dana pittauerova karlsbad thermal springs - uni-bremen.de · radioactivity of thermal springs in...

Radioactivity measurements laboratory

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Radioactivity of thermalsprings in Karlsbad

Viktor Goliáš 1

Daniela Pittauerová 1,2

Zdeněk Třískala 1

Radek Procházka 1

Tomáš Vylita 3,4

1 Faculty of Science, Cherles University in Prague2 IUP, University of Bremen3 Mineral water bureau of Karlovy Vary spa resort (SPLZaK)4 Reference Laboratory for Natural Therapeutic Sources ofthe Czech Republic


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Contents

• Motivation• Introduction• Measurement device• Field work, sampling of the waters• Method of measurements and calculations• Short-term gamma activity• Radioactive equilibrium• Permanent gamma activity• Radon activity• Conclusions


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Motivation

• Increased radioactivity of Karlovy Vary (Karlsbad) waters first measured by Mache and Meyer (1905). They found activity varying from 11,8 to 515 Bq/l. Similar conclusions were acquired later by other authors (Vylita 1990, Vrba 1996).

• In previous studies the waters were sampled into vessels and their activity was determined after some interval in a laboratory. For the medical purposes, however, waters are used immediately at their outlet into spring vases.

• In this study activities of hot springs measured as soon as possible after sampling.

– Mache H., Meyer S. (1905): Über die Radioaktivität der Quellen der böhmischen Bädergruppe: Karsbad, Marienbad, Teplitz-Schönau-Dux, Franzensbad sowie von St. Joachimsthal. Aus den Sitzungsbereichten der kaiserl. Akademie der Wissenschaften in Wien. Mathem.-naturw. Klasse. 114. Abt. II.a. Wien.

– Vylita B. (1990): A walk through Karlovy Vary with a geologist. (In Czech - S geologem po Karlových Varech). Czech Geol. Survey. Praha.

– Vrba J. (1996): Thermal mineral water springs in Karlovy Vary. Environmental Geology, 27 (2): 120-125.


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Motivation

• Projects supported by Mineral water bureau of Karlovy Vary spa resort– 2003: Determination of short-term gamma activity and evaluation of

radioactive equilibrium of mineral waters– 2004: Determination and evaluation of short-term alpha activity of

radon in liquid and gas components of mineral waters

• Characterization of short-term gamma activity of springs and radon activity of springs and separated gas

• Gamma activity measurement in time series: estimation of radioactive equilibrium

• Radioactive equilibrium evolution in short time after sampling (X hours)


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Motivation

• Project supported by Czech Science Foundation– 2007: Karlovy Vary hot spring radionuclides as one of important

factors of balneological effect of mineral waters

• Determination of mineral waters short-term gamma and alpha activity and radioactive equilibrium evaluation

• Long-term observation of "Hot spring" activity• Long-living radionuclides determination in thermal waters• Determination of radionuclides content in sinters and study of their

mineralogical bond• Calculation of radionuclides intake during the course of treatment and

after its termination


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Karlovy Vary - Karlsbad

• Western part of the Czech republic, 120 km fromPrague, at rivers Ohře and Teplá

• Karlovy Vary is the largest spa city in the Czech Republic


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Karlovy Vary - Karlsbad

• The hottest and the most substantial mineral spring is theHot Spring (Brudel)

• The largest and most popular esplanade is Mill Colonnade

• The best known products: Moser glassware, Becherovka herbal liqueur, Mattoni mineral water, spa wafers, Thun porcelain


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Balneology

• Tens of mineral springs with varying yields, some are controlled and used for drinking cure

• Mineral springs in Karlsbad used for healing ofdigestive tract disorders, metabolic disorders, diabetes, gout, obesity, locomotor system disorders, diseases of the liver, pancreas, gall bladder, and biliary ducts, oncologicalconvalescents, neurological diseases, and many others...

• Low doses of radioactivity (222Rn) and its short-lived progeny (218Po, 214Pb, 214Bi and 214Po) often considered to have positive (healing) effects and are applied in form of baths, drinking cure or inhalation.

– Deetjen P., Falkenbach A., Harder D., Jöckel H., Kaul A., Philipsborn H. V. (2005): Radon als Heilmittel. Terapeutische Wirksmkeit, biologischer Wirkungsmechanismusund vergleichlende Risikobewertung. - Verlag Dr. Kovac. Hamburg. 111s.


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Balneology

• Besides the direct curative effects of waters the beneficial health effect can show also an increased ionisation of air and presence of nonfilterable particles (so called “geoaerosols“) measured in the vicinity of tectonic structures in Karlovy Vary.

– Krčmář B., Vylita T. (2001): Unfilterable„geoaerosols“, their use in the search for thermal mineral and mineralized waters, and their possible influence on the origin of certain types of mineral waters. Environmental Geology, 40 (6): 678-682.


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1.271

Fe2+

0.098

Mn2+

0.011

UO22+

0.059

Zn2+

0.48

Sr2+

124.4

Ca2+

45.20

Mg2+

0.0650.01293.2416992.91mg/l

Be2+Cu2+K+Na+Li+Cations

0.359

HPO42-

0.203

HAsO42-

2150

HCO3-

0

NO2-

0

NO3-

1629

SO42-

00.0251.398598.56.45mg/l

HS-I-Br -Cl-F-Anions

94.812.33mg/l

H2SiO3HBO2Non-disolved

comp.

813,2mg/l6.906 450 mg/l

CO2pHTotal mineralization

Chemical composition (BJ-70)

• The basic composition of various springs is quite similar• The temperatures and contents of CO2 differ


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Springs:1. BJ-35, 36, 37 (Vřídlo, Hot S., Brudel)2. BJ-74 (Charles IV. S.)3. BJ-86 (Market S.)4. (Upper Chateau S.)5. BJ-79 (Lower Chateau S.)6. Palatin7. BJ-41 (Mill S.)8. Tereziiny9. BJ-48 (Rusalka S.)10. BJ-53 (Prince Václav I. S.)11. (Prince Václav I. S.)12. BJ-53 (Libuše S.)13. BJ-96+97 (Rock S.)14. BJ-93 (S. of Liberty)15. BJ-91 (Snake S.)

16. BJ-88 (Park S. new)17. č. 64 (Park S. old)18. č. 84 (Iron S.)19. BJŠ-5 (Štěpánka S.)


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Measurement device 2003

• Measurement device placed in the building of SPLZaK• Setup: scintillation detector NaI(Tl) 75*75 mm with energy

resolution 7,1%, 7 cm Pb shielding• 4096 channel analyzer Canberra Series 10 Plus• Connected to PC


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May 2003

• Primary data obtained during 73 hour non-stop measurement

• 160 spectra obtained


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Sampling 2003

• Waters sampled and sealed into 1 l PP Marinelli beakers at the spring outlets

• Measurement of gamma activity as soon as possible after sampling – hot waters need cooling


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Measurement device 2007

IMPROVEMENTS:• Active cooling of Al lining and the detector• Canberra DSA 2000 analyzer and Genie 2000 software


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Sampling 2007

• Waters sampled and sealed into 1,5 l HDPE Marinelli beakers at the spring outlets

• Measuring without previous cooling

• Starting measurement in 2-3 minutes after sampling


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Obtaining data

• Sealed and cooled samples put in Pb-shielding and measured for 10-20 min

• Spectra transferred into PC for later processing• Readings of total count (Ntot) and integral counts in ROIs

used for prompt data processing – optimalization of measurement process

• Most of the samples measured in time series: estimation of gamma-activity evolution connected with radioactive equilibrium

• Totally 25 samples measured


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• Certified RaCl2 standard solution (Eurostandard CZ)• Additionally: standard Th(NO3)4 solution and deionized

water

• Volume activity: Av [Bq/l]• Due to use of Ra standard it is necessary to use unites

eRa („radium equivalent“) for TC (total count)

Standards and units


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• Difference between samples of waters comparing to standards is the absence of isotope 226Ra in waters: lower discrimination level set to 220 keV – above this energy samples and standards qualitatively equal

• Calculation of TC of archived spectra in MS Excel:

Av=(Nt/t-n bkg )/at, where

Av... volume activity of the sample [Bq/l eRa],Nt... total count t... measurement timenbkg...background countat... sensitivity constant calculated of known standard activity

Calculation of total gamma activity


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214Bi activity

volume activity of 214Bi calculated using similar algorithm as TC

0

200

400

600

800

1000

1200

0 200 400 600 800 1000 1200 1400 1600

214 Bi609 keV

214 Bi769 keV

214 Bi1120 keV

214Pb352 keV

214Pb295 keV214Pb

242 keV

PbKα, 77keV ROI (214Bi)

554-674 keV

ROI (TC)220-1585keV

ROI (214Pb)323-394keV

ROI (214Pb and 214Bi) the same relative ROI width ∆∆∆∆E/E[%]


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• Part of energy emitted by 214Bi undergoes Compton scattering and contributes also to 214Pb ROI

• Stripping method: subtraction of Compton continuum

• PROBLEM: not possible to use classical stripping factor calculation of 2 independent standards, because both isotopes are in genetical dependence – impossible to make such standards

• SOLUTION: use of registration efficiency coefficients of both energies by analogous scintillation crystal: tables by Vartanov and Samojlov (1975)

– Vartanov N.A., Samojlov P.S. (1975): Applied scintillation gamma spectroscopy. (In Russian Prikladnaja scintilacionnaja gamma-spektrometrija.) Atomizdat. Moskva.

214Pb activity: stripping method


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stripping koeficient = compton (ROI 214Pb) / (NROI 214Bi – Nbkg ) = 0,7976

Rn standard spectrum:• Net area of 214Bi by AREA function• from 214Pb peak subtracted proportional

part of its area which belongs to 214Pb (ratio according to sensitivity of detector to given energies), the rest is Compton from 214Bi - 54%

• total peak area of 214Bi peak by INTEG function and background subtraction0

100

200

300

400

500

330 430 530 630

214 Bi609 keV

214Pb352 keV

Stripping coefficient estimation


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Detected radionuclides

• Only 2 gamma emitters: 214Pb a 214Bi (222Rn progeny)• Most of short-term gamma-activity of Karlsbad mineral

waters caused by radon• Gamma activity vanishes by manipulation with non-sealed

samplesZElement


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0

200

400

600

800

1000

1200

0 200 400 600 800 1000 1200 1400 1600

V36

HD2

bkg

214 Bi609 keV

214 Bi769 keV

214 Bi1120 keV

214Pb352 keV

214Pb295 keV

214Pb242 keV

PbKα, 77keV

Detected radionuclides


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Total gamma activity distribution

• Histogram of all 144 values of total gamma activity• Most common values: 0-50 Bq/l eRa (Vřídlo – Hot Spring and springs

in its vicinity)• activities >50 Bq/l eRa: springs at the periphery of spring structure

(Park old and new, Snake, Štěpánka, Tereziiny springs)• 600-900 Bq/l eRa: Iron spring

Histogram of gamma activity values

Total gamma activity TC [Bq/l eRa]

Num

ber


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Karlovy Vary 2007

• 18 springs measured in time series, some of them several times (Charles IV. sampled even nine times)

• Gamma activities obtained (after stabilization):

6,6 – 567 Bq/l eRn

mean 72,4 Bq/l eRnmedian 18,6 Bq/l eRn


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Permanent activity

• Original archived samples measured with the same measurement device at the Radiometric laboratory ÚGMNZ

• Measurement after decay of short-lived radon progeny after more than 3 weeks

• Caused by dissolved radioactive elements, mainly radium• Due to low activity it was only possible to estimate the total gamma

activity

RESULTS:• the lowest: 0,78 Bq/l eRa – Iron spring• the highest: 3,39-5,22 Bq/l eRa – Hot spring• Karel IV., Václav I., Rock, Park new, Štěpánka, Lower Chateau – about

3 Bq/l eRa


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Permanent activity

• Contents of 238U and 232Th in Karlovy Vary hot springsmeasured by ICP-MS (Mihaljevič, Vylita, unpublished data):

0.02 Bq/l 238U and less then 0.01 Bq/l 232Th

• Mineral Water Bureau of Karlovy Vary archive data:238U maximum activity: 0.05 Bq/l


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Modelled evolution of radioactive equilibrium of radon and its progeny

0,0

0,5

1,0

1,5

2,0

2,5

3,0

0,0 60,0 120,0 180,0 240,0 300,0 360,0

t [min]

rela

tive

activ

ity

total alfa: 222Rn+218Po+214Po total gama: 214Pb + 214Bi214Bi, 214Po214Pb218Po222Rn

c

Radioactive equilibrium


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2 types of radioactive disequilibrium

• disequilibrium between dissolved 222Rn and both gamma-emitting decay products (estimated by comparing total activity immediately after sampling and after its stabilization)

• disequilibrium between 214Pb a 214Bi (estimated by comparing activities of both nuclides)



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2 trends of gamma activity evolution

1. INCREASING TREND – mostly with cooler springs• this trend can be described by theoretical model• similar is also disequilibrium between both radionuclides

and TC – in the beginning of the equilibrium evolution often AV214Pb>TC > AV214Bi

• in the sample first 214Pb is cumulating and the equilibrium is stabilized only 4-5 hours after sampling



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0

50

100

150

200

250

300

00:00 04:00 08:00 12:00 16:00 20:00 00:00 04:00 08:00 12:00 16:00

time [h]

activ

ity [B

q/l]

Železnatý /10Hadí 2

Štěpánka

Sadový nový

Skalní

Mlýnský 2

Libuše

Rusalka

Václav I 2

Tereziiny

Increasing trend


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Increasing trend

0

50

100

150

200

250

300

-100,0 -50,0 0,0 50,0 100,0 150,0 200,0 250,0 300,0 350,0 400,0

time [min]

tota

l gam

ma

activ

ity [B

q/l e

Ra]

Hadí pramen

Pramen Libuše

Mlýnský pramen

Pramen Sadový nový

Skalní pramen

Pramen Štěpánka

Železnatý pramen / 5

Initial activity A0 [Bq/l] radioactive equilibrium factor A0/Amax= 22-70%residence time tr [min] – 20-66 min


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2. DECREASING TREND – typically with hotter springs• characterized by initial sharp decrease until approximately

1,5-2 hours after sampling followed by slight decrease or stabilization

• at the time of sampling the system is enriched with decay products of Rn (disequilibrium with Rn gas)


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0

50

100

150

200

00:00 02:00 04:00 06:00 08:00 10:00 12:00 14:00 16:00 18:00 20:00 22:00 00:00

time [h]

activ

ity [B

q/l]

Mlýnský 1

Sadový starý

Tržní

Václav I 1

Vřídlo V362

Karel IV 1

Karel IV 2

Karel IV 4

Decreasing trend


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Possible explanation of decreasing trend

Escaping of dissolved gas into gaseous phase with pressure decrease and elution of short-term progeny

from gasseous phase of hot spring

+ different inclination of different spring curves – convolution of activity decrease (“foreign products”) and “own products”accumulation (Rn daughters)

+ occurrence of radioactive equilibrium where AV214Bi >TC in case of Hot spring and Charles IV. - 214Pb deficiency

- 3 springs (Mill s., Liberty s. and Václav I.) show both trends – increasing and decreasing for different samples

- inclination of curves at the “stabilized” part are steeper than expected according to the model


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Activities estimated:

214Pb [Bq/l]214Bi [Bq/l]TC [Bq/l eRn]

• Measurement in time series

• Recording spectra each 5 min during 5 hours (each sample - 60 spectra)

• In 10 days round 3000 spectra measured

November 2007


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Total activity evolution - time series


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• volume activity of Rn in waters –17 springs sampled at the spring outlets

• volume activity of Rn in separated gas – sampled at 4 gas separators

• measured using emanometer RP-25 with ionization chamber 0.43l

• standardization: diluted liquid 226Ra standard (Czech metrological institute)

Radon activity measurements 2004


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emanometer RP-25

Radon activity measurements


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1

10

100

1000

1 10 100 1000

gama aktivita [Bq/l eRa]

aktiv

ita r

adon

u [B

q/l]

Tržní

Karel IV.

Vřídlo

Václav I.

Svobody

Zámecký dolní

Rusalka

LibušeMlýnský Sadový

nový

SkalníTereziiny

ŠtěpánkaSadový

starý min.

Hadí

Železnatý

Sadový starý max.

gamma activity [Bq/l eRa]

222 R

n ac

tivity

[Bq/

l]

Radon activity vs. gamma activity


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Radon activity measurements

• In case of 4 springs, 222Rn volume activities estimated for both water and separated gas

• gas/water ratio: 0,27-0,29


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Alpha-activity measurements 2007


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Conclusions• Most of the gamma activity caused by 222Rn progeny – 214Pb a 214Bi.

Rn origin in autometamorphic granite• Radioactivity is bonded to the gaseous phase, during manipulation with

water the activity is decreasing• Gamma activity of the waters is rather low, for most of the springs the

total gamma activity does not reach 50 Bq/l eRa. Higher activity only show springs at the periphery of the spring structure (Park springs old and new, Snake s., Štěpánka, Tereziiny)

• From radiohygienic point of view (Radiation protection decree, Spa law), radioactivity is low: the waters are not considered to be radioactive

• However, from the balneological point of view, radioactivity can be one of the substantial healing components

• Should radioactivity be considered to be a healing component of hotsprings, the patients are advised to use fresh water, straight at the spring outlet, if possible


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Thank you for your attention!

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