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1
2 ｨC
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6 13 ｨC ｨC - ｨC ｨC ｨC - - ｨC ｨC ｨC ｨC ｨC AOP ｨC Advanced Oxidation Processes CFD - Computational Fluid Dynamics DNS - Direct Numerical Simulation EDC - Endocrine Disrupting Compounds ESI - ElectroSpray Ionization IDA - LES - Large Eddy Simulation NP1EC - NTA - PhACs - Pharmaceutically Active Compounds PCP - Personal Care Products RANS - Reynolds-Averaged Navier-Stokes equations SST - Shear Stress Transport TT - 6
7
8 13 ｨC 8
9
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11 O
12 %,
13 13 Microsoft Office Excel SME 00InPULSe - Integrated Pulsed ULtraviolet
14 13 - (2013), 00 03`(2014), XLII. 14
15 131. ｨC, AOP - Advanced Oxidation Processes) ｨC, 15
16 [1] - [2]. [3]. [1,2,4,5], 16
17 13 [6] ,,, (). ｨC - [7] 17
18 13 60 (-1) [8,9] [10] [11] [10], H 2 O 2 [12], Na 2 S 2 O 8, NaClO, NaBrO [13] [14] [15]. 18
19 13 [16]., 60 Co ( 50%) [3]., 137 Cs 90 Sr [11]. - ph = 1. [8] - ｨC 238, 239, ｨC87 %, 241 ｨC95 %, 244 ｨC95 %. [17]. [13] [12, 18, 19] KMnO 4 [3]., [20]. - [21], [22]. [23, 24]. 19
20 13. [24, 25]: 6ｦ1 ), - ph 12-13, [12] 20
21 13 60 Co 54 Mn [12, 26, 27] ( [22]. [3] - ｨC [28] 21
22 13 6ｦ1 6ｦ1 6ｦ1 2 2 [29],, -3). - ; [30]. [31] 2 2 [32]., -- ｨC [33] [34]. [35, 36, 37]. 22
23 13 [3] - - [38] NｨCH C=N) [39] 23
24 [40] (V-UV UV- UV- 315 UV- [41] [3] [7] AOP-AOP ｨC - [42] [38] ( -1 [41] 10 9 ｨC ｦ1 ( - 3 6ｦ1[43]). [44] 24
25 13 - [14] [45] O O 2 2 [46] [44] 2 2 O 2 2 O 2 2 O 2 ; 2 2 -,
26 13 2 O 2 AOP (-4) [47], [48]. [49]. AOP 26
27 13 [50]: Endocrine Disrupting Compounds (EDC) ｨC Pharmaceutically Active Compounds (PhACs) ｨC Personal Care Products (PCP) ｨC [51], : NP1EC (TT) -,, [43]. 27
28 13 ; ; EDC, -70% [49] -95% [52] [53]. ), [54]. ｪ ｪ ｨC - [49] 28
29 13 - ｨC [55] [56]. AOP ph [57] , 29
30 13 [58] ; 4 ｨC - - 0,3 2. [59]Light Sources, Inc 16 30
31 13[60]. - -5) ,,,, 10 ｨC [62]
32 [63][64], ｨC )., [65] - [66]. - 32
33 13, [67] [68] [69], ( -8). 33
34 ), ) - [70] [71] [72, 73].,,, 34
35 13 [74] ) ｨC ). [15].. (-11). 35
36 13-2 ) ｨC.. ｨC - 36
37 13 ｨC [53,75-82]. 1.2.,, ｨC [84] [85], 37
38 13 DNS) - 1 [86]: u i ｨC t ｨC x i ｨC ｨC 3 ; p ｨC ｨC g ｨC 2. [87] Tflops/s. [88] DNS [89] RANS). LES) 1 38
39 13 - [89]: ｨC - [89]: u i ｨC t ｨC x i ｨC ｨC 3 ; p ｨC ｨC g ｨC 2. LES LES-DNS [90] DNS[88]. (RANS) 39
40 13 [91]: ｨC - u i ｨC t ｨC x i ｨC ｨC 3 ; p ｨC ｨC g ｨC 2., [92], 40
41 13 ｨC ｨC. k [91]: ; ; ; ; [91]. [91]. 41
42 13 ; ; ; ;,,,, CFD) [91]. (SST) k- k- [93, 94]. k- k-k. k- k- F 1 k- k- (1-F 1 ) F 1 [94]: 42
43 13 (RANS). DNS LES [95] i- [96]: i ｨC i ｨC D i ｨC 43
44 13 D t [97]: [96]: d 1 ｨC ｨC r ｨC - F j ｨC
45 % % ,5 ｨC ｨC 20 1 ｨC ｨC ｨC 0,4 0,1 ｨC 0, ｨC ｨC ｨC ｨC 45
46 13 ｨC 3, , ; 46
47 13 2. :, ;
48 132.,, ) ( 2 ) [98]
49 13 [98] 278 t - S - L - Q- 3 [49] Technologies, Inc, [99].,, 49
50 13-1. : (DO, k- ｨC 2.2., DNS 50
51 13 [90].,, RANS ｨC [100] LES ｨC [101]. [101] LES ｨC (-2). RANS.,, RANS. RANS 51
52 13-4 k-k-, k- k-, k- 50- [91], k-., -3 ( [102]). 52
53 13 53
54 13, k ｨC 3 ｨC ｨC ｨC ANSYS v 54
55 13 [101] [100], k- CFX-Mesh No Slip, [103] ANSYS CFX ｨC Streamline ｨC ), Time on Streamline [103]) ), -9-55
56 ). 56
57 ,, 57
58 ,, [104] [105] U 0 C, L, R 0 d l p 0 ) U 0. R p U p., L. R 0. U l U r 58
59 13 : : ; ; [106] [107]: - 59
60 13 [108] ): ｨC ) [108]. [104] 60
61 13 ｨC [104] : ｨC ｨC - ｨC ｨC [105] ｨC 20 (2-15) 61
62 13 2 0,, ,9 10 3/ exp ｨC 3 ; ｨC ｨC 1 Xe 0 12, 6 (11594) 23 1,38 10 ｨC 1 (1 ) ｨC ｨC 16 3, (1 ) 1 exp ｨC j- ｨC j- 0 ). 0 62
63 13 -: 1/ , / ,9 10 exp ｨC ｨC ( ) (1 ) [109]: 63
64 137,55 10 (1 ) ｨC [110] -[111]: ｨC Z ｨC ｨC ; ｨC ｨC ｨC - ｨC [105] - -- [112]: (2-28) 64
65 13 ｨC [104]; ｨC [112]) [109]: , , exp ｨC 0ｨC 300.,, 65
66 , 0.57, , ( 190) ( ) [104]: ,9 10 ' 0,9 1 exp( ) 5 7 1,44 10 exp 1 : 15 11,9 10 ' 0,9 1 exp( ) ,44 10 exp , ' 0,9 1 exp( ) ,44 10 exp 1 ｨC 66
67 ln 1000 ( ) ,, 5% [100] 67
68 ). ｨC ｨC,, 68
69 13 (2-34) -,, ; -,, : [113]: 69
70 13 ｨC, ｨC ｨC ｨC ｨC. : ｨC, [113].,. [114],,,, [113]: 70
71 13 -,, ｨC ｨC, [113] [115]:, 2.6.,, 71
72 13., ｨC, ｨC,, (. 2.4, 5) -,, [101] [100], - 72
73 13. c ( ). c , 73
74 13,, [49] [100]. [114]., 74
75 13, ,, -14,,,, 75
76 13. ) : -1 ), 2 2 ),
77 13 77
78 13-35%
79 13 ( -23). 35% 2.8.,... 79
80 PURITEC
81 13-2 ; 81
82 13 3 ; V8 G1);, ｨC ｨC,, 3 82
83 13,, ｨC ｨC,
84 ( -, 8,6-10,0. 84
85 13 Fe(III) Ti(IV) ,,
86 13 -ｨC 0,5 (0, ｨC - ｨC ｨC ｨC ;,
87 ,,, - Osram PURITEC HNS 15W l NaOH. [116] [117], 87
88 13, [76] - [117] - Bi(NO 3 ) 3 *5H 2 O
89 13 0 ｨC ｨC t ｨC k ｨC ln(c 0 /C) ｨCt. 89
90 13 90
91 ,0281-0, ,0026-0, ,0071 0,0211 0,0144 0, ,0002-0, ,0019 0,0274 0,0041 0,
92 13 ｨC t ,72 (7,1) 0,66 (6,5) 0,82 (8,1) 0,92 (9,1) 0,88 1,11 (8,7) (11,0) t, ,16 (1,55) 0,20 (1,96) 0,24 (2,4) 0,22 (2,2) 0,31 (3,1) 0,42 (4,1) 92
93 ) - 5 [118, 119] 93
94 ｨC ESI). LabSolutions LCMS Ver NIST MS Search 2.0f, MassBank service METLIN Metabolite Search ), (1 ｨC ) -ｨC -8)
95 13, ｨC -, - - NaNO NaNO ,2`,2``- - - [31]. 95
96 [120] NaNO 3 ｨC
97 13 1 NaNO : - 2 ), N- S NaNO 3 97
98 NaNO 3 ( 0,6 0,9 1,2 1,5 1,7 1,8 1,9 2 2,1 2,2 NaNO 3 ( 1,5 2,6 3,5 4,3 4,9 5,5 6,1 6,9 7,5 7,9 98
99 13 7 ｨC -2, 0,4; 0,08-7) ｨC ) ｨC ) ｨC
100 13 100
101
102 ｨC 3 ) , ｨC
103 % ,9 29,2 28,4 24,7 35,4 26,9 28,6 39,7 35,6 60,0, IDA,, 103
104 ,, [121] : 6 104
105 , 105
106 ( )
107 13 107
108 ,6). m/z 173,5 [EDTA- 4H+Co(II)]2, / m/z 346,9 [EDTA- 4H+Co(III)], / m/z 347,9 [EDTA- 3H+Co(II)], / O 3 2,63 7,09 2,98 O 3 1,46 7,13 1,84 O 3 0,76 5,50 1,24 O 3 0,45 4,10 0,8 O 3 0,24 2,10 0,4 O 3 0,07 1,00 0,1 UV/ O 3 0,63 8,24 1,01 UV/ O 3 0,27 4,10 0,23 UV/ O 3 0,08 0,87 0,05 UV/ O 3 0,02 0,03 0,
109 13,
110 13 - -, 9,5- Na + ｨC 6,4; K + ｨC 3,9; Mg 2+ ｨC 14,0; Ca 2+ ｨC 50,0; Cl - ｨC 5,7; SO 2-4 ｨC 35,0; HCO - 3 ｨC 192; ), - Fe(III) Ti(IV)
111 , NaNO 3, 1 7, , ,
112 ｨC 3,8--0,6--10,2-10,4. -(1,6-2,0) ﾁ104, 134 Cs- (1,0-4,3) ﾁ10 3, 60 Co-(1,4-3,8) ﾁ (2,1-3,5) ﾁ Cs, 134 ( 10%). 112
113 Cs 60 Co I 50 2,2 II >190 1,5 I + II >9450 3,3 I 14 2,6 II >570 1,6 I + II >7900 4,3 I 11 2,6 II >695 1,6 I + II >7900 4,2 I 14 2,6 II >720 1,9 I + II >9900 5,0 I 12 2,0 II 202 1,4 I + II ,9 I 14 1,7 II >695 1,4 I + II >9900 2,3 113
114 (
115 ｨC -; - - ; 115
116
117 ｨC ｨC ｨC ｨC ｨC ﾀ (200 ｭ
118 13 - Fe(IIIAl(III). 2 ｨC ｨC 120 ｨC ｨC - [122] ｱ
119 em
120 13 em em [123] - Al(III) ｨC -Fe(III). Fe(III 120
121 13-32, ｨC 8,0. - NaOH 121
122 13[122] -33 ｨC Al 2 (OH) 5 Cl -33 Fe(III). Fe (III 122
123 13,, ｨC ｨC = 7,0, [HemFe(III)] = 0,5, -33). ｨC ｨC W ｨC ｨC,, 1,17%. 0-0 ｨC - NaOH 123
124 ｨC,, Fe(III),, 124
125 [53, 106] CO 2 H 2 O - ｨC 125
126 13(3-10) RH ｨC ｨC, ｨC e 3 ｨC ｨC
127 em ,
128 13 ｨC ) 3-128
129 = ,, ｨC 8,0; ｨC ｨC
130 , 60., 5 130
131 V V 3 V 3 V 3 ), - - Fe (III ｨC FeCl 3 *6H 2 O V 3 - ｨC ｨC 8,0 - ｨC
132 13V = , 11 (V 3 0 ｨC 3 V (10%) ｨC 132
133 V ｨC 3- V ｨC Fe (III) V 11- V V ｨC ph 6- V 13 ｨC - 20,21 ｨC ｨC 3 133
134 , -, 190-,
135 13 135
136
137 ) %, - 137
138 13-8 ｨC
139 // Seliverstov A.F., Lagunova Y.O., and Ershov B.G. Recovery of Radioactive Cobalt from Aqueous EDTA Solutions Using Concentrated Ozone // 139
140 13Radiochemistry Vol. 51. No. 3. pp Garnov A.Y., Gogolev A.V., and Shilov V.P. Catalytic Decomposition of Organic Anions in Alkaline Radioactive Waste: 1. EDTA Oxidation // Radiochemistry Vol. 44. No. 5. pp Venkatadri R., Peters R.W. Chemical Oxidation Technologies: Ultraviolet Light/Hydrogen Peroxide, Fenton's Reagent, and Titanium Dioxide-Assisted Photocatalysis // Hazardous Waste & Hazardous Materials Vol. 10. No. 2. pp Seliverstov A.F., Ershov B.G., and Kamrukov A.S. Oxidative Degradation of EDTA in Aqueous Solutions under UV Irradiation // Radiochemistry Vol. 50. No. 1. pp
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142 1329. Appaw C., Adewuyi Y.G. Destruction of carbon disulfide in aqueous solutions by sonochemical oxidation // J. Hazard. Mater No. 90. pp. 237ｨC William H.G., Joon-Wun Kang, and Douglas H.C. The chemistry of water treatment processes involving Ozone, Hydrogen Peroxide and ultraviolet radiation. // Ozone science & engineering Vol. 9. pp Ku Y., Wang L., and Shen Y. Decomposition of EDTA in aqueous solution by UV/H2O2 process // J. Hazard. Mater Vol. 60. pp Avramenko V.A., Zheleznov V.V., and Kaplun E.V. Sorption-reagent method in liquid radioactive waste management // : Materials Research Society Symposium - Proceedings Scientific Basis for Nuclear Waste Management XXV. Boston Avramenko V., Mayorov V., and Marinin D. Macroporous catalysts for hydrothermal oxidation of metallorganic complexes at liquid radioactive waste treatment // : Proceedings of the International Conference on Radioactive Waste Management and Environmental Remediation, ICEM. "ASME th International Conference on Environmental Remediation and Radioactive Waste Management ICEM2010" Braehler G., Rieck R., and Avramenko V.A. Nuclide separation by hydrothermal treatment and ion exchange: a highly effective method for treatment of liquid effluents // : Proceedings of the International Conference on Radioactive Waste Management and Environmental 142
143 13Remediation, ICEM. "ASME th International Conference on Environmental Remediation and Radioactive Waste Management, ICEM 2011" Block SS, editor. Disinfection, Sterilization, and Preservation. 5th ed. Philadelphia: Lippincott Williams & Wilkins, pp. 40. ISO Process for Determining Solar Irradiances Novikov D.O., Lagunova Y.O., and Kamrukov A.S. Photo-oxidative degradation of oxalate ions with concentrated ozone using high-intensity pulsed continuum UV radiation // High Energy Chemistry Vol. 48. No. 6. pp Beltran F.J. Ozone Reaction Kinetics for Water and Wastewater Systems. CRC Press, pp / 44. Rekab K., Lepeytre C., and Dunanda M. H2O2 and/or photocatalysis under UV-C irradiation for the removal of EDTA, a chelating agent present in nuclear waste waters // Applied Catalysis A: General Vol pp Seshadri H., Sinha P.K. Efficient decomposition of liquid waste containing EDTA by advanced oxidation nanotechnology // J. Radioanal. Nucl. Chem Vol pp Rekab K., Lepeytre C., Goettmann F., and Dunand M. Degradation of a 143
144 13cobalt(II)ｨCEDTA complex by photocatalysis and H2O2/UV-C. Application to nuclear wastes containing 60Co // J. Radioanal. Nucl. Chem Janssens I., Tanghe T., and Verstraete W., "Micropollutants: A bottleneck in sustainable wastewater treatment," // Water Science and Technology, Vol. 35, No. 10, pp Worthington, "Organic Micropollutants in the Aqueous Environment," // Studies in Environmental Science, Vol. 29, pp. 235ｨC Wennmalm, Gunnarsson, "Public Health Care Management of Water Pollution with Pharmaceuticals: Environmental Classification and Analysis of Pharmaceutical Residues in Sewage Water," // Therapeutic Innovation & Regulatory Science, Vol. 39, No. 5, pp Insa, Petrovic, and Barcelｨｮ, "Occurrence and spatial distribution of EDCs and related compounds in waters and sediments of Iberian rivers," // Science of The Total Environment, Vol , pp Baranda A., Fundazuri O., and Martｨｪnez I., "Photodegradation of several triazidic and organophosphorus pesticides in water by pulsed light technology," // Journal of Photochemistry and Photobiology A: Chemistry, Vol. 286, pp
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148 Vartanian GM, editor. Ultraviolet Disinfection Guidelines for Drinking Water and Water Reuse. 3rd ed. Fountain Valley, CA: National Water Research Institute, pp Menter. Methoden, Moglichkeiten, Grenzen numerischer Stromungsberechnungen. Kurzlehrgang NUMET 2002: Numerishe Methoden zur Berechnung von Stromungs- und Warmeiibertragungs-problemen. Erlangen pp. 88. Spalart P.R., "Strategies for turbulence modeling and simulation," // Int. J. Heat Fluid Flow, Vol. 21, pp Wilcox D. Turbulence Modeling for CFD. 2nd ed. Anaheim: DCW Industries, 148
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151 S02rensen M., Frimmel F.H., "Photochemical degradation of hydrophilic xenobiotics in the UV/H 2 O 2 process: Influence of nitrate on the degradation rate of EDTA, 2-amino-1-naphthalenesulfonate, diphenyl-4-sulfonate and -diaminostilbene--disulfonate," // Water Research, Vol. 31, No. 11. pp Jiraroja, Unoba F., and Hagege A., "Degradation of PbｨCEDTA complex by a H2O2/UV process.," // Water Research, Vol. 40, pp Chen Z., Sun Q., Xi, and Owens G., "Speciation of metalｨcedta complexes by flow injection analysis with electrospray ionization mass spectrometry and ion chromatography with inductively coupled plasma mass spectrometry.," // J. Sep. Sci., Vol. 31, pp ｨC
152 13 152
153 13 153
154 13 154
155 13 155
Fig. ph Si-O-Na H O Si- Na OH Si-O-Si OH Si-O Si-OH Si-O-Si Si-O Si-O Si-OH Si-OH Si-O-Si H O 6
NMR ESR NMR 5 Fig. ph Si-O-Na H O Si- Na OH Si-O-Si OH Si-O Si-OH Si-O-Si Si-O Si-O Si-OH Si-OH Si-O-Si H O 6 Fig. (a) Na O-B -Si Na O-B Si Fig. (b) Na O-CaO-SiO Na O-CaO-B -Si. Na O-. CaO-. Si -. Al O
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