Review Reports - Elemental Associations in Stream and Alluvial Sediments of the Savinja and Voglajna Rivers (Slovenia, EU) as a Result of Natural Processes and Anthropogenic Activities

Round 1

Reviewer 1 Report

The manuscript: Geochemical associations in stream and alluvial sediments of the Savinja and Voglajna Rivers (Slovenia, EU) as a consequence of natural processes and anthropogenic activities presents the geochemical analysis of sediments and their interpretation. The article correspond to its title, it is well organized, the maps are good quality and the geochemical method is correct, but the methodology has not properly described: statistical as well as geochemical. The title suggest that geochemistry is depend on anthropogenic and natural sources, and it is obvious because of location and characteristics of the research area. Title should show better defined problem to be solved. Maybe more important problem is connected with some rare elements (e.g. tellurium) and then the title should take it into consideration.

In details:

Geochemistry is the consequence of mineralogy, the mineralogy of the sediments must be included
Conclusions incompletely correspond to the aims of the manuscript
The figure 3 (twice) and 4 are barely visible due to their description.
What does mean "fine fraction" of sediments ?
Some key citation are lacking
It is essential to join the linguistic correction using scientific vocabulary.

In my opinion the manuscript cannot be published in present form. I recommend reject this version, rewrite some part, e.g. the aims and conclusions, to add the mineralogical studies, correct the figures 3-4, correct English language and submit it again to Minerals.

Author Response

Dear reviewer.

Thank you for your time to review this manuscript and for all the constructive comments, which helped me to drastically improve the manuscript (I hope). I tried to address your comments at my best. Major improvements:

- x-ray diffraction is added, supporting the interpretation,

- some parts are rewritten,

- extensive English language improvements,

- improved figures,

- new references are added,

- graphical abstract added.

Please find some point by point replies.

In details:

Geochemistry is the consequence of mineralogy, the mineralogy of the sediments must be included

>>> Mineralogy of the sediments is included. Another reviewer pointed out the same issue, so I decided to do some XRD measurements and incorporate them into the results & discussion. I hope the MS is improved now.

Conclusions incompletely correspond to the aims of the manuscript

>>> I tried to improve conclusions.

The figure 3 (twice) and 4 are barely visible due to their description.

>>> I have improved them, hopefully they are better now.

What does mean "fine fraction" of sediments ?

>>> This is a common terminology in sedimentology. Sediments can be fine (small grain size) or coarse (large grain size). I re-checked the text and I do no see any error here.

Some key citation are lacking

>>> I added some new citations. If you can advise me about some other key citations, I can include them.

It is essential to join the linguistic correction using scientific vocabulary.

>>> Language was checked again by the native English speaker.

Reviewer 2 Report

The trivial fact of chemical elements accumulation in fine fractions. If this is shown for the first time for the district, it should be reflected in the conclusions. Two curves for fractions less than 0.063 and 0.063-0.125 complicate the perception of graphs.
K/Al, Al/Ti look not enough for interpreting of deposits genesis. It will be good to add demolition area indicators (Cullers, 2000). (Fe+Mn)/Ti is an indicator of pyroclastic components. To estimate the intensity of weathering in the demolition area.
Only 22 chemical elements were included in the factor analysis. On what basis they are chosen. What is the critical value of the correlation coefficient.
The presence of Ag, In, Sn, Bi, Mo is not explained in F1. The anthropogenic factor takes into account only the modern period or long period?
The behavior of Te can be explained using the «Geochemical atlas of Europe», 2005.

Author Response

Dear reviewer.

- x-ray diffraction is added, supporting the interpretation,

- some parts are rewritten,

- extensive English language improvements,

- improved figures,

- new references are added,

- graphical abstract added.

Please find some point by point replies.

The trivial fact of chemical elements accumulation in fine fractions. If this is shown for the first time for the district, it should be reflected in the conclusions. Two curves for fractions less than 0.063 and 0.063-0.125 complicate the perception of graphs.

>>> The first part - added sentence in the results and conclusion chapters. It is true, that graphs are overwhelming with information. However, I personally think it is not too bad, perhaps the redaction can make them slightly larger to increase visibility. I also exposed line for finer fraction, and improve other features, and I hope it is now slightly better.

K/Al, Al/Ti look not enough for interpreting of deposits genesis. It will be good to add demolition area indicators (Cullers, 2000). (Fe+Mn)/Ti is an indicator of pyroclastic components. To estimate the intensity of weathering in the demolition area.

>>> Fe+Mn/Ti really shows good trend, I added that! I couldn't find references you suggested, and I am sorry but I do not understand what did you mean by "demolition area indicator".

Only 22 chemical elements were included in the factor analysis. On what basis they are chosen. What is the critical value of the correlation coefficient.

>>> I have improved corresponding explanation in the materials and methods. I also found some errors there. "Elements, which tend not to be loaded in any of the first four factors, or have the highest factor loading below the value of 0.8, were excluded from the factor analysis."

The presence of Ag, In, Sn, Bi, Mo is not explained in F1. The anthropogenic factor takes into account only the modern period or long period?

>>> I do not understand this comment. Ag, In, Sn, Bi and Mo are loaded in F1. This factor takes into account modern (stream) and past (alluvial profiles) anthropogenic records.

The behavior of Te can be explained using the «Geochemical atlas of Europe», 2005.

>>> Thank you, added.

Reviewer 3 Report

This manuscript by Zibret presents major and trace element data from Savinja and Voglajna Rivers to determine the impacts of natural and anthropogenic factors in influencing sediment transport and deposition. I recommend the following revisions to the MS:

Authors cover many aspects in this manuscript, however, some of them seem to be touched a little bit but the provided data is not strong enough to conclude a solid conclusion. For example, authors use Al/Ti ratio to indicate the alkalinity of the source rocks. However, it has been proved that the “sedimentary Al/Ti” ratio can deviate extremely from the natural composition of terrestrial source materials” (Zebel et all, 1999). Author didn’t discuss and exclude the other impacts in their provenance/tectonic setting analysis and directly concluded. More details are provided in the line-by-line reviews below.

Author is suggested to dig deeper into the dataset and differentiate different physical, chemical, and anthropogenic factors in influencing the sediment transport and deposition, taking the weather and climate pattern into consideration. Author could also consider adding age control to the sampled sediments and differentiating the river sediments between the thalweg and terraces in the channel. An advantage of this studied area is that the provenance analysis has been done by other researchers, author could make full use of the ICP-MS results to tell a more complete story of sediment source to sink process.

Several important terms or concepts in the MS need to be well defined and introduced before being used in the discussion section, such as how do you conduct factor analysis, what software or program you were using, explain how and why you classified the four geochemical associations, define “factor scores”. More details are provided in the line-by-line reviews below.

Author is suggested to show the comparison between the analyzed elemental data and EU UC data by a figure, it will certainly be more efficient and clear to visualize the elemental compositions, depletion, and abundance, giving readers a big picture in mind.

There are many statements in the manuscript that lack citations. Author is expected to thoroughly go through the MS and add all the necessary references when necessary.

Last, the manuscript needs a thorough review for grammar and typographical errors. Check the paper for proper sentence structure, use of hyphens, space, and punctuation. Author needs to revise and proofread before further submission.

Below is a line-by-line review of the MS:

L22-38: no reference is cited, but apparently there are many statements that need citations to be added.

L58: “natural background”, the studied area is a result of a combined impact from both natural and anthropogenic factors, how do you define the “natural background”?

L63: “Danube river” if this is necessary to be introduced, please mark it in Fig 1 map, otherwise readers have no idea of the river position.

L64: “Its spring” whose spring?

L69: “Celje basin”, what is the outline of this basin in Fig 1 map, is that the black area?

L72: “Sava folds” where is it? Mark it on Fig 1.

L73: “Paleosoic” typo

L76: “most” what does it mean?

L77-116: add references

L162: “separately”, Table 1 is not showing stream and bank sediments separately, are they mixed?

L163: how do you conduct factor analysis, what software or program you were using

L222: 48+24+14+9=95, rather than 96

L223: Explain how do you group and define the geochemical associations.

L229: define “factor scores”

L231-232: grammar errors

L241: figure 4 should be 5

L261: how do you define base levels, again, your analyzed results are from a combined impact of many factors

L273-283: other important factors that influence the K/Al ratio need to be discussed

Figures:

Fig. 1: (1) what do the three black areas mean (2) add latitude, longitude, and scale in the two upper figures. (3) Line 100, “8” should be 10. (4) L103, what are others, they need to be all listed.

Figure numbers need to be corrected, there are two Figure 3 right now.

Tables 1 and 2, the comma is decimal point?

Author Response

Dear reviewer.

- x-ray diffraction is added, supporting the interpretation,

- some parts are rewritten,

- extensive English language improvements,

- improved figures,

- new references are added,

- graphical abstract added.

Please find some point by point replies according to the attachment.

Author Response File: Author Response.pdf

Reviewer 4 Report

The manuscript entitled Geochemical associations in stream and alluvial sediments of the Savinja and Voglajna Rivers (Slovenia, EU) as a consequence of natural processes and anthropogenic activities investigates multielemental composition of sediments from the Savinja and Voglajna rivers with the aim of recognizing grouping of elements, their spatial distributions and relations and assessing anthropogenic influence.

General comments

The paper is well written and constructed, minor English corrections are needed and there are misspelled words.

The discussion would benefit if mineralogical analysis was included.

Please refer to specific Figures and tables in the MS when describing results, in the discussion as well as in the study area.

The map of the area in Figure 1 is of poor quality.

The author should avoid beginning the sentence with a number, or a sign (<).

Specific comments

Lines 33-37: please include some references

Line 44: this refers to alluvial sediments?

Line 52: pollutants

Line 111: unclear sentence, please rewrite

Line 139: please review this sentence, the digestion is for ICPMS, not by ICPMS

Lines 144 - 159: is it necessary to include all these details?

Lines 186 - 193: this should be moved to the method section, and the table with these parameters could go into supplementary

Lines 200-201: please check the font

Lines 213-214: please include names and locations in the map

Line 227: this could go into supplementary information

Line 229: remove bold

Line 253: This should be figure 4 and also the font is different

Line 257: Figure 5 not 4

Line 298: Sb is repeated

Lines 329-330: please rewrite, this is unclear

Line 345: figure 6

Line 348: zircon mineral – what is the name?

Author Response

Dear reviewer.

- x-ray diffraction is added, supporting the interpretation,

- some parts are rewritten,

- extensive English language improvements,

- improved figures,

- new references are added,

- graphical abstract added.

Please find some point by point replies.

General comments

The paper is well written and constructed, minor English corrections are needed and there are misspelled words.

>>> Manuscript was checked again for the grammar errors and improper use of hyphens etc.

The discussion would benefit if mineralogical analysis was included.

>>> Thank you for this comments. Since another reviewer pointed out the same issue, I decided to include XRD measurements of sediments to assist the discussion part.

Please refer to specific Figures and tables in the MS when describing results, in the discussion as well as in the study area.

>>> Thank you, I included some more references to figs and tables.

The map of the area in Figure 1 is of poor quality.

>>> I added some new elements to Fig. 1.

The author should avoid beginning the sentence with a number, or a sign (<).

Specific comments

Lines 33-37: please include some references

>>> Some references are included.

Line 44: this refers to alluvial sediments?

>>> Yes, I corrected.

Line 52: pollutants

>>> Corrected.

Line 111: unclear sentence, please rewrite

>>> Corrected.

Line 139: please review this sentence, the digestion is for ICPMS, not by ICPMS

>>> Corrected.

Lines 144 - 159: is it necessary to include all these details?

>>> Reviewers usually require all these details, this is why I decided to include them.

Lines 186 - 193: this should be moved to the method section, and the table with these parameters could go into supplementary

>>> I partially agree. Sometimes it is better to have QC/QA results next to the basic statistics, because the reader can quickly evaluate whether the results are trustworthy or not. If I move these data away, then if you like to check QC/QA results you must seek them around the MS / supplementary. This is why I decided to keep them where they are.

Lines 200-201: please check the font

>>> Thank you, corrected. Some mistakes were made in the redaction...

Lines 213-214: please include names and locations in the map

>>> I do not understand you well. Which names? Did you mean the names of the towns? I intentionally omitted them, because even now the map is packed with information, and results are barely visible at some places. I presented all of this in the Fig. 1, and the reader can easily compare locations, in my opinion.

Line 227: this could go into supplementary information

>>> This is one of the main results of the study, so I think it is better to keep this table in the text.

Line 229: remove bold

>>> Thank you, another mistake made in the redaction.

Line 253: This should be figure 4 and also the font is different

>>> Figure numeration was corrupted during redaction. I corrected that, thank you!

Line 257: Figure 5 not 4

>>> See above.

Line 298: Sb is repeated

>>> Thank you, corrected.

Lines 329-330: please rewrite, this is unclear

>>> Thank you, corrected.

Line 345: figure 6

>>> Thank you, corrected.

Line 348: zircon mineral – what is the name?

>>> Thank you, corrected.

Round 2

Reviewer 1 Report

The manuscript: Elemental associations in stream and alluvial sediments of the Savinja and Voglajna Rivers (Slovenia, EU) as a result of natural processes and anthropogenic activities contain all needed part of scientific work, including introduction, methodology, results, and conclusions, and have been corrected according last review. The wrong part is associated with XRD results and Rietveld analysis; according to them sediments contain possible phases in quantities less than 3%, e.g.: Eucriptite - LiAlSiO4, Wroewolfeite, and completely not probable in alluvial and stream sediments other phases as : Potassium Cadmium Gallium Selenide, Rubidum Iodide. Lead as metal??, and Zinc Tetrahiodigallate. This phases should be omitted. Most of the phases described in Table 3 as Potential Compounds in traces are not possible to be in sediments, because they are not minerals, they are very rare or not occur in natural environments, and their presence necessarily have to be confirmed by the other methods. As potential compounds could be found: chlorites, hematite and zeolite, but it have to be confirmed as well. XRD method using to mineral identification needs at least 3 separate peaks of different crystal d - values , and they not to be overlapped on peaks from another mineral. There is not possible to determined some minerals on Figure 7a, e.g.: Pb-Wr, which could be generated by Kaolinite or Chlorite, Bellite on the Fig. 7 b – only 2 peaks are present, one peak from RbI on the Fig.7d – that phases names should be deleted on attached diffractogram, and the table 3 should be modified.

In my opinion after minor correction the manuscript can be published in Minerals .

Author Response

Dear reviewer!

Thank you again for your kind checking the manuscript and useful comments regarding X-ray diffraction.

The census of including individual phases was the presence of three most significant peaks. Without these phases some peaks remain unexplained. However, our mineral database is not the best one and this might be the reason for that. But you are right, it might be better to omit some exotic phases. I decided to keep Eucryptite, because there are pegmatites in catchment areas. Wroewolfeite could be present there because it can be supergene, by oxidation and weathering of some Cu minerals, which could be present in Zn ores, which are dumped in the area. I agree with you not to mention many other exotic compounds. I decided to keep Pb as metal, because it is likely to have some grains with metallic Pb in the middle. After all, it was a Pb-Zn smelter, its purpose was to produce metallic Pb and Zn. I have corrected Fig. 8 and Tab. 3 accordingly.

Many thanks again for your time and patience!

Best regards, Gorazd

Reviewer 3 Report

The following review letter is based on my first round review and author’s response:

>>> I completely agree with you. The problem is that past geochemical studies in the area dealt with ore prospection (between 50s and 80s), and later with anthropogenic pollution. There are no past lithogeochemical studies available for the area in a similar way it common for the USA, Canada, Australia etc. This is the first study which aims to shine light on such ratios in this study area. Due to the lack of proper lithogeochemical data it is hard to make any solid interpretations and in-depth analyses of the datasets. I tried to do this in my paper, hopefully encouraging other scientist in the area to do similar. With the increasing pool of data more detailed analyses will be possible.

Response: At least author should include some sentences in Discussion talking about other potential impact possibilities and cite the corresponding references, even when there is no available data at the studied area. The resubmitted MS in Line 338 still states “Al/Ti ratio is an indication of alkalinity of the host rocks.” which is not always true.

>>> Thank you for the suggestions. Graphs show factor scores distributions, so not compatible with the EC/EC data.

Response: In Results, authors states “the composition of stream and alluvial sediments is comparable with the European average values for most elements.” and has shown the elemental levels in Table 1 together with EU and UC data, I don’t think there could be any problem to plot them into a readable figure.

There are many statements in the manuscript that lack citations. Author is expected to thoroughly go through the MS and add all the necessary references when necessary.

>>> Regarding citations - see specific comments. Many citations are only in Slovene and not very well accessible for international scientific community, so I decided not to include them, for clarity reasons. At some parts there are obvious and generally well known thinks which in my opinion does not need citations.

Response: Well-known doesn’t mean it doesn’t need to be cited.

line-by-line review:

L77-116: add references

>>> All of them are in Slovene. Some are under maintenance now... I do not think readers would gain a lot of new information, so I decided not to put them in the paper for clarity.

Response: The purpose of citing references is to give credit and to provide a source for readers to search on their own. It has nothing to do with “gaining a lot of new information”. I don’t think author should avoid citing any references if these data are not completed by author.

Figures:

Fig. 1: (1) what do the three black areas mean (2) add latitude, longitude, and scale in the two upper figures.

>>> I corrected that, except adding lon/lat for the upper images. I think from the silhouette it is obvious the study area is located in Europe, and adding lon/lat will not contribute to clarity, rather the opposite, I suppose?

Response: (1) black areas are not explained; (2) don’t agree.

Author Response

Dear reviewer!

Thank you again for your kind checking the manuscript and useful comments. Please see my responses below.

>>> Some more potential impacts are described in discussion.

>>> I included the plot as suggested.

Response: Well-known doesn’t mean it doesn’t need to be cited.

>>> Reference about factor scores added.

>>> I added references as suggested.

Response: (1) black areas are not explained; (2) don’t agree.

>>> I am sorry, but I really have no idea what did you mean by "black areas". I added LON/LAT information on the map of Europe.

Many thanks again for your time and patience!

Best regards, Gorazd