Purpose This study provides a novel resource utilization strategy for the carbonized soil derived from lubricant-contaminated soil. Materials and methods In this study, the lubricant-contaminated soil was treated by pyrolysis and ball milling with manganese carbonate to obtain Mn-loaded carbonized soil (Mn@BCS), which was then reused to activate peroxymonosulfate (PMS) oxidation for degradation of aniline (AN) in wastewater. Results and discussion When the dosage of Mn@BCS and PMS was both 1 g/L, 100 mg/L of AN was almost completely removed within 6 h. Three reactive oxygen species (ROS), including <InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="11368_2025_3960_Article_IEq1.gif" Format="GIF" Height="20" Rendition="HTML" Resolution="72" Type="Linedraw" Width="40" /> </InlineMediaObject> <EquationSource Format="TEX">${\text{SO}}_{4}^{\bullet -}$</EquationSource> <EquationSource Format="MATHML"><math> <msubsup> <mtext>SO</mtext> <mrow> <mn>4</mn> </mrow> <mrow> <mo>∙</mo> <mo>-</mo> </mrow> </msubsup> </math></EquationSource> </InlineEquation>, •OH and <InlineEquation ID="IEq2"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="11368_2025_3960_Article_IEq2.gif" Format="GIF" Height="18" Rendition="HTML" Resolution="72" Type="Linedraw" Width="27" /> </InlineMediaObject> <EquationSource Format="TEX">${}^{1}{\text{O}}_{2}$</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <mmultiscripts> <mrow /> <mrow /> <mn>1</mn> </mmultiscripts> <msub> <mtext>O</mtext> <mn>2</mn> </msub> </mrow> </math></EquationSource> </InlineEquation>, were detected and verified. The probe-based kinetics models were established with atrazine, nitrobenzene and metronidazole as probes to quantify the generation of ROS. The exposure of the <InlineEquation ID="IEq3"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="11368_2025_3960_Article_IEq3.gif" Format="GIF" Height="20" Rendition="HTML" Resolution="72" Type="Linedraw" Width="40" /> </InlineMediaObject> <EquationSource Format="TEX">${\text{SO}}_{4}^{\bullet -}$</EquationSource> <EquationSource Format="MATHML"><math> <msubsup> <mtext>SO</mtext> <mrow> <mn>4</mn> </mrow> <mrow> <mo>∙</mo> <mo>-</mo> </mrow> </msubsup> </math></EquationSource> </InlineEquation>, <InlineEquation ID="IEq4"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="11368_2025_3960_Article_IEq4.gif" Format="GIF" Height="14" Rendition="HTML" Resolution="72" Type="Linedraw" Width="35" /> </InlineMediaObject> <EquationSource Format="TEX">$\bullet \text{OH}$</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <mo>∙</mo> <mtext>OH</mtext> </mrow> </math></EquationSource> </InlineEquation> and <InlineEquation ID="IEq5"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="11368_2025_3960_Article_IEq5.gif" Format="GIF" Height="18" Rendition="HTML" Resolution="72" Type="Linedraw" Width="27" /> </InlineMediaObject> <EquationSource Format="TEX">${}^{1}{\text{O}}_{2}$</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <mmultiscripts> <mrow /> <mrow /> <mn>1</mn> </mmultiscripts> <msub> <mtext>O</mtext> <mn>2</mn> </msub> </mrow> </math></EquationSource> </InlineEquation> at 6 h was 5.32 × 10–11, 5.40 × 10–12, 2.52 × 10–10 M s, which contributed 33.62%, 2.02% and 2.98% to AN degradation, respectively. The main active sites include Mn–O, oxygen containing groups and graphitized carbon. The Mn–O and oxygen containing groups can activate PMS to produce <InlineEquation ID="IEq6"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="11368_2025_3960_Article_IEq6.gif" Format="GIF" Height="20" Rendition="HTML" Resolution="72" Type="Linedraw" Width="40" /> </InlineMediaObject> <EquationSource Format="TEX">${\text{SO}}_{4}^{\bullet -}$</EquationSource> <EquationSource Format="MATHML"><math> <msubsup> <mtext>SO</mtext> <mrow> <mn>4</mn> </mrow> <mrow> <mo>∙</mo> <mo>-</mo> </mrow> </msubsup> </math></EquationSource> </InlineEquation> and <InlineEquation ID="IEq7"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="11368_2025_3960_Article_IEq7.gif" Format="GIF" Height="18" Rendition="HTML" Resolution="72" Type="Linedraw" Width="27" /> </InlineMediaObject> <EquationSource Format="TEX">${}^{1}{\text{O}}_{2}$</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <mmultiscripts> <mrow /> <mrow /> <mn>1</mn> </mmultiscripts> <msub> <mtext>O</mtext> <mn>2</mn> </msub> </mrow> </math></EquationSource> </InlineEquation>, respectively. The graphitized carbon promotes AN degradation by generation of <InlineEquation ID="IEq8"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="11368_2025_3960_Article_IEq8.gif" Format="GIF" Height="20" Rendition="HTML" Resolution="72" Type="Linedraw" Width="40" /> </InlineMediaObject> <EquationSource Format="TEX">${\text{SO}}_{4}^{\bullet -}$</EquationSource> <EquationSource Format="MATHML"><math> <msubsup> <mtext>SO</mtext> <mrow> <mn>4</mn> </mrow> <mrow> <mo>∙</mo> <mo>-</mo> </mrow> </msubsup> </math></EquationSource> </InlineEquation> and accelerating direct electron transfer. Conclusions Ball milling with manganese carbonate significantly improves the activation performance of carbonized soil for PMS oxidation, and thus promote the resource utilization of post-remediation soil.

Mn-assisted ball milling enhances catalytic property of carbonized soil and reuse as PMS activator: quantification of ROS with probe-based kinetics model and mechanism insights

期刊论文
发表日期：

2025年1月17日

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Xin Xie,
Wei Liu,
Mingxin Wang,
Xinxing Pan,
Jinjuan Xue,
Meng Yao

摘要

Purpose

This study provides a novel resource utilization strategy for the carbonized soil derived from lubricant-contaminated soil.

Materials and methods

In this study, the lubricant-contaminated soil was treated by pyrolysis and ball milling with manganese carbonate to obtain Mn-loaded carbonized soil (Mn@BCS), which was then reused to activate peroxymonosulfate (PMS) oxidation for degradation of aniline (AN) in wastewater.

Results and discussion

When the dosage of Mn@BCS and PMS was both 1 g/L, 100 mg/L of AN was almost completely removed within 6 h. Three reactive oxygen species (ROS), including ${\text{SO}}_{4}^{\bullet -}$ ${SO}_{4}^{∙ -}$ , •OH and ${}^{1}{\text{O}}_{2}$ $^{1} O_{2}$ , were detected and verified. The probe-based kinetics models were established with atrazine, nitrobenzene and metronidazole as probes to quantify the generation of ROS. The exposure of the ${\text{SO}}_{4}^{\bullet -}$ ${SO}_{4}^{∙ -}$ , $\bullet \text{OH}$ $∙ OH$ and ${}^{1}{\text{O}}_{2}$ $^{1} O_{2}$ at 6 h was 5.32 × 10^–11, 5.40 × 10^–12, 2.52 × 10^–10 M s, which contributed 33.62%, 2.02% and 2.98% to AN degradation, respectively. The main active sites include Mn–O, oxygen containing groups and graphitized carbon. The Mn–O and oxygen containing groups can activate PMS to produce ${\text{SO}}_{4}^{\bullet -}$ ${SO}_{4}^{∙ -}$ and ${}^{1}{\text{O}}_{2}$ $^{1} O_{2}$ , respectively. The graphitized carbon promotes AN degradation by generation of ${\text{SO}}_{4}^{\bullet -}$ ${SO}_{4}^{∙ -}$ and accelerating direct electron transfer.

Conclusions

Ball milling with manganese carbonate significantly improves the activation performance of carbonized soil for PMS oxidation, and thus promote the resource utilization of post-remediation soil.