Formation waters the history of radium bearing waters
Formation waters – the history of radium bearing waters treatment (226 Ra and 228 Ra) Stanisław Chałupnik BCR – Silesian Centre for Environmental Radioactivity
Very first reports on treatment of formation waters (as we know. . ) • Russia, 1922, Bogoiavlienskiy – radium in brine from former oil rig, 226 Ra concentration up to 290 k. Bq/m 3. In 1931, Komi Republic, beside the Vodny settlement production of 226 Ra started. About 150 g of pure radium was produced. Equipment was poorly designed (wooden pipes and barrels were used) and safety measurements were ignored. In 1956, activity was stopped leaving 3000 km 2 of radioactively contaminated land. • in 1937 the production of barite has been started in Eccles Colliery (UK), production lasted till 1970 reaching up to 3000 tonnes/y, no information of radioactivity available • In Poland: early 70’s - first measurements of radium (226 Ra) in brines in southern part of the Upper Silesia Coal Basin, in 80’s – investigations of environmental pollution, in 90’s – implementation of mitigation measures 2
Radioactivity of formation waters in Poland need for treatment • The most important fact, related to the treatment of mine waters to remove radium was the presence of barium in some brines and scaling of pipelines in mines • In early 80 s, a huge pipeline system was designed and constructed to collect brines from a dozen of collieries in southern part of the coal basin (OLZA Collector) • Within 10 years of exploitation the pipeline was scaled and effectively blocked. Due to the fact it was a need for barium (radium) removal in few mines. Scaling started near the inflow of non-radioactive, sulphate rich waters. 3
Scales inside pipes
First regulations related to Mining Industry • The law, applicable for mining industry: • The radium isotopes content in discharge waters should not exceed (0. 01 ALI/m 3): • 0. 7 k. Bq/m 3 Ra-226; • 0. 9 k. Bq/m 3 Ra-228 • Act of April 10, 1986 - Atomic Law, M. P. No. 1986 No. 12, item 70 followed by Order of the President of the National Atomic Energy Agency dated on 19 May 1989 on the principles of classifying waste as radioactive waste and its classification and evidence, as well as the conditions for its neutralization, storage and disposal M. P. 1989 No. 18 item 125, valid until 1. 01. 2003 (cancelled by amendements in Atomic Law 2002 (Prawo Atomowe) - that was the legal basis for mine water treatment for radium removal. 5
Radioactivity of effluents in Polish law • In the year 2002 amendements to the Atomic Law were issued, changing it significantly and effectively cancelled the Order of PAA President. • 10 MBq/m 3 Ra-226, 10 MBq/m 3 Ra-228 in discharge waters from nuclear installations - Regulation of the Council of Ministers, dated on 3 rd of December 2002 on radioactive waste and spent nuclear fuel. Journal of Laws 2002 No 230, item 1925, valid until 25. 11. 2015 not applicable for non-uranium mining. • Despite that situation the Environmental Protection Department of Silesian Voivodeship decided to keep the level of radium below 0. 7 k. Bq/m 3 for mine effluents and enforced construction of treatment station in some collieries/ This project has received funding from the Euratom research and training programme 2014 -2018 under grant agreement No 900009.
Current legal situation in Poland • Nowadays – no regulations regarded directly mine waters, the exemption level for solid waste – 1 Bq/g (1 k. Bq/kg) - EU Directive Euratom/59/2013 – valid in Poland since February 2018. • Since 1989 mining industry regulations, related to The Geological and Mining Law – the mine waters with radium content Ra 226+Ra-228 > 1 k. Bq/m 3 should be treated as waters with enhanced radioactivity (first regulations issued by Ministry of Mining and Power Generation in December 1989). 7
Mine water treatment • Due to the Order of the Polish Atomic Energy Agency President from 1989, temporal decisions were issued for mines by Department of Environmnetal Protection of Silesian Voivodeship, requiring the implementation of the method of radium purification from mine effluents below the level of 0. 7 Bq/L until the certain date. • For KWK Piast, the last remedial decision was issued in 1995 with a demand of the commissioning of the treatment station until 2000. In KWK Piast, such a station was constructed and started to work in 1999. • In KWK Ziemowit the last remedial decision was issued in 2009, with the requirement to continue the purification of water from radium, as such an installation was launched in 2006. (despite the fact the PAA Order was cancelled in 2003) This project has received funding from the Euratom research and training programme 2014 -2018 under grant agreement No 900009.
In Polish mines two types of brines occur. 9
Treatment for radium removal • For sulphate rich waters most common technique is the use of barium chloride, leading to the co-precipitation of barium and radium sulphates (eq. 1. ). In case of barium rich waters, the carrier is already in the brine, therefore it is necessary to add sulphates to the water (eq. 2). In both methods the removal of radium is based on chemical reactions. Co=precipitation of radium with barium as sulphates (eq. 3). • These reactions are as follows. When barium chloride is used for this purpose, at first the barium chloride dissolves in the water. • Ba. Cl 2 Ba 2+ + 2 Cl(1) • Or • Ca. SO 4 Ca 2+ + SO 42(2) • Next step of the reaction is the co-precipitation of radium and barium ions as sulphates (in case of sulphate rich waters, the reaction is not stoichiometric): • Ba 2+ + Ra 2+ + 2 SO 42 - Ba. Ra(SO 2)4 (3) • As a result of the latter reaction, small crystals of barium sulphate are formed, need a certain time for sedimentation. This project has received funding from the Euratom research and training programme 2014 -2018 under grant agreement No 900009.
Treatment of barium rich waters laboratory experiments This project has received funding from the Euratom research and training programme 2014 -2018 under grant agreement No 900009.
Underground application in Krupinski mine the release - 6000 m 3/day This project has received funding from the Euratom research and training programme 2014 -2018 under grant agreement No 900009.
Results of purification in Krupiński Mine feeding 1 kg of gypsum/m 3 (stoeichiometric) This project has received funding from the Euratom research and training programme 2014 -2018 under grant agreement No 900009.
Treatment of sulphate rich waters First application • Total volume of the system - 100 000 m 3 - five paralel galleries with the length exceeding 1 km, a cross section roughly 23 m 2 • Flow rate - 6 m 3/min. i. e. 10 000 m 3/day • Radium concentration before treatment: – Ra-226 6 k. Bq/m 3 Ra-228 10 k. Bq/m 3 • Target concentration – Ra-226+Ra-228 < 0. 7 k. Bq/m 3
Sedimentation galleries This project has received funding from the Euratom research and training programme 2014 -2018 under grant agreement No 900009.
Containers with barium chloride
Feeder
First year of purification May 1999 - March 2000 [k. Bq/m 3] 14 Ra-226 wlot Ra-228 wlot Ra-226 wylot Ra-228 wylot 0. 7 k. Bq m/3 12 10 8 6 4 2 ch ar M 26 br Fe 25 26 Ja nu ua ry ar y r ec D 27 ov N 27 em be r r 28 O ct be em 28 Se pt Au 29 ob e r gu st ly Ju 30 ne 30 Ju ay M 31 1 M ay 0
Results for the surface
What did we achieve? • The unique underground treatment installation has been built in coal mine. • Implementation of the technology in the coal mine was difficult but possible. • Environmental effect of purification – decrease of radium release into Gostynka river, Vistula tributary (120 MBq/day).
Second application This project has received funding from the Euratom research and training programme 2014 -2018 under grant agreement No 900009.
Pumping station This project has received funding from the Euratom research and training programme 2014 -2018 under grant agreement No 900009.
Feeders This project has received funding from the Euratom research and training programme 2014 -2018 under grant agreement No 900009.
Barium chloride This project has received funding from the Euratom research and training programme 2014 -2018 under grant agreement No 900009.
Results of water treatment This project has received funding from the Euratom research and training programme 2014 -2018 under grant agreement No 900009.
Effects for the environment • In February 2006 the purification process has been started in the second colliery. Previously the total release of radium isotopes into settling pond was roughly 120 MBq/day. • After implementation of treatment technology the total activity is 20 MBq/day only – 1/6 th of the previous value. • The reduction of the release is of about 100 MBq per day i. e. 40 GBq per year! This project has received funding from the Euratom research and training programme 2014 -2018 under grant agreement No 900009.
Perspectives – at the end of 2007 and now • Important issues • Radium removal from mine waters in collieries and copper mines • Radium leaching from sediments – settling ponds • Ground reclamation methods – settling ponds • Future • Desalination? One desalination plant in Poland • Exploitation of deeper seams – new inflows of radium bearing brines – new problems, already visible in several mines in the last decade This project has received funding from the Euratom research and training programme 2014 -2018 under grant agreement No 900009.
Thank you very much? Not so easy, folks – we still have problems This project has received funding from the Euratom research and training programme 2014 -2018 under grant agreement No 900009.
This project has received funding from the Euratom research and training programme 2019 -2020 under grant agreement No 900009
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