A Tibetan ice core covering the past 1,300 years radiometrically dated with 39Ar.

Ice cores from alpine glaciers are unique archives of past global and regional climate conditions. However, recovering climate records from these ice cores is often hindered by the lack of a reliable chronology, especially in the age range of 100 to 500 anni (a) for which radiometric dating has not been available so far. We report on radiometric 39Ar dating of an ice core from the Tibetan Plateau and the construction of a chronology covering the past 1,300 a using the obtained 39Ar ages. This is made possible by advances in the analysis of 39Ar using the laser-based detection method atom trap trace analysis, resulting in a twofold increase in the upper age limit of 39Ar dating. By measuring the anthropogenic 85Kr along with 39Ar we quantify and correct modern air contamination, thus removing a major systematic uncertainty of 39Ar dating. Moreover, the 85Kr data for the top part of the ice core provide information on firn processes, including the age difference between the ice and its enclosed gas. This first application of 39Ar and 85Kr to an ice core facilitates further ice cores from nonpolar glaciers to be used for recovering climate records of the Common Era, a period including pronounced anomalies such as the Little Ice Age and the Medieval Warm Period.

Dual Separation of Krypton and Argon from Environmental Samples for Radioisotope Dating.

The noble gas radioisotopes 85Kr, 81Kr, and 39Ar are nearly ideal environmental tracers because of their chemical inertness and simple transport mechanisms. Recent advances in Atom Trap Trace Analysis have enabled measurements of 85Kr and 81Kr using 10-20 kg of water or ice, and 39Ar in only a few kilograms, making these tracers available to be applied in the earth sciences on a large-scale. To meet the resulting increase in demand, we have developed an automated process for the dual separation of krypton and argon from environmental samples based on titanium gettering and gas chromatography. 0.5-4 L STP air samples have been purified, demonstrating purities and recoveries of >90% for krypton and >99% for argon within 90-120 min of processing time. Samples of high methane admixtures, a challenge regularly encountered in groundwater applications, have been purified by exploiting the full potential of titanium gettering at high temperatures (>1000 °C). Samples with 0.4-48 L STP of methane admixture are processed in 2-5 h without compromising purity or recovery. The applicability of the purification system is further demonstrated using actual groundwater samples with carbon dioxide and methane content in the extracted gas up to 16 L STP and 42 L STP, respectively.

A magnetically enhanced RF discharge source for metastable krypton production.

We describe a high intensity metastable Kr source based on a helical resonator RF discharge. By adding an external B-field to the discharge source, the metastable Kr flux is enhanced. The effect of geometric configuration and magnetic field strength has been studied and optimized experimentally. Compared to the helical resonator discharge source without an external B-field, the new source showed an enhancement factor of 4-5 in producing metastable Kr beams. This improvement has a direct impact on the radio-krypton dating applications as it can increase the atom count rate, resulting in a higher analytical precision.

Fast atom-trap analysis of 39Ar with isotope pre-enrichment.

We demonstrate fast analysis of 39Ar/Ar at the 10-16 level using a mass spectrometer for isotope pre-enrichment and an atom trap for counting. An argon gas sample first passes through a dipole mass separator that reduces the dominant isotope 40Ar by two orders of magnitude while preserving both the rare tracer isotope 39Ar and a minor stable isotope 38Ar for control purposes. Measurements of both natural and enriched samples with atom trap trace analysis demonstrate that the 39Ar/38Ar ratios change less than 10%, while the overall count rates of 39Ar are increased by one order of magnitude. By overcoming the analysis-speed bottleneck, this advance will benefit large-scale applications of 39Ar dating in the earth sciences, particularly for mapping ocean circulation.

An atom trap system for 39Ar dating with improved precision.

Cosmogenic 39Ar dating is an emerging technique in dating mountain glacier ice, mapping ocean circulation, and tracing groundwater flow. We have realized an atom-trap system for the analysis of the radioactive isotope 39Ar (half-life = 269 years) in environmental samples. The system is capable of analyzing small (1-5 kg) environmental water or ice samples and achieves a count rate of 10 atoms/h for 39Ar at the modern isotopic abundance level of 8 × 10-16. By switching frequently between counting 39Ar atoms and measuring the stable and abundant isotope 38Ar, drift effects in the trapping efficiency are largely suppressed, leading to a more precise measurement of the isotope ratio 39Ar/38Ar. Moreover, cleaning techniques are developed to alleviate cross-sample contamination, reducing the background 39Ar count rate down to <0.5 atoms/h. These advances allow us to determine the 39Ar age in the range of 250-1300 years with precisions of <20%.

Monitoring atmospheric 85Kr by atom counting.

Radioactive 85Kr is a major gaseous fission product emitted into the air by the nuclear fuel reprocessing industry. Measuring atmospheric 85Kr has applications in environmental monitoring, atmospheric transport model validation and dating of environmental water samples, including groundwater, sea water and glacier ice. We present an ultra-sensitive method for fast analysis of atmospheric 85Kr at 10-5 parts per trillion level. This method is based on laser cooling and trapping and is capable of counting individual 85Kr atoms. Measurements at the 3% precision level can be made on krypton extracted from 1L STP of air with a turnaround time of 1.5 h. Moreover, we have realized a system for continuous air sampling over days to weeks. Based on this atom-counting technology and a portable air sample integrator we have realized atmospheric 85Kr baseline monitoring in Hefei, China, for over 20 months. The technological advances presented in this work lay the ground for a global atmospheric 85Kr monitoring network.