138 European Atlas of Natural Radiation | Part 6 - Radionuclides in water and river sediments

Chapter 6
Radionuclides in water
and river sediments

The water we use for domestic and public consumption While uranium is chemically toxic, radium, radon and
comes from ground and surface water. Depending on its daughter isotopes, lead and polonium, can be radi-
its age and chemical properties, natural water contains oactive hazards and thus pose health challenges. Trit-
different natural radionuclides in varying concentration. ium and 14C occur in concentrations that do not pose
These radionuclides, together with other mineral com- any health hazards, and so can be used to date ground
ponents, are released from rock surfaces. Water with water.
very long contact time with rocks, e.g. ground water,
may have higher radionuclide concentration, whereas Alpha-, beta- or gamma-spectrometry is typically ap-
surface water generally shows lower values. plied to measure radionuclide concentration in water.
Water volumes and sampling procedures differ be-
Besides radionuclides in the uranium and thorium se- tween the radionuclides, depending on their chemical
ries (including radon), 40K, 3H, 14C and other natural ra- properties. Gross alpha and gross beta values are de-
dionuclides may occur in water. 3H and 14C may also termined by liquid scintillation spectrometry. To detect
come from recent anthropogenic sources, together single radionuclides, alpha spectrometry or high-puri-
with 90Sr, 131I, transuranium products and other beta- ty germanium detectors (HPGe) may be applied. These
and gamma-emitters released from industrial or methods are often used to analyse sediments as well.
medical activities. The detection limits are generally below 20 Bq/l, for
most radionuclides even below 0.1 Bq/l.
Because radon is a highly soluble gas, its concentra-
tion in ground water is generally higher than that of According to recent international studies, the concen-
the parent radium isotopes. In very old and highly tration of natural radionuclides in water and river sed-
mineralised ground water, radon activity may be more iments varies at least as much as that in their host
or less in equilibrium with that of radium. The solubil-
rocks. In most countries, however, this does not exceed
ity of other radionuclides in water differs as a function
levels in drinking water. Countries with granitic bed-
of their chemical properties. rocks and possibly enhanced concentrations of organ-
ic matter (due to wetlands), as in Scandinavia, are at
In river water, radionuclides may precipitate to sedi- risk of having higher concentrations of radionuclides in
ments. When fixed on high-surface matter such as drinking water.
clay, they are more easily immobilised or transported
under turbulent conditions and thus increase radionu-
clide concentration in the sediment.

Clockwise from top-left:

Water flux during snow melt, Castellano river, Ascoli Piceno, Italy.
Source: Ferdinando Cinelli.
Water fall on Castellano river, Ascoli Piceno, Italy.
Source: Ferdinando Cinelli.
Water source, Austria.
Source: Valeria Gruber.
View of Lake Maggiore, Italy, which provides drinking water for bordering communities.
Source: Tore Tollefsen.
Waves crashing on cliffs, Vico Equense, Napoli, Italy.
Source: Ferdinando Cinelli.
Domestic use of water.
Source: DO'Neil (CC BY-SA 3.0).

Part 6 - Radionuclides in water and river sediments | European Atlas of Natural Radiation 139
Radionuclides in water and river sediments

6.1 Introduction 14
C also constitutes a trace proportion of natural carbon. In
ground water, the contribution of carbon stems mainly from
Water is a potential source of direct exposure to radionuclides carbonate minerals with usually low 14C activity. Specific activity
through consumption of liquids and foodstuffs (e.g. fish, shellfish, of 14C is therefore low in natural ground water, and human
Radionuclides of anthropogenic or technological origin may be present
aquatic plants), but also through leisure and sports activities (e.g. exposure is negligible under natural conditions.
in water from several sources (WHO, 2018), such as: radionuclides
fishing, swimming). Indirect human exposure arises from use discharged from nuclear fuel cycle facilities; manufactured radionuclides Ground water is typically more prone than surface water to
of water for irrigation and watering of livestock or from use of (produced and used in unsealed form in medicine or industry) entered into accumulate naturally-occurring radionuclides because of the
algae or sludge as soil amendments. An additional contribution drinking-water supplies as a result of regular or incidental discharges; influence of water-rock reactions and the large solid/solution
to indoor radon concentration stems from radon gas dissolved and radionuclides released in the past into the environment, including ratios in aquifers. Furthermore, the residence time between water
in water and released from domestic washing, showering, toilet drinking water sources. and the geological environment in an aquifier is usually longer.
flushing and food preparation or occupational exposure in water- 137
Cs present in the environment stems mostly from nuclear power Ground water is a regionally important and strategic resource
supply settings. plant accidents. It is important to monitor its activity concentration in for both public and private supply. Table 6-1 shows how the
The water we use and consume comes from two main surface water and in sediments, especially as higher observed values of proportion of water demand covered by ground water varies
sources: ground water and surface water. Ground water is
137
Cs may be an indicator of some nuclear accident. widely over a number of European countries.
defined as water found underground in cracks and spaces in Tritium, 3H, is a very important nuclide for detecting potential In order to make valid judgments about management and
soil, sand and rock. It is stored in and moves slowly through radioactive or nuclear contamination of surface waters, especially as its hazards of natural radionuclides in ground water, it is necessary
geologic formations of soil, sand and rocks called aquifers origin in water is mostly anthropogenic and not natural. to understand the specific behaviour of these radionuclides in
(from https://www.groundwater.org). Surface water comprises Radiocarbon, 14C, is an important radioisotope for hydrogeology the aquifer chemical systems, which in turn requires detailed
river, lake, or seawater. studies, and its origin could be natural from cosmic radiation and artificial knowledge of ground water pH and redox potentials, with rock
from nuclear power plants. By monitoring the activity concentration of materials (Foss & Brooker, 1991). Chemical reactions, such as ion
Ground water contains naturally occurring radionuclides that 14
C, one can evaluate if there has been a nuclear accident that directly
originate from the thorium and uranium decay series. These can exchange, chemical complexing, and equilibration reactions with
affected surface water. After nuclear bomb testing and nuclear accidents
arise from natural processes in the ground or human activities, minerals, and physical processes, such as alpha recoil (Osmond &
(like Chernobyl, which mainly affected European countries), artificially
such as uranium mining and other extractive industries. For most produced radioisotopes such as 137Cs and 14C were deposited in rivers Cowart, 1976; Osmond et al., 1983, 1984), can cause considerable
people, the source of water for domestic consumption and other and accumulated in sediments. By measuring the activity concentrations deviation from decay equilibrium within the uranium decay series.
uses is ground water, often obtained from shallow, private wells, of those two isotopes, one can construct a scale of past nuclear events
but more often obtained from public, community wells tapping and also determine some characteristics of surface water. Country Percentage of water demands supplied
the aquifer (Engelbrecht, 2012). Surface water is one of the The most comprehensive database collections of monitoring results by ground water (%)
environmental compartments to which radioactive effluents from for isotope content in precipitations and rivers are the IAEA Global Denmark 100
nuclear installations are authorised to be discharged (Engelbrecht, Network of Isotopes in Precipitation (GNIP) and the Global Network of
Austria 99
2012). Radionuclides in surface water can be found in the water Isotopes in Rivers (GNIR).
Italy 91
phase or associated with suspended particles and can eventually
become incorporated into sediments and living species. Hungary 89
Sediment is an accumulator of radionuclides that are insoluble Switzerland 75
The Council Directive parametric value for indicative dose is
and adsorbed on insoluble material on the aquatic system 0.1 mSv/a, a value that EU Member States may estimate via Germany 73
and hence an indicator of the presence of such radionuclides. measurements of gross alpha and gross beta activity or from Poland 72
Sediments in all types of water may be a source of contamination specific radionuclides. Derived concentrations for radionuclides Luxembourg 70
to aquatic organisms. are given in the Drinking Water Directive, for which Member
Netherlands 70
States can assume that the indicative doses are less than the
Belgium 65
parametric value of 0.1 mSv. WHO recommends screening water
samples for gross alpha and gross beta, with guideline values of Greece 64
0.5 Bq/l and 1 Bq/l, respectively (WHO, 2017). France 57
Malta 50
6.2 Natural radionuclides in ground and Sweden 47

surface water Finland 45

United Kingdom 30
Natural waters contain both alpha and beta emitters in widely
varying concentrations which give relatively small contributions Spain 22
to the total dose received from natural and artificial radioactivity. Ireland 17
In every monitoring programme, measurement of gross alpha Norway 15
and beta activity in a water sample is the first analysis that Sweden 13
should be made as a screening approach. If gross alpha and/or
Table 6-1.
gross beta activity concentration is higher than the recommended Percentage of water demands supplied by ground water
reference/screening levels, then some additional nuclide-specific for a number of European countries.
Source: Zektser and Everett, 2004; table 5.1.2.2.
Lake Fiastra during summer time, Macerata, Italy. measurement methods should be used in order to quantify the
Source: Ferdinando Cinelli.
individual radioisotopes that are present in water. 6.2.1 Radon
Alpha activity is mostly due to dissolved uranium isotopes
Drinking water may contain radionuclides that could present a
(234U, 235U and 238U) and 226Ra. The main source of gross beta Radon is a radioactive noble gas that exists naturally as
risk to human health, but this risk is normally low compared to
activity in waters is 40K and short-lived daughters of 238U, 234Th three isotopes: 222Rn, 220Rn, 219Rn. Radon is the heaviest of all
risk from microorganisms and chemicals. Usually the radiation
and 234mPa (Forte et al., 2007). noble gases. The most stable and environmentally relevant
dose resulting from ingestion of radionuclides in drinking water
Natural radionuclides can be found in ground and surface isotope is 222Rn (hereafter called radon (Rn)), formed from
is much lower than that received from other radiation sources.
water as a result of either natural processes (e.g. reaction with alpha decay of 226Ra, in the 238U decay chain. 222Rn is a short-
Naturally occurring radionuclides in drinking water usually give
aquifer minerals and absorption from the soil) or technological lived isotope with a half-life of 3.82 days. During decay, an
radiation doses higher than those provided by artificially produced
processes involving naturally occurring radioactive materials (e.g. alpha particle is ejected, and emitted radon is propelled by
radionuclides and are therefore of greater concern (WHO, 2017,
mining and processing of mineral sands or phosphate fertiliser kinetic energy from the decay site in the opposite direction.
2018).
production) (WHO, 2017). Anthropogenic sources of radioactivity This alpha recoil can alter crystal lattices and enhance radon
The Drinking Water Directive (Council Directive 2013/51/
include transuranium products, 14C, 3H, 90Sr and 131I and other leaching from the crystal surface. By recoil, radon can be
Euratom; European Union, 2013a) stipulates requirements for
gamma emitters, released in controlled/authorised quantities transported as a dissolved gas in pore water or be retained in
protecting public health from radioactive substances in water
from nuclear installations, medical or industrial facilities, or from the mineral structure (see Figure 6-1). See Section 2.2.2 and
intended for human consumption, and specifies parametric
past bomb-testing or nuclear accidents. Chapter 5 for more details about radon.
values for radon, tritium and ‘indicative dose’. For radon and
The dominant radionuclides in ground and surface water that The emanation power or emanation coefficient of radon
tritium, the parametric values are 100 Bq/l with requirements for
can pose a potential health hazard under natural conditions are (proportion released to ground water compared to the total radon
detection at 10 Bq/l for each. For radon, EU Member States may 210
Po, 210Pb, 210Bi, 222Rn, 226Ra and 228Ra in the 232Th series. The produced) is a function of recoil and diffusion, and is affected
set national limits as judged inappropriate to be exceeded, which
health hazards from uranium isotopes are due more to chemo- by radium distribution in the host rock, surface geometry, grain
may be greater than 100 Bq/l but at most 1 000 Bq/l. The upper
than radiotoxicity. Other isotopes in these series are generally surface moisture and rock porosity (see e.g. Nazaroff & Nero,
value of 1 000 Bq/l is considered through degassing to contribute
not present in ground water in significant quantities because of 1988). Water-filled pores can reduce recoil into mineral grains
around 100 Bq/m3 to indoor air (WHO, 2011), a value comparable
low presence, low solubility in water and/or very short half-lives. and hence increase emanation efficiency relative to air-filled
to the WHO Reference Level for indoor-air radon (100 Bq/m3)
Activity of environmental 40K is not considered a hazard as K is pores. Nonetheless, the emanation coefficient in saturated
recommended to minimise health hazards.
an essential element in human metabolism, and K metabolism is aquifers is typically lower than 30 % (Wanty et al., 1992). More
strongly self-regulated (more details in Section 3.3). details are given in Section 2.2.2 and Chapter 5.

140 European Atlas of Natural Radiation | Chapter 6 - Radionuclides in water and river sediments
 Dissolved radon typically shows poor correlation with dissolved greater solubility of radium over thorium. In freshwater, radium
uranium and radium (Veeger & Ruderman, 1998) because of is found in highest concentrations in limestone regions where it
their differing states, solubilities, sorption properties and redox is more soluble in HCO-waters. 228Ra is also found in excess of its
Radium atom Soil/Rock dependencies. Activities of radon in ground water are often parent 232Th in natural waters.
Radon atom much higher than can be accounted for by equilibrium decay of Higher activities have also been found in saline ground water,
observed dissolved radium, suggesting the presence of additional including oilfield brines and other formation waters. Activities of
Transport radon from mineral surfaces (e.g. radium on adsorption sites or tens to hundreds of Bq/l have been reported for 226Ra and 228Ra in
B fracture precipitates). oilfield brines from the USA (Spaite & Smithson, 1992), with activity
α High radon activities in ground water are often associated with commonly correlating positively with ground water/brine salinity.
uranium-rich rocks such as granite, granite gneiss and pegmatite Radium has physical properties and displays behaviour similar
(Skeppström & Olofsson, 2007; Przylibski et al., 2004; Vinson to that of barium, strontium and calcium, and its mobility is
et al., 2009; Veeger & Ruderman, 1998; Knutsson & Olofsson, controlled by geochemical reactions that affect these elements
α
2002). Some of the highest radon concentrations ever recorded, (dissolution/ precipitation, sorption). Radium has only one
Pore
α have been found in granitic terrains of Scandinavia (e.g. Banks et oxidation state (+2) in natural systems. The element occurs in
A al., 1998; Åkerblom & Lindgren, 1997) and in Stockholm county solution mainly as free Ra2+ or as RaSO4 and also forms strong
(e.g. 63 560 Bq/l) (Skeppström & Olofsson, 2007). High values aqueous complexes with carbonate (Wanty & Nordstrom, 1993).
C (up to 5 000 Bq/l) have also been reported from granitic areas in Mobility of radium in water may be enhanced by alpha recoil
Pore water
α south-west England (Talbot et al., 2000) and parts of Scotland (up but limited by sorption to iron and manganese oxides, clays
to 80 Bq/l) (Aldoorie et al., 1993). The number of measurements or co-precipitation with alkaline earth metals in BaSO4, SrSO4
of radon activity in ground water, and hence the data availability, and CaCO3. Sorption of radium to metal oxides and clays is
are extremely variable across Europe. pH-dependent, being less significant under acidic conditions
D Maps of radon concentration in ground water have been prepared (e.g. Almeida et al., 2004). Loss of radium through sorption in
for some European countries, e.g. the UK (Young et al., 2015). water treatment systems has also been documented (Hill et
An evaluation of international research data (UNSCEAR, 2000) al., 2018). Complexation of radium with chlorine, SO4 and CO3
Figure 6-1. concluded that, on average, 90 % of the dose attributable to radon ligands is possible in saline fluids. Radium activity is typically
Schematic illustration of radon recoil trajectories in and between soil/ in drinking water comes from inhalation rather than ingestion. higher in anaerobic ground water due to reductive dissolution
rock grains: A) Radon is released into pore water; B) Radon is released into
pore air; C) Radon remains in grain; D) Radon absorbed by neighbour grain Therefore, controlling the inhalation pathway rather than the of iron oxides, in aquifers with poor sorption capacity (low iron-
(if the thickness of the mineral grain is higher than the recoil range of ingestion pathway is the most effective way to control doses oxide content) and those with high concentrations of competing
10-70 nm).
Source: modified after Nazaroff & Nero, 1988. from radon in drinking water. The percentage of radon present in cations (calcium, magnesium, barium and strontium) as well as
drinking water that is released into indoor air will depend on local HCO3 (Szabo et al., 2012).
As radon is an inert gas, its mobility in water is controlled by conditions, such as the total consumption of water in the house, As a result of co-precipitation and sorption, radium activities
physical rather than chemical processes. Alpha recoil accounts the volume of the house and its ventilation rate, and it is likely can be high in scale deposits (sulphates, carbonates, silicates,
for radioactive disequilibrium in ground-water systems (Wanty & to be highly variable (WHO, 2017). Higher radon doses by radon oxides). Many studies have been carried out on Naturally Occurring
Nordstrom, 1993). Radon neither precipitates in mineral phases inhalation may occur for workers in water supplies. In several Radioactive Materials (NORM) in scales, and activities of several
nor participates in sorption reactions. Activities in ground water countries, therefore, water supplies are listed as specific types of thousands of Bq/g have been reported in scales produced in the
are higher than in surface water because of mineral interactions, workplaces where radon in air needs to be controlled according to oil and gas industry (IAEA, 2003). Radium-bearing scales also
longer contact time in host aquifers and loss by degassing from the Basic Safety Standards Directive, Article 54 (European Union, occur in geothermal production waters.
surface water. 2013b). In Europe, only a few studies have been made of radium in
Radon decays rapidly and does not accumulate in ground water ground water, e.g. in Serbia (Onishchenko et al., 2010).
along flow paths, because decay rates are typically faster than
those of ground water flow. As a result, high radon concentrations 6.2.3 Uranium
in ground water are indicative of local uranium (radium) sources.
High radon contents in ground water are related to uranium and Uranium (U) is a heavy element in the actinide series
radium content of aquifer minerals and of the ground water, as well (atomic number 92) with two main natural, primordial, long-
as ground water flow rates. For a given aquifer uranium content, lived radionuclides, including the more abundant 238U (half-
higher radon concentrations in ground water are expected in rocks life of 4.5 × 109 years, 99 % of uranium total mass) and the
of lower porosity, higher density or higher emanation efficiency less abundant 235U (half-life of 7.0 × 108 years, 0.72 % of
(Wanty et al., 1992). The extent of transport from a radium decay uranium total mass), both decaying separately through long
site is also determined by the permeability (primary or secondary) and complex radioactive decay series ending with stable lead
of the host rocks. High radon concentrations are typically not found (206Pb and 207Pb, respectively). Another natural uranium isotope,
in zones of high transmissivity in aquifers due to reduced rock/
234
U, (half-life of 2.4 × 105 years, 0.0056 % of total natural
water ratios and dilution of emanating radon (Lawrence et al., uranium), is the third decay product in the 238U radioactive
1991). Once radon is in ground water, its transport is controlled by decay series. This uranium isotope is generally considered in
advection and diffusion. equilibrium (to slightly deficient) with its progenitor 238U. The
As for other gases, the solubility of radon in water is
238
U/235U ratio, currently about 138, has increased over time
temperature-dependent, with solubility decreasing by about 3 % Skógafoss waterfall situated on the Skógá River, due to faster radioactive decay of 235U.
per °C as temperature increases from 10 °C to 20 °C (Figure 6-2). Iceland at the cliffs of the former coastline.
Source: Samuel Wong on Unsplash.
Uranium occurs in three oxidation states: U(IV), U(V) and U(VI),
Solubility is also affected by barometric pressure, though this is although U(V) is meta-stable and rarely found in nature.
likely less influential than other physical controls (Lindsey & Ator, In oxic conditions (with oxygen), the oxidised form, U(VI), is
1996; Clever, 1979; Schubert et al., 2007; Lerman, 1979). 6.2.2 Radium stable in aqueous solution, although mobility is controlled by pH
0.5 The main isotopes of radium, viz. 226Ra, 228Ra, and 224Ra, are and concentrations of inorganic and organic carbon. In oxic water
derived from U and Th decay. 226Ra and 224Ra are alpha emitters; at pH<5, uranyl, U(VI)O22+, is the dominant dissolved form. At
228
Ra is a beta emitter. All are relatively short-lived with half-lives neutral pH, the mobility of U(VI) may be diminished by adsorption
0.4 of 1 600 years, 5.75 years and 3.6 days, respectively. to iron oxides (e.g. Villalobos et al., 2001; Payne et al., 1994),
226
Ra and 228Ra are the most important radium isotopes present phosphate minerals, organic matter and clays (Ivanovich, 1994).
coefficient of solubility

in water. Arising respectively from the decay of 238U and 232Th, The affinity of U(VI) is especially strong for poorly-structured iron
0.3 their concentration depends on the content of their parents in the oxides (Kohler et al., 2004). Sorption of U(VI) is generally less
substratum. Since thorium is about three times more abundant strong at high pH≥8.
than uranium in the lithosphere but has a decay constant about Dissolved U(VI) concentrations can be high in acidic mine
three times that of uranium, the global inventories of 226Ra and waters. At higher pH, the uranyl ion forms stable complexes with
0.2
228
Ra should be roughly equal; however, local specific geological carbonate ions, notably UO2(CO3)22- and at higher pH, UO2(CO3)34-.
structures of terrains lead to a great variability in the ratio Complexes with phosphate can occur at near-neutral pH (Drever,
between these two isotopes. 1997) and with sulphide and fluoride under acidic conditions
0.1
In general, radium concentration in fresh ground water is (Langmuir, 1978; Drever, 1997). Chlorine and SO4 may be
usually low, typically in the mBq/l range. Radium concentration in important ligands in saline waters (Porcelli & Swarzenski, 2003).
surface water is even lower than in most ground water (Eisenbud Uranium(VI) also forms complexes with dissolved organic carbon
0
0 20 40 60 80 100
& Gesell, 1997). at pH values between 3.5 and 7 (Higgo et al., 1993; Arey et al.,
temperature (°C) Some mineral and thermal waters exhibit 226Ra concentration 1999; Cothern & Lappenbusch, 1983), although U(VI) may be
values up to several Bq/l. 226Ra, the daughter of 230Th, is generally removed by sorption to humic acid (Wanty & Nordstrom, 1993).
Figure 6-2.
Plot of coefficient of solubility for radon as a function of water temperature. found in excess of its parent in most natural water due to the In most continental waters (glaciers, rivers and lakes, i.e.
Source: Cothern, 1987, p. 3.

Chapter 6 - Radionuclides in water and river sediments | European Atlas of Natural Radiation 141
Radionuclides in water and river sediments

surface water excluding seawater), the uranium concentration that of its progenitor,210Pb. With a half-life of 22.3 years, 6.3 Measurement methods
ranges from less than 0.1 to 10 µg/l (approximately from ingrowth of 210Pb is slow and its environmental transport
< 2.5 to 250 mBq/l). In Germany, regionally highly variable 238U largely controls the distribution of 210Po. If 222Rn decays in
concentrations (from 0.5 to 310 mBq/l) were reported (Diehl, situ then the chemistry of 210Pb will largely control the fate 6.3.1 Introduction
2003). In Austria 238U concentrations were found in the same of 210Po subsequently produced. In river/estuarine systems,
for example, the concentrations of 210Po and 210Pb in water Typical radiometric procedures for measuring radioisotopes in
ranges, up to 1 Bq/l for some ground waters from granite areas
and sediments depend on the geology of the watershed and water and sediments are alpha, beta and gamma spectrometry,
(Gruber et al., 2009).
weathering conditions, while the geochemistry of the parent liquid scintillation counting (LSC) or gas-flow proportional
In some regions of the world, where naturally radioactive 238
U and its speciation also play a significant role. In surface counting. Table 6-2 (EPA, 2000) presents the most commonly
minerals are particularly abundant, uranium concentration can
and coastal waters, the deposition of 222Rn decay products used procedures for some radionuclides. In Section 2.5 the
reach much higher values, up to several mg/l. In areas with
from the atmosphere is assumed to provide the main flux methods are discussed in general. In this chapter the sample
uraniferous granitic intrusions, e.g. in Finland, 238U activity
of 210Po, particularly deposition of 210Pb, while for deeper preparation process and determination for the radionuclides in
concentrations higher than 100 Bq/l have been detected (Salonen
oceans it is more associated with in situ decay of 226Ra. In water and sediments are discussed in detail.
& Huikuri, 2002). marine and estuarine sediments 210Po associates with settling
Although 234U and 238U should be in secular equilibrium in and deposited materials, and its residence time in coastal
rock, the energetic recoil associated with disintegration of 238U, Sample Radionuclides Procedure
waters may vary from a few months to 2 years. Applications
different chemical properties of intermediates (234Th and 234Pa) type or radiation
of 226Ra,210Pb and 210Po allow estimation of rates at which measured
in the decay chain and differences in oxidation states between reactive elements are removed from water by adsorption
the two uranium isotopes often lead to a relative enrichment onto particles [see Section 6.5.5]. The possibility of health Water Gross alpha Liquid scintillation spectrometer
Gas-flow proportional counter
of 234U in water. Uranium is much less mobile under reducing effects for humans and other organisms associated with Solid-state scintillation detector
conditions. The reduced U(IV) form may be stabilised as uraninite 210
Po arises because of its α-particle emission—although,
again, 210Pb is also associated with relatively high radiation Gross beta Liquid scintillation spectrometer
(UO2), although sorption of U(IV) to organic matter and clays has
Gas-flow proportional counter
also recently been demonstrated (Bone et al., 2017). exposure (UNSCEAR, 2000). Indeed, 210Po is considered to be
Modern laboratory analysis by inductively coupled plasma one of the most toxic naturally occurring radionuclides, and
137
Cs, 60Co, 226Ra HPGe spectrometer, NaI(Tl)
one of the most important environmental radionuclides due ( Bi), 232Th
214
mass spectrometry (ICP-MS) has facilitated collection of data for (228Ac), 234, 235,
U in European water. to its wide distribution and potential for human radiation 238
U , 40K
Uranium has no known metabolic function in the human exposure through ingestion and inhalation. It has been
widely reported that 210Po is concentrated in many marine
234, 235, 238
U; Alpha spectrometry with multichannel
body. Furthermore, due to its chemical properties, it is, like other 238, 239, 240
Pu; analyser -solvent extraction; surface
organisms, particularly in the digestive glands of molluscs and
heavy metals, nephrotoxic. The radiotoxic effect of uranium is 227, 228, 230, 232
Th; barrier detector; pulse height analyser
crustaceans, and is the largest contributor to the radiation
considered to be low. other alpha
dose received by marine organisms. emitters
(Extract from Matthews et al., 2007)
6.2.4 Thorium 3
H Liquid scintillation spectrometer
222
Rn Gamma-ray spectrometry,
Thorium (Th) is an actinide series element with an atomic 6.2.6 Tritium emanometry,
number of 90 and atomic mass of 232. Thorium is radioactive Natural tritium is produced in the atmosphere from the interaction liquid scintillation counting
with one main natural isotope, the primordial long-lived of cosmic radiation with atmospheric nitrogen (Madruga, 2008). Sediment 137
Cs, 60Co, 226Ra HPGe spectrometer, NaI(Tl)
radionuclide 232Th, which has the longest half-life (1.41 × 1010 Anthropogenic production has disturbed the natural levels of (214Bi), 232Th
years) of all known radioactive isotopes and comprises (228Ac), 234, 235,
tritium by nuclear weapons tests, and tritium is being released into 238
U, 40K
99.98 % of thorium total mass. Thorium decays through a the atmosphere through weapons manufacturing, the operation of
long radioactive decay series ending with the stable lead
234, 235,238
U; Alpha spectrometry with multichannel
nuclear power plants and reprocessing of nuclear fuels (Pujol &
isotope 208Pb.
238,239,240
Pu; analyser -pyrosulfate fusion and
Sanchez-Cabeza, 1999; Nikolov et al., 2013). The average natural 227,228,230,232
Th; solvent extraction; surface barrier
The fate and mobility of thorium in environmental media (cosmogenic) concentration of tritium in environmental waters has other alpha detector; pulse height analyser; 1-g
are governed by its chemical and biological behaviour. The been estimated to range from 0.12 to 0.9 Bq/l (Mook, 2001; Palomo emitters sample; 16-h
quadrivalent thorium compounds are very stable towards et al., 2007; Baeza et al., 2001). Tritium most commonly enters the Table 6-2.
reducing agents. Thorium discharged as ThO2 into surface environment in gaseous form (T2) or as a replacement for one of Typical radiometric procedures for radioisotope measurements in surface
water and sediments, (EPA, 2000).
waters from mining, milling and processing will be present as the hydrogen atoms in water (HTO, called 'tritiated water' instead Source: Modified from EPA, 2000.
suspended particles or sediments in water because of its low of ordinary, non-radioactive H2O) (Budnitz, 1971; Nikolov et al.,
solubility. Other soluble thorium ions in water will hydrolyse, 2013). HTO’s properties are very similar to those of water because
forming a Th(OH)4 precipitate or hydroxy complexes. of their relatively small difference in atomic weight. HTO is taken
The hydroxy complexes will be adsorbed by particulate As a minimum, any method used to determine radionuclides in
up by organisms and environmental media far more readily than water must be capable of measuring activity with detection limits
matter in water, with the result that most of the thorium
molecular tritium. When tritiated water enters the body, it acts just as specified in the Drinking Water Directive (European Union,
will be present in suspended matter or sediment, and the
like normal water, spreading throughout the body and delivering a 2013a); see Table 6-3.
concentration of soluble thorium in water will be very low.
In most cases, sediment resuspension and mixing may control uniform radiation dose to all soft tissues, with a biological half-life
the transportation of particle-sorbed thorium in water; but in of about 10 days (Diehl, 2003; McKone et al., 1997).
Beginning in 1953, atmospheric testing of fusion weapons Parameters and radionuclides Detection limit (Bq/l)
some cases, the concentration of dissolved thorium in waters
dramatically increased the inventory of tritium on the Earth’s Tritium 10
may increase due to formation of soluble complexes with
carbonate, humid materials or other ligands in the water. surface, with the highest increase resulting from nuclear tests Radon 10
(Extract from Guogang et al., 2008.) in 1962 (Eriksson, 1965; Carter & Moghissi, 1977). These Gross alpha activity 0.04
Low activity concentrations of 230Th, 234Th and 232Th, up to atmospheric bursts more than doubled the tritium inventory on
Gross beta activity 0.4
1 mBq/l, 0.4 mBq/l and 0.4 mBq/l, respectively, are found in the Earth’s surface, with most of the tritium finally ending up in
the world oceans (Miskel, 1973; Michel, 2005).
238
U 0.02
shallow ground waters (IAEA, 2003), and they are typically
not detectable at all. As such, Th activities and concentrations Tritium activity concentration is commonly reported in 234
U 0.02
are rarely measured or reported in ground water studies. Low tritium units (TU). The TU is the ratio of tritium atoms to stable 226
Ra 0.04
activities and concentrations are a function of paucity of Th- hydrogen-1 atoms or 3H/1H, prior to weapons testing, and 228
Ra 0.02
bearing minerals, slow dissolution, and preferential sorption represents the number of tritium atoms per 1 018 hydrogen 210
Pb 0.02
(Langmuir & Herman, 1980). atoms. Hence, one TU is equivalent to 0.118 Bq/kg of water.
Prior to nuclear testing, tritium concentrations in rain were
210
Po 0.01
of the order of a few tritium units, with the highest ones found 14
C 20
6.2.5 Lead and polonium
in mid-continental areas. During 1963 tritium concentrations Table 6-3.
Detection limit for methods used for
210
Pb is a radioactive isotope of lead (Pb; Z=82) and is a in precipitation peaked in the northern hemisphere, rising to a radionuclides in water determination.
member of the 238U decay series, separated from 222Rn by six few thousand tritium units in most mid-continental locations Source: European Union, 2013a.

short-lived alpha- and beta-emitters. 210Pb is a beta-emitter (IAEA, 1981, 1992). Smaller increases were seen in the tritium
with a half-life of 22.3 years. The 210Pb isotope decays to 210Po concentrations of oceanic and continental surface waters in the
(polonium, Po) via the intermediate 210Bi (bismuth, Bi) and has mid-1960s (Stewart, 1966; Dockins et al., 1967). After deposition 6.3.2 Sampling of water and sample pre-
a half-life of 5 days by beta-decay. 210Po (Z=84) has a half-life on the continents, tritium entered into vadose zones, surface treatment
of 138 days and is an alpha-emitter. water and ground water (Michel, 2005).
Tritium is important as a global transient tracer for studying In general, sampling and preparation of water samples for
210
Pb and 210Po are therefore ubiquitously distributed in
the rocks and soils making up Earth’s crust, and in the dynamics in the hydrological cycle, recharge, renewal rate, flow analysis is not an easy task due to various problems that may
atmosphere and natural waters as a result of decay of velocity, and in conjunction with radiocarbon to determine ground occur, which are not common to other sample matrices.
222
Rn and subsequent deposition. The natural distribution water age (Libby, 1953; Pujol & Sanchez-Cabeza, 1999), see The problems are principally caused by two situations: the
of 210Po in the environment is integrally dependant on Section 6.3. samples are two-phase systems (i.e., the water contains some

142 European Atlas of Natural Radiation | Chapter 6 - Radionuclides in water and river sediments
 to evaporate a known volume of the sample to dryness and
measure the activity of the residue (Engelbrecht, 2012). When
water samples have a high content of total dissolved solids,
there is a concern that reliability and sensitivity of the method for
alpha determination may be reduced as alpha radiation is easily
absorbed within a thin layer of solid material. The determination
of gross beta activity using the evaporation method includes
the contribution from 40K (Engelbrecht, 2012). An additional
analysis of total potassium is therefore required if the gross
beta screening value is exceeded. The co-precipitation technique
excludes the contribution due to 40K; therefore, determination of
total potassium is not necessary. This method is not applicable for
assessing water samples containing certain fission products, such
as 137Cs. However, under normal circumstances, concentrations of
fission products in ground water used for drinking water (natural
springs and wells) are extremely low, below the detection limits.
According to the Drinking Water Directive (Council Directive
2013/51/Euratom; European Union, 2013a), the analysis method
Water sampling in a pump house of a waterworks, Austria.
Source: Valeria Gruber.
used for gross alpha and gross beta measurements in water must,
as a minimum, be capable of measuring activity concentrations
with a detection limit of 0.04 Bq/l and 0.4 Bq/l respectively. The
insoluble material) and the sometimes unpredictable behaviour settling down to the bottom of the container. The MnO2 precipitate screening level recommended for gross alpha activity is 0.1 Bq/l
of many substances at very low concentrations (Engelbrecht, is finally dissolved in a small volume (<5 l) and transferred to and for gross beta activity is 1.0 Bq/l. The most common standard
2012). Another issue could be various compositions of available a plastic bottle, which is prepared for gamma-spectrometry methods for gross alpha/beta measurements are proportional
natural waters as well as different pre-treatment procedures analysis (Lehto et al., 2011). counter or solid-state scintillation counters (ISO 9696, 2007; ISO
needed for different analyses. In the case of ground water For measuring 222Rn concentration in water, there are some 9697, 2008; ISO 10704, 2009). The counting efficiency of these
samples, the sample composition may vary according to the methods which require special sampling techniques; this will be methods is strongly affected by the total dissolved solids and the
geology surrounding the natural spring. explained in Section 6.3.5. For simultaneous measurements of surface density of the sample (Jobbagy et al., 2014).
Since some radionuclides may stick to the wall of sampling different radioisotopes in water samples, it is essential to collect In addition to the above techniques, ultra-low-level alpha/beta
vials, the sample is usually acidified in order to reduce this risk. water samples in glass bottles and to take the first sample for 222Rn in discrimination liquid scintillation counters (LSCs), because of
The longer the storage time before analysis, the more important water measurement or to collect a separate sample for this analysis. their high detection efficiency (up to 100 %) and low background
it is to acidify water samples (Engelbrecht, 2012). In most After that, the rest of sample should be acidified, and by bubbling air rate, are useful tools for determining alpha- and beta-emitting
cases acidification is a good option, but, when measuring 222Rn through the water all remaining 222Rn could be completely expelled. radionuclides (Schönhofer, 1995). The basic steps of the chemical
in water by some direct method with available alpha detectors, There are some conventional radiochemical analysis procedures pre-treatment during sample preparation for LSC are relatively
acidised samples may cause problems during measurements. which are used for sample preparation for different measurement simple. The main steps are thermal pre-concentration, pH
Also for measuring 14C concentration in ground water in the methods of separate radionuclides of interest. adjustment and sample mixing with scintillation cocktail (ISO
case of some hydrological study, acidification of water sample For surface water some of the sampling methods are automatic 11704, 2009). There are a lot of advantages in using LSC for
allows 14C to escape from the volume. Most environmental and continuous, generally designed to give an early warning in gross alpha/beta measurements:
waters are close to neutral, and acidification of 0.1-0.5 N is case of an accidental release. In all cases, additional information • samples do not suffer from self-absorption;
adequate. At this acidity, radioactive substances in particles in on the river flow rate is very important. Samples can be taken • LSC methods show the best results for measuring low-energy
the sample can be leached (perhaps slowly) and appear in the continuously (or daily) and are then bulked into a monthly or beta emitters such as 3H and 14C (Schönhofer, 1995);
solution, resulting in a considerable increase in the original quarterly analysis; or alternatively, spot samples are taken
• and LSC is a very accurate method for measuring radon in
soluble radioactivity (Engelbrecht, 2012). Another way to prevent periodically and analysed individually. The time and frequency
water (Salonen, 2010; Todorović et al., 2014; Gruber et al.,
sorption of radionuclides on vial’s walls between sampling and of sampling are very important for rivers with large seasonal
2009; Nikolov, 2018).
analysis is to freeze samples. This method is only practical for hydrological variations (Engelbrecht, 2012). In collecting surface
small samples, and there could be some problems with treating water from rivers, care should be taken to avoid stagnant areas. Furthermore, semi-qualitative information can be obtained
insoluble portions. Lake water samples should not be taken near the shoreline. in the form of alpha-beta spectra. The main disadvantage
If the sample has been stored before analysis, particularly at its International Standards dealing with water sampling are the is quenching (chemical, colour and physical), which reduces
natural acidity, it is advisable to transfer the sample to a second ISO 5667 group, under the general title: Water quality – Sampling. the counting efficiency especially in the case of ground water
container with a solution, usually an acid, in which the sought-for They provide guidance for different water samplers (ISO 5667- measurements as that water can very often be coloured and/
activity is soluble (Engelbrecht, 2012). The 'wash' solution can 1:2006 and ISO 5667-3:2018): lakes (ISO 5667-4:2016), rivers or contain some other chemical elements and impurities. To
be added to the original solution or analysed separately. Special and streams (ISO 5667-6:2014), marine water (ISO 5667- overcome this problem, there are some possibilities in adjusting
attention has to be given to verifying the washing procedure; it 9:1992), and ground water (ISO 5667-11:2009). appropriate Pulse Shape Analysis (PSA) parameters (Stojković et
has to be verified experimentally. If suspended and dissolved al., 2017). Another issue could be the separation of beta energies
from all alpha energies, which can be difficult because it depends
fractions need to be separated for the analysis, then the safest 6.3.3 Determination of gross alpha/beta on many factors in LSC counting (Rusconi et al., 2006; Schönhofer,
pre-treatment procedure is to filter water through membrane
filter paper during sample collection on the field and acidify the
activities 2012). So, the optimal setting of the different parameters (type of
sample immediately after collection. The acid can already be Gross alpha/beta activity measurements are widely applied vial, cocktail, alpha/beta pulse discrimination, counting efficiency)
introduced into the receiving flask during filtration. This is the as a screening technique as the first analysis of any kind of is essential for gross alpha/beta measurements by LSC (Jobbagy
only way to ensure that water is not in contact with container water sample. These analyses are obligatory for drinking water et al., 2014; Stojković et al., 2017).
walls until after acidification. according to many different national and international standards It has been shown that gross methods are not as simple as
During sampling in the field, it is sometimes impractical to and recommendations. The main advantages of the gross alpha/ usually stated (Montaña et al., 2012; Semkow et al., 2004), and
follow a pre-defined method, in which case the water sample can beta methods are the relatively low costs, rapidity and simplicity that they are far from accurate (Jobbagy et al., 2014). Advances
only be collected in situ, and as soon it arrives in the laboratory, (Jobbagy et al., 2014). Although gross alpha/beta measurement is in gamma spectrometry, alpha spectrometry, and LSC and
it has to be acidified immediately prior to filtration. Any inactive one of the simplest methods, it is also one of the most disputed spectrometry for alpha and beta emitters have obviated many
carriers or radioactive tracers used in the analysis should be added radioanalytical methods because the determination of gross alpha of the reasons for measuring total activity; but low-cost gross
as soon as possible to the sample, preferably before any other and beta activities faces some specific problems that may affect measurements, preferably applying alpha/beta-separated LSC
pre-treatment method (acidification, filtration or evaporation). measuring results. There are many sources of interference in gross measurements (Pujol & Sanchez-Cabeza, 1995; Zapata-García,
When measuring water samples with gamma spectrometry, it alpha/beta measurements that may corrupt the reliability of the et al., 2009; Palomo et al., 2011), may still serve as a screening
is essential to pay special attention to possible change in counting measurement results (Arndt & West, 2004; Rusconi et al., 2006; procedure (Engelbrecht, 2012). Some recommendations say
geometry which will affect the efficiency of the measurement. Semkow et al., 2004; Montaña et al., 2012). During gross alpha/ that gross alpha/beta measurement should be avoided and only
Changes in counting geometry may occur when finely divided beta activity measurement, a mixed radionuclide composition must used for monitoring after the radionuclide composition is known
species become fixed on the container walls during counting. It simultaneously be measured (Jobbagy et al., 2014). Drinking-water from radionuclide-specific analysis of representative samples
is important to filter the sample, evaporate and acidify it if the samples may contain different, naturally occurring alpha (238U, (Jobbagy et al., 2014).
suspended material is soluble in diluted acid. 234
U, 232Th, 226Ra and 210Po) and beta (40K, 228Ra and 210Pb) emitters,
MnO2 coprecipitation can be used for pre-concentration of and artificial radionuclides (241Am, 90Sr) in various concentrations
radionuclides from large water volumes. In this method, the (UNSCEAR, 2000). Moreover, most of these are members of a
water sample is collected in a large container and with some complex decay chain; therefore, the ingrowths of the daughter
intermediate steps (adding HCl, KMnO4 and NaOH; see Lehto et products influence the measurement result.
al., 2011), a MnO2 suspension is built and the radionuclides will The most common approach for analysing drinking water
coprecipitate with MnO2. The precipitate formed is collected after for gross alpha and gross beta activities (excluding radon) is

Chapter 6 - Radionuclides in water and river sediments | European Atlas of Natural Radiation 143
Radionuclides in water and river sediments

6.3.4 Measurement methods for uranium originates from the surrounding bedrock. There are international standard (ISO 13164-3, 2013) in order to diminish the influence
standards dedicated to radon in water measurements such as ISO of radon in the air which could be present in the laboratory (from
and its daughter radioisotopes 13164-3 (ISO 13164-3, 2013) and ISO 13164-4 (ISO 13164-4, outdoors and/or building materials).
Because of their greater mobility, uranium and 226Ra are usually 2015). Beside the technical parts, they describe the principles
depleted relative to 230Th on the surfaces of soil or rock particles, of the methods, some of the sampling issues and approaches, Emanometry is based on sample degassing followed by
e.g., minerals and particulate organics (Engelbrecht, 2012). 238U, transportation and storage conditions. Those aspects are the most alpha-particle detection by various detection systems (Jobbagy
234
U, and 226Ra are, therefore, present in greater abundance in important and challenging ones for measuring 222Rn in water in et al., 2017). When a water sample is degassed, 222Rn is
ground water than 230Th. 222Rn enters the water by alpha recoil order to get a representative sample and reliable measurement transferred to a measurement cell either by an inert gas flow
and/or leaching, and migrates. 210Po and 210Pb also migrate to a results (Gruber et al., 2009; Jobbagy et al., 2017). or air circulation or vacuum. Several detection techniques
lesser extent and are in disequilibrium with other isotopes in the The most commonly used measuring methods for 222Rn can be applied to determine radon activity concentration in
238
U series (Upchurch et al., 1991). in water measurements are gamma-ray spectrometry, the gas phase, including scintillation cells such as Lucas cell,
Determination of uranium by measuring radioactivity is a highly emanometry and Liquid Scintillation Counting (LSC) (Jobbagy semiconductor silicon detector and ionisation chamber. Most
sensitive technique; it requires, however, knowledge of the other et al., 2017) (see Section 2.5 for a general description of the emanometry techniques are sensitive to water temperature, but
radionuclides present in the sample. Either the uranium must be methods). Those methods cover a wide range of techniques from even more important is detector contamination. As 222Rn also has
separated from interfering radionuclides, or it must be possible simple, cheap but straightforward ones to more sophisticated longer-living daughter products (like 210Po), it is essential to check
to make appropriate corrections for their interference. Uranium and expensive detection techniques. The Drinking Water Directive detector contamination prior to measurement in order to ensure
in equilibrium with its decay products may be conveniently from 2013 (European Union, 2013a) allows EU Member States that there is no build-up. Another issue is that some waters
determined by measuring the gamma activity of its daughters. to use various screening strategies to indicate the presence can contain 220Rn (thoron) which can affect the measurement
There are different techniques used to determine uranium in of radioactivity in water intended for human consumption, results, but there are instruments which can differentiate those
ground water samples, such as alpha spectrometry, Neutron but these methods have to be reliable (Jobbagy et al., 2017). two radioisotopes. One degassing approach is to place a water
Induced Fission Technique, and Inductively Coupled Plasma There are some requirements for minimal detection limits and sample in a degassing cell and introduce radon-free air or inert
Mass Spectrometry (ICP-MS) (see Section 2.5). sampling techniques from drinking water supplies. According to gas in a closed system (Jobbagy et al., 2017). This allows radon
The main advantage of the ICP-MS technique is its ability the directive, techniques for measuring radon concentration in to be purged from the sample and directed to the counting cell or
to measure multiple isotopes of the same element. ICP-MS water have to be capable of measuring activity concentrations detector by the appropriate pump. A second degassing approach
instrumentation can also precisely measure isotope ratios. Rapid with a detection limit of 10 Bq/l for radon, which is 10 % of its will be to inject a small volume of sample directly into a partially
techniques with ICP-MS have been developed e.g. by Qiao & Xu parametric value of 100 Bq/l (European Union, 2013a; Jobbagy vacuumed scintillation cell with a syringe. This approach ensures
(2018). et al., 2017). All the aforementioned detection techniques comply that radon is released from the water, after which by introducing
There are numerous alpha-counting methods available for with this detection limit requirement. radon-free or inert gas the pressure is adjusted to normal
uranium that has been separated from other alpha-emitting Measurement methods for radon in water can be grouped ambient pressure. There are few instruments specially designed
nuclides. But there are also some complications in those analyses. according to some key aspects, such as the application of phase for radon measurements, with some additional kits for radon in
The most important source of error results from the variation in transfer, analysis location, detection systems (Jobbagy et al., water measurements, that are a good choice especially for in situ
abundance of the uranium isotopes. The abundance ratios vary 2017). A technique that does not require any phase transfer is and rapid low-cost measurements. However, if better accuracy
more in natural ground waters than in primary uranium minerals, a direct measurement of the sample by gamma spectrometry. is needed, then they do not perform as well as the laboratory
as is to be expected from geochemical considerations of the Some other techniques involve phase transfer; during this process measurement methods.
uranium series (Barker et al., 1965). Alpha spectrometry, using 222
Rn is transferred from the aqueous phase to another phase. In
solid-state detectors, is a method frequently used to determine the case of emanometry techniques, it is transferred from liquid Liquid scintillation counting (LSC) for radon measurement is
individual uranium isotopes, even when other alpha emitters are to gas phase. In the case of liquid scintillation counting, the target based on the extraction of 222Rn from the water to the immiscible
present. Neutron-activation methods are suitable for analysing matrix is an organic phase of a liquid scintillation cocktail which scintillation cocktail (Jobbagy et al., 2017). Mixing an appropriate
uranium in very low concentrations. traps 222Rn and prevents it from emanating from water to outer volume of water sample (around 10 ml) with water immiscible
Isotopic analysis for most of the above radionuclides could air. Contrary to those in situ, laboratory measurements require scintillation cocktail which is already in the measuring vial
be performed with LSC using ultra-low-level spectrometers. To careful transport of the samples and storage under well-defined gives a two-phase sample, with clearly separated phases. All
measure Unatural and 226Ra, it is very important to acidify samples conditions (Jobbagy et al., 2017). Samples should be measured 222
Rn from the water sample is transferred to the scintillation
with HNO3 down to a pH of about 2 and filter to remove the as soon as possible after sampling due to the short half-life of cocktail and trapped in it. It is important to take the samples
suspended solid particles (Pereira et al., 2015). 226Ra can be 222
Rn (3.8 days), and decay corrections must be applied not only well below the surface and to introduce them slowly into the
measured by an indirect method using 222Rn as a tracer after for time elapsed between sampling and measurement but also in LSC vial below the cocktail by using a gas-tight syringe. After
isotopic equilibrium is reached following the procedure described the case of methods which require longer measurement times. preparation (mixing and shaking) of the sample, the LSC vial is
by Forte et al. (2007). It is very important to remove all radon The sampling of water presents the main source of error stored in a dark place and at a stable temperature for around 3
present in the sample before measuring 226Ra. The uranium in measuring radon in water for both in situ and in laboratory hours, after which time the sample is ready for measurement. For
isotopes have to be previously extracted with a mixture of measurement methods, so it is not easy to get a reliable and LSC measurements the most important issue is to adjust alpha/
a scintillation cocktail and bis-(2-ethylhexyl) phosphate in representative sample for the analysis. There are different beta discrimination and to avoid effects of photoluminescence
accordance with Salonen (1993) and Salonen & Hukkanen (1999). approaches with the same aim: if possible it is necessary to and chemiluminescence. There are different scintillation cocktails
The Pulse Shape Analysis (PSA) and the best counting time have assure that water will not be in contact with air during sampling that can be used for measuring 222Rn in water. The degree of
to be previously evaluated for each sample. The detection limits and sample preparation. One way to overcome this is to take the extraction of 222Rn progenies and therefore the calibration errors
that can be achieved for the activity of uranium isotopes are samples directly into measuring vials. For the LSC method the best depend on the scintillation cocktail, and it is suggested that the
1.5 mBq/l (0.15 µBq/l, for Unatural), 0.01 Bq/l for 226Ra. Liquid-liquid option is to put the liquid scintillation cocktail in the measuring vial cocktails should be studied case-by-case (Jobbagy et al., 2017).
extraction, ion-exchange chromatography, and barium sulphate and then to add an appropriate volume of water directly in situ; The great advantage of this method is the volume of the sample
or barium carbonate precipitation are the usual separation after mixing water with appropriate scintillation cocktail the risk of needed for analysis, for one measuring sample only 10 ml, and
techniques used for 226Ra. Analysis of 226Ra may involve inferring losing some 222Rn activity concentrations is minimal. stability of the obtained sample; once radon is trapped in the
the radium activity from measuring the ingrown daughter, 222Rn scintillation cocktail, it cannot escape easily.
(Engelbrecht, 2012), or by applying pulse shape analysis to In gamma spectrometry, 222Rn activity concentration is
determine 226Ra alpha particles. measured via activity concentrations of its daughter products For all the above methods for measuring 222Rn in water, the
To determine low-level activity concentrations of 210Po in 214
Bi and 214Pb. As those radioisotopes have a short half-life, measurement uncertainties are typically below 20 % (coverage
water samples, large-volume samples (> 1 l) have to be provided secular radioactive equilibrium is established within 3 hours. factor, k=1). The main difference between these methods is the
(Engelbrecht, 2012). The samples have to be pre-concentrated, The main problem for measuring radon in water by gamma initial sampled volume; it varies from 10 ml up to a few litres,
since direct evaporation of large volumes is very time-consuming spectrometry is the presence of 226Ra in water. When 226Ra is duration of the measurement and the possibility to perform in
and susceptible to loss of polonium. Therefore, co-precipitation present in the water sample, due to constant production of new situ measurements. Emanometry methods are usually portable,
with iron hydroxide, followed by a solvent extraction step with radon in the sample it is necessary to wait for secular equilibrium and there are some small LSC detectors which can also be used
an extractant, has commonly been used. Additional chemical between 226Ra and 222Rn, which is established after more than in the field, but they do not have appropriate shielding, and
purification using strontium resin (Vajda et al., 1997) or various one month. Subsequently, the measurement should be repeated therefore those LSC detectors are not suitable for measuring low-
solvent extractions prior to the final auto-deposition of polonium in order to precisely determine the activity concentration of 222Rn activity concentrations of 222Rn in water. It is almost impossible to
may be applied. Methods to determine 226Ra, 228Ra, 210Pb and in water. Solid-state scintillation detectors based on NaI are used use in situ gamma spectrometry to measure 222Rn in water due
210
Po are discussed by e.g. Landstetter & Katzlberger (2005). only for screening, while qualitative and quantitative analysis by to a very high background in the case of HPGe detectors and very
gamma spectrometry requires detectors with better resolution, poor resolution in the case of NaI detectors.
6.3.5 Radon so high-purity Germanium (HPGe) detectors are mostly used. A The biggest problem that all methods suffer from measuring
lot of factors can affect the efficiency of detection, and therefore 222
Rn in water is to calibrate the instruments. To improve the
Most of the methods used for 226Ra in water measurements the accuracy of the performed measurement of radon in water, situation of the available calibration options, there were some
rely on an indirect method using 222Rn as a tracer after isotopic such as sample density, homogeneity which is directly correlated international efforts to make reliable primary radon standards
equilibrium is reached about 30 days after sampling. So the to the water temperature, suspended materials and air bubbles. It and to further develop secondary standards (De Felice, 2007;
methods described for 222Rn in water measurements may also be is necessary to purge the immediate surroundings of the detector Jobbagy et al., 2017). Due to the short half-life of 222Rn, the
used for 226Ra in water measurements. and sample during measurement as recommended by ISO 13164 method most commonly used to calibrate instruments is the
222
Rn in water is mainly of concern in ground water as it mostly

144 European Atlas of Natural Radiation | Chapter 6 - Radionuclides in water and river sediments
226
Ra calibration approach, but there are also some practical Sampling procedure iodide detector beyond placing the sample in a known geometry
examples of radon-in-water standard sources (Forte et al., for which the detector has been calibrated. The samples can be
Conventional collection of sediment is done by a dredge
2007). For calibrating gamma detectors there are two options, measured as they arrive at the laboratory, or the sample can be
dropped from a boat. The dredge mechanism is activated by
experimentally by means of a 226Ra standard source or by dried, ground to a uniform particle size, and mixed to provide a
contact with the benthos. For river sediments, it is of interest
using Monte Carlo simulations, which need a lot of precise more homogeneous sample.
to describe the stream flow conditions that lead to benthal
parameters as input. On the other hand, emanometry methods
deposition and the movement of the sediment, as well as the Gross beta analysis
allow calibration of alpha counting efficiency of a scintillation
characteristics of the sediment such as particle-size distribution, Once the sediment sample has been prepared, a small
cell by using radon in air calibration chambers with accurately
soil type, ion-exchange capacity, and organic content. Drying portion is dissolved, fused or leached to provide a clear solution
established 222Rn activity concentrations (Jobbagy et al., 2017).
at low temperatures (50 °C) to avoid the loss of radionuclides containing the radionuclide of interest. The only way to ensure
In the case of LSC, the 226Ra standard is usually used (Todorović
from the soil and hand mixing of soils or sediments prior to that the sample is solubilised is to completely dissolve the
et al., 2014).
sub-sampling should be acceptable for gamma spectrometry sample. However, this can be an expensive and time-consuming
All the above methods have low detection limits and fulfil the
where a relatively large sub-sample is used (e.g. 150 - 500 g). step in the analysis. In some cases, leaching with strong acids
requested 10 % from guidance levels for specific radioisotopes.
However, drying, grinding, and sieving prior to sub-sampling can consistently provide greater than 80 % recovery of the
should be carried out where a small sub-sample (e.g., 5-10 g) radionuclide of interest and may be acceptable for certain
6.3.6 Measurement methods for tritium is to be taken for radiochemical analysis (Engelbrecht, 2012). applications. Gross beta measurements may be performed on the
Natural levels of tritium, especially in ground water, are very Commercially available grinders, mills, pulverisers, mixers and material that has not been dissolved. After dissolution, the sample
low, so the water samples have to be purified by distillation, blenders are suitable. Hardened metals are best for the grinding is purified using a variety of chemical reactions to remove bulk
followed by an isotopic enrichment procedure using electrolysis surfaces, and it is not likely that radioactive contamination will chemical and radionuclide impurities. The objective is to provide
through a direct current (Florkowski, 1992). In order to increase the be introduced into a sample with this equipment, except by cross- a chemically and radiologically pure sample for measurement.
tritium concentration to an easily measurable level, electrolytic contamination from a highly radioactive sample. To prevent this, Examples of purification techniques include precipitation, liquid-
enrichment must be applied (Nikolov et al., 2013). The best thorough cleaning of equipment between samples is advisable. At liquid extraction, ion-exchange chromatography, distillation, and
method for measuring low activity concentrations of 3H in water this stage, a portion may be taken for gamma-ray spectrometry. electrodeposition.
samples is LSC. After electrolysis and distillation, one aliquot If vegetation and organic debris are not discarded, the roots,
of water is withdrawn to a scintillation vial with a scintillation mat and vegetation should be cut into very fine particles so as to
cocktail. Tritium (and its daughter 3He) can also be measured be distributed evenly; if they are to be discarded, these materials 6.4 Activity concentration of natural
using mass spectrometry, but other dissolved gases (H2O, CO2, O2, should be collected and weighed. Stones should be collected, radionuclides in water
N2, etc.) must be removed first (Clark & Fritz, 1997). Due to the weighed, and discarded. It can be assumed that the large rocks
contain an insignificant fraction of the activity and are in effect Table 6-4 shows the results of some studies performed in
specific characteristics of tritium (gas, relatively easily oxidised
voids in the sample. The mass of the discarded material should European countries to determine the radionuclide content in
to HTO), combined with the omnipotent presence of water vapour,
be taken into account, but not in calculating the specific activity ground and surface water.
the assay of low levels of tritium requires consideration of various
types of contamination, the magnitude of which depends strongly of the sediment. It provides, however, additional information to
on specific procedures of sample handling, on the ambient tritium indicate the overall makeup of the growing area.
concentrations during sampling, storage and analysis, and on the The sediment should be crushed, ground or pulverised to a
type of containers used to store the samples before the analysis particle size predetermined by the analytical requirements. The
(Engelbrecht, 2012). With the electrolytic enrichment technique, need for preparing the material will also depend on the nature
detection limits on the order of 0.1 - 0.01 TU (11.8 - 1.18 mBq/ of the soil; for example, beach sand may not need grinding. In
kg) is achievable (see Section 6.2.6 for the definition of TU). In general, the soil should pass a mesh size of 2 mm. Activity in soil
ground water the expected activity concentrations of 3H are in sediment samples is reported on a dry weight basis in Bq/kg and
the range of 1-3 TU, which means that electrolytic enrichment on an area basis in Bq/m2 (Engelbrecht, 2012).
is necessary for the analysis of ground water samples as the
Methods for sample preparation
results are mainly used in hydrological studies.
Analysis of beta emitters
6.3.7 Radionuclides in river sediments Laboratory sample preparation is an important step in the
Sediment is an indicator and accumulator of radionuclides that analysis of sediment samples for beta-emitting radionuclides.
are insoluble and adsorbed on insoluble material of the aquatic The laboratory will typically have a sample preparation procedure
system. Sediment in all types of water may be a source of that involves drying the sample and grinding the soil so that
contamination to aquatic organisms. For example, contaminated all of the particles are less than a specified size to provide a
sedimentary materials used as fertilisers may increase the homogeneous sample. A small portion of the homogenised
radioactivity levels of soil (IAEA, 1989). sample is usually all that is required for the individual analysis
(Engelbrecht, 2012).
Analysis of gamma emitters
Table 6-4.
There is no special sample preparation required for counting Concentration of natural radionuclides in water in some European countries
sediment samples using a germanium detector or a sodium [means and ranges], methods used for the analysis, objectives of the study
and spatial resolution.

Country Media Radioisotope Reference Activity concentration (Bq/l) Methods Objectives Spatial resolution Reference
level (Bq/l)
Finland Ground water: 226
Ra 0.5 Drilled wells: Gamma spectrometry Determination in 308 drilled Study area of about 400 km2: Asikainen et al. (1979)
drilled and dug median: 0.06 5' × 4' NaI(Tl) and 58 dug wells in Helsinki geologically highly variable,
wells mean: 0.30 region dominated by granites,
maximum: 9.5 amphibolites and migmatites
Dug wells:
median: 0.004
mean: 0.015
maximum: 0.37
222
Rn 100 Drilled wells: Gamma spectrometry
median: 925 5' × 4' NaI(Tl)
mean: 2.04 × 103
maximum: 23.6 × 103
Dug wells:
median: 31.5
mean: 96.2
maximum: 1.37 × 103
Drinking water 222
Rn 100 Drilled wells: Liquid scintillation Systematic study of natural Salonen (1988)
from drilled, dug mean: 2.4 × 103 counter radioactivity in drinking
wells and springs; Dug wells: water in Finland
ground water in mean: 220
bedrock and soil Ground water in bedrock:
mean: 1.02 × 103
Ground water in soil:
mean: 92

Chapter 6 - Radionuclides in water and river sediments | European Atlas of Natural Radiation 145
Radionuclides in water and river sediments

Country Media Radioisotope Reference Activity concentration (Bq/l) Methods Objectives Spatial resolution Reference
level (Bq/l)
Finland Drinking water Gross alpha 0.1 Ground water in bedrock: Conventional Systematic study of natural Salonen (1988)
(cont'd) from drilled, dug mean: 2.4 radiochemical procedure radioactivity in drinking
wells and springs; Ground water in soil: water in Finland
ground water in mean: 0.17
bedrock and soil
(cont'd)
Gross beta 1 Ground water in bedrock:
mean: 2.3
Ground water in soil:
mean: 0.33
U For 238U: 3.0 Drilled wells: Alpha spectrometry
For 234U: 2.8 238
U mean: 3.9
Dug wells:
238
U mean: 1.8
Ground water in bedrock:
mean: 4.2
Ground water in soil:
mean: 0.61
226
Ra 0.5 Drilled wells: Separation with a barium
mean: 0.55 sulphate method, zinc-
Dug wells: sulphide scintillation
mean: 0.23 counter
Ground water in bedrock:
mean: 0.44
Ground water in soil:
mean: 0.04
210
Pb 0.2 Drilled wells: Alpha spectrometry
mean: 0.43
Dug wells:
mean: 0.076
Ground water in bedrock:
mean: 0.43
Ground water in soil:
mean: 0.08
210
Po 0.1 Drilled wells: Alpha spectrometry
mean: 0.22
Dug wells:
mean: 0.035
Ground water in bedrock:
mean: 0.22
Ground water in soil:
mean: 0.04
Drinking water 222
Rn 100 mean: 460 Liquid scintillation Random sampling: 500 Vesterbacka et al.
counter spectrometer wells (all drilled wells and (2005)
a random sample of dug
226
Ra 0.5 mean: 0.05 Alpha spectrometry
wells)
234
U 3.0 mean: 0.35
238
U 2.8 mean: 0.26
210
Pb 0.2 mean: 0.04
210
Po 0.1 mean: 0.05
Greece and Drinking water 222
Rn 100 Greece: Alpha spectrometry Cyprus and Greece (Attica, Nikolopoulos et al.
Cyprus range: 0.8 - 24 Crete), 42 water samples (2008)
mean: 5.4 collected from various
sites
Cyprus:
range: 0.3 - 219
mean: 5.9
Hungary Drinking water 222
Rn 100 mean: 5.56 Lucas cell 125 tap water, 29 wells, 27 Somlai et al. (2007)
maximum: 24.3 springs frequently visited
and regularly used in
Hungary
Spring water 222
Rn 100 range: 153 - 219 Liquid scintillation Csaoka Spring in Sopron Mainly gneiss and mica schists, Freiler et al. (2016)
spectrometry Mountains, West Hungary formed from granitic and clastic
sedimentary rocks
Poland Ground water 222
Rn 100 median: 2.03 Ultra-low-level liquid Analysis of ground water Mainly Sudeten Mountains, Przylibski et al. (2014)
mean: 541.4 scintillation spectrometer from southern Poland, north-east part of Bohemian
maximum: 3.04 × 103 focused on shallow- Massif (the largest crystalline
circulation ground water massif in Central Europe)
from first aquifer; >500
measurements from
2008 - 2013
226
Ra 0.5 median: 0.05
mean: 0.19
maximum: 1.77
Spain Ground water, wells 222
Rn 100 < 30 Alpha spectrometry La Garrotxa volcanic region, La Garrotxa region mainly Moreno et al. (2014)
and springs Catalonia, Spain, with 53 consists of quaternary volcanic
points selected to measure and non-volcanic formations
radon concentration (42 over a tertiary substratum
private and public wells and
11 springs)
Spring water 222
Rn 100 range: 1.4 – 104.9 Ultra-low-level liquid Spring water in the south of Natural spring water located Fonollosa et al. (2016)
scintillation counting Catalonia (15 samples) in two contrasting lithologies:
igneous rocks (granites) and
226
Ra 0.5 range: 2 - 91 × 10-3 Zinc-sulphide scintillator
soils of marine origin (e.g.
counter
limestones, marls and clays and
238
U, For 238U: 3.0 For 238U: < 0.2 - 21.6 × 10-3 Alpha spectrometry carbonate formations)
234
U For 234U: 2.8 For 234U: 4 - 55 × 10-3

146 European Atlas of Natural Radiation | Chapter 6 - Radionuclides in water and river sediments
6.5 Applications (Avery et al., 2018; Gleeson et al., 2018; Cook et al., 2003), both instruments to the SI by means of an unbroken chain of calibrations
onshore and offshore (Burnett et al., 2006). These measurements or comparisons, linking them to relevant primary standards of the SI
can be especially effective when used in combination with other units of measurement. This approach guarantees that radioactivity
6.5.1 Introduction tracers (e.g. CFCs, SF6, δ18O, δ2H, water temperature, CH4). test results on the same type of samples are comparable over time
Observing increased radon activity in ground water has also and between different test laboratories worldwide.
Most of the world’s population is directly affected by the
been suggested as a precursor, and therefore warning system, for Quality assurance is required by the IAEA Basic Safety
availability of water resources and the means to supply them.
major seismic activity (Hauksson, 1981; Wakita, 1996), although Standards (IAEA, 2014), and, hence, should be an integral part
All natural or anthropogenic processes that modify the water flux
evidence for causal links between the two remains inconclusive. of environmental monitoring programs (Engelbrecht, 2012). As
and quality have a direct influence on human lives. Radioactive
tracers can be extremely useful for studying such processes, a minimum, an adequate quality assurance program satisfies
and thus help to investigate the common problems and find 6.5.4 Ground water provenance and the general requirements established by the regulatory body.
In order to minimise incidents, such as mixing up samples or
adequate solutions. Problems such as water pollution, erosion, processes
river sedimentation, and the loss of storage capacity of water biased analyses, quality control and quality assurance concepts
Many of the radionuclides described above can also be used to have been developed to assist the laboratory personnel in the
reservoirs, thereby reducing fish stocks, can cause great damage
study ground water provenance, weathering processes, flow paths, following objectives: to achieve a higher degree of transparency of
and negatively affect the well-being of local populations (IAEA,
redox controls and sources of contaminants (Ivanovich, 1994). procedures; to minimise potential sources of error; to standardise
2015). There are several radionuclides commonly used as
Among others, radon, radium and uranium, 234U/238U and 87Sr/86Sr the handling of samples, instruments, and data; and, in the end,
environmental tracers (e.g. Tritium (HTO), 82Br, 198Au, 210Pb/210Po,
ratios have been used to distinguish between ground water and to decrease the rate of nonconforming results.
U/Th/Ra isotopes and the geological dating). Also anthropogenic
baseflow from distinctive rock types (e.g. granite, mineralised Uncertainty in environmental monitoring results arises
radionuclides still available in the environment from nuclear
weapons tests and nuclear accidents can be used as tools for rocks) (e.g. Riotte & Chabaux, 1999). Some of the radionuclides primarily from design errors, the non-representativeness of
environmental studies (e.g. 137Cs). This topic is not within the are pH- and redox-sensitive, giving insight into weathering and samples and/or measurements, and measurement uncertainty.
scope of this Atlas, but more details can be found in e.g. IAEA redox processes. Uranium is redox-sensitive, and uranium and These uncertainties, as well as human errors, cannot be fully
(2015). Also natural radionuclides are used for environmental radium behave differently in different redox conditions. 234U/238U eliminated but can be reduced as far as possible.
studies and applications such as ground water dating, mixing of activity ratios have been used to delineate redox boundaries Non-representativeness occurs when the sampling or field
fresh and saline water or sedimentation rates. These applications (Andrews & Kay, 1982). Measurements of 234U/238U activity measurement is unable to capture the complete extent of variability
are studied in more detail below. ratios have also been used to identify uranium-bearing fertilisers that exists for the radionuclide distribution in a survey unit. Since
(Bigalke et al., 2018; Barisic et al., 1992). Moreover, radionuclides it is impossible to always measure the residual radioactivity at
also have obvious applications for investigating processes, flow
6.5.2 Ground water dating paths, reaction kinetics and environmental impacts in the context
every point in space and time, the results will be incomplete to
some degree. It is also impossible to know with complete certainty
Natural radionuclides have a wide range of applications for of nuclear facilities and repositories. the residual radioactivity at locations that were not measured,
assessing ground water age, provenance, processes and fluxes. so the incomplete survey results give rise to uncertainty. The
Radionuclides can be used to trace the time since exposure at 6.5.5 Sedimentation rates greater the natural or inherent variation in residual radioactivity,
surface and hence date the ground water recharge. the greater the uncertainty associated with a decision based on
One of the radioisotopes most widely used for age dating is The radioactive isotopes 137Cs (half-life of 30.2 years)
and 14C (half-life of 5 730 years) are used as suitable tools the survey results. Representativeness in sampling and/or in field
14
C which is produced by cosmic-ray bombardment in the upper measurements can be optimised by means of an appropriate
atmosphere and decays by beta-emission with an established to study lake sediments. Global changes in the atmosphere
have been reflected in the whole environment, and they are sampling and measurement scheme as described above.
half-life of 5 730 years. Although complications arise with
particularly noticeable in lake sediments that preserve records In the case of water and sediment measurements, sampling
the contribution of other sources of carbon (biogenic and rock
of anthropogenic alterations. Therefore, the record of 137Cs is the biggest challenge and determines the quality/reliability of
carbonate) and require appropriate corrections, this method has
and 14C radioisotopes in recent carbonate sediments can be the measurement result. It is not easy to collect a representative
been effective for determining ground water age up to around
used to determine sedimentation rate, the response of the lake and reliable sample. Due to different characteristics of water,
35 000 years. Applications of measuring 4He, which is produced
environment/sediment to anthropogenic contamination of the different mixing of water, the measured activity concentration
in the deep subsurface by radioactive decay of uranium and
atmosphere, as well as to follow environmental processes of of radioisotopes in a sample does not always give a clear picture
thorium, can supplement age data acquired from 14C.
carbon geochemistry (Horvatinčić et al., 2014). of the present radioisotopes in water. Also, sampling frequency
Tritium has also been widely used for age dating. Tritium is
210
Pb occurs naturally as one of the radioisotopes in the 238U should be clearly defined. Sampling frequency of drinking water
also produced naturally by cosmic-ray bombardment in the upper
decay series. In sediments 210Pb has two sources: The first one is defined in The Drinking Water Directive (European Union,
atmosphere and decays to 3He through beta emission with a half-
is 222Rn, produced in local rocks and sediments, escapes to the 2013a), and IAEA has established the Global Network of Isotopes
life of 12.4 years. Activities of 3H rose sharply in the atmosphere
as a result of atomic bomb testing in the 1950s, providing a atmosphere and decays there via short-lived isotopes to 210Pb. in Precipitation (GNIP) and Global Network of Isotopes in Rivers
greatly enhanced tracer for hydrogeological applications. Since
210
Pb is removed from the atmosphere by adsorption to aerosols (GNIR) for river water.
then, however, its value has gradually diminished as the 3H and in precipitation or dry deposition and is incorporated into the In some cases, gross alpha/beta should be the first screening
activities of atmospheric precipitation has decayed from a 1963 upper sediment layer (unsupported or excess 210Pb). The other method performed. On the other hand, according to the conclusions
peak to near-background values, and age estimates do not source is 210Pb produced in the sediments in situ (supported). The from a European interlaboratory comparison exercise (Jobbagy
give solutions. Hydrogeologists tend to quote 3H in tritium units
210
Pb method is based on the radioactive decay of unsupported et al., 2014), gross alpha/beta methods are not fit to be used as
(where 1 TU is equivalent to 0.118 Bq/l). Today, precipitation in
210
Pb, which has been calculated as the difference between total an independent method to assess activity concentration. Gross
the northern hemisphere has a 3H activity of around 5–30 TU
210
Pb and supported 210Pb. With a half-life of 22.3 years, 210Pb measurement should be used for monitoring only after the
and in the southern hemisphere slightly lower value of 2–10 TU, is an ideal indicator of modern sedimentation rates. Several radionuclide composition is known from radionuclide-specific analysis
compared to previous values in the thousands, making 3H a much models based on 210Pb (unsupported) measurements in sediment of representative samples. It can be used as a complementary or
less distinctive isotopic tracer in modern investigations. columns have been extensively used (Horvatinčić et al., 2014). As substitute method for radionuclide-specific measurement only
Short ground water residence times also have been
137
Cs is derived from a different source than 210Pb, it provides a with some important restrictions: (1) no temporary change is
investigated using the combined 3H-3He technique, which extends valuable cross-check of the 210Pb results. expected in the radiochemical composition (no significant growth of
the capability of 3H as a tracer. The amounts of 3He and of 3H The activity concentration ratio of 228Ra/226Ra has been used as progenies during the measurement); (2) no complex decay chains
remaining, together establish the total original 3H, which in an indicator of the geochemical source of sediment particles along are present; (3) a true, standardised method is used; and (4) the
turn determines the date of ground water recharge. The 3H-3He the Danube River (Maringer et al., 2009, 2015). measurement parameters are fixed. Radionuclide-specific analysis
method has been useful for determining age up to around 40 should be repeated on a regular basis in accordance with the
years (Plummer et al., 2001). 6.6 Challenges to improving Drinking Water Directive from 1998 concerning check and audit
By contrast, the long-lived 36Cl and 81Kr radionuclides have monitoring (European Communities, 1998). Any suspected change in
been successfully used to investigate very old ground water on radioactivity measurements in water parameters requires more frequent nuclide-specific analysis.
long flow paths in aquifers, and beyond the scope of 14C dating and developing a European map However, due to different requirements for sample pre-treatment
(Edmunds et al., 2003; Shand & Edmunds, 2009). 36Cl decays for different radioisotope techniques, simultaneous measurements
with a half-life of 301 000 years and is potentially suitable for Comparable and fit-for-purpose results are an essential requirement methods should be improved. It is important to have all radioisotopes
dating ground water of around 1 million years or more. 81Kr for decisions based on radioactivity measurements, and international measured in the same sample whenever it is possible.
decays with a half-life of 229 000 years with a similar age-range standards of tested and validated radionuclides test methods are
Mapping natural radionuclides in water at European level is
capability (Sturchio et al., 2004). As the radionuclide 129I occurs an important tool for producing such measurements. It is essential
not an easy task and it has not been sufficiently explored in the
both naturally as a result of cosmic-ray bombardment and from that all testing laboratories use agreed and appropriate methods and
present version of the Atlas. Hence, the following challenges have
nuclear weapons testing and has a half-life of 15.7 million years, procedures for sampling, handling, transporting, storing and preparing
been identified:
it has potential applications for dating very old ground water and of test samples, the test method, and for calculating measurement
• Collect data on sampling and measurements of natural
for tracing modern ground water. uncertainty. In this framework, the normative approach based on
radionuclides in water;
international standards aims to ensure the accuracy or validity of
the test results through calibrations and measurements traceable to • Work on harmonisation procedures since data of natural
6.5.3 Ground water flux The International System of Units (SI, abbreviated from the French Le radionuclides in water have been obtained with different
Measurements of radon and radium activities in surface water Système international d'unités). The test laboratory should establish techniques and methods;
have been widely used to estimate ground water discharge fluxes traceability of its own measurement methods and measuring • Explore different mapping methodologies.

Chapter 6 - Radionuclides in water and river sediments | European Atlas of Natural Radiation 147