With the rapid development of chemical industry, a large number of polycyclic aromatic hydrocarbons(PAHs) enter into the soil, which causes serious soil pollution. How to use sodium persulfate(Na2S2O8 ) to efficiently remedy the phenanthrene -contaminated soil, and to identify the influence on the soil in the process of remediation has became the core problem. In this paper, the effects of different environmental variables such as temperature, water-soil ratio, pH on the degradation of phenanthrene and the effects on soil during the degradation of phenanthrene were explored according to the reaction efficiency of sodium persulfate. In this experiment, when the temperature was 60°C, the water-soil ratio was 20:1, and the solution was slightly acidic, the Na2S2O8 utilization rate was the highest and also the overall degradation efficiency of the oxidation system was the highest. Na2S2O8 oxidation system can effectively degrade phenanthrene in soil, and thermally activated Na2S2O8 degradation of phenanthrene in soil conforms to quasi-first-order reaction kinetics. In the process of oxidation of phenanthrene with Na2S2O8 , soil structure was destroyed, caused acidification, and reduced the content of organic matter，which also had a negative impact on soil fertility and subsequent soil use function, the green and sustainable remediation should be considered.
Research Article
Influence Factors and Soil Properties of Phenanthrene Contaminated Soil Remediation by Sodium Persulfate
https://doi.org/10.21203/rs.3.rs-1604335/v1
This work is licensed under a CC BY 4.0 License
Version 1
posted
You are reading this latest preprint version
Sodium Persulfate
PAHs
Contaminated Soil
Soil Properties
Lands are the resources on which human depends(Peters et al. 2019, Song &Tan 2015, Wang et al. 2019). With the acceleration of urbanization and industrial transfer in China, a large number of complex and diverse soil pollution sites caused by the suspension and relocation of pollution enterprises seriously threaten the health and safety of mankind and ecological environment, and becomes an urgent soil environment problem(Li et al. 2011, Peluffo et al. 2018, Ye 2012). The pollution of soil by organic pollutants, especially PAHs, has attracted much more attention of researchers(Chan et al. 2021, Ding et al. 2021, Oleszczuk et al. 2019).
Polycyclic aromatic hydrocarbons(PAHs) refer to hydrocarbons with two or more benzene rings and heavy ring forms connected in the molecule, which have strong carcinogenicity, pathogenicity(Kan et al. 2021, Luo et al. 2020). It is a class of refractory organic pollutants (Lau et al. 2014). More and more attention has been paid to rapidly eliminating PAHs in the environment, reducing the pollution of PAHs to the ecological environment and the harm of human health (Galiulin et al. 2002, Peng 2010, Zhou et al. 2019).
The remediation technologies for PAHs-contaminated soil mainly include physical remediation, bioremediation and chemical remediation. Among them, chemical oxidation remediation is more commonly used, which uses the strong oxidizing property of oxidants to destroy the structure of pollutants and transform them into non-toxic and harmless substances. The most common oxidants are H2O2, permanganate, Fenton's reagent, and persulfate(Watts &Teel 2006). The unstability of H2O2 leads to its insufficient contact with contaminants and reduce the degradation efficiency. Fenton reagent has been shown to produce free radicals only under the catalysis of Fe2+ -chelator, and its degradation effect on PAHs in soil is still lower than that of Na2S2O8(Chen et al. 2019). In the traditional Fenton system, iron participates in the reaction as a reactant rather than a catalyst, therefore it cannot be recycled. Continuous addition is required to maintain the continue of reaction, while the reaction process takes place under strong acid conditions(pH < 3), so the cost will increase(Zepp et al. 1992).
Persulfate are promising soil remediation technologies(Dong et al. 2021, Khajeh et al. 2021, Mustapha et al. 2021). persulfate is more stable, easy to transfer and has a wide range of pH applications than hydrogen peroxide under normal conditions. In practical applications, persulfate is often activated in different ways to improve the degradation efficiency of organic pollutants(Huang et al. 2021). Its degradation efficiency is mainly affected by temperature, pH, water-soil ratio and other factors.
In terms of temperature, thermal activation is a relatively well-studied and mature method to activate persulfate, which is mainly used for in situ chemical oxidation remediation of groundwater or soil, degradation of water pollutants(organic substances, inorganic substances) and so on. When activated, S2O82− breaks -O-O- to produce SO4−·under heating (Chen et al. 2016, Yang et al. 2011). During the study, it was found that the degradation speed and degradation rate of contaminants were different at different temperatures and followed a first-order reaction kinetic model when persulfate was in excess (Zhang et al. 2015). Increasing the temperature and the concentration of persulfate can significantly increase the removal rate of PCA. However, it is not the temperature increase, the greater the degradation rate of pollutants, it´s have a suitable temperature(Chen et al. 2014a, Hori 2008, Hori &Osawa 1987, Hori H 2006, Huang et al. 2005). Therefore, in the process of thermal activation of persulfate, attention must be paid to the choice of temperature, not necessarily the higher the better.
About the pH, the typical study is alkali-activated persulfate(García-Cervilla et al. 2020), the mechanism is that persulfate(S2O82−) is catalytically hydrolyzed to peroxymonosulfate(SO52−) and sulfate(SO42−). S2O82− formed a complex with hydroxide thus weakening the S-O bond. Subsequently, the S-O bond fission occurs, and the remaining S-O bond in SO52− fission similarly to form SO42− and HO2− (Furman et al. 2010). Persulfate is hydrolyzed in a process activated by base to produce HO2−, which reduces another S2O82− to produce SO·- 4and SO2- 4, while HO2− is oxidized to superoxide(O.- 2). The total reaction of persulfate activated under alkaline conditions is:
Some researchers have found that alkaline conditions could effectively activate PMS, thus greatly promoting the reaction process(Ge et al. 2017). When persulfate is activated, SO4− · mainly exists in the solution at pH around 2 to 7; while when the pH of the solution is > 10, OH·(Liang et al. 2008) is the main oxide species for the degradation of the solution(Liang et al. 2008).
In the part of the ratio of sustained-release materials(water-soil ratio, water-sand ratio, etc.), some researchers use water, sand and cement to prepare persulfate sustained-release material matrix materials within a certain adaptation range, which can effectively achieve the sustained-release of persulfate, while increasing the content of persulfate in sustained-release materials can improve the release rate of materials and prolong the service life of materials(Chen et al. 2014b). In addition, the sustained release effect of sodium persulfate is significantly different under different ratios of sodium persulfate, cement, sand and water, and the material can release persulfate persistently and stably when sodium persulfate: cement: sand: water = 1:1.4:0.24:0.7(Tsitonaki et al. 2010).
In recent years, persulfate advanced oxidation technology has developed rapidly, and has made great progress in practical engineering and scientific research. It can be well applied to the remediation of soil and groundwater, but there will also be certain problems in the repair process. Persulfate in the oxidation process may cause changes in the physical and chemical properties of soil and groundwater, affect the activity of enzymes in soil and microbial communities, and will retain a large number of H + and SO42− in soil, while residual persulfate in soil will cause soil salinization. In order to achieve good remediation, a large amount of persulfate is often added, which not only increases the cost of the agent, but also causes pollution of groundwater by residual SO42 − and causes a decrease in pH (Besha et al. 2018).
Previous studies have mostly focused on the degradation efficiency of pollutants. In this study, on the basis of how to select the appropriate reaction parameters, fully consider the possible effects of each factor, optimize various parameters, so that the persulfate oxidation system achieves the optimal effect, observe the changes of soil in the remediation process, explore the changes of soil structure, organic matter content, pH, etc. Comprehensively analyze the remediation effect, provide an economical, environmentally friendly, and efficient technical reference for the removal of target pollutants.
3.1 Experimental materials and instruments
The phenanthrene(C14H10) selected for this experiment was purchased from Bailingwei Technology Co., Ltd., with a purity of 95%. The surfactant was an anionic surfactant: sodium dodecyl diphenyl ether disulfonate(C12-MADS), with a purity of analytical pure, and was purchased from Guangzhou Wengjiang Chemical Reagent Co., Ltd. N-Hexane and acetone were purchased from Aladdin, with purity of chromatographically pure; calcium chloride(CaCl2), ferrous sulfate(FeSO4), sodium hydroxide(NaOH), sodium bicarbonate(NaHCO3), sodium chloride(NaCl) and ceric ammonium sulfate standard solution for titration(NH4)4Ce(SO4)4) were purchased from China National Pharmaceutical Group Corporation, with purity of analytically pure.Sstructure and properties of C14H10 and C24H32O7S2Na2 was showed at Table 1& Fig. 1. The experimental instruments were showed at Table 2.
|
Reagent |
Molecular formula |
Molar Mass(g/mol) |
CMC(mmol/L) |
log Kow |
|---|---|---|---|---|
|
Phenanthrene |
C14H10 |
202.3 |
- |
4.88 |
|
Sodium Dodecyl Diphenyl Ether Disulfonate |
C24H32O7S2Na2 |
542 |
0.692 |
- |
|
Name |
Model |
Manufacturer |
|---|---|---|
|
Electronic analytical balance |
AL204 |
METTLEL |
|
Desktop high-speed refrigerated centrifuge |
2-16KL |
Shanghai Sigma |
|
Potentiometric Titrator |
ZDJ-4A |
INESA |
|
pH meter |
PHs-25 |
INESA |
|
Thermostatic shaker |
BSD-WX(F)1350 |
Boxun |
|
Gas chromatography mass spectrometry |
GCMS-QP2010NC Ultra |
Shimadzu Japan |
3.2 Experimental Methods
3.2.1 Preparation of phenanthrene contaminated soil
The soil used in the experiment was red loam with collection depths ranging from 10 to 20cm. Soil pH was 6.89, organic matter content was 2.911%, and cation exchange capacity was 24.67 mol/kg. The collected soil was naturally air-dried, ground and stored through a 100-mesh sieve. A certain amount of phenanthrene standard sample(95%) was weighed and dissolved in acetone, and contaminated soil samples with phenanthrene concentration of 100 mg/kg were prepared using acetone solution and placed in a fume hood for air drying for 60 days.
3.2.2 Experiments under different environmental variables
According to previous studies, the combination of sodium dodecyl diphenyl ether disulfonate(C12-MADS) and heat-activated persulfate can not only significantly improve the oxidation of PAHs and improve the utilization efficiency of oxidants, but also stabilize persulfate at both ambient temperature and high temperature(Wang et al. 2017). At the same time, it was found that the repair effect was better when the concentration of Na2S2O8 was 2.5×104 mg/L and the concentration of C12-MADS was 5×103 mg/L. Therefore, in this experiment, the concentrations of Na2S2O8 and C12-MADS were set as 2.5×104 mg/L and 5×103 mg/L, respectively. Other experimental conditions were set as follows:
- Experiment on the effect of temperature on the oxidative degradation of phenanthrene: The temperature was set at 25, 40, 60, and 80°C, 1g of soil was weighed and placed in a 40 mL Teflon bottle, and 20 mL of C12-MADS solution containing 5×103 mg/L was added at room temperature, respectively, and three parallel groups were set for each group, and three blank controls were set. Put the sample bottle in a constant temperature oscillator at 150 rpm(perform oscillation), at 25, 40, 60 and 80℃, respectively.
- Experiments on the effect of water-soil ratio: Water-soil ratio was set at1:1, 5:1, 10:1, 20:1, and 30:1. One gram of soil was weighed into a 40 mL Teflon bottle, and 1 mL, 5 mL, 10 mL, 20 mL, and 30 mL of solution containing 2.5×104 mg/L Na2S2O8 and 5×103 mg/L C12-MADS were added, respectively, and three groups of parallel were set for each group. Place the sample bottle in a constant temperature shaker at 150 rpm and respectively shake at 60℃. Samples were removed at designated intervals(1, 4, 8, 12, 16 h).
- Effect of pH on oxidative degradation of phenanthrene: The pH was set to 6, 7, and 8. All solutions were prepared with 0.1 mol/L phosphate buffer, and the pH value of the solution changed by less than 0.3 during the reaction. One gram of soil was weighed and put into a 40 mL Teflon bottle, and 20 mL of solution containing 2.5×104 mg/L Na2S2O8 and 5×103 mg/L C12-MADS was added, respectively, three groups of parallel were set up for each group. Place the sample bottle in a constant temperature shaker(150 rpm), and respectively shake it at 60℃. Samples were removed at designated intervals(1, 4, 8, 12, 16 h).
3.2.3 Effects of remediation process on soil
Weighed 1 g of soil into a 40 mL Teflon bottle, add 20 mL of solution containing 2.5×104 mg/L Na2S2O8 and 5×103 mg/L C12-MADS, respectively, each group has three parallel groups, and add only 20 mL of deionized water as the control sample. Place the sample bottle in a constant temperature shaker, and shake it at 150 rpm and 60℃. Samples were removed at designated intervals(1, 4, 8, 12, 16 h). Changes in soil physicochemical properties were measured before and after the reaction and in the group without added solution, include cation exchange capacity, organic matter content, pH.
3.2.4 Analytical Procedures
The determination of phenanthrene in soil was performed by gas chromatography mass spectrometry(GCMS-QP2010Ultra) with an ion source as the EI source, a column of HP-5MS(30m×0.25mm×0.25µm), a carrier gas of high-purity helium, splitless sampling, and a column flow rate of 1.2mL/min. Temperature program of column oven: initial column temperature: 60℃, keep for 1min, 20℃/min; then heat up to 290℃ at the rate of 10℃/min, keep for 10min.
4.1 Effect of different environmental variables
a.The effect of different temperatures on the oxidative degradation of phenanthrene. The Fig. 2 showed that the oxidative degradation of phenanthrene was greatly affected by temperature, the higher the temperature, the higher the degradation efficiency of phenanthrene. When the reaction time was 16h, the degradation efficiencies of phenanthrene at 25, 40, 60, and 80°C were 33.31%, 71.33%, 89.80%, and 94.08% respectively. When the temperature was 25℃, the degradation effect of phenanthrene is not obvious. When the temperature was increased to 40℃, the degradation effect of phenanthrene was significantly increased. When the temperature is further increased to 60℃, phenanthrene begins to be rapidly oxidized and degraded. However, when the temperature was increased to 80°C, the degradation efficiency of phenanthrene did not increase significantly, and there was no obvious difference compared with 60°C(p > 0.05). The residual amount of Na2S2O8 was 23.97×103mg/L at 25°C, 15.77×103mg/L at 40°C, 10.64×103mg/L at 60°C, and 2.95×103mg/L at 80°C. When the reaction temperature increased from 60°C to 80°C, the reaction efficiency of the oxidation system decreased from 52.77–36.01%(the reaction efficiency was the ratio of phenanthrene degradation in the oxidation system to sodium persulfate decomposition).Therefore, the excessive reaction temperature will have a negative impact on the Na2S2O8 oxidation system, and the reaction efficiency of the oxidation system will decrease when the consumption of reaction raw materials was significantly increased.
In the system of phenanthrene degradation by oxidation of thermally activated Na2S2O8, it is due to the generation of SO4−· by Na2S2O8 at a certain temperature, not due to the oxidation of Na2S2O8. However, at 25°C, the content of phenanthrene in the soil was reduced because of the solubilization of C12-MADS, which dissolved phenanthrene in the soil into the aqueous phase. When the temperature was low, Na2S2O8 cannot be activated and SO4−· was not generated. The excessive temperature can cause the waste of resources and have limitations in practical applications. Therefore, it is very important to select the appropriate temperature for phenanthrene degradation by thermally activated Na2S2O8. The experimental results showed that 60°C was the optimal temperature for activation. Meanwhile, with the increase of reaction time, the oxidation degradation efficiency of phenanthrene increased and then gradually tended to be flat.
The experimental data were fitted according to the quasi-first-order kinetic equation(Eq. (2)), in which Ci and C0 are the concentration(mg/L) of phenanthrene in the oxidation system at time t and time zero of the reaction, respectively, and k is the kinetic constant(h− 1) of the quasi-first-order reaction. The quasi-first-order reaction kinetic constant k of phenanthrene at different temperatures can be obtained, and the results are shown in Table 3. It can be seen from the table that the quasi-first-order reaction kinetic equation can well describe the phenanthrene oxidation process in soil at different temperatures, and the k also gradually increases with the growth of temperature(Fig. 3), which indicates that the better the thermal activation of sodium persulfate to degrade phenanthrene.
|
Temperature |
k(h− 1) |
R2 |
Ea(kJ/mol) |
|---|---|---|---|
|
25℃ |
0.0558 |
0.9805 |
|
|
40℃ |
0.0868 |
0.9867 |
|
|
60℃ |
0.1271 |
0.9801 |
|
|
80℃ |
0.1719 |
0.9809 |
The activation energy of the phenanthrene oxidation process of Na2S2O8 can be calculated by using the Arrhenius equation(Eq. (3)) through the temperature and quasi-first-order reaction kinetic constant k.
A is the pre-exponential factor(frequency factor), Ea is the activation energy of the reaction(J/mol), R is the molar gas constant(8.341J/K mol), and T is the thermodynamic temperature(K).
According to the Arrhenius equation, the apparent reaction rate k at different temperatures is fitted with the reaction temperature of the system, and it is found that lnk is linear with 1/T, as shown in Fig. 4. The activation energy Ea was 117.77 kJ/mol(R2 = 0.9947). The activation energy Ea obtained in this p aper is similar to obtained by Ghauch and other researchers(Ghauch &Tuqan 2012) at 40°C ~ 70°C when Bisoprolol(bisoprolol) is oxidized by heat-activated persulfate =(119.8 ± 10.8) kJ/mol.
b. The effect of different water-soil ratios on the oxidative degradation of phenanthrene. Figure 5 showed that the removal efficiency of phenanthrene under different water-soil ratios at a Na2S2O8 concentration of 2.5×104 mg/L and at temperature of 60°C. When the mass ratio(water-soil ratio) of deionized water to phenanthrene contaminated soil ranged from 5:1 to 20:1, the phenanthrene removal efficiency gradually increased with the growth of water-soil ratio. But the water-soil ratio increased to 30:1, the phenanthrene removal efficiency no longer continued to increase. The reaction was 16h, it could be seen that the phenanthrene removal efficiencies were 68.95%(5:1), 74.60%(10:1), 89.80%(20:1), and 90.01%(30:1) under different water-soil ratios, and when the water-soil ratio increased from 20:1 to 30:1, the phenanthrene removal efficiency increased by only 0.21% when the water-soil ratio increased from 20:1 to 30:1. This showed that with the increase of the mass ratio of water and phenanthrene polluted soil in the system, the mass of Na2S2O8 involved in the reaction also increases, the water and soil mixing was more uniform, and the oxidative degradation efficiency of phenanthrene in the soil also went up.
Table 4 showed the kinetic parameters of phenanthrene oxidation process under different water-soil ratios. It can be seen that with the increase of water-soil ratio, the quasi-first-order reaction kinetic constant k also increases. From the k value, it can also be seen that when the water-soil ratio increases from 5:1 to 20:1, the reaction rate was significantly increased, and the oxidation degradation effect of phenanthrene was also increased, which was because the water-soil mixture was uniform, and the SO4− · in the system had sufficient contact with phenanthrene in the soil, which leads to the increase of k.
|
Water-soil ratio |
Quasi-first-order reaction kinetic constant k(h− 1) |
R2 |
|
|---|---|---|---|
|
5: 1 |
0.0731 |
0.9903 |
|
|
10: 1 |
0.0856 |
0.9942 |
|
|
20: 1 |
0.1427 |
0.9933 |
|
|
30: 1 |
0.1440 |
0.9919 |
|
c. Effect of different pH on oxidative degradation of phenanthrene. The effect of different pH on the oxidative degradation of phenanthrene was investigated at a system temperature of 60°C, Na2S2O8 concentration of 2.5×104mg/L, and C12-MADS concentration of 5×103 mg/L. The results in Fig. 6 shows that when the pH was 6–8, the removal efficiency of phenanthrene decreased from 89.80–31.64% at 16 h with the increase of pH. The results illustrate that the higher pH of the system was more unfavorable to the oxidative degradation of Na2S2O8. Thus, alkaline conditions are not conducive to the oxidative degradation of phenanthrene, because alkaline conditions SO4−· will produce OH ·(Eq. (4)) with OH− in solution (Furman et al. 2010), and these two free radicals will react with each other(Eq. (5)), thereby reducing the removal efficiency of phenanthrene. Under acidic conditions, it is conducive to the decomposition of Na2S2O8 to play a catalytic role, and the lower the pH of the system, the easier it is to decompose Na2S2O8 to produce SO4−· under heating conditions. Zeng and other researchers(Zeng et al. 2018) found that the decolorization rate of methyl violet decrease with the increase of pH in the study of oxidation of methyl violet by heat-activated sodium persulfate.
Without adjusting the pH, the pH in the system was 3.7, and the pH decreased to 1.8 as the reaction progressed, which maybe caused by the production of some acidic substances and H + in the system. The degradation efficiency of phenanthrene in the system without pH adjustment was significantly higher than that in the system with buffer solution. The oxidation efficiency of SO4−· is reduced because PO3 − 4competes with phenanthrene production in the SO·− 4reaction and system. At the same time, due to the low pH of the system without pH adjustment, it is beneficial to promote the decomposition of Na2S2O8 to produce SO4−·(Deng et al. 2013).
4.2 Effect of Sodium Persulfate on Soil in Oxidative Degradation of Phenanthrene
The effects on soil during phenanthrene oxidation by sodium persulfate were shown in Fig. 7, Fig. 8, and Fig. 9. It can be seen from Fig. 8 that the pH of the soil gradually decreases with the progress of the oxidation reaction. In the process of phenanthrene oxidation with sodium persulfate, the pH decreased rapidly within 1 hour after reaction, and decreased slowly at the later stage, from pH = 6.89 to pH = 2.95, while the pH of the control group changed relatively little before and after reaction. Since Na2S2O8 would react with water to generate a large amount of H + after dissolving in water,SO4−· would be produced in the activation process, and some S2O2- 8 would remain in the soil after reaction, thus resulting in that the soil system was acidic.
Soil organic matter is an important component of soil solid phase. Although organic matter is a small part of the whole soil, it has a great impact on soil formation and soil fertility, and is also of great significance for environmental protection and sustainable agricultural and forestry development. It can be seen from the results in Fig. 8, with the progress of oxidation reaction, the content of organic matter in the soil gradually decreases. Since Na2S2O8 will not only react with phenanthrene in the soil during the oxidative degradation process, but also consume the organic matter in the soil (Di et al. 2018) .
The cation exchange capacity of the original soil was 24.67mol/kg, which decreased to 16.82 mol/kg after adding 20 mL deionized water and heating at 60°C for 1 h. The cation exchange capacity in the soil changed to 0.92 mol/kg after 16 h of reaction after adding C12-MADS and Na2S2O8. The cation exchange capacity will change with the change of soil pH and the pH of soil will directly affect the dissociation of H + in the functional groups on the colloidal surface, thus affecting the amount of variable charge, the lower the pH of soil, the lower its cation exchange capacity. At the same time, with the increase of temperature, the H+ content in the solution increases, the negative charge on the surface of soil colloidal particles decreases, and their cation exchange capacity also decreases. The amount of organic matter content will also have an effect on the size of cation exchange capacity in the soil, which is because the humus in the organic matter contains a large number of functional groups such as -COOH and -OH. When they decompose H+, they will bring the negative charge to the surface of soil colloids. Also, due to the large dispersion of humus and a large number of absorption surfaces, the cation exchange capacity of the soil with high organic matter content is also higher than that of the soil with low organic matter content.
The above results showed that in the process of enhancing Na2S2O8 phenanthrene oxide by surfactants would affect the soil, cause the destruction of soil structure to a certain extent, and acidify the soil. The decrease of organic matter content would also have a negative impact on soil fertility and affect the soil´s function. At the same time, the existence of soil organic matter also led to the increase of oxidant dosage, which increased the cost of remediation.
Surfactant enhanced Na2S2O8 oxidation system can effectively degrade phenanthrene in soil. When the temperature was 60℃, the water-soil ratio was 20:1, and the solution was slightly acidic,the utilization rate of Na2S2O8 was the highest and the overall degradation efficiency of the oxidation system was the highest, which will not cause less waste and reduce the difficulty of practical operation. But at the same time, the remediation process was also caused damage to the soil.
1. The degradation of phenanthrene in soil was affected by reaction temperature, soil water ratio, pH, etc. A. The degradation of phenanthrene was greatly affected by temperature. The degradation efficiency of phenanthrene in soil by thermal activation conforms to the quasi first-order reaction kinetics. In a certain range, the degradation efficiency of phenanthrene increased with the rose of temperature, but the high reaction temperature had a negative effect on the oxidation system of Na2S2O8;
B. In the range of experimental conditions, the higher the ratio of water to soil in the Na2S2O8 oxidation system, the better the oxidation degradation effect of phenanthrene; C. The pH of the solution had an important influence on the oxidation degradation of phenanthrene by Na2S2O8. Under alkaline conditions, SO4−· and OH− in the solution produce OH·, which leads to the obvious reduction of the oxidation degradation efficiency of phenanthrene.
2. In the process of oxidation of phenanthrene with Na2S2O8, soil structure was destroyed, caused acidification, and reduced the content of organic matter, which also had a negative impact on soil fertility and subsequent soil use function. Therefore, in the evaluation of the effect of a remediation technology, the removal efficiency of the target pollutants can not be used as the only evaluation index. We should also consider the comprehensive utilization of the soil after remediation and the environmental pollution, and choose the environment-friendly remediation method.
Author Contributions
All authors contributed to the study conception and design. The first draft of the manuscript was written by Yanjie Zhao, Siying Hou, Yirong Deng. Experiment design, Material preparation, data collection and analysis were performed by Haijian Lu, Zaoquan Hunag, Qusheng Li, and Zhaohui Li. All authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.
Funding
This work was supported by National Key Research and Development Program of China(Grant number: 2018YFC1800205, 2018YFC1800806), the Major Projects of Fundamental and Applied Basic Research in Guangdong Province(Grant number: 2019B030302013), Special Fund Project for Science and Technology Innovation Strategy of Guangdong Province(Grant number: 2019B121205004), the National Natural Science Foundation of China(Grant number: U1911202) and State Key Laboratory of Organic Geochemistry, GIGCAS(Grant number: SKLOG-201618).
Ethical Approval and Consent to Participate
Not applicable
Consent to Publish
Not applicable
Competing Interests
The authors declare that they have no competing interests.
Availability of data and materials
The datasets used or analysed during the current study are available from the corresponding author on reasonable request.
- Besha AT, Bekele DN, Naidu R, Chadalavada S (2018) Recent advances in surfactant-enhanced In-Situ Chemical Oxidation for the remediation of non-aqueous phase liquid contaminated soils and aquifers. Environ Technol Innov 9:303–322
- Chan W, Jin L, Sun Z, Griffith S, Yu J (2021) Fabric Masks as a Personal Dosimeter for Quantifying Exposure to Airborne Polycyclic Aromatic Hydrocarbons. Environ Sci Technol 55:5128–5135
- Chen CC, Huang KC, Lee CC (2014a) : A comparison of the reduction efficiency of indoor formaldehyde and VOCs concentration by using ventilation removal and SBMS. Indoor Air 2014–13th International Conference on Indoor Air Quality and Climate, 23–30
- Chen FY, Yang Y, Lian XY, Jiang YH, Bei-Dou XI, Ding-Long LI, Zhang JB, Zhi-Fei MA (2014b) Influence factors of the release properties of the slow-release persulfate material. China Environ Sci 34:1187–1193
- Chen Q, Cai W, Chen J, Zhao HB, Chang-Xin LI, Yun-Feng HE (2019) Degradation effects of different chemical oxidants on polycyclic aromatic hydrocarbons in soil. J Zhejiang Univ (Engineering Science) 53:2437–2444
- Chen XQ, Murugananthan M, Zhang Y (2016) : Degradation of p-Nitrophenol by thermally activated persulfate in soil system.Chemical Engineering Journal,1357–1365
- Deng J, Shao Y, Gao N, Deng Y, Zhou S, Hu X (2013) Thermally activated persulfate (TAP) oxidation of antiepileptic drug carbamazepine in water. Chem Eng J 228:765–771
- Di S, Zhang C, Yan Z, Bai L, Zhou Y, Wang X, Li F (2018) Oxidative Degradation Effect of Sodium Persulfate on Polycyclic Aromatic Hydrocarbons in Typical Chinese Soils. Res Environ Sci 31:95–101
- Ding J, Zhang Y, Lu S, Zhang X, Li Y, Zhong Y, Zhang H (2021) A novel strategy using persulfate activated with thiosulfate for strong enhancement of trace 2,2′-dichlorobiphenyl removal: Influencing factors, and mechanisms. Chem Eng J 415:128969
- Dong X, Yang X, Hua S, Wang Z, Cai T, Jiang C (2021) Unraveling the mechanisms for persulfate-based remediation of triphenyl phosphate-contaminated soils: Complicated soil constituent effects on the formation and propagation of reactive oxygen species. Chem Eng J 426:130662
- Furman OS, Teel AL, Watts RJ (2010) Mechanism of Base Activation of Persulfate. Environ Sci Technol 44:6423–6428
- Galiulin RV, Bashkin VN, Galiulina RA (2002) Review: Behavior of Persistent Organic Pollutants in the Air-Plant-Soil System. Water Air Soil Pollut 137:179–191
- García-Cervilla R, Santos A, Romero A, Lorenzo D (2020) Remediation of soil contaminated by lindane wastes using alkaline activated persulfate: Kinetic model. Chem Eng J 393:124646
- Ge YJ, Cai XW, Han L, Xu MY, Shen YT (2017) Base Activation of Peroxymonosulfate for the Degradation of Ciprofloxacin in Water. Huanjing Kexue 38:5116–5123
- Ghauch A, Tuqan AM (2012) Oxidation of bisoprolol in heated persulfate/H2O systems: Kinetics and products. Chem Eng J 183:162–171
- Hori H, Osawa S (1987) Origin and evolution of organisms as deduced from 5S ribosomal RNA sequences. Mol Biol Evol 4:445–472
- Hori H (2008) Development of Decomposition Techniques for PFOS, PFOA and Related Chemicals. Environ Conserv Eng 37:320–325
- Hori HYA, Kutsuna S, Yosui to Haisui (2006) Persulfate-induced photochemical decomposition of perfluoroctanoic acid (PFOA) and its related chemicals in water. Yosui to Haisui 48:1081–1087
- Huang K-C, Zhao Z, Hoag GE, Dahmani A, Block PA (2005) Degradation of volatile organic compounds with thermally activated persulfate oxidation. Chemosphere 61:551–560
- Huang W, Sa X, Zhong H, Yan M, Yang X (2021) Activation of persulfate by carbonaceous materials: A review. Chem Eng J 418:129297
- Kan H, Wu D, Wang T, Qu G, Zhang P, Jia H, Sun H (2021) Crystallographic manganese oxides enhanced pyrene contaminated soil remediation in microwave activated persulfate system. Chem Eng J 417:127916
- Khajeh M, Amin M, Fatehizadeh A, Aminabhavi T (2021) Synergetic degradation of atenolol by hydrodynamic cavitation coupled with sodium persulfate as zero-waste discharge process: Effect of coexisting anions. Chem Eng J 416:129163
- Lau EV, Gan S, Ng HK, Poh PE (2014) Extraction agents for the removal of polycyclic aromatic hydrocarbons (PAHs) from soil in soil washing technologies. Environ Pollut 184:640–649
- Li CP, Chen MF, Luo YM, Song J, Chun-Fa WU, Luo F, Wei J (2011) Contaminants of Concern and Adverse Environmental Impact for Key Industries. Adm Technique Environ Monit 23:7–13
- Liang C, Huang CF, Chen YJ (2008) Potential for activated persulfate degradation of BTEX contamination. Water Res 42:4091–4100
- Luo Z, Min Y, Qu L, Song Y, Hong Y (2020) Remediation of phenanthrene contaminated soil by ferrous oxalate and its phytotoxicity evaluation. Chemosphere 265:129070
- Mustapha NA, Liu H, Ibrahim AO, Huang Y, Liu S (2021) Degradation of aniline in groundwater by persulfate with natural subsurface sediment as the activator. Chem Eng J 417:128078
- Oleszczuk P, Rakowska M, Bucheli TD, Godlewska P, Reible DD (2019) Combined Effects of Plant Cultivation and Sorbing Carbon Amendments on Freely Dissolved PAHs in Contaminated Soil. Environ Sci Technol 53:4860–4868
- Peluffo M, Mora VC, Morelli IS, Rosso JA (2018) Persulfate treatments of phenanthrene-contaminated soil: Effect of the application parameters. Geoderma 317:8–14
- Peng S (2010) Migration behavior of environmental pollutants in soil medium. Chong Qing University, p 82
- Peters M et al (2019) Climate–land-use interactions shape tropical mountain biodiversity and ecosystem functions. Nature 568:1–5
- Song C, Tan W (2015) THE HISTORICAL VENATION OF SOIL SCIENCE IN THE PAST 30 YEARS—BASED ON THE BIBLIOMETRIC ANALYSIS. Acta Pedol Sin 52:957–969
- Tsitonaki A, Petri B, Crimi M, Mosb?K H, Siegrist RL, Bjerg PL (2010) In Situ Chemical Oxidation of Contaminated Soil and Groundwater Using Persulfate. Crit Reviews Environ Sci Technol 40:55–91
- Wang J, Luo Z, Song Y, Zheng X, Qu L, Qian J, Wu Y, Wu X, Wu Z (2019) Remediation of phenanthrene contaminated soil by g-C3N4/Fe3O4 composites and its phytotoxicity evaluation. Chemosphere 221:554–562
- Wang L, Peng L, Xie L, Deng P, Deng D (2017) Compatibility of Surfactants and Thermally Activated Persulfate for Enhanced Subsurface Remediation. Environ Sci Technol 51:7055–7064
- Watts R, Teel A (2006) Treatment of Contaminated Soils and Groundwater Using ISCO. Practice Periodical of Hazardous. Toxic and Radioactive Waste Management 10:7–9
- Yang S, Yang X, Shao X, Niu R, Wang L (2011) : Activated carbon catalyzed persulfate oxidation of Azo dye acid orange 7 at ambient temperature. Journal of hazardous materials 186, 659 – 66
- Ye M (2012) REVIEW OF REMEDIATION OF POPs CONTAMINATED SITES WITH SOIL WASHING METHOD. Acta Pedol Sin 49:803–814
- Zeng XL, Tang HL, Zhang Y, Luo WS, Zhang YL, Ding WC (2018) STUDY ON OXIDIZING METHYL VIOLET BY HEAT ACTIVATED SODIUM PERSULFATE. Environ Eng 36:54–57
- Zepp RG, Faust BC, Hoigne J (1992) Hydroxyl radical formation in aqueous reactions (pH 3–8) of iron(II) with hydrogen peroxide: the photo-Fenton reaction. Environ Sci Technol 26:313–319
- Zhang Y, Tran HP, Hussain I, Zhong Y, Huang S (2015) Degradation of p-chloroaniline by pyrite in aqueous solutions. Chem Eng J 279:396–401
- Zhou Z, Liu X, Sun K, Lin C, Ma J, He M, Ouyang W (2019) Persulfate-based advanced oxidation processes (AOPs) for organic-contaminated soil remediation: A review. Chem Eng J 372:836–851
