Country report: Air pollution & mineral resources FY2016 FNCA Joint Workshop on Research Reactor Network project and Neutron Activation Analysis Project Country report: Air pollution & mineral resources DAMDINSUREN Gantumur g.damdinsuren@seas.num.edu.mn School of Engineering and Applied Sciences Nuclear Research Center National University of Mongolia

Country profile Total Area: 1.5 million km.sq (19st) Population: 3 million (138th) Population density: 1.97 km2 Capital: Ulaanbaatar /Red Hero/ Location: land-locked Province: 21 Language: Mongolia 90%; Kazakh and other Religion: Buddhism (53%) Shamanism (4%); Islam (3%)

Outline REE in Mongolia Poly-metal resources Air pollution in Ulaanbaatar

REE in Mongolia

Introduction of REE in Mongolia Schematic location map of major Mongolian REE deposits REE resources: 31 million tons (2009 estimation by the U.S. Geological Survey) 16.77 percent of the world’s total six REE provinces in Mongolia Number REE deposits Resource, ton 1 Khotgor 1260880 2 Mushgia Khudag 338998.9 3 Khalzan Burged 3429500 4 Lugiin Gol 13505.5

Optimization of NAA by MT-22 Experiment data MT-22 average current: 7 μA Irradiation time: 1.5 hour Wait time: 2, 24, 48, 120 hours Measure time: 1(5) hour № Sample name Weight, g 1 Ore 1 6.0433 2 Ore 2 4.3892 3 Ore 3 5.0014 4 УСЗ-44-2006 2.3688 5 УСЗ-44-2007 2.4761 Cu-monitor Cu weight, g 1 0.2440 2 0.2618 3 0.2485 4 0.2650 5 0.2467 6 0.2609 Figure. Lugiin gol deposits (Sampling)

Assessment of half-life /REE/

Comparison of results Example: La-140 Isotope Gamma energy, keV Wait time УСЗ-44-2007 reference sample, ppm Experiment value Reference value [6] 57La140 329 2 hours 492±33 434±34 ppm 24 hours 473±25 48 hours 448±25 120 hours 454±30 487 498±46 459±17 439±14 366±39 867 561±62 353±40 509±52 401±39 1596 486±18 450±16 447±15 529±59 2521 369±70 580±48 452±25 378±60

УСЗ-44-2007 reference sample, ppm Results № Isotope Gamma energy, keV Wait time, hour УСЗ-44-2007 reference sample, ppm Experiment value Reference value [6] 1 29Cu64 511 24 25.1±3.1 27.37±6.13 2 33As76 559.1 274±67 224±24 3 58Ce143 293.3 48 1100±100 1000±80 4 59Pr141 1575 112±28 122±10 5 62Sm153 103.2 92.5±17.0 120±5 6 63Eu152m 344.3 8.6±0.3 8.3±1.1 № Elements, Sample name Ore 1 Ore 2 Ore 3 1 Cu, ppm 10±1 32.5±3.3 29.7±2.5 2 As, ppm 128±12 236±12 - 3 La, % 5.38±0.03 1.36±0.01 2.03±0.01 4 Ce, % 3.33±0.07 0.91±0.04 1.14±0.04 5 Pr, % 1.57±0.02 0.15±0.01 0.14±0.04 6 Sm, % 1.42±0.01 0.85±0.01 0.66±0.01 7 Eu, ppm 150±18 127±15 180±22

Poly-metal resources in Mongolia

Introduction of Poly-metal Located at Dornod Province, Mongolia, in the middle of the cross section between China, Russia and Mongolia and at the center of Derbugan’s international metallogenic belt (Duoemuote mine area) with high grade poly-metal mineralization (Ag, Au, Cu, Mo, Pb, Zn, Sb, U...). Ulaan deposit Tsav deposit Deposit: 6800 Mt Deposit: 900 Mt Zn: 2% Zn: 2.5% Pb: 1.2% Pb: 4.1% Au: 0.21 ppm Au: 0.25 ppm Ag: 53 ppm Ag: 155-288 ppm

Goals To study results of XRF analysis comparison by NAA To determine elements of major and minor deposit by NAA

XRF Methods and Experiment SPECTRO XEPOS XRF spectrometer Measuring time was 300 sec. The results of measurements were processed by X-LabPro 5.1 and AXIL software with SDD detector (resolution of 155 eV, at 5.9 keV), Peltier cooling, X-ray tube with Pd anode, optimum excitation using polarization and secondary targets. X-ray tube Target changer with up to 8 polarization and secondary targets (Mo, Pd, Zr, AlO, Cs, Zn, Co, HoPG ) SDD detection system Sample tray with samples REEs reference materials: TRLK, TRM-2, TRHB and other

Some elements contents in Poly-metals ore samples from Ulaan deposit by ED-XRF (±15%) Samples number x1 x2 x7 x8 x9 x11 x12 x16 x17 x19 Si 21.45 24.81 20.09 23.97 21.92 27.98 24.23 23.84 25.9 23.7 K 4.03 3.72 2.92 3.17 3.25 4.77 3.42 2.89 3.59 2.50 Ca 1.76 1.94 2.01 4.27 2.35 1.04 1.47 2.13 2.25 2.55 Ti 0.042 0.055 0.059 0.068 0.058 0.079 0.048 0.072 Mn 0.234 0.243 0.455 0.468 0.584 0.300 0.276 0.436 0.530 0.486 Fe 4.38 4.33 5.63 6.33 8.21 3.94 4.59 4.64 6.11 7.32 Cu 0.186 0.237 0.214 0.188 0.113 0.165 0.206 0.281 1.526 Zn 5.21 2.41 6.65 1.91 2.65 1.19 3.73 1.00 1.61 As 0.207 0.120 0.103 0.170 0.094 0.154 0.034 0.037 Rb 0.0167 0.0142 0.0149 0.0185 0.0178 0.0231 0.0150 0.0125 0.0215 0.0134 Sr 0.0077 0.0091 0.0163 0.0279 0.0173 0.0078 0.0103 0.0168 0.0181 0.0186 Y < DL 0.0021 0.0013 0.0008 0.0018 0.0009 0.0003 Zr 0.0370 0.0418 0.0472 0.0493 0.0401 0.0567 0.0432 0.0461 0.0532 0.0402 Ba 0.0579 0.0387 0.0465 0.0425 0.0469 0.0535 0.0482 0.0292 0.0627 0.0381 La 0.0093 0.0062 0.0024 0.0057 0.0073 0.0071 0.0033 0.0016 Ce 0.0089 0.0157 0.0316 0.0144 0.0129 0.0220 0.0082 0.0199 0.0092 Nd 0.0136 0.0059 0.0028 0.0045 0.0056 0.0096 Pb 1.92 2.27 2.05 0.64 0.82 0.59 2.46 3.26 0.91 0.78 Th 0.0022 0.0007 0.0019 0.0026 0.0037 0.0032

Some elements contents in Poly-metals ore samples from Ulaan deposit by ED-XRF (±15%) Samples number x3 x4 x5 x6 x10 x13 x14 x15 x18 x20 Si 12.6 31.1 25.2 9.64 9.44 8.14 22.8 19.5 11.2 11.7 K 1.16 1.93 1.48 0.86 0.84 0.66 1.39 1.09 0.29 0.47 Ca 1.94 1.06 1.11 1.86 1.82 1.52 0.99 1.84 5.16 4.33 Ti 0.054 0.092 0.14 0.044 0.046 0.061 0.11 0.13 0.064 0.07 Mn 0.342 0.222 0.178 0.335 0.347 0.331 0.234 0.258 0.729 0.665 Fe 11 9.28 9.51 10.3 10.6 8.16 9.85 12.2 18.7 20.4 Cu 0.691 0.732 0.365 0.831 0.958 0.612 0.392 0.167 0.432 Zn 4.16 0.98 3.75 3.79 3.73 2.36 2.14 2.24 As 0.086 0.251 0.0136 0.063 0.074 0.065 0.111 0.095 0.101 0.207 Rb 0.084 0.0242 0.213 0.058 0.056 0.042 0.127 0.024 0.041 Sr 0.036 0.06 0.031 0.014 0.0026 Y 0.0031 0.0041 0.0022 0.0021 0.0018 0.0037 0.0033 Zr 0.0238 0.0317 0.0311 0.0241 0.0228 0.0235 0.0303 0.0329 0.0281 0.0283 Ba 0.0313 0.0172 0.0273 0.0384 0.0373 0.0368 0.0287 0.0411 0.0176 0.0247 La 0.09 0.091 0.097 0.12 0.17 0.18 Ce 0.094 0.051 0.107 0.114 0.133 0.155 Nd 0.0162 0.0069 0.0045 0.0046 0.0034 0.0009 0.0054 0.0155 Pb 0.91 0.65 1.05 1.08 1.13 0.92 1.07 0.75 Th 0.0087 0.00131 0.0047 0.0065 0.0064 0.00157 0.0013 0.0091 0.0086

NAA Methods and Experiment In the case of activation analysis (AA), the neutron and gamma flux from Electron Accelerator MT-25 at JINR was used. Energy of the accelerated electrons is 25 MeV and average current is 14µA. Flux of gamma rays= 1014 sec-1 The density of the thermal neutron flux= 109 n/cm2×sec Measurement condition Characteristics of Poly-Metal samples Mass of sample ≈4 g Excited time 6 hours Waited time 2, 20, 80 hours Measured time 300, 900, 1800 sec CRM СНК-2, ПИЭН611, SL-1 Measurement results of activation analysis were processed by the Canberra S100, FitzPeaks Gamma Analysis and MS EXCEL software programs

Some elements contents in Poly-metals ore samples from Ulaan deposit by NAA Samples number x3 x9 x10 x12 x19 Na, ppm 1797±533 1643±538 1693±526 2962±553 2090±534 K, % 2.61±0.51 2.47±0.68 2.83±0.70 3.53±0.69 1.61±0.60 Sc, ppm 14.4±1.7 30.1±2.8 24.0±1.9 17.7±2.1 15.3±1.7 Mn, % 0.394±0.058 0.624±0.062 0.425±0.61 0.290±0.059 0.392±0.058 Fe, % 5.50±0.33 9.54±0.42 6.56±0.38 4.70±0.47 7.51±0.37 Co, ppm 218±15 214±16 312±18 62±12 30±9 Zn, % 2.56±0.01 1.890±0.097 3.04±0.012 1.86±0.097 0.973±0.0164 Ga, ppm 16.1±1.3 24.6±1.6 12.6±1.4 9.3±0.9 19.6±1.4 As, ppm 3615±27 5681±79 5156±54 3850±33 936±14 Sn, ppm 0.33±0.02 0.85±0.02 0.05±0.01 0.11±0.02 0.87±0.02 Sb, ppm 29.3±2.6 19.0±1.8 47.5±3.0 50.2±3.6 52.2±3.4 Ba, ppm 43±5 118±8 60±15 64±12 312±16 La, ppm 85.0±1.2 114.3±0.8 115.4±1.3 107.4±0.9 59.2±1.4 Eu, ppm 0.60±0.08 0.20±0.05 0.10±0.03 0.40±0.05 0.08±0.02 W, ppm 50.2±2.6 12.9±1.4 53.5±3.2 14.4±1.0 19.5±1.3 Au, ppm 0.72±0.03 1.00±0.04 0.69±0.03 0.06±0.01 U, ppm 301±3 473±6 177±5 231±5 487±8

The comparison of the XRF results obtained for the sample (x9, x19) with the NAA and CGL

Air pollution in Ulaanbaatar

Results of the air samples collected during 2008-2015 at the NRC, NUM Sample collection and analytical methods Duration: 2009 June – 2016 Dec Height of sampling: 3m Sampling frequency: Twice a week Sampler: GENT Sampler with Polycarbonate filters Flow rate of sampler: 16 l/мin (18-14) ВС measurement: M43D Digital Smoke Stain Reflectometer Аir Quality Index Air Quality Index Value 0 ~ 50 Clean 51 ~ 100 Normal 101 ~ 250 Slightly Polluted 251 ~ 400 Polluted 401 ~ 500 Heavily Polluted 501 ~ Seriously Polluted http://www.ub-air.info/ub-air/en/

Statistics for PM2.5 , PM10-2.5 and elemental concentrations at NRC site Average Max Min Std/DeV PM2.5 79960.6 699654.2 2721.1 69508.0 Na 2126.8 8480.7 111.0 1411.3 Mg 944.6 4794.2 221.0 569.1 Al 274.0 2051.1 27.0 222.3 Si 667.2 5582.1 30.2 573.0 P 280.6 3196.1 86.7 212.0 S 2994.6 23800.7 46.0 3784.8 Cl 222.8 1454.0 30.3 170.0 K 409.4 3294.0 30.5 305.8 Ca 728.9 6886.2 27.7 613.8 Ti 167.7 1621.9 49.9 109.1 Mn 63.8 589.1 11.0 41.0 Fe 547.9 4747.9 70.6 417.8 Ni 44.6 367.3 6.3 33.3 Cu 14.0 132.6 5.1 13.8 Zn 47.0 281.5 7.8 35.7 Pb 45.7 558.2 11.5 52.9 BC 6160.4 30503.3 1003.3 5020.2 Average Max Min Std/DeV PM10-2.5 153991.4 5342995.2 4668.5 278771.6 Na 6109.1 23209.3 205.6 4246.3 Mg 3825.7 13860.7 243.1 2675.6 Al 1725.2 6571.1 29.5 1354.2 Si 4838.3 18255.0 68.9 3824.5 P 377.3 3248.6 99.8 231.5 S 1987.1 12093.9 18.6 1919.2 Cl 663.4 4368.1 93.7 514.1 K 3260.4 12469.2 54.1 2719.5 Ca 5701.6 19605.9 149.1 3997.1 Ti 530.1 1769.5 70.7 344.7 V 17.5 41.3 9.9 5.7 Cr 23.5 56.4 8.1 9.5 Mn 160.3 691.7 27.4 93.6 Fe 4453.1 16734.6 127.2 3479.8 Ni 44.9 329.0 6.7 34.6 Cu 114.5 5.0 16.2 Zn 65.1 248.1 10.0 38.8 Pb 46.0 935.5 5.9 84.8 BC 3335.4 11199.5 188.9 2103.6

Bio-monitoring technique by NAA The moss bio-monitoring technique was applied to air pollution study in the city of Ulaanbaatar. Sampling: The samples of the terrestrial mosses Rhytidium rugosum and Entodon concinnus were collected in the southern part of the city in September 2015 in accordance with the sampling strategy of the UNECE ICP Vegetation moss survey programme. Methods: INAA using epithermal neutrons at the IBR- 2M reactor, FLNP, JINR Atomic absorption spectrometry at Central Geological Laboratory (CGL) of Mongolia Results: 42 elemental concentrations Fig. Satellite image of Ulaanbaatar city. 1-built-up area; 2-Ger area; 3-forest; 4-grass; 5-soil; 6-water. The size of the area is 28 km × 20 km.

Thank you for kind attention 

Assessment of detection limits Spectrum of SL-1 reference sample Sample weight: 1.18 g Irradiation time: 5 hours Wait time: 12 hours Measurement time: 1 hours Cmin= dm = θ∙C∙3∙dS / Sγ

Assessment of detection limits МТ-22 average current ~ 8 μА Sample weight: 1-10 g Irradiation time: 5 hours Measurement: 1 hour Information La Eu Content, ppm 52.1 ± 3.1 1.6 Eγ, keV 1596 842 Sγ 710 ± 60 16800 ± 420 Detection limit, ppm 15.6 0.066 Isotopes Sc-45 Y-89 Gd-158 Tb-159 Dy-156 Er-170 Yb-174 LOD, ~ ppm 100 1000 La-139 Ce-140 Ce-142 Pr-141 Sm-154 Eu-151 10 0.01