利用富里酸原位制备富集铁修复石油污染土壤研究

Study on Remediation of Oil-Contaminated Soil by in-situ Preparation of Aggregated Iron Using Fulvic Acid

  • 摘要: 为得到一种高效去除土壤中总石油烃(TPH)的原氧化技术,利用富里酸(FA)在土壤中原位制备富集铁并进行石油污染土壤修复研究,探究了富集铁组和非富集铁组对不同质地和有机质(SOM)含量的石油污染土壤(S1、S2)氧化效果的影响,以及富集铁组高效原位氧化TPH的机制. 结果表明:①在S1、S2石油污染土壤(土壤S1、S2中TPH的初始含量分别为16 074.33、14 528.17 mg/kg)中,富集铁组中TPH的氧化量分别高达7 550.32、8 747.78 mg/kg,均高于非富集铁组Ⅰ中的相应值(分别为6 364.43、5 730.73 mg/kg),说明富集铁组可以高效氧化土壤中的TPH. ②在土壤S1、S2中,富集铁组对中链(C19~C24)烷烃的氧化率分别为20%、22%,对长链(C25~C30)烷烃的氧化率分别为23%、20%,分别高于土壤S1中非富集铁组Ⅰ(17%、18%)和土壤S2中非富集铁组Ⅰ(19%、12%)的相应值. ③电子顺磁共振波谱仪(EPR)测定结果表明,富集铁组中羟基自由基(·OH)强度(S1,36.61 a.u.;S2,16.06 a.u)高于非富集铁组Ⅰ中相应指标(S1,27.78 a.u.;S2,7.11 a.u.),并且羟基自由基持续时间(S1,50 h;S2,55 h)也高于非富集铁组Ⅰ中相应指标(S1,45 h;S2,40 h). ④XPS测定结果显示,富集铁组中峰面积较高的FeOOH(S1,503.52;S2,850.01)和α-FeOOH(S1,399.40;S2,769.62)提高了·OH的瞬时强度,增加了·OH产量. 而3D-EEM测定结果显示,富集铁组中类富里酸荧光区域标准体积(S1,1 554 047.24 au·nm2;S2,1 110 373.00 au·nm2)明显高于非富集铁组Ⅰ中相应值(S1,1 100 706.21 au·nm2;S2,716 069.98 au·nm2),表明高含量的FA有利于FeOOH和α-FeOOH在土壤中的富集. 研究显示,富集铁组实现了高效催化H2O2氧化土壤中TPH,为原位化学氧化修复石油污染土壤提供了一个经济有效的方法.

     

    Abstract: In order to obtain an in-situ Fenton technique for effective oxidation of total petroleum hydrocarbons (TPH) in soils, the remediation of oil-contaminated soil by in-situ preparation of aggregated iron using fulvic acid (FA) was studied. The study focused on the effects of the aggregated iron groups and non-aggregated iron groups on the oxidation of the two types of oil-contaminated soils (S1, S2) with different textures and soil organic matter (SOM), as well as the mechanism of efficient in-situ oxidation of TPH in the aggregated iron groups. The results showed that: (1) In oil-contaminated S1 and S2 soils (the initial concent of TPH was 16,074.33 mg/kg and 14,528.17 mg/kg in S1 and S2 soils, respectively), the TPH oxidation level was as high as 7,550.32 mg/kg (S1) and 8,747.78 mg/kg (S2) in the aggregated iron group, which were higher than the corresponding values in the non-aggregated iron group Ⅰ (6,364.43 mg/kg, 5,730.73 mg/kg). It indicated that the aggregated iron group could remove TPH efficiently from soils. (2) In the S1 and S2 soils, the oxidation rates of medium-chain alkanes (C19-C24) were up to 20% and 22%, and long-chain (C25-C30) alkanes were 23% and 20% in the aggregated iron group, which were higher than the oxidation rates of non-aggregated iron group Ⅰ in S1 soil (17%, 18%) and S2 soil (19%, 12%), respectively. (3) Electron paramagnetic resonance (EPR) technology showed that the intensity of hydroxyl radicals (·OH) in the aggregated iron group (S1, 36.61 a.u; S2, 16.06 a.u.) was higher than the corresponding indicators in the non-aggregated iron group Ⅰ (S1, 27.78 a.u.; S2, 7.11 a.u.), and the hydroxyl radical durations (S1, 50 h; S2, 55 h) were also higher than the corresponding indexes in the non-aggregated iron group Ⅰ (S1, 45 h; S2, 40 h). (4) The high contents of FeOOH (S1, 503.52; S2, 850.01) and α-FeOOH (S1, 399.40; S2, 769.62) measured by XPS increased the instantaneous strength and yield of ·OH in the aggregated iron group. The 3DEEM results confirmed that the standard volume of the fluorescence region of fulvic acid in the aggregated iron group (S1, 1,554,047.24 au·nm2; S2, 1,110,373.00 au·nm2) was significantly higher than the corresponding values in the non-aggregated iron group (S1, 1,100,706.21 au·nm2; S2, 716,069.98 au·nm2), indicating that high FA content is beneficial for the aggregation of FeOOH and α-FeOOH in soils. Our study indicated that the aggregated iron group effectively catalyzed the removal of TPH from soils by H2O2, providing an economical and effective method for in-situ chemical oxidation remediation of oil-contaminated soil.

     

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