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Up to the present the low salinity solutions were evaporated (by adding sodium-hydroxide) till 400 g/dm 3 salt content (pH~13) and after solidification by cementing buried. There is about 6000 m 3 concentrated evaporator bottom residue in the tanks of the PWR. In order to separate the inactive salt content before cementing a Liquid Wastewater Treatment Technology (LWT see Figure 1.) was developed to treat this wastewater before solidification and burial (Pátzay et al., 2006). The long-life radionuclides are present in very low concentration (10 -9 -10 -12 mol/dm 3 ) as ions, suspended, colloid particles and in complex (EDTA, oxalate, citrate) form. In this technology the SELION CsTreat cesium selective ion exchanger is used for the selectice separation of radiocesium isotopes ( 134 Cs, 137 Cs). The SELION CsTreat cyanoferrate based cesium-selective ion exchanger is not stable at pH>11 (see reaction equation below), so the use of CsTreat needs partial neutralisation of the evaporator bottom residue to pH~9-11, and during neutralisation sodium-borate crystals precipitate with about 15-30% of the radioactivity. [ ] 4 26 6 2 () 2 2 [()] ()K Co Fe CN OH K Fe CN Co OH −+ − +⇒+ + (1) The contaminated crystals should be washed to remove the radioactive isotopes from the crystals. To eliminate the generation of radioactive borate crystals and additional wastes we have developed a M 2 Ni[Fe(CN) 6 ] type cesium selective granulated ion exchanger (where M is an alkali ion) which has good stability even at pH>11. Based on this new cesium selective ion exchanger stable at pH>11 we have modified the radioactive evaporator bottom residue treatment technology at the nuclear power plant. The basic idea of the new technological scheme is the selective separation of all radionuclides with inorganic sorbent materials or reagents in very simple processes without any prior neutralization, dilution. After the separation of all radionuclides the inorganic salt content Waste Water - Evaluation and Management 204 Fig. 1. The Liquid Wastewater Treatment Technology (borates, partially nitrates) could be separated with crystallization using nitric acid neutralization and the inactive crystals could be treated as chemical waste. In the first part of this report this modified separation technology will be discussed. In the Nuclear Power Plant Paks at the bottom of some radioactive liquid waste containing tanks there are segregated sludge phases, containing more or less organic complex builder compounds (including EDTA, citrate and oxalate compounds). The radioactive waste water treatment technology, developed at the plant is not suitable to treat sludges, so a modified technology is needed using cementing as solidification. For this technology the detailed analysis of these sludge phases are of great importance. According to this problems we started a research work to investigate the international experience in the analysis of Analysis and Selective Treatment of Radioactive Waste Waters and Sludges 205 radioactive sludges and fulfilled laboratory scale experiments for chemical and radiochemical analysis of different sludge samples. In the second part of this report the analysis of these radioactive sludges will be discussed. 2. The modified liquid wastewater treatment technology The developed modified technology consists of the following parts: • Firstly the high salt content, strongly alkaline (pH~13-14) evaporator bottom residue is microfiltered. • Then the free EDTA, citrate, oxalate content is oxidized with underwater plasma torch and with Fenton oxidation (in this process Co isotopes removed by precipitation as oxide-hydroxide and can be separated by filtration). The treated solution is microfiltered and ultrafiltered. • Selective separation of the radioactive cesium isotopes ( 137 Cs, 134 Cs) using ion exchange material stable at alkaline pH. • Crystallization of borates from the mother lye by neutralization with nitric acid. The modified waste treatment technology was tested at the NPP. After microfiltration about 500 dm 3 evaporator bottom residue was oxidized with underwater plasma torch for the EDTA, citrate and oxalate removal. The oxidized evaporator bottom residue was then microfiltered and ultrafiltered to remove suspended matter and cobalt precipitation from the solution having a pH~12.3 The separation efficiency of the ultrafiltration is shown in Table 1. 60 Co activity concentration (Bq/kg) % 134 Cs activity concentration (Bq/kg) % 137 Cs activity concentration (Bq/kg) % Feed 2310 100 1350 100 181000 100 Permeate 258 11.2 1210 89.6 164000 90.6 Table 1. Ultrafiltration of the waste water after oxidation of the complex compounds 0 1000 2000 3000 4000 5000 6000 100 1000 DF DF Cs-137 throughput in bed volumes (BV) Fig. 2. Breakthrough curve of 137 Cs (BV-bed volume) Waste Water - Evaluation and Management 206 The solution purified from radioactíve cesium was then acidified with concentrated nitric acid in 20 dm 3 batches in a cooled mixed reactor till pH~9.0. The crystallization reactor is shown in Figure 3. Fig. 3. The crystallyzation reactor Fig. 4. The separated wet crystals by the original (left) and by the modified (right) technology The crystals were separated by filtration, dried at 50 0 C and weighted. The crystalline product contained mainly sodium-metaborate (NaBO 2 *8H 2 O). Heating the product above 55 o C the crystalline phase released four water molecules and NaBO 2 *4H 2 O formed. Figure 4 shows the separated wet crystals by the original and by the modified technology. The measured specific radioactivity of the separated, dried crystalls and the unconditional clearance limit values are summarized in Table 2. Analysis and Selective Treatment of Radioactive Waste Waters and Sludges 207 Radionuclide Measured specific activity (Bq/g) Unconditional clearance limit (Bq/g) 51 Cr 1.42E-02 30 54 Mn 1.19E-03 1 58 Co 1.01E-03 1 59 Fe 1.93E-03 0.9 60 Co 1.17E-03 0.9 65 Zn 2.66E-03 2 95 Nb 1.10E-03 0.9 95 Zr 1.81E-03 3 106 Ru 1.15E-02 1 110m Ag 1.83E-03 0.9 124 Sb 1.83E-03 0.9 125 Sb 7.63E-03 1 134 Cs 1.66E-03 0.9 137 Cs 1.11E-01 2 144 Ce 1.02E-02 30 154 Eu 2.59E-02 0.9 3 H 2.94E-02 2000 14 C 1.91E-05 200 55 Fe 3.01E-05 100 59 Ni 6.20E-06 800 63 Ni 2.72E-04 300 90 Sr 3.19E-02 1 99 Tc 7.19E-05 1 129 I 1.24E-09 0.9 234 U 4.69E-07 0.9 235 U 1.71E-07 0.9 238 U 1.09E-07 0.9 238 Pu 4.83E-07 0.9 239,240 Pu 3.62E-07 0.9 241 Am 5.48E-08 0.9 242 Cm 4.01E-07 0.9 244 Cm 4.26E-07 0.9 Table 2. The measured specific radioactivity of the separated, dried crystalls and the unconditional clearance limit values Based on our modification of the original wastewater treatment technology in the Hungarian Nuclear Power Plant we get beneficial results summarized as follows: • The use of the new cesium selective ion exchanger eliminates the acidification of the evaporator bottom residue before the cesium removal by ion exchange. • Hence we can avoid the formation of borate crystals contaminated with radionuclides of cesium etc. and the additional washing of the separated crystals for the radioactivity removal. • According to measured specific activity data we are able to release the dried solid crystals from the NPP and could be used as non-radioactive borate chemical. Waste Water - Evaluation and Management 208 3. Chemical and radiochemical analysis of radioactive sludges fron NPP Paks According to the international experiences the sampling process depends on the sludge characteristics. The first step of the sampling process is a previous sampling to determine the boundary between the supernatant and sludge layers. This is followed after 3-4 days by the sampling. For diluted, liquid type sludges below the supernatant layer we can detect very often a crystalline salt and amorf sludge layer too. Sampling are usually done from the top, intermediate and bottom layers using a sampling pipe and vacuum For the concentrated sludges the samples are taken from different layers of the sludge phase. Following the sampling the sludge samples are photographed and characterized. The samples for organic content determination (TC, TOC, TIC) are collected in glass bottles, the samples for ion chromatographic analysis are stored in polyethylene botles at 4 0 C. The liquid samples are analysed for pH. We investigated two times three sludge samples taken from the tanks 02TW30B001, 02TW01B001, 01XZ06B001 of the Paks NPP. The sample characteristics are summerized in Table 3. Sample Code Tank code Sample type Sampling time P3 02TW30B001 sludge from the evaporator, pH~13 2008. 11. 06. 11:45 P4 02TW01B001 settled sludge from diluted waste water tank, pH~8 2008. 11. 06. 11.45 P5 01XZ06B001 sludge from the wash-house waste 2008. 11. 07. 10.30 P3-2 02TW30B001 sludge from the evaporator, pH~13 2009.01.20. P4-2 02TW01B001 settled sludge from diluted waste water tank, pH~8 2009.01.20. P5-2 01XZ06B001 sludge from the wash-house waste 2009.01.20. Table 3. Sludge sample characteristics The samples P3 and P4 are seen on Picture 1. The P3 and P4 samples contained liquid phase too, while sample P5 contained only solid, consistent type phase. Picture 1. The samples P3 and P4 shaked(left) and settled(right) [...]... 87 132.97 0 0 0 0 3 .83 324 .89 8. 31 121.00 4731. 58 18. 82 1596.50 131.37 131.37 1596.50 62.42 5295. 08 264.22 264.22 5295.09 281 . 28 2 386 0. 98 1963.46 1963.46 53934.36 285 .66 24232.54 83 9.07 4306.67 987 56.14 Anions total equivalent capacity ditributed according to supernatant distribution 12.34 0.64 3.31 63.07 92.31 2.60 13.30 471.59 7225 .88 116.53 595.33 36913 .83 53.29 1. 68 8.60 272.26 312.03 6.49 33. 18. .. 8 a) P3-2 Composition NaOH Na2CO3 NaNO3 KNO3 Ca(NO)3)2 MgCO3 sum of ionic Fe(OH)3 Mn(OH)2 mekv/l sludge 16 18 2035 137 121 264 125 4300 2279.7 109.7 mmol/l sludge 16 18 1017.5 137 121 132 62.5 3 088 759.9 54 .85 mg/l sludge 63 084 .53 10 784 3.6 11644.27 16723 .8 13211.77 2634 .81 9 215142 .8 81209 487 9.5 mmol/l sludge 28. 73 81 .735 113.965 69 .85 5 35 .89 5 5.025 2 .86 1.715 339. 78 2044. 78 290.59 mg/l sludge 2441 .89 8... 239,240Pu 78. 5 8. 68 549 ±21.1 238Pu 238Pu 78. 1 8. 79 429 ± 18. 5 241Am 241Am 73 .8 ±3. 78 771 ±16.5 244Cm 11.9 ±1.47 244Cm 124 ±5.64 90Sr 90Sr 21500 ±1 080 10200 512 Sample P-5-2 Act conc σ Bq/kg Bq/kg 127 194 99 .8 54.5 20700 Table 9 The measured alpha- and beta-activities of the fused samples with KOH ±12.7 ±15.7 8. 82 ±5. 68 ±1040 Analysis and Selective Treatment of Radioactive Waste Waters and Sludges... 1196. 18 98. 43 98. 43 1196. 18 68. 49 7367.47 367.64 367.64 7367.47 136.66 14700.52 267. 58 267. 58 7350.26 1 18. 65 12763. 18 6 48. 74 662.27 13074. 38 Anions total equivalent capacity ditributed according to supernatant distribution 0 0 0 0 3 48. 30 9 .82 10.05 356.30 1741.50 28. 08 28. 73 1 781 .50 531.16 16. 78 17.16 543.36 161.09 3.35 3.43 164.79 0 0 0 0 11479.55 382 .65 391.44 11743.22 12612 .84 206.71 211.46 12902.54... 339. 78 2044. 78 290.59 mg/l sludge 2441 .89 8 86 62.995 11406.67 11324.5 5252 .85 3 4 78. 4353 751.7733 206.4219 40525.54 2 185 23.6 2 584 8 .81 b) P4-2 Composition NaNO3 Na2CO3 CaCO3 Ca(HCO3)2 Mg(HCO3)2 MgCl2 Mg3(PO4)2 MgSO4 Sum of ionic Fe(OH)3 Mn(OH)2 mekv/l sludge 28. 73 163.47 227.93 139.71 71.79 10.05 17.16 3.43 662.27 6134.34 581 . 18 214 Waste Water - Evaluation and Management c) P5-2 Composition NaCl NaNO3... year in recent decades 224 Waste Water - Evaluation and Management Fig 3 Box-whisker plots of total phosphorus in effluents of waste water treatment facilities in semiarid Spain Alcázar treated waste waters reach Las Tablas de Daimiel National Park, El Rocío treated waste waters enter Doñana National Park, and Las Rozas treated waste water are discharged to small brooks and streams running through... 1594.07 5 383 .97 316.70 1617.90 27504.34 11950. 68 3 98. 35 2035.02 61050.69 25030.54 84 3.03 4306.675 12 786 9.90 212 Na NH4 K Mg Ca Mn Sum F Cl NO3 PO4 SO4 OH CO3 HCO3 Waste Water - Evaluation and Management b) P4-2 Cations KOH fusion+HCl total (supernatant+fusion) mg/g dry sludge mg/l sludge mekv/l sludge mekv/l sludge mg/lsludge 39.04 4199.53 182 .67 196.20 4510.73 0 0 0 0 0 0 0 0 0 0 11.12 1196. 18 98. 43 98. 43... average of 4 18 ± 1 28 mm/year, ranging 189 -85 7 mm/year In fact, traditional approaches to water management in semiarid regions have been based more on the increase of water availability rather than improving the water quality of waste waters to make them feasible for future use In water shortage scenarios, domestic lifestyle adaptations and optimization of water consumption by both agriculture and industry... balance between water supply and demand However, although this balance could be achieved and the amount of waste water reduced, the characteristic low water flow of semiarid rivers makes impact of waste water discharge in freshwater ecosystems stronger Streamwater discharge to wetlands and lakes is highly variable over time in semiarid areas Fig 2 shows an example of these fluctuating water flows of... 449. 68 231 985 .21 151.4 77.71 1954.45 4572.75 12.742 mol/l sludge 43.32 16.13 149 .89 33 38. 5 492.605 75.7 38. 855 85 5.0033 1524.25 6.371 mg/l sludge 2531.742 1370.965 24573.63 11942.04 7 985 8.36 11077 .89 4676. 689 136031.3 16 289 5.3 566.73 Table 8 The calculated composition of the sludge samples Radiochemical composition The radiochemical composition of the sludge samples was determined using gamma- and . 2 38 U 2 38 U 2 38 U 239,240 Pu 78. 5 8. 68 239,240 Pu 549 ±21.1 239,240 Pu 127 ±12.7 2 38 Pu 78. 1 8. 79 2 38 Pu 429 ± 18. 5 2 38 Pu 194 ±15.7 241 Am 73 .8 ±3. 78 241 Am 771 ±16.5 241 Am 99 .8. of ionic 662.27 339. 78 40525.54 Fe(OH) 3 6134.34 2044. 78 2 185 23.6 Mn(OH) 2 581 . 18 290.59 2 584 8 .81 Waste Water - Evaluation and Management 214 c) P5-2 Composition mekv/l sludge mol/l. 17016.05 435.17 3790.07 87 132.97 NH 4 0 0 0 0 K 3 .83 324 .89 8. 31 121.00 4731. 58 Mg 18. 82 1596.50 131.37 131.37 1596.50 Ca 62.42 5295. 08 264.22 264.22 5295.09 Mn 281 . 28 2 386 0. 98 1963.46 1963.46