The adsorption and mechanism of the nitrification inhibitor nitrapyrin in different types of soils

The nitrapyrin was easily adsorbed by soil, but most current studies have focused on comparing the effects of nitrapyrin application at different soil organic matter levels and in different soil types. The adsorption kinetics and isotherm adsorption of the nitrification inhibitor nitrapyrin in black soil, chernozem and planosol were studied in this paper. The adsorption kinetics were fitted by quasi-second-order kinetic equation (R2 ≥ 0.8907, p < 0.05) with a lower acting energy of adsorption (Ea < 8.0 kJ mol−1). The isotherm was fitted by the Langmuir equation (R2 ≥ 0.9400*, p < 0.05). The adsorption mechanism was determined to involve a spontaneous endothermic reaction accompanied mainly by physical adsorption to the surface that belonged to the ‘L’ isotherm curve (n > 1). Temperature promoted the adsorption of nitrapyrin in these three soils, and the maximum adsorption occurring at different temperatures following the order of black soil > planosol > chernozem. The adsorption capacity and rate decreased with decreasing soil organic matter. For the black soil, the nitrapyrin EC adsorption rate was more than seven times higher than that of nitrapyrin CS. The result would determine the dose of nitrapyrin required for availability in different types of soils and to provide a theoretical basis for elucidating the adsorption of nitrapyrin in the soil environment.

Decision letter (RSOS-191684.R0) 30-Jan-2020 Dear Professor Gao: Manuscript ID: RSOS-191684 Title: "The adsorption and mechanism of the nitrification inhibitor nitrapyrin in different types of soils" Thank you for submitting the above manuscript to Royal Society Open Science. Your paper was sent to reviewers and their comments are included at the bottom of this letter. I apologise this has taken longer than usual.
In view of the concerns raised by the reviewers, the manuscript has been rejected in its current form. However, a new manuscript may be submitted which takes into consideration these comments.
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Yours sincerely, Dr Laura Smith Publishing Editor, Journals Royal Society of Chemistry Thomas Graham House Science Park, Milton Road Cambridge, CB4 0WF Royal Society Open Science -Chemistry Editorial Office On behalf of the Subject Editor Professor Anthony Stace and the Associate Editor Professor Tobias Hertel ********************************************** REVIEWER(S) REPORTS: Associate Editor Comments to Author (): RSC Associate Editor: Comments to the Author: 30-Jan-2020 RSOS-191684 -The adsorption and mechanism of the nitrification inhibitor nitrapyrin in different types of soils Dear Professor Gao, we regret to inform you that your manuscript has been rejected by our reviewers. We will, however, gladly review a resubmitted and thoroughly revised version of this manuscript that addresses the concerns voiced by our reviewers.
Most significantly the criticism was directed at a perceived lack of novelty since Jacinthe and Pichtel 1992, also cited in your manuscript, were mentioned as having previously discussed the mechanism and factors affecting adsorption of Nitrapyrin in various soils in detail. Other points of criticism were directed at the lack of error bars and margins which allow readers to assess the significance of your data. Comments to the Author(s) This work assesses the adsorption mechanism of nitrapyrin in three types of soils (black soil, chernozem and planosol) in northeast China. It discusses the adsorption kinetic and adsorption thermodynamics of nitrapyrin in the selected soil, and the adsorption rate of black soil to different dosage forms of nitrapyrin under different organic matter content. This study is meaningful for the adsorption of nitrapyrin in the soil environment. However, some revisions should be made to make the paper more convincing. 1.There are some grammatical errors in the manuscript. For example, Line 369, "study soils are shown in Figure 3" should be placed with "study soils were shown in Figure 3". And Line 326, "are listed in Table 6." should be "were listed in Table 6." etc. 2. Why do you choose the two dosage forms of nitrapyrin? 3. Line 334, what might be the chemical reaction? Why do not chemical adsorption occur in black soil? 4. Check the Fig. 2 and 3. For example, the curves are different but the names are the same in Fig.  2. 5. Line 370, why the contribution of the two processes to the adsorption of nitrapyrin was significantly different in three types of soils? 6. The conclusions are too simple to highlight the more profound significance of the study. 7. Lack error bars.

Reviewer: 2
Comments to the Author(s) Zhang and Gao conducted a study to assess the adsorption of the nitrification inhibitor nitrapyrin in different types of soils. This manuscript does not present novel results. The outcomes of this research are already expected. Jacinthe and Pichtel 1992, discussed the mechanism and factor affecting adsorption of Nitrapyrin in various soils in details.
Author's Response to Decision Letter for (RSOS-191684.R0) See Appendix A.

Do you have any ethical concerns with this paper? No
Have you any concerns about statistical analyses in this paper? No

Recommendation?
Accept with minor revision (please list in comments)

Comments to the Author(s)
Conditions, this paper studied the adsorption kinetics and isotherm adsorption of nitrapyrin in three types of soils. The factors affecting the adsorption capacity and the potential adsorption mechanisms of different soils are analyzed. The significance of this work is based on a practical problem, an ongoing Chinese policy, which provides the work with practical value. Therefore, I recommend a minor revision before its publication. The specific comments are listed below: 1. The abstract section lacked a brief summary of the background and significance of the research. 2. Please add the reference of the potassium dichromate volumetric method. 3. The original content of the organic matter was different in the three types of soil, does all samples conduct the H2O2 treatment in the same way? 4. Please modified the format of the table 3.

Are the interpretations and conclusions justified by the results? Yes
Is the language acceptable? No

Do you have any ethical concerns with this paper? No
Have you any concerns about statistical analyses in this paper? No

Recommendation?
Major revision is needed (please make suggestions in comments)

Comments to the Author(s)
1. Line 37, "caused by excessive nitrogen fertilizer use" should be revised as "caused by the excessive use of nitrogen fertilizer". 2. Line 40, "Goring et al. (Goring et al., 1962) first reported that" should be revised as " Goring et al. (1962) first reported that" 3. Line 82, when "NUE" first appears in the full text, please use its full name. 4. Line 110, "For organic matter removal from the soil" should be revised as "For removal of organic matter from the soil". 5. Line 138, when "HPLC" first appears in the full text, please use its full name: high performance piquid chromatography. 6. Line 247, "which", "and" are not used correctly. 7. The format of Table 3 is not well adjusted. 8. Line 279, "because ΔG# was more than 0" should be modified as "because ΔG# was larger than 0". 9. Line 335, "chernozem at 318K and planosol at 308 K and 318 K" should be modified as " chernozem(318 K) and planosol (308 K and 318 K ). 9. Line 399, "29.79, 26.38, 24.99, and 25.10%" should be modified as "29.79%, 26.38%, 24.99% and 25.10%". 10. Line 402, "19.69, 21.24, 24.19 and 21.02%" should be modified as "19.69%, 21.24%, 24.19% and 21.02%". 11. The past tense should be revised in the entire manuscript. 12. Line 434, "The decrease in organic matter content leads to the" should be modified as " The decrease in organic matter concentration led to the" 13. Line 436, "nitrapyrin EC is more higher than that of nitrapyrin CS" should be modified as "nitrapyrin EC is much higher than that of nitrapyrin CS" 14. The similar mistakes mentioned above should be revised in the entire manuscript carefully. 15. The mechanism of adsorption of nitrapyrin in different types of soils should be concluded and analyzed clearly. We hope you are keeping well at this difficult and unusual time. We continue to value your support of the journal in these challenging circumstances. If Royal Society Open Science can assist you at all, please don't hesitate to let us know at the email address below.
Dear Professor Gao: Title: The adsorption and mechanism of the nitrification inhibitor nitrapyrin in different types of soils Manuscript ID: RSOS-200259 Thank you for submitting the above manuscript to Royal Society Open Science. On behalf of the Editors and the Royal Society of Chemistry, I am pleased to inform you that your manuscript will be accepted for publication in Royal Society Open Science subject to minor revision in accordance with the referee suggestions. Please find the reviewers' comments at the end of this email.
The reviewers and handling editors have recommended publication, but also suggest some minor revisions to your manuscript. Therefore, I invite you to respond to the comments and revise your manuscript.
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Once again, thank you for submitting your manuscript to Royal Society Open Science. The chemistry content of Royal Society Open Science is published in collaboration with the Royal Society of Chemistry. I look forward to receiving your revision. If you have any questions at all, please do not hesitate to get in touch. ************************************* RSC Associate Editor Comments to the Author: Dear Dr. Gao, we hope you found the reviewers comments helpful when revising your manuscript.
We would like to publish your manuscript with minor revisions. Specifically, we noticed that some of the comments of reviewer 2 have been left unanswered and that no changes were made to the manuscript regarding several of his/her points of criticism.
Before proceeding with publication of this manuscript we would thus like to ask you to correct the following items including the last two which were added by the associate editor: -add the unabbreviated form of NUE in line 82 -table 3 is difficult to read, we ask you to revise the format to make it more accessible -with any reported quantity, use significant digits only. Suppose the error margins for Delta G values in table 4, for example, were 0.8 kJ/mol (here I am just guessing), this would suggest that the second numeral would be the significant digit. In this example 85 kJ/mol would be the appropriate quantity to report instead of 85.213 kJ/mol. -the use of a hashtag with thermodynamic potentials is highly unusual, use a double dagger instead whenever potentials are referenced to a transition state.
Sincerely, Tobias Hertel Associate Editor, RSOS ************************************** Reviewer comments to Author: Reviewer: 1 Comments to the Author(s) conditions, this paper studied the adsorption kinetics and isotherm adsorption of nitrapyrin in three types of soils. The factors affecting the adsorption capacity and the potential adsorption mechanisms of different soils are analyzed. The significance of this work is based on a practical problem, an ongoing Chinese policy, which provides the work with practical value. Therefore, I recommend a minor revision before its publication. The specific comments are listed below: 1. The abstract section lacked a brief summary of the background and significance of the research. 2. Please add the reference of the potassium dichromate volumetric method. 3. The original content of the organic matter was different in the three types of soil, does all samples conduct the H2O2 treatment in the same way? 4. Please modified the format of the table 3.

Reviewer: 3
Comments to the Author(s) 1. Line 37, "caused by excessive nitrogen fertilizer use" should be revised as "caused by the excessive use of nitrogen fertilizer". 2. Line 40, "Goring et al. (Goring et al., 1962) first reported that" should be revised as " Goring et al. (1962) first reported that" 3. Line 82, when "NUE" first appears in the full text, please use its full name. 4. Line 110, "For organic matter removal from the soil" should be revised as "For removal of organic matter from the soil". 5. Line 138, when "HPLC" first appears in the full text, please use its full name: high performance piquid chromatography. 6. Line 247, "which", "and" are not used correctly. 7. The format of Table 3 is not well adjusted. 8. Line 279, "because ΔG# was more than 0" should be modified as "because ΔG# was larger than 0". 9. Line 335, "chernozem at 318K and planosol at 308 K and 318 K" should be modified as " chernozem(318 K) and planosol (308 K and 318 K ). 9. Line 399,"29.79,26.38,24.99,and 25.10%" should be modified as "29. 79%,26.38%,24.99% and 25.10%". 10. Line 402,"19.69,21.24,24.19 and 21.02%" should be modified as "19.69%, 21.24%, 24.19% and 21.02%". 11. The past tense should be revised in the entire manuscript. 12. Line 434, "The decrease in organic matter content leads to the" should be modified as " The decrease in organic matter concentration led to the" 13. Line 436, "nitrapyrin EC is more higher than that of nitrapyrin CS" should be modified as "nitrapyrin EC is much higher than that of nitrapyrin CS" 14. The similar mistakes mentioned above should be revised in the entire manuscript carefully. 15. The mechanism of adsorption of nitrapyrin in different types of soils should be concluded and analyzed clearly. For example, Line 369, "study soils are shown in Figure 3" should be placed with "study soils were shown in Figure 3". And Line 326, "are listed in Table 6." should be "were listed in Table 6." etc.
Answer: Thanks for your good advice, the grammatical errors in the manuscript have been seriously modified.
The problem:(2) Why do you choose the two dosage forms of nitrapyrin?
Answer: Previous studies have shown that nitrapyrin was easily adsorbed by soil organic matter when it was applied to soil (Huang et al., 2001), especially for soils with high level of organic matter, and its availability was significantly reduced (Hendrickson et al., 1979;Chen et al., 1980;Sahrawat et al., 1987). So, in this study we choose two dosage forms of nitrapyrin and try to find which dosage form is better to reduce the adsorption of organic matter in the soils and improve the effect of kinetics and isotherm adsorption of the nitrification inhibitor nitrapyrin in black soil, chernozem and planosol were studied in this paper. The present work is an attempt to assess the adsorption mechanism on adsorption behaviour of nitrapyrin on three soils of china, which will help to determine the dose of nitrapyrin required for availability of this nitrification inhibitor in different types of soils and to provide a theoretical basis for elucidating the adsorption of nitrapyrin in the soil environment.
The study found that the adsorption capacity and rate of nitrapyrin in the soil decreased with decreasing soil organic matter. Therefore, an attempt was made to preliminarily explore the influence of organic matter on adsorption of nitrapyrin.
The study of " Effect of Soil Organic Matter on Adsorption of Nitrification Inhibitor Nitrapyrin in Black Soil" was also our research and was an important extension of this research. The paper mainly discussed the influence of organic matter on adsorption of nitrapyrin.
At the same time, this study provides basic theoretical support for developing new dosage forms of nitrapyrin to reduce the adsorption of organic matter and improve the effectiveness of nitrapyrin application.
We are looking forward to hearing from you soon. If you have any question, please connect me without hesitation. Thank you sincerely.