Uranium concentrations in the bedrock groundwater of the Riutta area results from 2009 sampling campaign Kaija Juha & Pullinen Arto

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1 Etelä-Suomen yksikkö K129/53/ Espoo 135/2013 Public Uranium concentrations in the bedrock groundwater of the Riutta area results from 2009 sampling campaign Kaija Juha & Pullinen Arto

2 Geological Survey of Finland 1 Authors Juha Kaija Arto Pullinen Type of report Confidential contract work Commissioned by Areva Resources Finland Title of report Uranium concentrations in the bedrock groundwater of the Riutta area results from 2009 sampling campaign Abstract Altogether 19 groundwater samples were taken from 13 boreholes: old boreholes R324, R325, R326 and new boreholes R1-R10. The bedrock is characterized by recently recharged dilute groundwater of the Ca-HCO 3 and Ca- Na-HCO 3 type. Uranium concentrations in bedrock groundwater from boreholes R324, R325 and R326 were low, variation being from 1,29 to 18,9 μg/l. Uranium concentrations in the new boreholes varied according to the pumped volume of groundwater: concentrations in first samples varied from 0,95 μg/l to 20,3 μg/l and after pumping from 1,3 to 28,1 μg/l. The highest uranium concentrations found during this sampling campaign were close to the median uranium concentrations of the Finnish bedrock drilled wells. Keywords Eno, Riutta, uranium, bedrock, groundwater Geographical area Finland, North Karelia, Eno, Riutta Map sheet Other information Report serial Archive code E320/42/2008 Total pages Appendis Language English Price Confidentiality Public Unit and section ESY 212 Project code Signature/name Signature/name Juha Kaija

3 Geological Survey of Finland 2 TABLE OF CONTENTS 1 INTRODUCTION 3 2 GROUNDWATER SAMPLING 3 3 CHEMICAL ANALYSES 3 4 COMPOSITION OF GROUNDWATERS Water types Dissolved uranium 4 5 CONCLUSIONS 5 6 REFERENCES 6 APPENDIX 1. CHEMICAL ANALYSES OF RIUTTA SAMPLING CAMPAIGN MAY-JUNE 2009

4 Geological Survey of Finland 3 INTRODUCTION This report describes the findings of the hydrogeochemical study conducted in May-June 2009 by the GTK at the Riutta area in the municipality of Eno. Altogether 19 groundwater samples were taken from 13 boreholes: old boreholes R324, R325, R326 and new boreholes R1-R10. The research activities were carried out based on the order of the AREVA Resources Finland Oy, order number 0829 and GTK s project number FinU1. 1 GROUNDWATER SAMPLING A series of groundwater samples were taken from 6 sections of 3 old boreholes R324, R325 and R326 (Appendix 1). Sampling technique was the same packer method that is described in Kaija et al Groundwater samples from new boreholes R1-R10 were taken with P Monsoon pump which was lowered to the preferred sampling depth. Depth varied from 9 m to 40 m depending on the borehole conditions. In order to find out the possible changes in water chemistry first samples were taken without any excessive pumping of the groundwater (so called first strike samples), second samples were taken after 1 hour pumping from the borehole, i.e. pumped volume varied from 115 to 180 liters. All these samples represent open-hole conditions, packers were not used in sampling. 2 CHEMICAL ANALYSES Chemical components were analyzed at the chemical laboratory of Labtium. Labtium is accredited by the Centre for Metrology and Accreditation according to the SFS-EN ISO/IEC standard covering the ICP-AES analysis of major elements and ICP-MS analysis of trace elements as well as Br, Cl, NO 3, SO 4 and F analyses. According to the charge balance calculations, the quality of chemical analyses is good, average charge balance error is below ±5% (see Appendix 1). 3 COMPOSITION OF GROUNDWATERS 3.1 Water types The Riutta area bedrock is characterized by dilute groundwater of the Ca-HCO 3 and Ca- Na-HCO 3 type. Calcium is the dominant cation of this HCO 3 type groundwater zone, which is typical for recently recharged shallow bedrock groundwater. Total dissolved solids (TDS) vary from 80 to 231 mg/l.

5 0 Geological Survey of Finland Dissolved uranium Uranium concentrations in the bedrock groundwater from isolated borehole sections of R324, R325 and R326 were low, variation being from 1,29 μg/l to 18,9 μg/l (Appendix 1). Uranium concentrations in the bedrock groundwater of the new boreholes varied according to the pumped volume of groundwater (see Figure 1 and Appendix 1). In general the first samples from open boreholes had lower uranium concentrations than after one hour pumping ( liter pumped volume). Uranium concentrations of the first strike samples varied from 0,95 μg/l to 20,3 μg/l, after the pumping the variation was from 1,3 μg/l to 28,1 μg/l. The highest concentrations are close to the median uranium concentrations of the Finnish bedrock drilled wells (see e.g. Lahermo et al. 1990). Although the uranium concentrations increased during the pumping, the concentrations remained low compared for example to the bedrock groundwater of the Palmottu uranium deposit where the highest concentrations of μg/l are found in the Ca-HCO 3 type water of the so called Eastern Granite (Blomqvist et al., 1998). Uranium μg/l R1 R6 R7 R1 R2 R4 R5 R6 R7 R8 R9 R R2 R5 R8 R10 R4 R9 0 Figure 1. Uranium concentrations in the bedrock groundwater of the Riutta area boreholes R1- R10, first column represents the uranium concentration before pumping (first strike sample) and second column uranium concentrations after one hour pumping ( liters).

6 Geological Survey of Finland 5 4 CONCLUSIONS The Riutta bedrock is characterized by dilute groundwater of the Ca-HCO 3 and Ca-Na- HCO 3 type. Calcium is the dominant cation of this HCO 3 type groundwater zone, which is typical for recently recharged shallow bedrock groundwater. The highest uranium concentrations found during this sampling campaign were close to the median uranium concentrations of the Finnish bedrock drilled wells. Although the uranium concentrations increased during the pumping, the concentrations are low compared for example to the bedrock groundwater in the Palmottu uranium deposit where the highest concentrations μg/l are found in the Ca-HCO 3 type water of the so called Eastern Granite.

7 Geological Survey of Finland 6 5 REFERENCES Blomqvist, R.; Kaija, J.; Lampinen, P.; Paananen, M.; Ruskeeniemi, T.; Korkealaakso, J.; Pitkänen, P.; Ludvigson, J.-E.; Smellie, J.; Koskinen, L.; Floría, E.; Turrero, M. J.; Galarza, G.; Jakobsson, K.; Laaksoharju, M.; Casanova, J.; Grundfelt, B.; Hernan, P The Palmottu natural analogue project. Phase I: Hydrogeological evaluation of the site. Final report - Phase I. European Commission Nuclear Science and Technology Series EUR EN. Luxembourg: Office for Official Publications of the European Communities. 98 p. Kaija, J., Ruskeeniemi, T. and Pullinen, A Uranium concentrations in the bedrock groundwater of the Riutta area. Contract work 0829 for areva resources Finland Oy. 14 pages, 3 Appendices. Lahermo, P.; Ilmasti, M.; Juntunen, R. and Taka, M Suomen geokemian atlas. Osa 1 : Suomen pohjavesien hydrogeokemiallinen kartoitus = The Geochemical Atlas of Finland. Part 1 : The hydrogeochemical mapping of Finnish groundwater. Espoo: Geologian tutkimuskeskus. 66 p. + 1 app.

8 Appendix 1. Chemical analyses of Riutta sampling campaign May-June 2009 Analysed by Labtium Oy Packered borehole length, m Laboratory ID Sample ID Date Pumped volume l Watertype TDS Charge balance T ph ph El.cond. Ca Mg ms/m, 25 C mg/l % C field lab (field) mg/l mg/l R L APPV Ca-Na-HCO ,4 15,3 8,5 7,8 20,3 24,4 1,69 R L APPV Ca-Na-HCO ,3 10,4 8,4 7,8 17,8 21,0 1,79 R L APPV Ca-Na-HCO ,3 9,4 8,5 7,8 17,8 21,2 1,90 R L APPV Ca-Na-HCO ,9 7,7 8,6 7,8 17,7 20,8 1,58 R L APPV Na-Ca-HCO ,5 9,3 9,4 8,8 10,3 7,50 1,01 R L APPV Ca-Na-HCO 3 -SO ,9 6,4 8,4 7,4 18,2 18,3 2,26 R L APPV Ca-Na-HCO ,0 7,1-7,9 17,1 20,5 2,42 R L APPV Ca-Na-HCO ,9 6,6 8,5 8,1 18,4 18,1 2,24 NEW BOREHOLES (open, not packered) Depth of the pump Laboratory ID Sample ID Date Pumped volume l Watertype TDS Charge balance T ph ph El.cond. Ca Mg ms/m, 25 C mg/l % C field lab (field) mg/l mg/l R1 (beginning) L APPV Ca-HCO ,3 6,9-7,5 14,5 21,6 2,10 R1 (1 hour pumping) 31 m L APPV ~150 Ca-HCO 3 -SO ,5 7,3-7,4 13,3 19,8 1,81 R2 (beginning) L APPV Ca-Na-HCO ,1 8,4-7,6 19,4 25,2 3,25 R2 (1 hour pumping) 40 m L APPV Ca-HCO ,4 7,1-6,5 9,0 11,9 1,38 R3 (1 hour pumping) 9 m L APPV ~150 Ca-Na-HCO ,0 7,5-5,9 13,6 17,7 2,67 R4 (beginning) L APPV Na-Ca-HCO ,3 8,1-7,3 19,3 15,2 2,11 R4 (1 hour pumping) 20 m L APPV ~150 Ca-Na-HCO ,1 7,7-6,6 15,7 15,6 2,19 R5 (beginning) L APPV Ca-Na-HCO ,5 8,2-7,1 19,5 26,7 3,48 R5 (1 hour pumping) 20 m L APPV ~150 Ca-Na-HCO ,2 10,8-7,0 19,1 26,9 3,52 R6 (beginning) L APPV Ca-HCO ,3 7,7-7,4 18,8 28,7 2,99 R6 (1 hour pumping) 20 m L APPV Ca-HCO ,5 8,7-8,0 18,9 29,6 2,70 R7 (beginning) L APPV Ca-HCO ,6 8,0-8,1 20,8 32,2 3,81 R7 (1 hour pumping) 20 m L APPV Ca-HCO ,2 9-8,1 18,7 28,7 3,18 R8 (beginning) L APPV Ca-Na-HCO ,5 9,7-8,1 18,9 20,2 1,57 R8 (1 hour pumping) 20 m L APPV Ca-Na-HCO ,3 8,7-7,3 16,7 21,1 1,32 R9 (beginning) L APPV Ca-HCO ,4 6,9-7,8 25,5 42,1 4,17 R9 (1 hour pumping) 20 m L APPV Ca-HCO ,3 6,2-7,1 12,1 17,5 1,67 R10 (beginning) L APPV Ca-HCO ,8 7,2-7,6 23,9 37,8 4,35 R10 (1 hour pumping) 36 m L APPV ~150 Ca-HCO ,6 6,1-7,2 15,4 23,2 2,53 Pump type used for sampling from new boreholes was Monsoon submersible groundwater pump 1 of 3

9 Appendix 1. Chemical analyses of Riutta sampling campaign May-June 2009 Analysed by Labtium Oy Packered borehole length, m Na K Cl SO 4 HCO 3 NO 3 Br F Si Fe Mn Sr B Ba Li Al Rb V Cr mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l R R R R R R R R ,0 0,58 0, <0.2 <0.1 1,7 6,22 0,07 16, ,4 0,85 1,01 9,84 1,68 0,25 0,20 14,3 0,58 0, <0.2 <0.1 1,3 5,65 0,14 16, ,5 0,80 0,65 6,69 1,20 0,13 <0.2 12,9 0,59 0, <0.2 <0.1 1,2 5,50 0,11 14, ,5 0,63 0,7 5,26 1,18 0,13 <0.2 13,6 0,49 0, <0.2 <0.1 1,5 5,69 0,08 10, ,6 0,58 0,62 6,53 1,00 0,11 <0.2 11,2 0,69 0,5 0,2 61,6 <0.2 <0.1 1,3 0,19 <0.03 8,52 73,8 11,7 0,46 0,59 4,24 1,55 0,11 <0.2 17,6 0,37 0, <0.2 <0.1 2,0 6,11 0,14 8, ,6 0,67 1,43 7,89 0,91 0,16 <0.2 11,9 0,42 0, <0.2 <0.1 1,1 5,34 0,04 9, ,1 0,52 1,29 5,74 0,93 0,17 <0.2 17,8 0,35 0, <0.2 <0.1 1,6 6,18 0,04 7, ,3 0,54 1,48 7,44 0,84 0,11 <0.2 NEW BOREHOLES (open, not packered) Depth of the pump Na K Cl SO 4 HCO 3 NO 3 Br F Si Fe Mn Sr B Ba Li Al Rb V Cr R1 (beginning) R1 (1 hour pumping) 31 m R2 (beginning) R2 (1 hour pumping) 40 m R3 (1 hour pumping) 9 m R4 (beginning) R4 (1 hour pumping) 20 m R5 (beginning) R5 (1 hour pumping) 20 m R6 (beginning) R6 (1 hour pumping) 20 m R7 (beginning) R7 (1 hour pumping) 20 m R8 (beginning) R8 (1 hour pumping) 20 m R9 (beginning) R9 (1 hour pumping) 20 m R10 (beginning) R10 (1 hour pumping) 36 m mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l 3,05 0,84 0, <0.2 <0.1 0,2 5,74 0,72 31,6 59,4 4,71 0,99 1,23 20,4 1,73 0,30 <0.2 2,63 0,82 0, <0.2 <0.1 0,1 4,74 0,55 39,8 43,5 3,51 0,90 0,77 4,19 2,22 0,27 <0.2 11,3 0,38 0, <0.2 <0.1 1,1 8,18 0,16 19, ,2 1,34 1,31 20,8 1,44 0,19 <0.2 3,57 0,64 0,5 6,9 50,0 <0.2 <0.1 0,2 4,94 0,14 25,6 56,2 4,06 1,56 0,73 39,4 2,22 0,34 <0.2 7,17 0,31 0,5 4,2 80,5 <0.2 <0.1 0,7 6,44 0,17 15, ,53 4,91 0, ,04 0,44 0,29 25,3 0,71 0, <0.2 <0.1 3,2 9,61 0,03 4, ,0 1,43 1,37 9,06 1,53 0,18 <0.2 15,7 0,77 0,7 6,5 91,5 <0.2 <0.1 1,8 7,43 1, ,7 15,7 2,78 1,14 91,2 1,96 0,44 0,45 9,89 0,73 0, <0.2 <0.1 1,3 6,80 0,04 23, ,3 1,64 1,56 64,0 1,50 0,32 <0.2 8,88 0,76 0,4 9,3 111,0 <0.2 <0.1 1,2 6,26 0,04 31, ,4 1,61 1,71 55,9 1,53 0,26 <0.2 6,30 0,66 0, ,9 <0.1 0,9 5,95 0,04 9, ,12 1,87 1,02 18,6 1,73 0,34 <0.2 5,43 0,65 0, ,1 <0.1 0,7 5,36 0,03 18, ,54 1,67 0,78 18,4 1,92 0,47 <0.2 4,88 0,97 0, ,3 <0.1 0,7 4,85 0,03 6, ,67 1,87 2, ,79 0,69 <0.2 4,52 1,00 0, ,9 <0.1 0,6 4,42 < , ,33 1,75 5, ,58 0,78 <0.2 18,2 1,12 2,1 7,7 117,2 <0.2 <0.1 1,2 3,81 0,31 39,5 75,9 23,5 2,92 5, ,95 0,59 <0.2 8,87 1,06 3,3 3,9 84,8 1,2 <0.1 0,4 5,15 1, ,9 10,3 7,13 4,31 72,3 3,03 0,65 0,28 4,15 2,33 4,0 1,7 153,2 <0.2 <0.1 0,2 7,32 0, ,2 19,8 1,81 18,8 3,46 0,57 0,36 2,05 0,95 1,7 2,6 62,2 0,7 <0.1 <0.1 4,77 2, ,5 3,77 8,64 0, ,81 0,47 0,67 5,96 1,65 2,0 2,7 145,8 <0.2 <0.1 0,5 5,34 0,51 74, ,9 20,8 1,63 35,7 3,02 0,37 0,20 3,67 1,07 1,3 3,4 86,6 0,4 <0.1 0,2 5,32 1, ,4 9,19 12,9 1, ,53 0,89 0,68 Pump type used for sampling from new boreholes was Monsoon submersible groundwater pump 2 of 3

10 Appendix 1. Chemical analyses of Riutta sampling campaign May-June 2009 Analysed by Labtium Oy Packered borehole length, m Co Ni Mo Cu Zn Cd Pb As Sb Th U µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l R R R R R R R R ,12 0,5 69,2 0,60 0,42 0,05 <0.05 0,86 0,02 0,16 2,82 0,06 0,31 37,8 0,45 <0.2 0,03 <0.05 0,08 0,02 0,06 4,89 0,05 0,25 38,6 0,69 <0.2 0,03 <0.05 <0.05 <0.02 0,03 5,46 0,04 0,24 36,4 0,40 <0.2 0,03 <0.05 <0.05 <0.02 0,02 2,33 0,02 0,15 18,8 0,42 <0.2 <0.02 <0.05 0,05 0,02 0,01 1,29 0,04 0,22 74,3 0,42 <0.2 0,05 <0.05 0,10 <0.02 0,01 9,12 0,05 0,26 49,0 0,35 <0.2 0,03 <0.05 0,05 <0.02 0,01 18,9 0,04 0,23 77,5 0,42 <0.2 0,05 <0.05 0,05 <0.02 0,01 2,15 NEW BOREHOLES (open, not packered) Depth of the pump Co Ni Mo Cu Zn Cd Pb As Sb Th U R1 (beginning) R1 (1 hour pumping) 31 m R2 (beginning) R2 (1 hour pumping) 40 m R3 (1 hour pumping) 9 m R4 (beginning) R4 (1 hour pumping) 20 m R5 (beginning) R5 (1 hour pumping) 20 m R6 (beginning) R6 (1 hour pumping) 20 m R7 (beginning) R7 (1 hour pumping) 20 m R8 (beginning) R8 (1 hour pumping) 20 m R9 (beginning) R9 (1 hour pumping) 20 m R10 (beginning) R10 (1 hour pumping) 36 m µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l 0,07 2,05 16,3 0,36 5,99 <0.02 0,11 0,11 0,03 0,02 14,6 0,30 0,67 13,6 0,24 1,27 <0.02 <0.05 0,09 0,02 < ,5 0,10 1,25 19,7 0,60 1,39 0,02 <0.05 0,07 0,02 0,03 2,86 0,19 1,08 19,9 7,42 3,28 0,02 <0.05 0,13 0,03 0,02 10,4 0,29 1,30 11,9 2,20 0,68 <0.02 <0.05 0,09 0,02 0,08 5,24 0,04 0,58 27,2 0,39 1,41 0,02 <0.05 <0.05 <0.02 0,01 0,95 0,68 3,21 19,2 1,06 4,20 <0.02 <0.05 0,27 0,11 0,07 2,75 0,10 2,07 27,0 0,43 1,68 0,02 <0.05 0,08 0,03 0,01 4,81 0,24 5,99 28,3 0,48 0,61 0,02 <0.05 0,23 0,09 0,01 10,8 0,08 0,59 69,4 1,28 1,51 0,05 0,11 0,13 0,07 0,01 20,3 0,10 0,76 66,3 0,77 0,28 0,05 <0.05 0,10 0,05 0,01 16,7 0,07 0,62 32,0 0,39 0,44 0,02 0,06 0,32 0,08 0,02 12,1 0,08 0,51 85,0 0,28 <0.2 0,06 <0.05 0,55 0,09 0,01 28,1 0,06 0,33 15,0 0,53 0,34 <0.02 <0.05 0,21 0,12 0,05 4,29 0,19 0,77 7,08 0,44 1,42 <0.02 <0.05 0,26 0,07 0,03 10,1 0,25 0,98 5,44 0,33 0,20 <0.02 <0.05 0,30 0,02 0,03 1,32 0,40 2,39 2,32 1,75 4,75 <0.02 <0.05 0,21 0,05 0,09 1,34 0,40 1,75 12,1 0,46 0,37 <0.02 <0.05 0,27 0,03 0,04 5,66 1,41 2,39 7,22 2,43 2,95 <0.02 0,07 0,48 0,05 0,17 7,60 Pump type used for sampling from new boreholes was Monsoon submersible groundwater pump 3 of 3