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Article
Peer-Review Record

Evaluation of Calcarenite Degradation by X-ray Photoelectron Spectroscopy Analysis inside the Rupestrian Church of San Pietro Barisano (Matera, Southern Italy)

Sustainability 2024, 16(11), 4634; https://doi.org/10.3390/su16114634
by Francesco Cardellicchio 1, Maria Assunta Acquavia 2, Mariangela Curcio 2 and Anna Maria Salvi 2,*
Reviewer 1: Anonymous
Reviewer 2: Anonymous
Reviewer 3: Anonymous
Reviewer 4: Anonymous
Reviewer 5: Anonymous
Sustainability 2024, 16(11), 4634; https://doi.org/10.3390/su16114634
Submission received: 27 March 2024 / Revised: 13 May 2024 / Accepted: 26 May 2024 / Published: 29 May 2024
(This article belongs to the Special Issue Sustainable Conservation of Urban and Cultural Heritage)

Round 1

Reviewer 1 Report

Comments and Suggestions for Authors

I have reviewed this article, “XPS indicators of calcarenite degradation: the rupestrian church of San Pietro Barisano as a study case for the sustainable recovery of the Unesco Site of Matera (Italy)". Thank you very much to the authors for this interesting contribution.

I think the title is somewhat extensive and long; it should be more specific and precise. The title and subtitle of an article should not exceed 14–15 words (more or less). The title of this manuscript has 27 words and does not adequately focus on the topic developed because the article focuses on the XPS analysis and the results obtained and not so much on the factors or circumstances that make the rock church of San Pedro a case study for the recovery of the Sassi of Matera. With the actual title, it remains to be answered or clarified more clearly why this church is a case study for the sustainable recovery of the UNESCO Site of Matera.

But, in general, I find the work to be very relevant and well done, with well-defined objectives, methodologically well developed, an adequate discussion, and fair and focused conclusions. The study is complete and soundly built, and I think the aim of the research is adequate and well expressed. Maybe it would be interesting to mention the novelty of the contribution in the abstract.

The authors have developed a well-founded methodology, and they explain in detail their procedures. The review of the literature is extensive and thoughtful. I think that the paper is well structured, the research is thoroughly developed, and it is ambitious. Generally speaking, I do not find important hindrances.

In relation to the figures (maps and graphs), the representation is correct, but the quality of the graphs must be better (figures 2, 5, and 6). Perhaps the most important aspect is that there is a lack of a location map of the city in Basilicata and in Italy. In addition to a location map of the rupestrian church of San Pietro Barisano within the city of Matera, these figures would contribute to better understanding the problem and the topic discussed.

 

Comments on the Quality of English Language

There are some minor spelling and grammar errors. Some English expressions could be enhanced.

Author Response

Comments and Suggestions for Authors

I have reviewed this article, “XPS indicators of calcarenite degradation: the rupestrian church of San Pietro Barisano as a study case for the sustainable recovery of the Unesco Site of Matera (Italy)". Thank you very much to the authors for this interesting contribution.

 

I think the title is somewhat extensive and long; it should be more specific and precise. The title and subtitle of an article should not exceed 14–15 words (more or less). The title of this manuscript has 27 words and does not adequately focus on the topic developed because the article focuses on the XPS analysis and the results obtained and not so much on the factors or circumstances that make the rock church of San Pedro a case study for the recovery of the Sassi of Matera. With the actual title, it remains to be answered or clarified more clearly why this church is a case study for the sustainable recovery of the UNESCO Site of Matera.

 

We have shortened the title maintaining the name of the church that effectively belongs to the archaeological Park of the rupestrian churches, part of Unesco Site of Matera together with the Sassi district.

 

But, in general, I find the work to be very relevant and well done, with well-defined objectives, methodologically well developed, an adequate discussion, and fair and focused conclusions. The study is complete and soundly built, and I think the aim of the research is adequate and well expressed. Maybe it would be interesting to mention the novelty of the contribution in the abstract.

 

We thank the reviewer for the appreciation and We hope that the revised Abstract fulfils now the above request of explaining the novelty of our contribution

 

The authors have developed a well-founded methodology, and they explain in detail their procedures. The review of the literature is extensive and thoughtful. I think that the paper is well structured, the research is thoroughly developed, and it is ambitious. Generally speaking, I do not find important hindrances.

 

In relation to the figures (maps and graphs), the representation is correct, but the quality of the graphs must be better (figures 2, 5, and 6). Perhaps the most important aspect is that there is a lack of a location map of the city in Basilicata and in Italy. In addition to a location map of the rupestrian church of San Pietro Barisano within the city of Matera, these figures would contribute to better understanding the problem and the topic discussed.

 

We did remake Fig.1 to give a more complete picture of the church location, of Matera city in Basilicata and in Italy. Thank you

 

Regarding the other figures we did check their resolution and it was Ok for Figures 2 and 5 while the resolution of Figure 6 was improved. We’ll be waiting to have some editorial output, eventually. In the meantime we have improved the test that is referring to them, as reported to previous reviewers.

 

Comments on the Quality of English Language

There are some minor spelling and grammar errors. Some English expressions could be enhanced.

 

We did reread the manuscript after completed all the revisions and we hope to have amended the English errors.

Reviewer 2 Report

Comments and Suggestions for Authors

Manuscript Number: sustainability-2924067

Title: XPS indicators of calcarenite degradation: the rupestrian church of San Pietro Barisano as a study case for the sustainable recovery of the Unesco Site of Matera (Italy)

I think this work is very interesting. However, there were a number of issues that needed further improvement to raise the level of the manuscript for publication in Sustainability.

Detailed improvement suggestions are as follows:

1. In the abstract, some acronyms appear for the first time and should be explained in detail.

2. Some significant peaks in Figure 5 are unmarked.

3. Figure 5, The following figure should be Figure 6? This diagram is ambiguous and should be modified. It can be seen from the O1s spectrum that there are other forms of oxygen.

4. The numbers in the chemical formula in Figure 7- Figure 12 should be subscripted.

5. The conclusion is a summary of the manuscript. Please delete references from the conclusion.

Author Response

Comments and Suggestions for Authors

Manuscript Number: sustainability-2924067

Title: XPS indicators of calcarenite degradation: the rupestrian church of San Pietro Barisano as a study case for the sustainable recovery of the Unesco Site of Matera (Italy)

I think this work is very interesting. However, there were a number of issues that needed further improvement to raise the level of the manuscript for publication in Sustainability.

Detailed improvement suggestions are as follows:

  1. In the abstract, some acronyms appear for the first time and should be explained in detail.

We have explained the acronym of the project. To our knowledge XPS and UNESCO are not required to be explained, following the editorial requirements but if approved can be added eventually readjusting the number of words (required not to exceed 200words):

X-ray Photoelectron Spectroscopy (XPS)

United Nations Educational, Scientific and Cultural Organization (UNESCO)

2. Some significant peaks in Figure 5 are unmarked.

We have given explanations in the Results section, lines 252-259 and caption of Figure 5

3. Figure 5, The following figure should be Figure 6? This diagram is ambiguous and should be modified. It can be seen from the O1s spectrum that there are other forms of oxygen.

We have checked the figures 5n and 6 and their resolution. They are better indicated and the relevant text modified to answer the above points at lines 294-299 of the Results section.

 

4. The numbers in the chemical formula in Figure 7- Figure 12 should be subscripted.

We have modified the chemical formula of Figures 7-12 as required

 

5. The conclusion is a summary of the manuscript. Please delete references from the conclusion.

We did remove the references from the revised Conclusions

We thank the reviewer for the appreciation and suggestions

Reviewer 3 Report

Comments and Suggestions for Authors

An interesting study is presented in which XPS is used as a characterization technique. The introduction is relevant about the place where the study is carried out, however it would be interesting to indicate some of the results obtained and the comparison with other possible studies carried out in the same church or the techniques used in other churches. This is in order to see the relevance and/or novelty of the study. A well-established curve fitting is mentioned, but not elaborated upon. Likewise, it would be interesting to delve into biotic and/or abiotic degradation; and its relevance to the study.

It is advisable to expand on the state of the art of the XPS technique used and with respect to the type of samples.

The quality of the spectra in Figure 5 and 6 (these spectra are not identified as Figure 6) can be improved. The discussion in this regard should be developed, based on adequate scientific support.

Lines 237-248, clarify the discussion presented. It is not clear to support it with adequate scientific literature. On this relevance, as well as what is indicated as pollutants. Clarify the explanation.

In analysis and correlation of results, it is recommended, in order to understand in detail the characteristics that impact on the presence of pollutants and harmful spices to the environment. As well as, to delve into the technique used and its relevance in the proposed study.

Author Response

Comments and Suggestions for Authors

An interesting study is presented in which XPS is used as a characterization technique. The introduction is relevant about the place where the study is carried out, however it would be interesting to indicate some of the results obtained and the comparison with other possible studies carried out in the same church or the techniques used in other churches. This is in order to see the relevance and/or novelty of the study. A well-established curve fitting is mentioned, but not elaborated upon. Likewise, it would be interesting to delve into biotic and/or abiotic degradation; and its relevance to the study.

It is advisable to expand on the state of the art of the XPS technique used and with respect to the type of samples.

We did enlarge the state of the art concerning XPS analysis, added references 21-23, as reported in the highlighted paragraphs of Introduction and enlarged XPS analysis sections, adding paragraphs on XPS and data elaboration by curve-fitting procedure.

The quality of the spectra in Figure 5 and 6 (these spectra are not identified as Figure 6) can be improved. The discussion in this regard should be developed, based on adequate scientific support.

We have tried to improve the quality of Figures 5 and 6, modified the legenda and paragraphs at lines 252-259 and 294-299 of the Results section, as reported to reviewer 1

Lines 237-248, clarify the discussion presented. It is not clear to support it with adequate scientific literature. On this relevance, as well as what is indicated as pollutants. Clarify the explanation.

We hope the modified sentences, highlighted in the Results and Discussions sections with added references, provide all the clarifications required by the reviewer together with more information on XPS technique and its relevance to this work.

In analysis and correlation of results, it is recommended, in order to understand in detail the characteristics that impact on the presence of pollutants and harmful spices to the environment. As well as, to delve into the technique used and its relevance in the proposed study.

In addition to the new sentences and new references 36 and 44 in Discussion, the Conclusion were also revised to delve into the various aspects, biotic and abiotic, of calcarenite degradation

 

 

Reviewer 4 Report

Comments and Suggestions for Authors

Dear authors,

The topic is interesting; however, the following issues should be addressed in the study:

Major comments:

1.       Title, Abstract, and Introduction

Title

·         The title could be more concise and clear. Avoid unnecessary details.

Abstract

·         Ensure that the abstract clearly states the primary objectives and outcomes of the study. Highlight the specific contributions to the field of heritage conservation.

·         The abstract should follow a logical flow, starting with a brief introduction, outlining the methods used, summarizing key findings, and concluding with implications or applications.

·         Clearly articulate the significance of the research and how the XPS analysis contributes to the understanding of calcarenite degradation and heritage preservation.

 

Introduction

·         Some details, such as the specific research project (SCN_00520) and its funding source, could be presented more succinctly to maintain focus on the main research objectives.

·         Ensure that the progression of ideas in the introduction follows a logical sequence, providing a clear framework for understanding the research context and objectives.

·         Clarify the specific objectives and scope of the research earlier in the introduction to provide a clear roadmap for the reader.

 

Literature review

·         The absence of the literature review section in the research study may lead to critical shortcomings. Emphasizing the importance of this section is crucial as it lays the groundwork for the research's credibility, originality, and relevance within the academic discourse. The literature review should showcase the depth of understanding, critical analysis, and synthesis of existing knowledge, thereby underpinning the rationale for the research questions, methodology, and potential contributions to the field.

 

2.       Materials and Methods

·         While describing the study site (Church of San Pietro Barisano), provide more specific details about its location, historical significance, and relevance to the research objectives.

·         Ensure that the sampling procedure is clearly described, including details on the selection criteria for sampling points and the methods used to collect samples without damaging the underlying structure.

·         Describe the sample collection process in more detail, emphasizing how care was taken to preserve the integrity of the deeper layers while focusing on surface patinas or degradation products.

·         Provide a more comprehensive description of the XPS analysis protocol, including details on sample preparation, instrument settings (e.g., operating voltage, current, mode), and data acquisition parameters (e.g., channel widths, resolution).

·         Explain the methodology used for data analysis, particularly in relation to curve fitting of XPS spectra, referencing standard compounds, and calculating semi-quantitative analyses (e.g., percent atomic composition).

 

3.       Results

·         The section lacks clear organization and structure. It's important to present the results in a logical sequence and highlight key findings in a concise manner.

·         The figures presented (e.g., Figures 7, 8, 9, 10, 11, 12) need more detailed explanations. The reader should be able to understand the significance of each chart and how the data contribute to the overall findings.

·         Provide more details on the analytical techniques used to interpret the XPS data. This includes the rationale behind curve-fitting, the selection of spectral regions, and how results were derived from these analyses.

·         The interpretation of results should be more explicit. Describe the implications of the identified components (e.g., carbonaceous compounds, calcium oxalate, sulphates) in relation to the degradation processes observed in the calcarenite material.

·         Address the variation observed in different samples (e.g., Samples #1 to #10) more comprehensively. Discuss how location within the church or specific environmental conditions might influence the composition of surface patinas and degradation products.

·         Link the current findings with prior research cited (e.g., references [31, 32]) to provide context and support for interpretations.

·         Emphasize how each set of results contributes to the broader research objectives, specifically addressing the study's focus on calcarenite degradation and implications for conservation efforts.

·         Summarize key findings and their implications succinctly. Provide a clear takeaway message that aligns with the study's objectives.

·          

 

4.       Discussion

·         The discussion lacks a clear and structured argument. It would benefit from organizing the points logically and linking each observation back to the main research objectives or broader implications.

·         While the predominance of organic carbon is noted, there is limited discussion on the significance of this finding. Consider expanding on why organic carbon is prevalent and how it relates to degradation processes or environmental factors.

·         The discussion of carbonate content across different samples (e.g., Samples #3, #9, #10) needs further contextualization. Why do some samples exhibit higher carbonate percentages, and what implications does this have for degradation patterns?

·         The XRD results mentioned provide valuable information on mineral composition, but there's a need to more directly link these findings with the XPS results discussed earlier. How do the deeper mineral layers identified by XRD relate to surface degradation as observed by XPS?

·         While efflorescence phenomena and soluble salts are mentioned, their specific impact on calcarenite degradation should be elaborated. Discuss how these processes contribute to structural damage and surface alterations.

·         The discussion on biodegradation and bioactivity could be expanded to clarify how microbial metabolism affects degradation products like calcium oxalate and sulphates. Additionally, explore implications for conservation strategies in light of ongoing bioactivity.

·         Consider discussing how environmental factors like humidity, climate, and human activities influence the observed degradation patterns. Connect these factors to the long-term preservation challenges faced by the UNESCO site.

·         The discussion would benefit from a more cohesive synthesis of findings. Conclude by summarizing key insights into calcarenite degradation and proposing implications for conservation strategies or further research.

·         Consider acknowledging any limitations in the study's approach or data interpretation. Discuss potential future research directions that could build upon the current findings to deepen understanding of calcarenite degradation processes.

 

5.       Conclusions

·         The conclusions should include more specific findings or insights derived from the XPS analysis. Rather than stating general capabilities of XPS, highlight specific correlations between surface composition and degradation causes observed in the San Pietro Barisano church.

·         While the article mentions previous work, it's important to explicitly state how the current findings build upon or differ from these prior studies. This context can provide a clearer understanding of the significance of the current research.

·         The section should elaborate on how exactly XPS contributes uniquely to the investigation of calcarenite degradation compared to other analytical techniques. Specify the advantages and limitations of XPS in this context.

·         The conclusion refers to Figure 13 as providing indicators, but the specific implications of these indicators for conservation efforts or further research should be explicitly discussed.

·         The conclusions should provide more actionable recommendations or implications for conservation strategies. How can the identified degradation factors inform future preservation efforts at the UNESCO site?

·         Elaborate on how the integration of XPS with other analytical techniques (biological analyses, architectural surveys) enhances the overall understanding of calcarenite degradation and preservation challenges.

·         While mentioning ongoing work with PCA, clarify how this analysis will contribute to refining degradation descriptors. Discuss potential future research directions based on current findings.

 

·         Provide a concise summary of how the findings align with the final aim of the SCN project and its implications for expert users in cultural heritage conservation.

Author Response

Comments and Suggestions for Authors

Dear authors,

The topic is interesting; however, the following issues should be addressed in the study:

Major comments:

  1. Title, Abstract, and Introduction

Title

  • The title could be more concise and clear. Avoid unnecessary details.

We have shortened the title as explained to reviewer 4

Abstract

  • Ensure that the abstract clearly states the primary objectives and outcomes of the study. Highlight the specific contributions to the field of heritage conservation.
  • The abstract should follow a logical flow, starting with a brief introduction, outlining the methods used, summarizing key findings, and concluding with implications or applications.
  • Clearly articulate the significance of the research and how the XPS analysis contributes to the understanding of calcarenite degradation and heritage preservation.

 

We have revised the abstract accordingly

 

Introduction

  • Some details, such as the specific research project (SCN_00520) and its funding source, could be presented more succinctly to maintain focus on the main research objectives.
  • Ensure that the progression of ideas in the introduction follows a logical sequence, providing a clear framework for understanding the research context and objectives.
  • Clarify the specific objectives and scope of the research earlier in the introduction to provide a clear roadmap for the reader.

 

We tried to remove some reference to SCN project. However, given that most aspects of the present work is based on the aims and collaborative research within that project it is still mentioned in the Introduction and in other Sections, mainly in Conclusions. 

Literature review

  • The absence of the literature review section in the research study may lead to critical shortcomings. Emphasizing the importance of this section is crucial as it lays the groundwork for the research's credibility, originality, and relevance within the academic discourse. The literature review should showcase the depth of understanding, critical analysis, and synthesis of existing knowledge, thereby underpinning the rationale for the research questions, methodology, and potential contributions to the field.

 

 We have searched and referred to the most recent reviews on the topic considered in our paper, added new references in the Introduction section together with additional paragraphs with the hope to meet the reviewer recommendations

 

  1. Materials and Methods
  • While describing the study site (Church of San Pietro Barisano), provide more specific details about its location, historical significance, and relevance to the research objectives.
  • Ensure that the sampling procedure is clearly described, including details on the selection criteria for sampling points and the methods used to collect samples without damaging the underlying structure.
  • Describe the sample collection process in more detail, emphasizing how care was taken to preserve the integrity of the deeper layers while focusing on surface patinas or degradation products.
  • Provide a more comprehensive description of the XPS analysis protocol, including details on sample preparation, instrument settings (e.g., operating voltage, current, mode), and data acquisition parameters (e.g., channel widths, resolution).
  • Explain the methodology used for data analysis, particularly in relation to curve fitting of XPS spectra, referencing standard compounds, and calculating semi-quantitative analyses (e.g., percent atomic composition).

 

As previously reported, we did amplify the description of the location in Figure 1 and relevant text, the paragraphs concerning XPS specificity and operatives modality including spectra acquisitions, sampling and data elaboration using the curve fitting procedure and given more details on the qualitative and semi quantitave analysis.

 

  1. Results
  • The section lacks clear organization and structure. It's important to present the results in a logical sequence and highlight key findings in a concise manner.
  • The figures presented (e.g., Figures 7, 8, 9, 10, 11, 12) need more detailed explanations. The reader should be able to understand the significance of each chart and how the data contribute to the overall findings.
  • Provide more details on the analytical techniques used to interpret the XPS data. This includes the rationale behind curve-fitting, the selection of spectral regions, and how results were derived from these analyses.
  • The interpretation of results should be more explicit. Describe the implications of the identified components (e.g., carbonaceous compounds, calcium oxalate, sulphates) in relation to the degradation processes observed in the calcarenite material.
  • Address the variation observed in different samples (e.g., Samples #1 to #10) more comprehensively. Discuss how location within the church or specific environmental conditions might influence the composition of surface patinas and degradation products.
  • Link the current findings with prior research cited (e.g., references [31, 32]) to provide context and support for interpretations.
  • Emphasize how each set of results contributes to the broader research objectives, specifically addressing the study's focus on calcarenite degradation and implications for conservation efforts.
  • Summarize key findings and their implications succinctly. Provide a clear takeaway message that aligns with the study's objectives.

 

We have given examples of the XPS methodology by reporting in details the analysis of the reference calcarenite and data representation in Table 1 and At% composition in Figure 7 and added explanations on the highlighted paragraphs of the Results section. For all the considered samples however the previous results sequence of the ten samples was maintained by referring for each sample to its location and the given finding. Further comments on the comparison and rationalization of the set of results were postponed in the Discussions section.           

 

  1. Discussion
  • The discussion lacks a clear and structured argument. It would benefit from organizing the points logically and linking each observation back to the main research objectives or broader implications.
  • While the predominance of organic carbon is noted, there is limited discussion on the significance of this finding. Consider expanding on why organic carbon is prevalent and how it relates to degradation processes or environmental factors.
  • The discussion of carbonate content across different samples (e.g., Samples #3, #9, #10) needs further contextualization. Why do some samples exhibit higher carbonate percentages, and what implications does this have for degradation patterns?
  • The XRD results mentioned provide valuable information on mineral composition, but there's a need to more directly link these findings with the XPS results discussed earlier. How do the deeper mineral layers identified by XRD relate to surface degradation as observed by XPS?
  • While efflorescence phenomena and soluble salts are mentioned, their specific impact on calcarenite degradation should be elaborated. Discuss how these processes contribute to structural damage and surface alterations.
  • The discussion on biodegradation and bioactivity could be expanded to clarify how microbial metabolism affects degradation products like calcium oxalate and sulphates. Additionally, explore implications for conservation strategies in light of ongoing bioactivity.
  • Consider discussing how environmental factors like humidity, climate, and human activities influence the observed degradation patterns. Connect these factors to the long-term preservation challenges faced by the UNESCO site.
  • The discussion would benefit from a more cohesive synthesis of findings. Conclude by summarizing key insights into calcarenite degradation and proposing implications for conservation strategies or further research.
  • Consider acknowledging any limitations in the study's approach or data interpretation. Discuss potential future research directions that could build upon the current findings to deepen understanding of calcarenite degradation processes.

 

We have implemented the Discussion section trying to include all the aspects considered by the reviewer:

clarifying the potentiality of XPS in combination with techniques having different analytical depths, providing experimental results related to SCN project aimed at the preservation of the UNESCO site and literature data,

adding two specific references and finally listing the XPS indicators of degradation linked to the results obtained from the analysis of the ten samples differently located inside the San Barisano church.

 

 

  1. Conclusions
  • The conclusions should include more specific findings or insights derived from the XPS analysis. Rather than stating general capabilities of XPS, highlight specific correlations between surface composition and degradation causes observed in the San Pietro Barisano church.
  • While the article mentions previous work, it's important to explicitly state how the current findings build upon or differ from these prior studies. This context can provide a clearer understanding of the significance of the current research.
  • The section should elaborate on how exactly XPS contributes uniquely to the investigation of calcarenite degradation compared to other analytical techniques. Specify the advantages and limitations of XPS in this context.
  • The conclusion refers to Figure 13 as providing indicators, but the specific implications of these indicators for conservation efforts or further research should be explicitly discussed.
  • The conclusions should provide more actionable recommendations or implications for conservation strategies. How can the identified degradation factors inform future preservation efforts at the UNESCO site?
  • Elaborate on how the integration of XPS with other analytical techniques (biological analyses, architectural surveys) enhances the overall understanding of calcarenite degradation and preservation challenges.
  • While mentioning ongoing work with PCA, clarify how this analysis will contribute to refining degradation descriptors. Discuss potential future research directions based on current findings.

 

  • Provide a concise summary of how the findings align with the final aim of the SCN project and its implications for expert users in cultural heritage conservation.

 

The Conclusions are remade trying to follow in each paragraph the list of suggestions of the reviewer hoping to have mostly succeeded in responding accurately, in the acknowledge of the review accuracy

 

 

Reviewer 5 Report

Comments and Suggestions for Authors

1. This study used the XPS technique to analyze the surface composition of the wall of the church of San Pietro Barisano. I understand the purpose of the work, but other routine techniques such as XRD and IR are also important to determine the compositions. Using one kind of characterization method may result in unconvincing conclusions. Please supplement the related results of some samples (not for all).
2. Authors should improve the quality of some figures, such as Figure 1 (with logo on the bottom?) and Figure 5 (too blurry!).
3. The main results of this work are based on Figure 6. However, this figure cannot be clearly presented. Also, the peaks can be split to be assigned to different kinds of bonds.
4. This work was supported by the “SCN_0520” or “SCN_00520”? Anyway, you do not need to mention this in the main text. We pay more attention to scientific results.

Author Response

Comments and Suggestions for Authors

1.This study used the XPS technique to analyze the surface composition of the wall of the church of San Pietro Barisano. I understand the purpose of the work, but other routine techniques such as XRD and IR are also important to determine the compositions. Using one kind of characterization method may result in unconvincing conclusions. Please supplement the related results of some samples (not for all).

We added paragraphs (highlighted) in Introduction to meet the reviewer request with added references 21-23, enlarged the relevant test highlighted in Discussion adding references 36 and 44 and also the modified Conclusions are all devoted to these requests- shared with reviewers 1 and 2. We hope to have succeeded on this regard and improved the comprehension of the manuscript

2.Authors should improve the quality of some figures, such as Figure 1 (with logo on the bottom?) and Figure 5 (too blurry!).
3. The main results of this work are based on Figure 6. However, this figure cannot be clearly presented. Also, the peaks can be split to be assigned to different kinds of bonds.

We did remove the logo in Figure 1 and made the changes of Figs 5 and 6 also adding explanations, highlighted in the Results section, as reported to previous reviewers

 

4.This work was supported by the “SCN_0520” or “SCN_00520”? Anyway, you do not need to mention this in the main text. We pay more attention to scientific results.

Unfortunately, to properly answer to the previous requests we had to refer again to collaborative work within that research project dedicated to the UNESCO site of Matera using multi-technique and multidisciplinary approaches, therefore, based also on other reviewers requests of providing more information on the role of XPS within the project, this request could be answered partially and only in some sections.

Round 2

Reviewer 3 Report

Comments and Suggestions for Authors

The different questions raised were answered. It is recommended to review the iThenticate analysis, a slightly high value is shown.

Reviewer 4 Report

Comments and Suggestions for Authors

The authors have made the changes satisfactorily. I suggest that the paper can be published.

Reviewer 5 Report

Comments and Suggestions for Authors

This manuscript can be accepted in the current form.

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