EGU Blogs

cosmic rays

ATTA and the Curious Case of Krypton-81

Ok, so I took some license with the title. This isn’t really a curious case and neither Krypton-81 nor ATTA are actually people. In fact, Krypton-81 (81Kr) is a radioisotope of the noble gas krypton and ATTA, which stands for atom trap trace analysis, is the revolutionary technique that has made its analysis possible. I recently heard about developments with ATTA at the IAEA Isotope Hydrology Symposium and have been doing some reading about the method and its revolutionary application to the dating of both young and ancient groundwater.

Lu in lab

Figure 1. Dr. Z-T Lu working on the ATTA system at Argonne National Labs. Used with permission.

81Kr has long been a bit of a dangling carrot for groundwater dating people like myself. 81Kr is a long lived radioisotope of Kr (half-life: 229,000 years) that is produced by cosmic ray interaction in the atmosphere with other krypton isotopes. This production results in about 5 atoms of 81Kr for every 10^13 atoms of the other Kr isotopes. This 81Kr then settles to the earth surface and is incorporated into groundwater recharge and can then used to date groundwater from 150 thousand to 1.5 million years old. The way this works is that once water reaches the water table no new krypton is added and the clock starts ticking as the 81Kr decays away. In order to use this method we assume that the initial concentration in the recharge is in equilibrium with the concentration of 81Kr in the atmosphere, which is well mixed. ATTA then measures the amount of 81Kr that is left in the water sample compared to the other Kr isotopes and an age can be calculated from the difference between this ratio and the intial ratio.

ATTA can also be used for the short-lived isotope krypton-85 (half-life: 10.8 years). 85Kr is produced by fission in nuclear reactors and is released during nuclear fuel reprocessing. The short half life of 85Kr makes it useful for dating recently recharged groundwater from 1 to 40 years old.

Dating ranges of 85Kr, 39Ar, 81Kr and other established radioisotope tracers. (Source). Used with permission.

Figure 2. Dating ranges of 85Kr, 39Ar, 81Kr and other established radioisotope tracers. (Source). Used with permission.

The reason krypton is such a useful tracer for groundwater dating is that as a noble gas the interaction of Kr with soils, rocks and the biosphere is minimal whereas other tracers such as 36Cl, 14C or 3H are often subject to retardation during transport or inputs from multiple sources which makes extensive corrections necessary or renders them completely unusable for dating. Furthermore, very few reliable tracers exist in the range that Kr isotopes cover making them extremely useful. One isotope that I haven’t mentioned as much is argon-39, which can be used to date water from 50-1000 years old, is also a noble gas, and can also be measured with ATTA.

Measurements of krypton can also be used for dating of ancient ice cores as well. Atmospheric gases including Kr are trapped in air bubbles in the ice and therefore, using the same method as groundwater dating, an absolute age for an ice core can be obtained. There are several other applications for Kr dating as well such as dating of deep crustal fluids and brines.

Sampling ice cores for Kr analysis by ATTA. Photo: V. Petrenko. Used with permission.

Figure 3. Sampling ice cores for Kr analysis by ATTA. Photo: V. Petrenko. Used with permission.

The development of atom trap trace analysis was first reported in Science in 1999 and since then has undergone several substantial improvements primarily aimed at reducing the required sample size required for an analysis of Kr. ATTA (Figure 4) works by trapping Kr atoms with a laser which causes a slight and temporary change in their atomic structure which lasts for about 40 seconds. During this period the Kr atoms in the laser beam are focussed and slowed and then trapped in an MOT (magneto optical trap) where they are held in place for an average of 1.8 seconds. Once the Kr atom is in the MOT it fluoresces as it returns to its original state. This fluorescence is detected by a camera which is sensitive enough to detect the emission from a single atom (Figure 5)!


Figure 4. Schematic layout of the ATTA-3 apparatus. (Source). Used with permission.

One of the key features of ATTA is that this laser induced fluorescence within the MOT occurs uniquely for every isotope as the laser frequency is tuned specifically! This means that only atoms of of the desired Kr isotope are trapped. Furthermore, this means that ATTA is completely immune to interference from other elements, isotopes, isobars, or molecules. In essence nothing can confuse the detection of the 81Kr atom once it fluoresces and therefore there is no background of spurious detections that need to be corrected for. Among low-level analytical techniques this is unique and a really big deal! As a user of AMS, which is another low level analytical method that does suffer from these issues, this is statement is an eye-catcher.

Fig 3a CCD image

Figure 5. A CCD image showing the response of an atom in the MOT. Used with permission.

Since its invention ATTA has evolved considerably. We are now on the 3rd iteration of ATTA and significant improvements have been made that make ATTA much more practical for routine use. Specifically, the amount of sample required for an analysis has been reduced drastically. The first version of ATTA could only be used for atmospheric measurements as the quantity of Kr needed was too large to be extracted from water. ATTA-2 required ~1000 kg of water to extract 50uL of Kr gas. Now, ATTA-3 only requires 5-10uL of Kr which can be obtained from only 100-200 kg of water or 40-80 kg of ice. This advancement means that ATTA is now usable for groundwater dating applications never before possible. This has been demonstrated by the use of ATTA to date groundwater in Egypt to around 500,000 years old and even older water in Brazil up to 800,000 years. Other dating methods have confirmed that ATTA measurements are accurate.

Now that the sample sizes required for an 81Kr or 85Kr analysis have been lowered so dramatically the method is even more useful to the geoscience community. One of the messages from Dr. Lu’s talk at the IAEA meeting was that this technique is open for business and the geoscience community is strongly encouraged to reach out for collaboration and discussion. Furthermore, it may also be possible to use ATTA to measure argon-39, calcium-41 and potentially lead-205, strontium-90 and cesium-137,135 at extremely low levels.

Note: During the writing of this blog I corresponded with Dr. Z-T Lu, one of the creators of ATTA. I would like to thank him for allowing me to use his personal photos in this post. Dr. Lu is now establishing a radiokrypton dating centre at the University of Science and Technology of China.


Lu Z-T, Schlosser P, Smethie WM, Sturchio NC, Fischer TP, Kennedy BM, et al. Tracer applications of noble gas radionuclides in the geosciences. Earth-Science Rev. 2014;138:196–214.

Chen CY. Ultrasensitive Isotope Trace Analyses with a Magneto-Optical Trap. Science (80-). 1999;286(5442):1139–41.

Du X, Purtschert R, Bailey K, Lehmann BE, Lorenzo R, Lu Z-T, et al. A New Method of Measuring 81Kr and 85Kr Abundances in Environmental Samples. Geophys Res Lett. 2003;30(20):2068. Available from:

Aggarwal PK, Matsumoto T, Sturchio NC, Chang HK, Gastmans D, Araguas-Araguas LJ, et al. Continental degassing of 4He by surficial discharge of deep groundwater. Nat Geosci. 2014;8.

Lu Z-T. Atom Trap, Krypton-81, and Saharan Water. Nucl Phys News. 2008;18(2):24–7.

It’s rainin’ isotopes…

This post is kind of a continuation of Laura Roberts excellent guest post on the Solar Storms and the Earth’s Magnetic field. However, this is a bit of a different spin on it. I am not writing about what get’s kept out, but rather what slips by the shield and gets in. Of course, I am speaking about cosmic rays and the wonderfully useful isotopes they produce that rain down upon us. Yes, it is literally raining isotopes…all the time! I know that this sounds weird, when I first learned about this phenomenon it came as a complete surprise to me. Not only are isotopes raining down all the time, but there is a lot that we can learn about our planet by analyzing these  amazing by-products of cosmic ray collisions.

What are cosmic rays?

Cosmic rays are incredible things. The Earth is constantly being bombarded by them and we are protected from this massive influx of extra-terrestrial radiation by our magnetic field and atmosphere, which deflects about 90% of the low energy cosmic rays. Check out last weeks awesome guest post about Earth’s magnetic field. There are two types of cosmic rays. Primary cosmic rays generally originate outside of our solar system and travel throughout space occasionally bumping into things like planets. In fact, it has only recently been discovered exactly where they come from. In February, 2013 a paper came out in Science called: Evidence Shows That Cosmic Rays Come From Exploding Stars that (surprise) stated primary cosmic rays are produced by exploding stars aka. supernovae in which an ancient star blows up, releasing massive amounts of energy, elements and cosmic rays!

File:Keplers supernova.jpg

Kepler’s Supernova (Source)

Primary cosmic rays are 99% protons and alpha particles (two protons and two neutrons) and the remaining 1% are the nuclei of heavy atoms or beta particles (electrons). These bits of atoms and radiation fly around in space and bang into everything. Sometimes, actually more often than sometimes, they bang into the Earth. In fact, they bang into the Earth a lot! There are billions of collisions every day. Some of the particles crashing into the Earth have low energies while others have high energies. The frequency that these low energy particles collide is many times greater than high energy ones. There are about 10,000 collisions per square meter per second for giga-eletronvolt particles. For the higher energy rays the rate of collision is less. They might arrive with a frequency of 1 per square metre per second, as is the case with tera-electronvolt particles. The decrease in collision frequency continues as energy increases up until the very highest energy of the exa-electronvolt which collides about 0nce per square kilometre per century.

When cosmic rays pass through the Earth’s magnetic field is when things start to get really interesting, from a geochemical perspective that is. When primary cosmic rays enter the Earth’s atmosphere they start banging into all of the molecules and atoms floating around up there and produce secondary cosmic rays. Basically imagine a bowler throwing a strike. The bowling ball represents the primary cosmic ray and the pins are the molecules in the atmosphere. When the ball collides with the pins they fly off in every direction, which is analogous to the process occurring constantly in our atmosphere. When this takes place in the atmosphere the collision is so energetic the molecules and atoms can actually break apart. This is called spallation and results in a cascade of neutrons, protons and atoms called an air shower.


A simulation of a cosmic ray shower formed when a proton with 1TeV (1e^12 eV) of energy hits the atmosphere about 20km above the ground. The ground shown here is a 8km x 8km map of Chicago’s lakefront. This visualization was made by Dinoj Surendran, Mark SubbaRao, and Randy Landsberg of the COSMUS group at the University of Chicago, with the help of physicists at the Kavli Institute for Cosmological Physics and the Pierre Auger Observatory. (Source)

What is produced?

Air showers produce all sort of radioactive isotopes that are formed no other way. Some are very short lived and decay away quickly, while others are extremely long lived and have half lives of millions of years, allowing them to accumulate in the environment.

A list of the major cosmic ray isotopes and their half lives. The ones in bold have geologic applications.

Other isotopes are produced when cosmic rays reach the ground and collide with minerals. This can cause other isotopes to form within the mineral crystal lattice. For example, the cosmogenic isotope, aluminum-26 is produced when a cosmic rays strikes a quartz crystal and transforms some of the silicon in the quartz structure into aluminum. These are referred to as in-situ cosmogenic isotopes.

The next part of the process concerns what happens to all of these isotopes once they have sprung into existence thousands of metres above our heads. The fate of these isotopes is varied and they all live in the atmosphere for a little while before becoming part of the hydrologic cycle. Eventually they fall down to Earth either stuck onto aerosols or incorporated into rain and begin to interact with water bodies, enter groundwater, stick to soil particles or get absorbed into people, plants or animals. Essentially, they begin cycling through the environment until they decay away. Since these isotopes get cycled through various parts of the environment we can use them as tracking tools to trace the pathways they take and learn about their interactions with other components of environmental cycles.

What is the use?

Cosmic rays isotopes are useful for more than just getting a good tan! In fact, the list of possible questions that can be applied to cosmogenic isotopes just goes on and on. I’ll just briefly cover a few of them since each one of these applications is a whole blog post by itself I’ll just give the highlights here.

Exposure age dating: Exposure age dating is one of the principle uses of cosmogenic isotopes and several different ones have been employed to this end. Exposure age dating is when we use cosmogenic isotopes to date how long something has been exposed to secondary cosmic rays at the Earth’s surface. For example, a rock at the toe of a glacier may have just been exposed to cosmic rays a year ago and its exposure age date will tell us this. Another rock, 20 metres further from the glacier toe may have been exposed 5 years ago and this difference will be recorded. Basically, the clock starts ticking once cosmic rays are able to reach the rock or bone, or whatever material is being dated. Exposure age dating has the power to date materials that range from only a few thousand years to millions of years depending on the half lives and concentrations of the nuclides in question. The way exposure dating works is that when a secondary cosmic ray impacts a rock containing Si (silicon) or O (oxygen) some of the neutrons on the silicon or oxygen are knocked off and the result is the production of aluminum-26 or beryllium-10 right in the mineral lattice. One common mineral that contains both silicon and oxygen is quartz. Quartz is pretty much everywhere and in everything, which opens the door for a wide range of materials that can be exposure age dated. All they have to contain is a bit of quartz. The decay of 26Al and 10Be allows the material to be dated. There are other isotopes that can be used for exposure age dating besides these two and other minerals that contain Si or O can also be used as well. The figure below shows the wide range of applications that exposure age dating can be applied to. For example, if you want to date a volcanic eruption it is easy to exposure age date the lava or ash, both of which have a lot of Si. It is also possible to date landslides, erosion rates, burial ages, the list goes on and on. There are many other isotopes that can be used as well besides 26Al and 10Be.

CLOUD Project: The CLOUD project is a CERN experiment that is investigating the possible linkage between cosmic rays and cloud formation. It has been hypothesized that cosmic rays can cause clouds to form by forming aerosols and it has been noticed by satellites that an increase in the cosmic ray bombardment can increase the amount of cloud cover. Cloud cover has a profound influence on the Earth’s energy balance and hence climate. It has been proposed that throughout geologic time changes in the cosmic ray flux have been responsible for climate change. However, proving this is difficult given the length of time in question and the evolving states of the cosmic ray flux and Earth’s magnetic field. However, CLOUD has set out to find the linkage between cosmic rays, clouds and climate if one exists.

Carbon-14: Carbon 14 is unquestionably the most used of any of the cosmogenic isotopes. It has applications in geology, archaeology, paleontology, anthropology, hydrogeology, and many other -ologies as well. 14C is produced primarily when neutrons collide with nitrogen in the atmosphere replacing a proton in the nitrogen nucleus and transforming it into carbon-14, although atmospheric nuclear weapons testing also produced a substantial amount of 14C. The primary use of 14C, or radiocarbon, is radiocarbon dating. Once radiocarbon is produced it enters the global carbon cycle and disperses throughout the environment. Since it is part of the carbon cycle it becomes incorporated into all living things, including people and animals. 14C continues to enter our bodies while we are alive. Once we die, there is no further addition of 14C and therefore, the clock starts ticking on its use as a dating tool. 14C has a 5,730 year half life and is therefore useful as a dating tool for biological materials up to ~45,000 years ago.

Cosmic rays are some of the most mysterious, yet useful phenomena on our planet and have allowed for incredible advances in many sciences. As new, more sensitive technology becomes available look for the use of cosmic rays and the isotopes they produce to accelerate as we find new questions they can be used to answer.

Cheers and thanks for reading,