1. MOUNTAINS, WITNESSES OF GLOBAL CHANGES Research in the Himalaya and Karakoram: SHARE-Asia Project Rome, November 2005

2. Ev-K 2 -CNR RATEAP project Responsible Dr. Mario Gallorini Remote Areas Trace Elements Atmospheric Pollution CNR - Institute of Metrology “G.Colonnetti” Unit of Radiochemistry and Spectroscopy c/o University of Pavia - Italy

3. ELEMENTAL CHARACTERIZATION OF HIMALAYAN AIRBORNE PARTICULATE MATTER COLLECTED AT 5,100 M OF ALTITUDE. E.Rizzio 1, G.Giaveri 1, L.Bergamaschi 1, A.Profumo 1, G.Tartari 2, M.Gallorini 1 1 CNR Institute of Metrology “G.Colonnetti” Unit of Radiochemistry and Spectroscopy c/o University of Pavia (Italy) 2 CNR- IRSA, Brugherio-Milano (Italy) Corresponding author: gallorin@unipv.it

5. Goals of the project: Obtaining information about the concentrations of trace elements (TE) in the air particulate in the Himalayas, contributing to study the Asian Brown Cloud Checking for possible air pollution and identification of those TE that may be considered of non local and/or of anthropic origin; Evaluation of possible origin and direction of long distance transport phenomena and their variation with seasonal/meteorological conditions;

6. The project is carried out thanks to: The use of the “Pyramid” laboratory of the CNR at 5050m a.s.l. in the Himalayas (Nepal) in the surroundings of mount Everest The financial support of the Ev-K 2 - CNR Committee The logistic support of “Mountain Equipe” s.r.l.– Bergamo, Italy

7. The sampling equipment specifically developed and supplied by Zambelli s.r.l. (Bareggio, Milan)

8. The use of the research nuclear reactor TRIGA Mark II of the University of Pavia, Italy

9. The expertise matured by the working group of Pavia in the field of trace element air pollution, including previous studies on lichens, collected in the same region, and used as biomonitors

10. - aspiration pumps (for low pressure conditions) - filters (Teflon®, 0.5 µm porosity, by Pall), blank study - training for working in extreme conditions Plateau Rosa, Italian Alps - 3500m 2001 - Preparation

11. Samplings 2002: Pre-monsoon ( March – May ) 2003: Post-monsoon (October) - Samples of 3 airborne particulate fractions: TSP, PM10, PM2.5 120m 3 of aspired air (sampling time 80 –120h) for each sample - field blanks, soil samples, lichen samples Sampling site near the pyramid Use of the pyramid’s laboratory

12. Weather conditions acquired from the Epson Meteo station settled at the Pyramid Temperature (daily mean range) Precipitation (daily median) Mean Relative Humidity Atmospheric Pressure Wind speed and direction

13. Analyses Carried out by INAA and ETAAS - Blank study - Quality control filters of TSP filters of PM10 filters of PM2.5 INAA (26 elements) ETAAS (5 elements) - Soil samples to calculate Enrichment Factors (EF) - Lichens (air pollution biomonitors)

14. Elemental content (nanograms) in blank filters and field-blank filters (0.5 um 47 mm diameter Zefluor TM, PALL-USA) determined by INAA

15. Trace elements content in the different particles size fractions of air particulate matter collected at 5100 m a.s.l. (Khumbu valley-CNR Pyramid, March-May 2002). Concentration in ng/Nm 3 Himalayas Ispra Milan Br 1.0 – 3.1 8 - 14 280 – 758 Cd 0.02 – 0.05 0.35 – 0.34 1.7 – 6.3 Ni 0.8 – 2.0 6.7 – 15 3.9 – 167 Pb 2.4 – 6.8 61 – 154 75 - 3200 Sb 0.08 – 0.65 4.0 – 6.1 55 –125

16. Trace elements content in the different particles size fractions of air particulate matter collected at 5100 m a.s.l. (Khumbu valley-CNR Pyramid, October 2003). Concentration in ng/Nm 3

17. Post – monsoon period Variation (%) of the elemental concentrations in the Hymalaian airborne particulate fractions between the pre-monsoon (March-May 2002) and the post-monsoon (October 2003) periods. TSP PM 10 PM 2.5 Cr -89 % -89 % -92 % Co -70 % -82 % -89 % Br +18 % -14 % -2.5% I +84 % +137 % +125 %

18. Seasonal frequency of days with precipitations in 2000 - 2004 Days

19. Mean 0.14 ± 0.04 (28 %) Elemental characterization of Himalayan airborne particulate at CNR Pyramid (5050 msl) pre-monsoon period: March – May 2002 and post-monsoon (October 2003) As ng/Nm 3 Mean 0.064  0,02 (31%) Variation: - 54% pre-monsoonpost-monsoon

20. Mean 0.43 ± 0.12 (28 %) Elemental characterization of Himalayan airborne particulate at CNR Pyramid (5050 msl) pre-monsoon period: March – May 2002 and post-monsoon (October 2003) Co ng/Nm 3 Variation: - 70% pre-monsoon post-monsoon Mean 0.10  0.04 (40%)

21. Mean 11.2 ± 5.4 (49 %) Elemental characterization of Himalayan airborne particulate at CNR Pyramid (5050 msl) pre-monsoon period: March – May 2002 and post-monsoon (October 2003) Zn ng/Nm 3 Mean 4.14  1.70 (41 %) Variation: - 63% pre-monsoon post-monsoon

22. Mean 1.1 ± 0.4 (36 %) Elemental characterization of Himalayan airborne particulate at CNR Pyramid (5050 msl) pre-monsoon period: March – May 2002 and post-monsoon (October 2003) I ng/Nm 3 Mean 2.0  0.6 (30%) Variation: + 85% pre-monsoon post-monsoon

23. Variation (%) of the elemental repartition in the PM10 and PM2.5 fractions of the Hymalaian airborne particulate between the pre-monsoon and the post- monsoon periods

24. Variation of the elemental repartitions of PM 10 and 2.5 fractions, between pre-monsoon (March/April 2002) and post-monsoon (October 2003) periods. Ca TSP/ PM 2.5 Pre-M = 7.4 TSP/ PM 2.5 Post-M = 2.4

25. Variation of the elemental repartitions of PM 10 and 2.5 fractions, between pre-monsoon (March/April 2002) and post-monsoon (October 2003) periods. Mn TSP/ PM 2.5 Pre-M = 10.4 TSP/ PM 2.5 Post-M = 7.7

26. Variation of the elemental repartitions of PM 10 and 2.5 fractions, between pre-monsoon (March/April 2002) and post-monsoon (October 2003) periods. Se TSP/ PM 2.5 Pre-M = 5.7 TSP/ PM 2.5 Post-M = 2.0

27. Variation of the elemental repartitions of PM 10 and 2.5 fractions, between pre-monsoon (March/April 2002) and post-monsoon (October 2003) periods. I TSP/ PM 2.5 Pre-M = 2.8 TSP/ PM 2.5 Post-M = 2.3

28. SUMMER - MONSON Air mass Trajectory – Winter - Dry (2000 – 2004)

29. WINTER - DRY Air mass Trajectory – Summer Monsoon (2000 – 2004) Arabic Sea

30. Comparison between the trace elements EF calculated in airborne particulate matter and in lichens collected at high altitude in the Himalayas (Khumbu valley - CNR Pyramid, March-May 2002) Cx APM / Cn APM EF = --------------------- Cx Soil / Cn Soil Where Cx is the concentration of the X element whose EF is to be determined Cn is the concentration of the normalizing element assumed to be uniquely characteristic of the background

31. Data Quality Assurance All the results have been checked and evaluated for the analitycal quality control by using the certified reference material SRM 2783 “Trace Elements on Filter Media” NIST - USA

35. IAEA Laboratories Seibersdorf, Austria; M. Bogovac, A. Mendoza; A. Markowicz A. Mendoza; A. Markowicz ANSTO, Australia; I. Orlic Ghent University, Belgium; W. Maenhaut University of São Paulo, Brazil; P. Artaxo Rudjer Boškoviç Institute, Croatia; M. Jakašiç Nuclear Physics Institute, Czech Republic; J Ku č era University of Pavia, Italy, M. Gallorini; E. Rizzio U.S. EPA, Research Triangle Park, NC, USA; J. Weinstein

36. Conclusions INAA has demonstrated its great capability in performing multielemental analyses at 10 -9 g (nanogram) level on fractions of few milligrams of air dust collected onto filters The first and preliminary elemental characterization of the airborne particulate matter collected in the Himalayas region at 5100 m a.s.l. during the pre-monsoon and post-monsoon periods (2002/2003) has been accomplished As expected, all the concentration values found in this work are very low and can be taken as baseline values of unpolluted high altitude remote areas Nevertheless, the Enrichment Factors indicate that some elements found in the Himalayan air particulate are partially of a non–local origin. Their concentrations in the PM2.5 suggests the presence of long distance transport phenomena.

37. A sensible seasonal variation between pre and post monsoon periods has been noticed for all the elements present in the airborne particulates being their concentrations, much lower in the post-monsoon period Iodine and, to some extent bromine, show in the post-monsoon period an enrichment of their concentrations that may be explained with the arrival of a southern air mass component coming from the Arabic Sea The quite good correspondence of EF values of many elements found in lichens and in the airborne particulate may suggest the use of lichens as trace metals permanent biomonitors also in this part of the world

38. Further research Obtain information about the trace elements concentration and their distribution in the aerosols dispersed in the different layers of the Himalayan troposphere; evaluation of the elements concentration variation with altitude (2650- 3570-5050 m a.s.l.) along a North-South transect during the pre and post monsoon seasons; this can give important information about the elemental composition of the pollutant aerosols present in the northern margin of Asian Brown Cloud ; the results will furnish fundamental data for assessing both air quality and possible trans-boundary air pollution phenomena in the Himalayan region.