A New Method of Measuring 81Kr and 85Kr Abundances in Environmental Samples

We demonstrate a new method for determining the 81Kr/Kr ratio in environmental samples based upon two measurements: the 85Kr/81Kr ratio measured by Atom Trap Trace Analysis (ATTA) and the 85Kr/Kr ratio measured by Low-Level Counting (LLC). This method can be used to determine the mean residence time of groundwater in the range of 10^5 - 10^6 a. It requires a sample of 100 micro-l STP of Kr extracted from approximately two tons of water. With modern atmospheric Kr samples, we demonstrate that the ratios measured by ATTA and LLC are directly proportional to each other within the measurement error of +/- 10%; we calibrate the 81Kr/Kr ratio of modern air measured using this method; and we show that the 81Kr/Kr ratios of samples extracted from air before and after the development of the nuclear industry are identical within the measurement error

Tracer Applications of Noble Gas Radionuclides in the Geosciences

The noble gas radionuclides, including 81Kr (half-life = 229,000 yr), 85Kr (11 yr), and 39Ar (269 yr), possess nearly ideal chemical and physical properties for studies of earth and environmental processes. Recent advances in Atom Trap Trace Analysis (ATTA), a laser-based atom counting method, have enabled routine measurements of the radiokrypton isotopes, as well as the demonstration of the ability to measure 39Ar in environmental samples. Here we provide an overview of the ATTA technique, and a survey of recent progress made in several laboratories worldwide. We review the application of noble gas radionuclides in the geosciences and discuss how ATTA can help advance these fields, specifically determination of groundwater residence times using 81Kr, 85Kr, and 39Ar; dating old glacial ice using 81Kr; and an 39Ar survey of the main water masses of the oceans, to study circulation pathways and estimate mean residence times. Other scientific questions involving deeper circulation of fluids in the Earth's crust and mantle also are within the scope of future applications. We conclude that the geoscience community would greatly benefit from an ATTA facility dedicated to this field, with instrumentation for routine measurements, as well as for research on further development of ATTA methods

Stable isotope investigations of chlorinated aliphatic hydrocarbons.

Stable isotope ratio measurements for carbon (C) and chlorine (Cl) can be used to elucidate the processes affecting transformation and transportation of chlorinated aliphatic hydrocarbons (CAHs) in the environment. Methods recently developed in our laboratory for isotopic analysis of CAHs have been applied to laboratory measurements of the kinetic isotope effects associated with aerobic degradation of dichloromethane (DCM) and with both anaerobic and aerobic cometabolic degradation of trichlomethene (TCE) in batch and column microbial cultures. These experimental determinations of fractionation factors are crucial for understanding the behavior of CAHs in complex natural systems, where the extent of biotransformation can be masked by dispersion and volatilization. We have also performed laboratory investigations of kinetic isotope effects accompanying evaporation of CAHs, as well as field investigations of natural attenuation and in situ remediation of CAHs in a number of contaminated shallow aquifers at sites operated by the federal government and the private sector

Ar-39 Detection at the 10^-16 Isotopic Abundance Level with Atom Trap Trace Analysis

Atom Trap Trace Analysis (ATTA), a laser-based atom counting method, has been applied to analyze atmospheric Ar-39 (half-life = 269 yr), a cosmogenic isotope with an isotopic abundance of 8x10^-16. In addition to the superior selectivity demonstrated in this work, counting rate and efficiency of ATTA have been improved by two orders of magnitude over prior results. Significant applications of this new analytical capability lie in radioisotope dating of ice and water samples and in the development of dark matter detectors

Ar39 Detection at the 10\u3csup\u3e-\u3c/sup\u3e16 Isotopic Abundance Level with Atom Trap Trace Analysis

Atom trap trace analysis, a laser-based atom counting method, has been applied to analyze atmospheric Ar39 (half-life=269yr), a cosmogenic isotope with an isotopic abundance of 8×10-16. In addition to the superior selectivity demonstrated in this work, the counting rate and efficiency of atom trap trace analysis have been improved by 2 orders of magnitude over prior results. The significant applications of this new analytical capability lie in radioisotope dating of ice and water samples and in the development of dark matter detectors. © 2011 American Physical Society

Model-independent X-ray imaging of adsorbed cations at the crystal-water interface.

Abstract We describe an approach to directly image three-dimensional elemental distributions at the crystal-liquid interface with $1 A spatial resolution. This method, based on the Fourier synthesis of X-ray standing wave data, is demonstrated by imaging the distribution of Sr 2þ , Zn 2þ and Y 3þ adsorbed to the rutile (1 1 0)-water interface with no a priori assumptions. The approach resolves distinct sites and is robust for systems with single or multiple simultaneous adsorption sites. The observed ion distributions reveal unexpected differences in the adsorption sites of these cations that are needed to interpret electrical double-layer phenomena using surface complexation models. Published by Elsevier B.V

An Atom Counter for Measuring \u3csup\u3e81\u3c/sup\u3eKr and \u3csup\u3e85\u3c/sup\u3eKr in Environmental Samples

Due to its simple production and transport processes in the terrestrial environment, the long-lived noble-gas isotope 81Kr is the ideal tracer for old water and ice in the age range of 10 5-10 6 years, a range beyond the reach of 14C. 81Kr-dating, a concept pursued in the past four decades by numerous laboratories employing a variety of techniques, is now available for the first time to the earth science community at large. This is made possible by the development of ATTA-3, an efficient and selective atom counter based on the Atom Trap Trace Analysis method and capable of measuring both 81Kr/Kr and 85Kr/Kr ratios of environmental samples in the range of 10 -14-10 -10. The instrument was calibrated with 12 samples whose 85Kr/Kr ratios were independently measured using Low Level Decay Counting, including six samples that were measured in a blind arrangement. Compared to the previously reported ATTA-2 instrument, the counting rates of ATTA-3 are higher by two orders of magnitude and the required sample size lower by one order of magnitude. For 81Kr-dating in the age range of 150-1500kyr, the required sample size is 5-10μL STP of krypton gas, which can be extracted from approximately 100-200kg of water or 40-80kg of ice. Moreover, a laser-induced quenching scheme was developed to enable measurements of both the rare 81,85Kr and the abundant 83Kr, whose isotopic abundances differ by 11 orders of magnitude. This scheme allows ATTA-3 to directly determine 81Kr/Kr and 85Kr/Kr ratios without other supplemental measurements. Combining the significant reduction in sample size with numerous advances in the measurement procedure, ATTA-3 represents the state-of-the-art instrument for routine analysis of these rare noble gas tracers in a wide range of earth science applications. © 2012 Elsevier Ltd

The brief international cognitive assessment for multiple sclerosis (BICAMS): Normative values with gender, age and education corrections in the Italian population

Background: BICAMS (Brief International Cognitive Assessment for Multiple Sclerosis) has been recently developed as brief, practical and universal assessment tool for cognitive impairment in MS subjects. It includes the Symbol Digit Modalities Test (SDMT), the California Verbal Learning Test-2 (CVLT2) and the Brief Visuospatial Memory Test-Revised (BVMT-R) . In this study we aimed at gathering regression based normative data for the BICAMS battery in the Italian population.Methods: Healthy subjects were consecutively recruited among patient friends and relatives. Corrections for demographics were calculated using multivariable linear regression models. Test-retest reliability was assessed using the Pearson correlation coefficient.Results: The BICAMS battery was administered to 273 healthy subjects (180 women, mean age 38.9 ± 13.0 years, mean education 14.9 ± 3.0 years). Test-retest reliability was good for all the tests.Conclusions: The study provided normative data of the BICAMS for the Italian population confirming good test-retest reliability which can facilitate the use of the battery in clinical practice, also for longitudinal patient assessments