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Isotope : Investigating contamination Environmental are used to study serious problems by V. Dubinchuk, K. Frohlich, and R. Gonfiantini

During the past 100 years, groundwater has become nant surface , in fact, was believed to be the source an increasingly important source of world- of infirmities. wide for domestic, agricultural, and industrial uses. The Lately, however, groundwater quality has worsened almost ubiquitous occurrence of water-bearing forma- in many regions, with sometimes serious consequences. tions, the quality of groundwater, and the development Decontaminating groundwater is an extremely slow of -drilling techniques have all helped to bring this process, and sometimes impossible, because of the about. generally long residence time of the water in most geo- Since it is naturally protected, groundwater has been logical formations. immune from contamination for a long time. It has been Major causes of contamination are poor groundwater cleaner and more transparent than . From management (often dictated by immediate social needs) the time of Hipprocrates in the 5th century B.C., stag- and the lack of regulations and control over the use and disposal of contaminants. Agricultural practices, with Messrs Dubinchuk and Frohlich are staff members in the the sometimes indiscriminate and frequently excessive hydrology section of the IAEA Division of Physical and Chemical use of fertilizers, herbicides, and , are among Sciences, and Mr Gonfiantini is Head of the section. the most relevant sources of groundwater contamina-

Illustration of the

24 IAEA BULLETIN, 1/1989 Features tion. For instance, levels of nitrates often traceable to fertilizer usage are increasing in shallow . Industrial and domestic contaminants are among the most dangerous. This is partly due to the fact that they are produced mainly in urbanized areas, where water de- 400 mand is higher and groundwater exploitation more in- tense. Here, as the groundwater pressure is lowered, contaminated surface may be able to penetrate to depths where artesian pressure had previously prevented . 300 In coastal regions, over-development is frequently the cause of seawater encroachment and consequent groundwater salinization. In arid areas, over- development usually invites a rapid decline of ground- 200 , which are insufficiently recharged by prevailing climatic conditions. In addition, poorly designed schemes may hasten the salinization of , which eventually becomes sterile. 100 An investigation of groundwater in the Mexicali Val- ley in arid northwestern Mexico, for example, has helped researchers find the source of salinization. alone could not solve the problem whether the groundwater's deterioration was being caused by poor irrigation practices or by bank infiltration from the 0 10 20 30 40 50 60 Presal Morelos or Wellton-Mohawk drain. Using Tritium content in tritium unit (1 TU = 0.12 Bq per litre) isotope techniques, investigators examined the linear correlations between concentrations of chloride and -18 and between the two heavy isotopes deu- terium and oxygen-18. Results (reported in 1979 by Payne, Quijano, and Latorre) clearly indicated mixing with the Wellton-Mohawk drain, which was thus identi- 60- fied as the major source of contamination. These and other types of problems have prompted an 50- QJ increasing demand for investigations directed at gaining \ insight into the behaviour of contaminants in the hydro- 8. 40- x logical cycle. Major objectives are to prevent pollution i ft) V and degradation of groundwater resources, or, if con- lao- tamination already has occurred, to identify its origin so £ that remedies can be proposed. c & 20-

Environmental isotopes have proved to be a powerful tool for studies. These isotopes 0 04 08 12 16 Iog(1/Tp) are generally rare isotopes, both stable and radioactive, Increasing age of groundwater » occurring in the environment in low and varying concen- Notes: T is the age of groundwater. Tp is the time period trations with respect to the most abundant isotope of the between the occurrence of tritium from atmospheric same element. Environmental isotopes are natural or weapons tests and the implementation of the field study. man-made. In either case, their distribution in the en- vironment is governed by natural processes. Although small, the variations in concentrations of environmental isotopes are measured with high accuracy and provide These figures show the correlation between nitrate and tritium concentration observed In an unconflned Permian valuable information on hydrological systems. In the German Democratic Republic. The correlation Processes in the hydrological cycle and interactions Indicates that the nitrate has been transported into the groundwater by the infiltration of water. between the and atmosphere are responsi- ble for isotopic variations observed in natural waters. (See accompanying figure.) As a general rule, stable iso-

IAEA BULLETIN, 1/1989 25 Features

Tritium in and radiocarbon in atmospheric carbon dioxide in Middle Europe

Radiocarbon in PMC

I I Tritium

•• Radiocarbon

200

-150 10-

100

1950 53 56 59 62 65 68 71 74 77 80 83 86

Note: Tritium content in tritium unit (TU); 1 TU = 0.12 Bq per litre. PMC = Per cent of modern carbon; 1 PMC = 0.23 Bq per gram carbon.

topes, which are invariant over time, are used to identify hydrological importance, this information provides a the origin of groundwater and mixing processes. Radio- tool to assess the potential risk of contamination of a active isotopes, whose decay over time can be detected, given groundwater body. If tritium is present, the transit are used to assess the dynamics of groundwater. Chemi- time of water from the recharge area to the aquifer is cal analysis generally provides complementary informa- short, as is the residence time of groundwater in the tion and is carried out in parallel with the isotopic aquifer. This lowers the chance of any contaminant dis- investigation. solved in the recharge water to become adsorbed by the Isotopes frequently used in hydrological investiga- aquifer matrix. Consequently, the contamination risk is tions include tritium and carbon-14 which are naturally potentially high. produced by secondary cosmic radiation. These have The movement of radionuclides in groundwater is been injected into the atmosphere in large quantities by one of the major subjects of investigation. Natural radio- the atmospheric thermonuclear tests conducted until nuclides of the uranium and thorium decay series enter 1963 by the United Kingdom, , and USSR. groundwater through dissolution from the aquifer Only minor amounts have been produced later by matrix. They can be used, under favourable circum- Chinese and French tests. (See accompanying figure.) stances, to assess the groundwater dynamics. The decrease of tritium and carbon-14 concentrations in Incidentally, studies on the geochemical behaviour of precipitation and in atmospheric carbon dioxide after the these radionuclides are also of increasing interest for the Partial Test Ban Treaty of 1963 has provided new and assessment of nuclear sites, particularly nuclear waste invaluable insight into atmospheric processes. disposal sites. The problem is to evaluate the rate of ad- Tritium, with a half-life of only 12.43 years, can be sorption-desorption of these isotopes on various rock used to reveal the occurrence of modern groundwater matrices and to determine the velocity of their migra- recharge (that is, to detect recharge that has occurred tion, based on the knowledge of the migration velocity over the past three decades). In addition to being of great of the groundwater itself.

26 IAEA BULLETIN, 1/1989 Features

Stable isotopes of major elements used in Radionuclides used in groundwater studies

Approximate initial Isotopes Abundance in _ . activity Sources of .... natural compounds (%) Nuclide HaiMiie . .. concentration in production . . groundwater Hydrogen-1 99.984 (mBq per liter) Hydrogen-2 0.015 Carbon-12 98.89 Tritium 12'4 Secondary cos- 600 (before 1954) _ . H0 ... (Hydrogen-3) mic radiation; Carbon-13 1.11 atmospheric -14 99.634 tests of ther- Nitrogen-15 0.366 monuclear Oxygen-16 99.76 devices; nuclear Oxygen-18 0.2 facilities (mainly reprocessing Sulphur-32 95.02 plants) 4 21 Su'Phur-34 ' Carbon-14 5730 Secondary cos- 3 mic radiation; atmospheric tests of ther- monuclear devices; nuclear facilities (mainly reprocessing plants) A nuclear logging technique can help to determine the Silicon-32 105 Secondary cos- 5 x 10~3 rate of water in the unsaturated zone (the mic radiation zone of the shallow aquifer above the water ). Cou- Chlorme-36 301 000 Secondary cos- 3 x 10~3 pled with environmental and artificial isotope data, the mic radiation; technique has been used in the Chernobyl area in the atmospheric USSR to evaluate the time necessary for pollutants to tests of ther- monuciGcir reach groundwater from the land surface. devices; natural The IAEA has had a co-ordinated research nuclear reac- programme since 1987 on the application of nuclear tions (subterranean) techniques to determine the transport of contaminants in * • iii • Argon-39 269 Secondary cos- 7 x 10~4 groundwater. An project is being mic radiation; launched within the framework of the IAEA's regional natural nuclear co-operative programme in Latin America (known as reactions ARCAL). Main objectives are the application of en- (subterranean) vironmental isotopes to problems of groundwater assess- Krypton-81 210 000 Secondary cos- 1 x 10~7 mic radiation ment and contamination in Latin America. In 1989, 7 another co-ordinated research programme is planned rypton- 5 10. Nuclear facili- less than 2 x 10~ ties (mainly (before 1950) under which isotopic and other tracers will be used for reprocessing the validation of mathematical models in groundwater plants) transport studies

IAEA BULLETIN, 1/1989 27