過硫酸鹽氧化法結合生物復育法處理受柴油污染土壤之研究

為解決發展過程中因人類工業化活動導致洩漏於土壤中之總石油碳氫化合物(Total Petroleum Hydrocarbon as Diesel, TPH-d)污染，開發具經濟效益、有效且對環境友善的整治工法有其必要性。本研究之主要目的包括：(1) 探討鹼活化過硫酸鹽程序對不同比例催化劑之處理成效；(2) 評估鹼活化過硫酸鹽搭配生物復育法之處理成效；(3) 探討生物復育以及鹼活化過硫酸鹽對不同污染物碳群間降解之差異。研究主軸為運用兩階段整治列車之觀念，在各批次實驗添加不同比例過碳酸鈉當作鹼活化催化劑之過硫酸鹽，以化學氧化搭配生物復育進行某場址受總石油碳氫化合物(主要為柴油)污染之土壤為期70天之整治處理，其所利用之六種條件分別為A組為無添加藥劑之對照組、B組為添加生物製劑、C組為添加10%過硫酸鈉、D組為添加1 : 0.5的過硫酸鈉與過碳酸鈉、E組為添加1 : 1 的過硫酸鈉與過碳酸鈉、F組為化學氧化搭配生物製劑。研究結果顯示，原始污染土壤TPH-d之初始濃度為8,323 mg/kg，第一階段在為期20天反應前期時觀察到，降解試驗中TPH-d降解率為D組＞E組＞C組＞B組，過硫酸鹽消耗率為D組＞C組＞E組，氧化實驗結果顯示，以E組過硫酸鹽消耗率最高而20天後之反應中期各組過硫酸鹽消耗則趨於平緩，第二階段70天時TPH-d降解率依序為E組＞B組＞F組＞D組＞C組，此時過硫酸鹽幾乎完全消耗。整理而言，生物復育法之B組，在第一階段前期對TPH-d降解效果不如施用化學氧化之C、D、E組，但在第二階段後期之TPH-d降解效果上升，優於C、D、F組。在探討各處理手段對碳群的影響時，可以發現，生物復育法B組分析圖譜在C12至C24之碳群有較佳降解效果，而C24至C34之碳群則與化學氧化法無明顯差異，化學氧化法下之C、D、E組降解時碳群變化較無明顯趨勢，顯示化學氧化反應不具選擇性與專一性。本研究成果顯示，以鹼活化過硫酸鹽氧化搭配生物復育法，處理受TPH-d污染之土壤為一可行之整治方式，未來應用於現場整治上各組處理方法皆可單獨進行，亦可以互相搭配加速污染物之移除，本研究之成果將可提供相關受污染場址進行整治之參考。

關鍵字

柴油；過硫酸鹽；現地化學氧化法；整治列車系統；總石油碳氫化合物

並列摘要

In order to address the pollution of total petroleum hydrocarbon as diesel (TPH-d) leaked into the soil due to human activities, it is necessary to develop economical, practical, and environmentally friendly remediation methods. In this study, we (1) discuss the effect of the alkali-activated persulfate procedure on catalysts applied in different ratios, (2) evaluate the feasibility of alkali-activated persulfate combined with biological regeneration, and (3) investigate the differences between bio-regeneration and alkali-activated persulfate on the degradation of different pollutant carbon groups. Using the two-stage remediation of trains concept, different proportions of sodium percarbonate as persulfate were added as an alkali activation catalyst in batch experiments, chemical oxidation then occurred, and biological restoration was finally used to target total petroleum hydrocarbons (mainly diesel) at a certain site. Contaminated soil was treated for 70 days under six conditions: group A was the control group (without any treatment), biological agents were added to group B, 10% sodium persulfate was added to group C, sodium persulfate and sodium percarbonate at a ratio of 1:0.5 were added to group D, sodium persulfate and sodium percarbonate were added at a ratio of 1:1 to group E, and group F went through chemical oxidation with biological agents. The initial concentration of TPH-d was 8,323 mg/kg. The first stage lasted 20 days. The reduction rate order of TPH-d in the degradation test was group D > group E > group C > group B, and the consumption rate order of persulfate was group D > group C > group E. Oxidation test results showed that in the early stage of the reaction, the consumption rate of persulfate was highest in group E. In the middle stage of the reaction, the consumption of persulfate in each group tended to be moderate. The order of the reduction rate of TPH-d within 70 days in the second stage was group E > Group B > group F > group D > group C. The persulfate was almost completely consumed by this time. Experimental results showed that the degradation effect of TPH-d in the first stage of the biological regeneration method in group B was not as good as chemical oxidation in groups C, D, and E, but the degradation effect on TPH-d in the second stageimproved. There were no significant differences with the chemical oxidation method. Degradation of the carbon groups treated with chemical oxidation were average, indicating that the chemical oxidation reaction is not selective and specific, and attacks all organic substances in the environment. The results of this study show that alkali-activated persulfate oxidation combined with biological restoration is a feasible remediation method for treating TPH-d-contaminated soil. In the future, each grouping of treatment methods can be applied individually or mutually in combination for the accelerated removal of contaminants. The results of this study will be helpful in designing practical systems using chemical oxidation coupled with bioremediation to remediate petroleum hydrocarbon-contaminated sites.