This is added [38,37].

Point 9: Lines 233-237. You deciphered three clusters based on chemical composition of soils, among these elements you didn’t present the amounts of Co and MnO in the table 1. However you use the Co and MnO variation in accumulated elements in soils.

Response 9: We have added new Table 4. The accumulation of the trace elements according to the ratio of concentrations in soil and parent rock (S/P)

Text correction: The studied soils in relation to the parent rock are characterized by the greatest accumulation of phosphorus (average S/P ratio is 2.1), as well as Si, Zn, K, Cu, Mn (1.4-1.2). However, the soil of the two cuts (plot CN 130) is especially noticeably different from all other objects in the accumulation of Si, Fe, Al, K, Ni, Cu, Co, Mn. In addition to the plot of CN 130, a significant accumulation (above average) was noted for the objects OT, OR (trenching soils of NW Crimea), CN 395 and CN 391-1.

Point 10: Line 239. Please add “of” after accumulation.

Response 10: Corrected

Point 11: Lines 243-248. As requested previously, the authors must show the Ke values to highlight the difference of weathering in the three soil clusters.

Response 11: The most informative geochemical indicators and average values by groups are presented in New Table: Table 2. The main geochemical indicators and their average values for soil groups

Point 12: How do you explain the differences in CEC values in the soils samples? What is the relationship between these values and the weathering state and the index of potential soil fertility (FI)? I suggest that this issue should be added in the discussion section.

Response 12: Text correction: The soils of NW Crimea, if shattered from plots in the Herakleian Peninsula, have a significant participation of magnesium and sodium in the cation exchange capacity, because of which the soils are less structural. The resulting regression equation showed that with increasing carbonates content (CO₂) from 3 to 27%, the CEC value is halved. Among the studied soils, only two cinnamonic soils near Cape Fiolent (CN 387 and CN 389) have a higher soil absorption capacity.

Author Response File: Author Response.doc

Reviewer 3 Report

The article is interesting. It reflects the new material of long-term multilateral research for the soils of 13 plots of Crimea, which are the territory of grape cultivation and wine production from ancient times from 2.4 thousand years ago. The geochemical approach is especially interesting. 17 chemical elements have been studied; the authors present a modification of some geochemical indices. Article need publish.

But the article requires some rework

1.Need change the article name: May be as such

Geochemical features of fallow land in ancient plots in the chora of Chersonesos Crimea and their impact on viticulture

2.Why in the summary content P2O5 is given in oxides, and does not as other elements

Table 1. Indicate that the properties are given for the surface soil horizon.

2. It is necessary to specify the data for the parent rock, as this is discussed in the article.

Table. 2

1. for Ca Al Fe you need to specify the content in the oxides, or the content of all components expressed in the elements

2. it is necessary to separate Ca carbonates from Ca-silicates

3. Instead of CO2 you need to write CO2 carbonates.

4. Instead of Avail. P avail. To write

Available
Р	К

5. Requires an explanation of the data table. 2. why at a high content of 25% CO2 carbonates the pH value (H2O) can be 7.9 and 8.5

Soils differ significantly in Corg, CaCO3 content, is there a link to Corg and CaCO3 content in grape growing?

6. It is necessary to consider how the content of elements in the studied soils differs from the Clarke of each element.

7. For lines 67, 68, 118, 133 need o give references to the author,

8. On line 149, an incorrect reference to methods was given [35]

Comments for author File: Comments.pdf

Author Response

Response to Reviewer 1 Comments

We would like to thank Reviewer 1 for high estimation of our work. Our answers on your remarks are below (not italics).

Point 1: Need change the article name: Geochemical features of fallow land in ancient plots in the chora of Chersonesos in Crimea and their impact on viticulture

Response 1: This addition is available in the first sentence of Abstract:

“Abstract: The ancient city of Chersonesos created an agricultural zone in the 4th and 3rd centuries BC (under the conditions of climate aridization); this zone was initially used for viticulture and the export of wine, and grain farming later developed at the distant chora (in northwestern Crimea).

Point 2: Why in the summary content P2O5 is given in oxides, and does not as other elements

Response 2: L164: the available P₂O₅ (mg kg-1) by Machigin’s method. All other elements were identified by us as oxides using the X – ray fluorescence analysis, but recalculated into elements (see explanation below).

Point 3: Table 1. Indicate that the properties are given for the surface soil horizon.

Response 3: Corrected

Point 4: 2. It is necessary to specify the data for the parent rock, as this is discussed in the article.

Response 4: Taking into account the chosen format of the article “Short Note”, we gave all the data on parent rock in a compressed form, like the soil relative to the parent rock (S/P). L250-260. We have added new Table 3. The accumulation of the trace elements according to the ratio of concentrations in soil and parent rock (S/P)

Point 5: Table. 2 1. for Ca Al Fe you need to specify the content in the oxides, or the content of all components expressed in the elements

Response 5: In the Table. 1 the content of all components is given in the form we used to build the Dendrogram of cluster analysis of soils. The transition from oxides to elements is justified and more accurate due to the different valences of the chemical elements. Corrected

Point 6: 2. it is necessary to separate Ca carbonates from Ca-silicates

Response 6: In Table 1 we gave Ca-silicates, and in Table 2 - Ca carbonates (see below).

Point 7: 3. Instead of CO2 you need to write CO2 carbonates.

Response 7: Corrected

Point 8: 4. Instead of Avail. P avail. To write

Response 8: Corrected

Point 9: 5. Requires an explanation of the data table. 2. why at a high content of 25% CO2 carbonates the pH value (H2O) can be 7.9 and 8.5

Response 9: The first four Soils are located in the NW of Crimea and are formed on the eluvium of carbonate rocks, which is very crushed, therefore here рН (H₂O) = 8.1-8.8. And the remaining Soils contain fragments of carbonate rocks, which determined some differences between CO2 carbonates and рН (H₂O). But all soils generally have рН (H₂O) = 7.9-8.5, i.e. the soils are mostly medium alkaline. This is indicated on L 221-222:

Such soils have high carbonate content, medium and strong alkaline reaction of soil solution

Point 10: Soils differ significantly in Corg, CaCO3 content, is there a link to Corg and CaCO3 content in grape growing?

Response 10: Of course, the relationship between these parameters exists and we presented the previously obtained results on this issue (L 36-60). This is an interesting question, but we have not studied the reaction of a vine plant, and this aspect of the problem is beyond the scope of this article.

Point 11: 6. It is necessary to consider how the content of elements in the studied soils differs from the Clarke of each element.

Response 11: We will answer the question of the reviewer “how the content of each element” from Clarke of each element: Clark would be correctly compared with the parent rock (but we did not provide this data - see the explanation on point 2). Due to the large range of Clark values, we consider it more correct to use in local conditions the ratio of the content for each element in the soil relative to the parent rock (S / P), which we have implemented in this article.7. For lines 67, 68, 118, 133 need o give references to the author, Corrected

Point 12: 8. On line 149, an incorrect reference to methods was given [35]

Response 12: L159.

The main analytical procedures were performed according to standard methods [35] in the Chemical-Analytical Complex of the Institute of Physical, Chemical and Biological Problems in Soil Science, Russian Academy of Sciences, Pushchino.

[35] Golyeva, A.; Khokhlova, O.; Lebedeva, M.; Shcherbakov, N.; Shuteleva, I. Micromorphological and chemical features of soils as evidence of bronze age ancient anthropogenic impact (Late Bronze Age Muradymovo settlement, Ural region, Russia). Geosciences (Switzerland). 2018, 8(9), 313. DOI: 10.3390/geosciences8090313

This reference is correct, because the authors of this article, as well as the authors (Golyeva et al., 2018) used the same Chemical-Analytical Complex and in this paper the standard methods are described in detail. We are in the section “2. Material and Methods ”focused on the original Methods.

Author Response File: Author Response.doc

Round 2

Reviewer 1 Report

The author improved the manuscript and is now ready to be published in the present form

Reviewer 2 Report

The manuscript was improved and the authors responded to all the comments.