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Risk Management of TNT/Heavy Metals in Active Firing Ranges by Mobility Control Using MKP/Bentonite
제일인산칼륨과 벤토나이트의 TNT/중금속 이동제어 작용을 이용한 운영 중 사격장 위해도 관리

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dc.contributor.advisor남경필-
dc.contributor.author정재웅-
dc.date.accessioned2017-07-13T06:37:43Z-
dc.date.available2017-07-13T06:37:43Z-
dc.date.issued2014-02-
dc.identifier.other000000017608-
dc.identifier.urihttp://hdl.handle.net/10371/118691-
dc.description학위논문 (박사)-- 서울대학교 대학원 : 건설환경공학부, 2014. 2. 남경필.-
dc.description.abstracthowever, the leachable fraction decreased to 10% of initial TNT when bentonite was also amended with MKP. When the amount of bentonite was higher than 10% of initial TNT, the increase in the amended amount of bentonite did not reduce the leachability of TNT, indicating that MKP and bentonite application at 5% and 10% of soil mass is the optimal condition for the minimizing the mobility of TNT.
At last, the risk reduction for the nearby residents of Darakdae firing range through the mobility reduction of TNT and heavy metals was quantified. The nearby residents of Darakdae firing range may use the Hantan River for the extraction of potable (drinking) and showering/bathing water. For the risk evaluation, carcinogenic and noncarcinogenic risk assessments were conducted. Furthermore, because of the great migration of contaminants from the firing range in summer due to the heavy rainfall, a monthly risk evaluation was conducted. The most significant contributors to the carcinogenic risk and noncarcinogenic hazard index were hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), a type of explosive, and TNT, respectively. Even MKP/bentonite application could not reduce the mobility of RDX, the carcinogenic risk was acceptable (< 10-4) regardless of MKP/bentonite treatment and thus the carcinogenic risk to the nearby residents of the firing range was not found to be a significant concern. In contrast, in untreated condition, the noncarcinogenic hazard index was inacceptable (> 1) due to the migration of TNT in February, July and August. However, it was estimated that the noncarcinogenic hazard index could be reduced less than 1 by MKP/bentonite amendment. Thus, it can be concluded that MKP/bentonite application can reduce the risk to the local residents of the firing range by reducing the mobility of contaminants, especially TNT, released from the firing range.
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dc.description.abstractRecently, firing range contamination has become an emerging environmental issue in Korea. The most critical aspect of firing range contamination is the migration of contaminants from firing ranges to nearby surface water and/or groundwater, which is used as a source of drinking water for local residents. The soils at the firing ranges usually contain divalent cationic heavy metals (e.g., Pb2+, Cu2+, Zn2+, and Cd2+) and explosives, released from unexploded ordnances (UXOs) and shells. Of the explosives, 2,4,6-trinitrotoluene (TNT) is a typical concern due to its high toxicity and carcinogenicity. Thus, the mobility control of TNT and the divalent cationic heavy metals is important for the environmental management of the active firing ranges.
It is known that K+ and PO43- can reduce the mobility of TNT and heavy metals via the specific sorption enhancement of TNT to clay mineral surfaces and heavy metals precipitation, respectively. Therefore, theoretically, monopotassium phosphate (MKP, KH2PO4), which contains both K+ and PO43-, can reduce the mobility of both TNT and heavy metals simultaneously and this study identified whether or not MKP can reduce the mobility of both TNT and heavy metals in soils collected from an active firing range, Darakdae firing range, located in Yeoncheon-gun, Gyeonggi Province, Korea.
Mobility control of heavy metals using phosphate has been widely investigated and the lab-scale and field-scale feasibility study of phosphate application has been widely conducted. On the other hand, no studies on the feasibility of potassium application for the mobility control of TNT in soil are available at the present time. The earlier studies on the sorption enhancement of TNT by K+ conducted using K+-saturated soil and have focused on the identification of the specific sorption mechanism only. For this, at first, it was identified that whether or not MKP application can enhance the specific sorption, and which specific sorption mechanism is dominant between n-π electron donor-acceptor (EDA) interaction and cation-polar interaction. In untreated soil, TNT was not specifically sorbed to soil but MKP application induced the specific sorption of TNT, which resulting in the TNT sorption enhancement. Also, it was identified that the mechanism of specific sorption was a cation-polar interaction.
Then, the simultaneous mobility reduction of TNT and heavy metals in soil by MKP application was studied. The mobility reduction was identified through synthetic precipitate leaching procedure (SPLP), and the leachability of TNT and heavy metals were greatly reduced by MKP application. It seems that mobility reduction is due to the sorption enhancement of TNT and heavy metals precipitation. The MKP application increased the sorption coefficient of TNT from 6.6 mg1-n kg-1 Ln to 12.1 mg1-n kg-1 Ln, and Pb, one of the concerned heavy metals in the firing range soil, was precipitated from soil. Finally, the mobility reduction of TNT and heavy metals was further elucidated using cyclodextrin and sequential extraction test, respectively, and both tests results revealed that the extractability of TNT and heavy metals decreased greatly (i.e., mobility of TNT and heavy metals greatly decreased).
This study also investigated the minimizing mobility of TNT by MKP application with bentonite by further enhancement of TNT sorption. The leachable fraction determined by SPLP was about 50% of initial TNT when only MKP was amended with 5% of soil mass (the maximum soluble amount of MKP in porewater when the soil moisture content is the maximum water holding capacity)
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dc.description.tableofcontentsCHAPTER 1. INTRODUCTION 1
1.1 Background 1
1.2 Objectives 5
1.3 Dissertation Structure 6
References 7
CHAPTER 2. LITERATURE REVIEW 12
2.1 Existing Technologies for TNT Treatment in Firing Range Soil 12
2.1.1 Environmental behavior of TNT in firing range soil 12
2.1.2 Existing treatment technologies of TNT in firing range soil 16
2.2 Mechanism of Sorption of TNT onto Clay Mineral Surfaces 21
2.2.1 n-π EDA complexation 21
2.2.2 Cation-polar interaction 28
2.3 Role of Phosphate Ion on the Precipitation of Divalent Cationic Heavy Metals in Soil 34
2.3.1 Formation of heavy metal phosphate 34
2.3.2 Mobility and bioavailability reduction by heavy metal phosphate formation 35
2.3.3 Identification of heavy metal phosphate 40
References 43
CHAPTER 3. SORPTION ENHANCEMENT OF TNT IN SOIL BY MKP APPLICATION 54
3.1 Introduction 54
3.2 Experimental 57
3.2.1 Materials 57
3.2.2 Identification of sorption enhancement of TNT by MKP 59
3.2.3 Sorption test of TNT varying the aqueous Ca2+ concentration 62
3.2.4 Sorption test of TNT varying the aqueous 2,4-DNT or HFB concentration 62
3.2.5 Analysis 63
3.3 Results and Discussion 63
3.3.1 Clay mineralogy of the soil 63
3.3.2 Sorption enhancement of TNT by MKP 66
3.3.3 Role of Ca2+ in TNT sorption 69
3.3.4 Competitive sorption of TNT with HFB or 2,4-DNT 70
3.4 Summary 73
References 74
CHAPTER 4. DUAL MODE EFFECT OF MKP IN TNT SORPTION ENHANCEMENT AND HEAVY METALS PRECIPITATION 80
4.1 Introduction 80
4.2 Experimental 82
4.2.1 Materials 82
4.2.2 Simultaneous TNT sorption enhancement and Pb precipitation by MKP application 83
4.2.3 Quantification of mobility reduction of both TNT and heavy metals by MKP application using leach and extraction tests 86
4.2.4 Analysis 88
4.3 Results and Discussion 89
4.3.1 Simultaneous TNT sorption enhancement and Pb precipitation by MKP application 89
4.3.2 Identification of the type of lead phosphate formed by MKP application 93
4.3.3 Mobility reduction of TNT and heavy metals by MKP application 98
4.4 Summary 107
References 108
CHAPTER 5. MINIMIZING THE MOBILITY OF TNT BY BENTONITE AMENDMENT WITH MKP 113
5.1 Introduction 113
5.2 Experimental 114
5.2.1 Materials 114
5.2.2 Sorption and desorption test of TNT 115
5.2.3 Quantification of mobility reduction of TNT by MKP/bentonite application using leach and extraction tests 116
5.2.4 Analysis 119
5.3 Results and Discussion 119
5.3.1 Sorption enhancement of TNT by MKP/bentonite application 119
5.3.2 Change in the desorptive behavior of TNT by MKP/bentonite amendment 121
5.3.3 Minimizing the mobility of TNT by bentonite amendment with MKP 128
5.4 Summary 131
References 132
CHAPTER 6. RISK EVALUATION OF MKP/BENTONITE TREATMENT SCENARIO 136
6.1 Introduction 136
6.2 Development of the Conceptual Model of the Firing Range 138
6.2.1 Site description and exposure pathway 138
6.2.2 Contaminants concentrations in the Firing Range soil 139
6.2.3 Estimation of contaminants concentrations in the river 144
6.3 Exposure Assessment 155
6.3 Toxicity Assessment 162
6.4 Risk Characterization 164
6.5 Summary 174
References 176
CHAPTER 7. CONCLUSIONS 182
ANNEX A SITE INSPECTION RESULTS OF THE FIRING RANGE 186
ANNEX B STATISTICAL INFORMATION AND DERIVED (1-α)100% UPPER CONFIDENCE LIMIT ON THE MEAN (UCL) OF CONTAMINANTS IN THE FIRING RANGE SOILS 196
ANNEX C THE METEOROLOGICAL VALUES FOR THE DETERMINATION OF THE DEPTH OF SURFACE (DSR) AND GROUNDWATER RUNOFF (DGR) USING SEVIEW SOFTWARE 200
ANNEX D PROCEDURE FOR THE DETERMINATION OF INPUT VALUES ON THE PARAMETERS FOR THE CALCULATION OF INTAKE AND DERMAL ABSORBED DOSE 203
초 록 208
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dc.formatapplication/pdf-
dc.format.extent2509921 bytes-
dc.format.mediumapplication/pdf-
dc.language.isoen-
dc.publisher서울대학교 대학원-
dc.subjectfiring range-
dc.subjectTNT-
dc.subjectheavy metals-
dc.subjectmonopotassium phosphate-
dc.subjectmobility reduction-
dc.subjectrisk evaluation-
dc.subject.ddc624-
dc.titleRisk Management of TNT/Heavy Metals in Active Firing Ranges by Mobility Control Using MKP/Bentonite-
dc.title.alternative제일인산칼륨과 벤토나이트의 TNT/중금속 이동제어 작용을 이용한 운영 중 사격장 위해도 관리-
dc.typeThesis-
dc.contributor.AlternativeAuthorJae-Woong Jung-
dc.description.degreeDoctor-
dc.citation.pagesxvi, 212-
dc.contributor.affiliation공과대학 건설환경공학부-
dc.date.awarded2014-02-
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College of Engineering/Engineering Practice School (공과대학/대학원)Dept. of Civil & Environmental Engineering (건설환경공학부)Theses (Ph.D. / Sc.D._건설환경공학부)
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