Complex Study of Settlements Dating from the Paleolithic to Medieval Period in the Ural Mountains on the Border of Europe and Asia

Round 1

Reviewer 1 Report (New Reviewer)

Comments and Suggestions for Authors

Dear Authors,

I have reviewed the manuscript titled "Complex Study of Settlements Dating from Paleolithic to Medieval Ages of Southern Urals on the Border of Europe and Asia."

It should be noted that the downloadable version of the manuscript includes notes and integrations, which unfortunately renders the text somewhat unclear and difficult to read.

This manuscript presents a comprehensive interdisciplinary investigation integrating soil science, geochemistry, microbiology and archaeology. The study provides valuable insights into the cultural layers (CLs) of ancient settlements. It sheds light on the environmental and anthropogenic factors that have influenced soil properties over time.

The manuscript has several notable strengths. It effectively synthesises soil science, geochemistry, microbiology and archaeology to provide a holistic understanding of the cultural layers associated with these ancient settlements. The authors have provided a thorough and detailed description of the methods used for soil sampling, analysis and archaeological excavation, which greatly enhances the reproducibility of the study.

In addition, the manuscript is supported by extensive data on soil properties, microbial biomass and geochemical composition, accompanied by a wealth of figures and tables. The study contextualises its findings within a broader historical and cultural framework. It discusses the significance of the settlements and their interactions with the natural environment and human activities over time. It also highlights the impact of ancient and modern human activities on soil properties and geochemical anomalies. This provides valuable insights into long-term environmental change.

However, my review has identified several areas in which the manuscript could benefit from improvement. A more concise and structured approach would improve the overall organisation and clarity of the writing. Some sections, particularly the results and discussion, are repetitive and could be streamlined to improve readability and focus. In addition, certain terms (e.g. 'clarke', 'biocenes area') are not clearly defined in the text. Providing clear definitions or explanations for these terms would greatly improve the clarity of the manuscript. While the data presentation is detailed, the interpretation of the results could be more robust. A deeper analysis of the implications of the results would contribute to the scientific value of the manuscript. Furthermore, the relevance of certain scientific data, such as microbial biomass, to the archaeological context is not always obvious. The overall impact of the study would be enhanced by strengthening these links.

Finally, the manuscript contains several grammatical errors and awkward phrases that detract from its readability. Thorough proofreading and linguistic editing would be highly beneficial.

Recommendations for Authors

To enhance the clarity and coherence of the manuscript, it is recommended to reorganize the content to eliminate redundancy and ensure a logical progression of ideas. This can be achieved by combining related sections and using subheadings to guide the reader through the text.

It is crucial to provide precise definitions for all technical terms and concepts. These definitions should be included either within the main text or compiled in a glossary to facilitate understanding.

The discussion section should be expanded to provide a broader interpretation of the results. This expansion should emphasise the significance and implications of the results in the context of ancient settlements. Highlighting these aspects will provide a deeper understanding of the topic.

Authors should clearly articulate how the scientific data underpins the archaeological interpretations. This involves demonstrating the correlation between the data and the interpretations, and elucidating the novel insights gained into the history and culture of the studied settlements.

 

Finally, a meticulous review of the manuscript for language and grammar is essential. Engaging a native English speaker or a professional editor can greatly enhance the quality of the text, ensuring it meets the highest standards of academic writing.

Author Response

Reply to reviewers
Comments and Suggestions for Authors
General comment
 The soil, geochemical, microbiological, and archaeological investigations carried out at the settlement sites are interesting. Though the interpretations can be further expanded, the profiling of the compositions of the diverse chemical elements, organic carbon as well as physical characteristics and microbial properties as a function of the stratigraphic layers is important. The archaeological results appear to have originated from other studies conducted earlier. The way the manuscript is written needs improvements.  Some of the results could have been better summarized in tabular formats.
Thank you very much for your thoughtful and comprehensive reviews of the article. They helped us greatly to improve article.
Also many thanks for the correction of the English language.
Unfortunately, due to my mistake, different texts were in two files of the article uploaded as RDF and Microsoft World files.
So. you had to read and reviewed text of the article, in which the Munsell color and soil structure were not indicated everywhere and some sections of the discussion were missing.
We apologize for the inconvenience caused in reading and editing the article.

Below are the responses to comments.
Please see the full text of the responses inside the article
It’s better to write The Late Medieval and Modern Ages

Text about definition of the CL was added in Introduction:
The CL is formed as a result of human activity at the settlements and consists of various materials: fragments of ceramics and metal products, buildings ruins, animal remains, etc. Its thickness varies depending on the duration of residence (Sycheva et al., 2004; Nowaczinski et al., 2013). 
I suggest you redesign the Table 1 with separate columns for Settlement, Archaeological Culture and Age.
Table 1 was redesigned, following your advice two vertical columns were added 

Please list the sites where samples were taken every 5 cm).?
For five sections samples were taken from successive layers with a thickness of 0–5 cm down to the parent material, in Ishkulovo, Kusimovo-8, Sabakty-1a site’s samples were taken every 10 cm.

Biocenosis what does it mean?
It would be more correct to write phytocenosis, including vegetation, since biocenosis is a biotic community including plants, fungi, microbes and animals existing in a common area. 
The objects are located in the forest-steppe zone, therefore they consist of steppe areas and climax forests (usually write forests)
About of the stone industry?
Elimbetovo site, Gamayun Culture. The phrase: settlement of the stone industry - removed, despite the fact that 15 stone tools were found in a small area. But further study is required. As shown earlier in the Gamayun Culture Community, the main tools were stone (2500 BP). In fact, they were at the final stage of the Stone Age in terms of development (Borzunov, 2018; Savelyev, 2018). 
dating of the Alakul culture?
Amangildino is a long-term settlement of the Late Bronze Age (Alakul culture 3900–3450 BP). This chronology is based on a generalization of  52 14C dates [36] Molodin et al, 2014
Answer Colors for soils  on the Munsell were added  in tab 2. Morphological data  
Please clarify the meaning of this statement?

The Elimbetovo-7 site is located 190 m from the Yangelka River, where people of the Gamayun culture lived. Sixteen ceramic fragments and 15 stone tools were found at a depth of 11–38 cm. It was identified as an archaeological site 70 years ago after the discovery of a large flint tool. This CL is a thin feature at 40 cm depth, directly underlain by diabase.

The Reviewer (Randal Southard) asked: “(Is the metal chemistry mostly a function of the near-by metal smelting?  If so, what is the connection with the ancient settlements?) It seems most of the CLs are affected by modern-day environments, including land-use and pollution from smelting. How do you distinguish from the ancient environments?

Answer We have added a new large section to the article discussion, where we write about the reasons for the increased content of heavy metals in the CLs. 
1. The main reason is the geological historical background associated with the high content of various ores - copper, iron, manganese, etc. in the Ural Mountains, where CLs are located. Moreover, the accumulation of heavy metals is noted in the entire profile of the CLs and soils, including in the parent rocks, they often contain more metals than in the surface horizons. And the content of metals throughout the profile is several times higher than the Clarke value – the average elements content in the Earth's geosphere. This is well known from the scientific literature published earlier.
2.Technogenic pollution from modern metallurgical plants, including the nearby Magnitogorsk plant, spread mainly to the surface horizons, since sites are located far from the plant 18–60 km. It has been proven that further than 5-10 km the plant has almost no effect on the soils (Il’in, Syso, 2003; Vodyanitskii et al., 2010). Similar conclusion was made by Professor Randal Southard in a joint article with Brazil soil scientists:  dos Santos, N.M.; do Nascimento, C.W.A.; de Soutza Júnior, V.S.; Southard, R.J.; de Olinda, R.A. Lead isotope distribution and enrichment factors in soil profiles around an abandoned Pb-smelter plant. Environ. Sci. Technol. 2017, 14(11), 2331–2343. DOI 10.1007/s13762-017-1320-
We have significantly expanded the discussion of articles devoted to the concentration of metals in the regional soils.
We have also used a coefficient of technogenic accumulation of metals and a discussion of the properties of chernozems that determine the fixation of heavy metals, etc.
   Zn is an essential plant nutrient; toxic if too concentrated.
Answer Sure. As other metals 
Why do you assume RGI-1103 is incorrect, and RGI-1104 is correct? Please give reasons?
Answer Kusimovo-8 site. 258±13 ka (RGI-1103, VSEGEI), obviously, the last date is overestimated. As in the Kusimovo-8 site found 121 chopping tools  and their shapes belong to the Karyshkin’ culture and are markers of the Lower Paleolithic Era (125–200 ka BP) at the Southern Trans-Urals region and were found at the Mysovaya and Karyshkino-11 sites, etc. (Kotov, 2023)

 Specific comments and suggestions
Line 42: .... large copper mines – Bakr-Uzyak and Kargaly, developed in the Neolithic and Bronze 42 Ages [2]; In Neolithic copper ore? Meaning?
Answer It is assumed that the Bakr-Uzyak mine began to developed in the Eneolithic era, but the exact date is missing. Kargaly  developed since 4.8 ka ca. BP.  Corrected:Large copper mines – Bakr-Uzyak and Kargaly – developed in the Bronze Age (Chernykh, 2008).
Lines 48-49: ... The aim of the complex study of the cultural layers of settlements was to determine, pedological, microbiological and geochemical properties of these layers in order to characterize the environments in which the population of different cultures had functioned and to obtain more detailed information
Answer The aim of a complex study of the settlements was to determine pedological, microbiological and geochemical properties to characterize the environment in which the ancient population lived and show the causes of accumulation of heavy metals in the area and resulting soil pollution.
Line 69: ... chronosequences of paleosols dated 2000 BC–1000 AD BP of the Southern Urals?  This text was removed
Line 85: ... the warmth remained, and humidity increased ...  text was removed 
Line 102: ... some mires peats ... Aren’t they different? ... several lake deposits ...
Answer sediments of lakes and swamps of the forest-steppe of the Southern Urals [9, 55–59]. 
Lines 106-107: needs re-writing .... was moist and t, warm; in the period 3900–3450 BP (Amangildino, Telyashevo-4) the climate was warm and humid, in 106 the stage 2700–2500 BP (Elimbetovo-7) the climate was chilly and moist.
Answer In the period of 3.9–3.4 ka BP ( Amangildino, Telyashevo-4) was warm and humid climate, at the stage of 2.7–2.5 ka BP (Elimbetovo-7 site) – cool and humid [11, 53, 61–64]. 
Line 113: Table: separate: Settlement, archaeological culture and age in three columns rather than congesting them in one.  WERE done new Table 2.
Line 136: ... a deep section ....
Line 139: ... sections was provided ....
Line 144-148: .... the by following methods: elemental analyzer CHNSO for determining Corg and total nitrogen, potentiometry for measuring pH in aqueous solution (suspension, 1:2.5), the amount of soil exchangeable Ca2+ and Mg2+ according to Shollenberger, the content of mobile P2O5 using photometric method, and analysis of granulometric composition by the pipette method with sodium pyrophosphate treatment [39].
Answer Soil properties were measured by the following methods: use of a CHNSO elemental analyzer for determining Corg and total nitrogen, potentiometry for measuring pH in aqueous solution (suspension, 1 : 2.5), the amount of soil exchangeable Ca2+ and Mg2+ was done for measuring according to Schollenberger, the content of mobile P2O5 was evaluated by the photometric method, analysis of granulometric composition was carried out by the pipette method with sodium pyrophosphate treatment [24
Line 153-156: The vials were then closed and placed in a thermostat at 22°C. The basal soil respiration (SR) was determined using a gas chromatograph after 2 days and again after the next two days, then the value of microbial biomass (Cmic) 154 was found in the same samples using the substrate induced respiration (SIR) method with 10 mg of glucose addition per 1 g of soil.
Answer The vials were then closed, placed in a thermostat at 22°C; basal soil respiration (SR) was determined on a gas chromatograph after 2 days and again after the next two days, (Cmic) was found in the same samples using the substrate-induced respiration (SIR) method with 10 mg of glucose addition per 1 g of soil.
Line 160: Clarkes values (or numbers?) are given .... Clarkes values
The consentration of soil elements were compared with the regional [6] and Clarkes values [26]. 
  Line 191-196: Better to give the information about the layers in a tabular form.
Line 201: ... chopping stone tools: axes, pikes, choppers ....
Pikes – delete (but were pikes like tools)
223-229: Consider to use a tabular presentation here as well for clarity. Same for 235-239 and similarly to the others too.
Line 261: 4. Results - This is already provided earlier. Delete it.
Line 284: Wouldn't the elevated levels of phosphorous and nitrogen in the top layers of some of the sites like, Elimbetovo-7, imply impacts of modern activities?
You are right. The contribution of modern natural biogenic processes to the elevated levels of most elements in the top layers does not exceed 20% of the total content (Vodaynitzkii et al, 2010).
Line 288-290: In the 0–10 cm layer, the content of total nitrogen varies 0.45–1.1% and the C/N ratio is optimal (for what?) 10.3–11.5. In Ishkulovo site the content of N is 0.12%, while the C/N ratio is 10.9.  
C/N ratio 10.3–11.5 is  optimal for plants. ( If C/N ratio more 15-20, N content is too less for plants.   optimal was delete) 
Line 295-300: Long sentences are used. Better to shorten them. It is not clear what the term 'optimal' refers to in the context of the values cited. Optimal for what purpose?
Line 308: .... compared to 0.12% in parent rock material.
Line 312: Is 950 mg/kg sulfur clarke number? Yes. You can see In all firures Clarke values were indicated Figure 7. Sulfur and its clarke 950 mg/kg. 
In most firures was added everage regionalal element content Figure 7. Zinc, its clarke 75, regional content 87 mg/kg  (Asilbekov, Khabirov. 2013). 
Also In all firures  we added vertical line for the Clarke value. It is clearly visible in which site the content of the element is greater or less than the Clarke value 950 mg/kg.
 
Line 329-330: The increased calcium content is found in all layers but except 5–10 cm layer. This is due to a specific chemical composition of diabase. But where it the calcium concentration profile provided?  
Answer The calcium content is very uniform (2%) across the profile at all sites. except Tashtui  in which there are carbonates occured  
Line 333: ... nickel and chrome – the elements of the 2nd hazard class are observed. They are 2–3 times higher than the clarkes values. 
Line 336: .... parent rock material. 
Line 338-339: ... (small-deleted) concentration of zinc and sulfur were found in the 0–20 cm layer. Their contents are 1.2 time greater than the clarkes.
Line 340: .... times higher than that in the .... 1.6–2.3 times higher
Line 341-342: ... those the in the soil-forming rock, but their amounts do not exceed the respective clarke values. 
Line 347-349: Very long sentence. Use short sentences instead. 
Line 345-347: 'Deposition of zinc, an element of the 1st toxicity category, in the 0–70 cm layer of this CL is observed, and its content is 1.3–1.9 times higher than the clarke and the parent material.' Since it is found in bones, metallo-enzymes, proteins, other biomolecules and the likes, could its elevated values, in the top layers, be linked to organic matter (excluding the exceptionally high values that could indicate contamination as described in later sections) 
? There are similar patterns noted when it comes to the distributions of sulfur, organic carbon, microbial biomass, phosphorous, nitrogen and zinc in the top layers of most of the sites under study.
Answer It is established that humic acids (are the main components of soil Corg) can absorb trace elements. Adsorption of elements by humic acids from the Trans-Urals Chernozems decreases in the following series: Cu > Mo > Cr > Zn > Zn >Ni > Pb > Ti > V (Nekrasova, Dergacheva, 2013). Humic acids form strong complexes with Zn, Cu, Ni (Ilyin, Syso. 2001). It was shown that clay minerals such as Na-bentonite adsorbed more Pb, in the presence of citric acid and lysine (Perelomov et al., 2016). 

Line 352: Where is the Mn data? from another reviewer? It is given in Figure 8b.
Line 354 ... amount of copper, nickel and chromium ... (use chromium in place of chrome - also check other parts in the text, like lines 361 and 378)
Line 356: XIX – the beginning of XX (When?) century AD - better if uniform age formatting is followed through out. Yes, 1–2 ka BP 
Line 394-395: Amangildino and Telyashevo-4 are long-term settlements of the Alakul culture 3900–3450 BP [36].
Line 412-413: The whole thickness of the sites has close to a neutral pH, and the pH values are almost the same throughout the vertical column. What does a reaction of solutions mean in this context? The sentence is suggested for a better clarity.
Answer A pH 6–7  value ensures the stability of many heavy metals which is important when they are elevated in CLs (Ilyin. 2013;  Syso., 2010),
Line 438-440: 'Significant enrichment of CLs with phosphorus and non-carbonate calcium at settlement sites is related to the input of these elements from animal bones containing stable calcium phosphates – apatite (https://xumuk.ru/encyklopedia/348.html) 
Was mineralogical investigation conducted on the soil samples?  No
How was the non-carbonate source of calcium established? Couldn't there be also other 
minerals contributing to the calcium content determined by XRF? 
Answer There are no calcium carbonates in soils and CLs because the samples do not effervescent from hydrochloric acid. Therefore, all total Ca is silicate minerals and a small part of biogenic calcium from bones ( bones was found by archaeologists in CLs).   
How was the significant input of phosphorus and calcium attributed to animal bones? Based on animal bone fragment concentrations – YES  (or some other information?
Line 447: How about the contribution to potassium from rock components in the cultural layer? Can it be totally ruled out? Yes, the elevated value could be associated with ash as it is well documented.
Answer There is no potassium accumulation in CLs, but only in a narrow black layer including many charcoals – Ishkulovo 80–82 cm.  
Line 459: It was described earlier [56]. In what context. Better to provide more information about what is described in the reference cited that has relevance to the sulfur-related discussion.  367
Answer Information on sulfur and other elements has been greatly increased in the Discussion section. Sulfur accumulates at the top of all CLs, compared to the bedrocks. This may be due to anthropogenic accumulation from the Magnitogorsk plant. We introduced the coefficients of technogenic accumulation of elements, for sulfur they are - 30-87%.
Line 461: .... at climate drying? 369  YES
Line 467: ... was observed lower the CL at 25–30 and 45–100 cm ... Needs re-writing. 375
Line 537: Aforementioned in-text citations
We have created TABLE 2 for the morphological description of soils and CL
Thank you very much for your thoughtful and comprehensive reviews of the article
Sincerely yours, 
Authors

 

Author Response File: Author Response.docx

Reviewer 2 Report (New Reviewer)

Comments and Suggestions for Authors

General comment

 The soil, geochemical, microbiological, and archaeological investigations carried out at the settlement sites are interesting. Though the interpretations can be further expanded, the profiling of the compositions of the diverse chemical elements, organic carbon as well as physical characteristics and microbial properties as a function of the stratigraphic layers is important. The archaeological results appear to have originated from other studies conducted earlier. The way the manuscript is written needs improvements.  Some of the results could have been better summarized in tabular formats.

 

Specific comments and suggestions

 

Line 42: .... large copper mines – Bakr-Uzyak and Kargaly, developed in the Neolithic and Bronze 42 Ages [2]; In Neolithic copper ore? Meaning?

Lines 48-49: ... The aim of the complex study of the cultural layers of settlements was to determine, pedological, microbiological and geochemical properties of these layers in order to characterize the environments in which the population of different cultures had functioned and to obtain more detailed information

Line 69: ... chronosequences of paleosols dated 2000 BC–1000 AD BP of the Southern Urals?

Line 85: ... the warmth remained, and humidity increased ...

Line 102: ... some mires peats ... Aren’t they different? ... several lake deposits ...

Lines 106-107: needs re-writing .... was moist and t, warm; in the period 3900–3450 BP (Amangildino, Telyashevo-4) the climate was warm and humid, in 106 the stage 2700–2500 BP (Elimbetovo-7) the climate was chilly and moist.

Line 113: Table: separate: Settlement, archaeological culture and age in three columns rather than congesting them in one.

Line 136: ... a deep section ....

Line 139: ... sections was provided ....

Line 144-148: .... the by following methods: elemental analyzer CHNSO for determining Corg and total nitrogen, potentiometry for measuring pH in aqueous solution (suspension, 1:2.5), the amount of soil exchangeable Ca2+ and Mg2+ according to Shollenberger, the content of mobile P2O5 using photometric method, and analysis of granulometric composition by the pipette method with sodium pyrophosphate treatment [39].

Line 153-156: The vials were then closed and placed in a thermostat at 22°C. The basal soil respiration (SR) was determined using a gas chromatograph after 2 days and again after the next two days, then the value of microbial biomass (Cmic) 154 was found in the same samples using the substrate induced respiration (SIR) method with 10 mg of glucose addition per 1 g of soil.

Line 160: Clarkes values (or numbers?) are given ....

Line 191-196: Better to give the information about the layers in a tabular form.

Line 201: ... chopping stone tools: axes, pikes, choppers ....

223-229: Consider to use a tabular presentation here as well for clarity. Same for 235-239 and similarly to the others too.

Line 261: 4. Results - This is already provided earlier. Delete it.

Line 284: Wouldn't the elevated levels of phosphorous and nitrogen in the top layers of some of the sites like, Elimbetovo-7, imply impacts of modern activities?

Line 288-290: In the 0–10 cm layer, the content of total nitrogen varies 0.45–1.1% and the C/N ratio is optimal (for what?) 10.3–11.5. In Ishkulovo site the content of N is 0.12%, while the C/N ratio is 10.9.

Line 295-300: Long sentences are used. Better to shorten them. It is not clear what the term 'optimal' refers to in the context of the values cited. Optimal for what purpose?

Line 308: .... compared to 0.12% in parent rock material.

Line 312: Is 950 mg/kg sulfur clarke number?

Line 329-330: The increased calcium content is found in all layers but except 5–10 cm layer. This is due to a specific chemical composition of diabase. But where it the calcium concentration profile provided?

Line 333: ... nickel and chrome – the elements of the 2nd hazard class are observed. They are 2–3 times higher than the clarke values.

Line 336: .... parent rock material.

Line 338-339: ... small concentration of zinc and sulfur were found in the 0–20 cm layer. Their contents are 1.2 time greater than the clarke.

Line 340: .... times higher than that in the ....

Line 341-342: ... those the in the soil-forming rock, but their amounts do not exceed the respective clarke values.

Line 347-349: Very long sentence. Use short sentences instead.

Line 345-347: 'Deposition of zinc, an element of the 1st toxicity category, in the 0–70 cm layer of this CL is observed, and its content is 1.3–1.9 times higher than the clarke and the parent material.' Since it is found in bones, metallo-enzymes, proteins, other biomolecules and the likes, could its elevated values, in the top layers, be linked to organic matter (excluding the exceptionally high values that could indicate contamination as described in later sections)? There are similar patterns noted when it comes to the distributions of sulfur, organic carbon, microbial biomass, phosphorous, nitrogen and zinc in the top layers of most of the sites under study.

Line 352: Where is the Mn data? from another reviewer? It is given in Figure 8b.

Line 354 ... amount of copper, nickel and chromium ... (use chromium in place of chrome - also check other parts in the text, like lines 361 and 378)

Line 356: XIX – the beginning of XX (When?) century AD - better if uniform age formatting is followed through out.

Line 394-395: Amangildino and Telyashevo-4 are long-term settlements of the Alakul culture 3900–3450 BP [36].

Line 412-413: The whole thickness of the sites has close to a neutral pH, and the pH values are almost the same throughout the vertical column. What does a reaction of solutions mean in this context? The sentence is suggested for a better clarity.

Line 438-440: 'Significant enrichment of CLs with phosphorus and non-carbonate calcium at settlement sites is related to the input of these elements from animal bones containing stable calcium phosphates – apatite.' Was mineralogical investigation conducted on the soil samples? How was the non-carbonate source of calcium established? Couldn't there be also other minerals contributing to the calcium content determined by XRF? How was the significant input of phosphorus and calcium attributed to animal bones? Based on animal bone fragment concentrations or some other information?

Line 447: How about the contribution to potassium from rock components in the cultural layer? Can it be totally ruled out? Yes, the elevated value could be associated with ash as it is well documented.

Line 459: It was described earlier [56]. In what context. Better to provide more information about what is described in the reference cited that has relevance to the sulfur-related discussion.

Line 461: .... at climate drying?

Line 467: ... was observed lower the CL at 25–30 and 45–100 cm ... Needs re-writing.

Line 537: Aforementioned in-text citations

Comments on the Quality of English Language

As mentioned earlier, the manuscript needs re-writing to improve clarity.

Author Response

Reply to reviewers

Comments and Suggestions for Authors

General comment

 The soil, geochemical, microbiological, and archaeological investigations carried out at the settlement sites are interesting. Though the interpretations can be further expanded, the profiling of the compositions of the diverse chemical elements, organic carbon as well as physical characteristics and microbial properties as a function of the stratigraphic layers is important. The archaeological results appear to have originated from other studies conducted earlier. The way the manuscript is written needs improvements.  Some of the results could have been better summarized in tabular formats.

Thank you very much for your thoughtful and comprehensive reviews of the article. They helped us greatly to improve article.

Also many thanks for the correction of the English language.

Unfortunately, due to my mistake, different texts were in two files of the article uploaded as RDF and Microsoft World files.

So. you had to read and reviewed text of the article, in which the Munsell color and soil structure were not indicated everywhere and some sections of the discussion were missing.

We apologize for the inconvenience caused in reading and editing the article.

 

Below are the responses to comments.

Please see the full text of the responses inside the article

It’s better to write The Late Medieval and Modern Ages

 

Text about definition of the CL was added in Introduction:

The CL is formed as a result of human activity at the settlements and consists of various materials: fragments of ceramics and metal products, buildings ruins, animal remains, etc. Its thickness varies depending on the duration of residence (Sycheva et al., 2004; Nowaczinski et al., 2013).

I suggest you redesign the Table 1 with separate columns for Settlement, Archaeological Culture and Age.

Table 1 was redesigned, following your advice two vertical columns were added

 

Please list the sites where samples were taken every 5 cm).?

For five sections samples were taken from successive layers with a thickness of 0–5 cm down to the parent material, in Ishkulovo, Kusimovo-8, Sabakty-1a site’s samples were taken every 10 cm.

 

Biocenosis what does it mean?

It would be more correct to write phytocenosis, including vegetation, since biocenosis is a biotic community including plants, fungi, microbes and animals existing in a common area.

The objects are located in the forest-steppe zone, therefore they consist of steppe areas and climax forests (usually write forests)

About of the stone industry?

Elimbetovo site, Gamayun Culture. The phrase: settlement of the stone industry - removed, despite the fact that 15 stone tools were found in a small area. But further study is required. As shown earlier in the Gamayun Culture Community, the main tools were stone (2500 BP). In fact, they were at the final stage of the Stone Age in terms of development (Borzunov, 2018; Savelyev, 2018).

dating of the Alakul culture?

Amangildino is a long-term settlement of the Late Bronze Age (Alakul culture 3900–3450 BP). This chronology is based on a generalization of  52 ¹⁴C dates [36] Molodin et al, 2014

Answer Colors for soils  on the Munsell were added  in tab 2. Morphological data 

Please clarify the meaning of this statement?

 

The Elimbetovo-7 site is located 190 m from the Yangelka River, where people of the Gamayun culture lived. Sixteen ceramic fragments and 15 stone tools were found at a depth of 11–38 cm. It was identified as an archaeological site 70 years ago after the discovery of a large flint tool. This CL is a thin feature at 40 cm depth, directly underlain by diabase.

 

The Reviewer (Randal Southard) asked: “(Is the metal chemistry mostly a function of the near-by metal smelting?  If so, what is the connection with the ancient settlements?) It seems most of the CLs are affected by modern-day environments, including land-use and pollution from smelting. How do you distinguish from the ancient environments?

 

Answer We have added a new large section to the article discussion, where we write about the reasons for the increased content of heavy metals in the CLs.

1. The main reason is the geological historical background associated with the high content of various ores - copper, iron, manganese, etc. in the Ural Mountains, where CLs are located. Moreover, the accumulation of heavy metals is noted in the entire profile of the CLs and soils, including in the parent rocks, they often contain more metals than in the surface horizons. And the content of metals throughout the profile is several times higher than the Clarke value – the average elements content in the Earth's geosphere. This is well known from the scientific literature published earlier.

2.Technogenic pollution from modern metallurgical plants, including the nearby Magnitogorsk plant, spread mainly to the surface horizons, since sites are located far from the plant 18–60 km. It has been proven that further than 5-10 km the plant has almost no effect on the soils (Il’in, Syso, 2003; Vodyanitskii et al., 2010). Similar conclusion was made by Professor Randal Southard in a joint article with Brazil soil scientists:  dos Santos, N.M.; do Nascimento, C.W.A.; de Soutza Júnior, V.S.; Southard, R.J.; de Olinda, R.A. Lead isotope distribution and enrichment factors in soil profiles around an abandoned Pb-smelter plant. Environ. Sci. Technol. 2017, 14(11), 2331–2343. DOI 10.1007/s13762-017-1320-

We have significantly expanded the discussion of articles devoted to the concentration of metals in the regional soils.

We have also used a coefficient of technogenic accumulation of metals and a discussion of the properties of chernozems that determine the fixation of heavy metals, etc.

   Zn is an essential plant nutrient; toxic if too concentrated.

Answer Sure. As other metals

Why do you assume RGI-1103 is incorrect, and RGI-1104 is correct? Please give reasons?

Answer Kusimovo-8 site. 258±13 ka (RGI-1103, VSEGEI), obviously, the last date is overestimated. As in the Kusimovo-8 site found 121 chopping tools  and their shapes belong to the Karyshkin’ culture and are markers of the Lower Paleolithic Era (125–200 ka BP) at the Southern Trans-Urals region and were found at the Mysovaya and Karyshkino-11 sites, etc. (Kotov, 2023)

 

 Specific comments and suggestions

Line 42: .... large copper mines – Bakr-Uzyak and Kargaly, developed in the Neolithic and Bronze 42 Ages [2]; In Neolithic copper ore? Meaning?

Answer It is assumed that the Bakr-Uzyak mine began to developed in the Eneolithic era, but the exact date is missing. Kargaly  developed since 4.8 ka ca. BP.  Corrected:Large copper mines – Bakr-Uzyak and Kargaly – developed in the Bronze Age (Chernykh, 2008).

Lines 48-49: ... The aim of the complex study of the cultural layers of settlements was to determine, pedological, microbiological and geochemical properties of these layers in order to characterize the environments in which the population of different cultures had functioned and to obtain more detailed information

Answer The aim of a complex study of the settlements was to determine pedological, microbiological and geochemical properties to characterize the environment in which the ancient population lived and show the causes of accumulation of heavy metals in the area and resulting soil pollution.

Line 69: ... chronosequences of paleosols dated 2000 BC–1000 AD BP of the Southern Urals?  This text was removed

Line 85: ... the warmth remained, and humidity increased ...  text was removed

Line 102: ... some mires peats ... Aren’t they different? ... several lake deposits ...

Answer sediments of lakes and swamps of the forest-steppe of the Southern Urals [9, 55–59].

Lines 106-107: needs re-writing .... was moist and t, warm; in the period 3900–3450 BP (Amangildino, Telyashevo-4) the climate was warm and humid, in 106 the stage 2700–2500 BP (Elimbetovo-7) the climate was chilly and moist.

Answer In the period of 3.9–3.4 ka BP ( Amangildino, Telyashevo-4) was warm and humid climate, at the stage of 2.7–2.5 ka BP (Elimbetovo-7 site) – cool and humid [11, 53, 61–64].

Line 113: Table: separate: Settlement, archaeological culture and age in three columns rather than congesting them in one.  WERE done new Table 2.

Line 136: ... a deep section ....

Line 139: ... sections was provided ....

Line 144-148: .... the by following methods: elemental analyzer CHNSO for determining Corg and total nitrogen, potentiometry for measuring pH in aqueous solution (suspension, 1:2.5), the amount of soil exchangeable Ca2+ and Mg2+ according to Shollenberger, the content of mobile P2O5 using photometric method, and analysis of granulometric composition by the pipette method with sodium pyrophosphate treatment [39].

Answer Soil properties were measured by the following methods: use of a CHNSO elemental analyzer for determining Corg and total nitrogen, potentiometry for measuring pH in aqueous solution (suspension, 1 : 2.5), the amount of soil exchangeable Ca²⁺ and Mg²⁺ was done for measuring according to Schollenberger, the content of mobile P₂O₅ was evaluated by the photometric method, analysis of granulometric composition was carried out by the pipette method with sodium pyrophosphate treatment [24

Line 153-156: The vials were then closed and placed in a thermostat at 22°C. The basal soil respiration (SR) was determined using a gas chromatograph after 2 days and again after the next two days, then the value of microbial biomass (Cmic) 154 was found in the same samples using the substrate induced respiration (SIR) method with 10 mg of glucose addition per 1 g of soil.

Answer The vials were then closed, placed in a thermostat at 22°C; basal soil respiration (SR) was determined on a gas chromatograph after 2 days and again after the next two days, (Cmic) was found in the same samples using the substrate-induced respiration (SIR) method with 10 mg of glucose addition per 1 g of soil.

Line 160: Clarkes values (or numbers?) are given .... Clarkes values

The consentration of soil elements were compared with the regional [6] and Clarkes values [26].

  Line 191-196: Better to give the information about the layers in a tabular form.

Line 201: ... chopping stone tools: axes, pikes, choppers ....

Pikes – delete (but were pikes like tools)

223-229: Consider to use a tabular presentation here as well for clarity. Same for 235-239 and similarly to the others too.

Line 261: 4. Results - This is already provided earlier. Delete it.

Line 284: Wouldn't the elevated levels of phosphorous and nitrogen in the top layers of some of the sites like, Elimbetovo-7, imply impacts of modern activities?

You are right. The contribution of modern natural biogenic processes to the elevated levels of most elements in the top layers does not exceed 20% of the total content (Vodaynitzkii et al, 2010).

Line 288-290: In the 0–10 cm layer, the content of total nitrogen varies 0.45–1.1% and the C/N ratio is optimal (for what?) 10.3–11.5. In Ishkulovo site the content of N is 0.12%, while the C/N ratio is 10.9. 

C/N ratio 10.3–11.5 is  optimal for plants. ( If C/N ratio more 15-20, N content is too less for plants.   optimal was delete)

Line 295-300: Long sentences are used. Better to shorten them. It is not clear what the term 'optimal' refers to in the context of the values cited. Optimal for what purpose?

Line 308: .... compared to 0.12% in parent rock material.

Line 312: Is 950 mg/kg sulfur clarke number? Yes. You can see In all firures Clarke values were indicated Figure 7. Sulfur and its clarke 950 mg/kg.

In most firures was added everage regionalal element content Figure 7. Zinc, its clarke 75, regional content 87 mg/kg  (Asilbekov, Khabirov. 2013).

Also In all firures  we added vertical line for the Clarke value. It is clearly visible in which site the content of the element is greater or less than the Clarke value 950 mg/kg.

Line 329-330: The increased calcium content is found in all layers but except 5–10 cm layer. This is due to a specific chemical composition of diabase. But where it the calcium concentration profile provided? 

Answer The calcium content is very uniform (2%) across the profile at all sites. except Tashtui  in which there are carbonates occured  

Line 333: ... nickel and chrome – the elements of the 2nd hazard class are observed. They are 2–3 times higher than the clarkes values.

Line 336: .... parent rock material.

Line 338-339: ... (small-deleted) concentration of zinc and sulfur were found in the 0–20 cm layer. Their contents are 1.2 time greater than the clarkes.

Line 340: .... times higher than that in the .... 1.6–2.3 times higher

Line 341-342: ... those the in the soil-forming rock, but their amounts do not exceed the respective clarke values.

Line 347-349: Very long sentence. Use short sentences instead.

Line 345-347: 'Deposition of zinc, an element of the 1st toxicity category, in the 0–70 cm layer of this CL is observed, and its content is 1.3–1.9 times higher than the clarke and the parent material.' Since it is found in bones, metallo-enzymes, proteins, other biomolecules and the likes, could its elevated values, in the top layers, be linked to organic matter (excluding the exceptionally high values that could indicate contamination as described in later sections)

? There are similar patterns noted when it comes to the distributions of sulfur, organic carbon, microbial biomass, phosphorous, nitrogen and zinc in the top layers of most of the sites under study.

Answer It is established that humic acids (are the main components of soil Corg) can absorb trace elements. Adsorption of elements by humic acids from the Trans-Urals Chernozems decreases in the following series: Cu > Mo > Cr > Zn > Zn >Ni > Pb > Ti > V (Nekrasova, Dergacheva, 2013). Humic acids form strong complexes with Zn, Cu, Ni (Ilyin, Syso. 2001). It was shown that clay minerals such as Na-bentonite adsorbed more Pb, in the presence of citric acid and lysine (Perelomov et al., 2016).

 

Line 352: Where is the Mn data? from another reviewer? It is given in Figure 8b.

Line 354 ... amount of copper, nickel and chromium ... (use chromium in place of chrome - also check other parts in the text, like lines 361 and 378)

Line 356: XIX – the beginning of XX (When?) century AD - better if uniform age formatting is followed through out. Yes, 1–2 ka BP

Line 394-395: Amangildino and Telyashevo-4 are long-term settlements of the Alakul culture 3900–3450 BP [36].

Line 412-413: The whole thickness of the sites has close to a neutral pH, and the pH values are almost the same throughout the vertical column. What does a reaction of solutions mean in this context? The sentence is suggested for a better clarity.

Answer A pH 6–7  value ensures the stability of many heavy metals which is important when they are elevated in CLs (Ilyin. 2013;  Syso., 2010),

Line 438-440: 'Significant enrichment of CLs with phosphorus and non-carbonate calcium at settlement sites is related to the input of these elements from animal bones containing stable calcium phosphates – apatite (https://xumuk.ru/encyklopedia/348.html)

Was mineralogical investigation conducted on the soil samples?  No

How was the non-carbonate source of calcium established? Couldn't there be also other

minerals contributing to the calcium content determined by XRF?

Answer There are no calcium carbonates in soils and CLs because the samples do not effervescent from hydrochloric acid. Therefore, all total Ca is silicate minerals and a small part of biogenic calcium from bones ( bones was found by archaeologists in CLs).  

How was the significant input of phosphorus and calcium attributed to animal bones? Based on animal bone fragment concentrations – YES  (or some other information?

Line 447: How about the contribution to potassium from rock components in the cultural layer? Can it be totally ruled out? Yes, the elevated value could be associated with ash as it is well documented.

Answer There is no potassium accumulation in CLs, but only in a narrow black layer including many charcoals – Ishkulovo 80–82 cm. 

Line 459: It was described earlier [56]. In what context. Better to provide more information about what is described in the reference cited that has relevance to the sulfur-related discussion.  367

Answer Information on sulfur and other elements has been greatly increased in the Discussion section. Sulfur accumulates at the top of all CLs, compared to the bedrocks. This may be due to anthropogenic accumulation from the Magnitogorsk plant. We introduced the coefficients of technogenic accumulation of elements, for sulfur they are - 30-87%.

Line 461: .... at climate drying? 369  YES

Line 467: ... was observed lower the CL at 25–30 and 45–100 cm ... Needs re-writing. 375

Line 537: Aforementioned in-text citations

We have created TABLE 2 for the morphological description of soils and CL

Thank you very much for your thoughtful and comprehensive reviews of the article

Sincerely yours,

Authors

 

Author Response File: Author Response.docx

This manuscript is a resubmission of an earlier submission. The following is a list of the peer review reports and author responses from that submission.

Round 1

Reviewer 1 Report

Comments and Suggestions for Authors

I lacked a final detailed summary of the research results, for which all this analyzes of the cultural layer of the settlements were done. What do the obtained results of chemical components say? Some processes, their development, changes? Did they change in time? Or note that this is, for example, a starting project and the results are preliminary, the work will be continued. As you wrote: "The aim of a complex study of the cultural layers of settlements was to determine,  pedological, microbiological and geochemical properties of these layers in order to characterize the natural components in which the population of different cultures had functioned and to obtain more detailed information".

Comments for author File: Comments.pdf

Reviewer 2 Report

Comments and Suggestions for Authors

This paper contains some interesting data.  However, as written, the overall objective of the paper is not clear to me.  I don't understand the connection between the archaeological sites and the metal pollution from modern-day smelting. Although human artifacts were found, there is little presentation or discussion of the results.  The geochemical data seem to be related to modern-day smelting, so have little meaning in the context of ancient environments. The cultural layers are (mostly) heavily influenced by modern activities, so it seems the artifacts represent the only meaningful data in relation to the archaeology. The reconstruction of paleoenvironments seems to be based on other papers, not on data from this study, so is not really relevant to this paper.  I suggest that you report the data in two papers: one that focuses on the distribution of metals in the soils from metal refining in the region (soil pollution, no connection with ancient sites or archaeology), and one that focuses on the artifacts  collected and how those are interpreted in the context of the paleoenvironments.  Both of these could be very interesting additions to the literature.

Comments for author File: Comments.pdf

Comments on the Quality of English Language

I edited for English, especially in the first half of the paper.  I edited less in the second half because I came to the conclusion that the paper was not ready for publication.  The objectives of the paper are not clear to me, and the geochemical data seem to have little connection to the archaeological context.