Lizbeth Laureano-Perez

Measurement of radon and xenon binding to a cryptophane molecular host

Xenon and radon have many similar properties, a difference being that all 35 isotopes of radon (195Rn–229Rn) are radioactive. Radon is a pervasive indoor air pollutant believed to cause significant incidence of lung cancer in many geographic regions, yet radon affinity for a discrete molecular species has never been determined. By comparison, the chemistry of xenon has been widely studied and applied in science and technology. Here, both noble gases were found to bind with exceptional affinity to tris-(triazole ethylamine) cryptophane, a previously unsynthesized water-soluble organic host molecule. The cryptophane–xenon association constant, Ka = 42,000 ± 2,000 M-1 at 293 K, was determined by isothermal titration calorimetry. This value represents the highest measured xenon affinity for a host molecule. The partitioning of radon between air and aqueous cryptophane solutions of varying concentration was determined radiometrically to give the cryptophane–radon association constant Ka = 49,000 ± 12,000 M-1 at 293 K.

Investigation into the standardization of 99Tc.

The standardization of (99)Tc by several primary methods was investigated. This was performed to support a new (99)Tc transfer standard that has been developed and will be disseminated by the National Institute of Standards and Technology (NIST) as Standard Reference Material SRM 4288B. The standardization for the (99)Tc content of the solution was based on 4pibeta liquid scintillation (LS) measurements with (3)H-standard efficiency tracing (CIEMAT/NIST method). Confirmatory determinations were performed by 4pibeta(LS)-gamma(NaI) live-timed anti-coincidence (LTAC) counting and an LS-based 4pibeta triple-to-double coincidence ratio (TDCR) method.

A new primary standardization of 229Th.

The National Institute of Standards and Technology (NIST) has certified a high-purity (229)Th Standard Reference Material as SRM 4328C, based on live-timed 4pialphabeta-gamma anticoincidence counting (LTAC) of the equilibrium solution. The LTAC system was optimized to minimize the uncertainty in the result due to the two short-lived ground-states present in the decay chain. Confirmatory measurements were carried out by four other methods. Furthermore, the present absolute activity and measured gamma-ray emission rates were combined to obtain gamma-ray emission probabilities.

Micelle size effect on Fe-55 liquid scintillation efficiency.

We used efficiency tracing techniques to study the micelle size effect on liquid scintillation counting of the electron capture nuclide, (55)Fe. We determined micelle hydrodynamic diameters for specific LS cocktails via dynamic light scattering, and sought trends in efficiencies as a function of micelle size. The presence of Fe(3+) or Mn(2+) ions in the cocktails did not significantly affect micelle sizes or fluorescence quenching. We did not detect any reductions in counting efficiencies due to the micelle size effect.

A novel application for 222Rn emanation standards: radon-cryptophane host chemistry.

In collaboration with the University of Pennsylvania, a (222)Rn emanation source was used for the determination of the binding affinity of radon to a cryptophane molecular host. This source was similar to a (222)Rn emanation standard that was developed and disseminated by the National Institute of Standards and Technology (NIST). The novel experimental design involved performing the reactions at femtomole levels, developing exacting gravimetric sampling methods and making precise (222)Rn assays by liquid scintillation counting. A cryptophane-radon association constant was determined, K(A)=(49,000±12,000) L mol(-1) at 293 K, which was the first measurement of radon binding to a molecular host.

Development of an Ultra-Pure, Carrier-Free 209Po Solution Standard

Ultra-pure, carrier-free 209Po solution standards have been prepared and standardized for their massic alpha-particle emission rate. The standards, which will be disseminated by the National Institute of Standards and Technology (NIST) as Standard Reference Material SRM 4326a, have a mean mass of (5.169 ± 0.003) g of a solution of polonium in nominal 2.0 mol▪L−1 HCl (having a solution density of (1.032 ± 0.002) g▪ mL−1 at 20 °C) that are contained in 5 mL, flame-sealed, borosilicate glass ampoules. They are certified to contain a 209Po massic alpha-particle emission rate of (39.01 ± 0.18) s−1▪g−1 as of a reference time of 1200 EST, 01 December 2013. This new standard series replaces SRM 4326 that was issued by NIST in 1994. The standardization was based on 4πα liquid scintillation (LS) spectrometry with two different LS counting systems and under wide variations in measurement and counting source conditions. The methodology for the standardization, with corrections for detection of the low-energy conversion electrons from the delayed 2 keV isomeric state in 205Pb and for the radiations accompanying the small 0.45 % electron-capture branch to 209Bi, involves a unique spectral analysis procedure that is specific for the case of 209Po decay. The entire measurement protocol is similar, but revised and improved from that used for SRM 4326. Spectroscopic impurity analyses revealed that no photon-emitting or alpha-emitting radionuclidic impurities were detected. The most common impurity associated with 209Po is 208Po and the activity ratio of 208Po/209Po was < 10−7.

Results of an international comparison of activity measurements of 68 Ge

An international key comparison, identifier CCRI(II)-K2.Ge-68, has been performed. The National Institute of Standards and Technology (NIST) served as the pilot laboratory, distributing aliquots of a 68Ge/68Ga solution. Results for the activity concentration, CA, of 68Ge at a reference date of 12h00 UTC 14 November 2014 were submitted by 17 laboratories, encompassing many variants of coincidence methods and liquid-scintillation counting methods. The first use of 4π(Cherenkov)β-γ coincidence and anticoincidence methods in an international comparison is reported. One participant reported results by secondary methods only. Two results, both utilizing pure liquid-scintillation methods, were identified as outliers. Evaluation using the Power-Moderated Mean method results in a proposed Comparison Reference Value (CRV) of 621.7(11)kBqg-1, based on 14 results. The degrees of equivalence and their associated uncertainties are evaluated for each participant. Several participants submitted 3.6mL ampoules to the BIPM to link the comparison to the International Reference System (SIR) which may lead to the evaluation of a Key Comparison Reference Value and associated degrees of equivalence.

Comparison of 14 C liquid scintillation counting at NIST and NRC Canada

An informal bilateral comparison of (14)C liquid scintillation (LS) counting at the National Research Council of Canada (NRC) and the National Institute of Standards and Technology (NIST) has been completed. Two solutions, one containing (14)C-labeled sodium benzoate and one containing (14)C-labeled n-hexadecane, were measured at both laboratories. Despite observed LS cocktail instabilities, the two laboratories achieved accord in their standardizations of both solutions. At the conclusion of the comparison, the beta spectrum used for efficiency calculations was identified as inadequate and the data were reanalyzed with different inputs, improving accord.

New determination of the 229Th half-life

A new determination of the 229Th half-life was made based on measurements of the 229Th massic activity of a high-purity solution for which the 229Th molality had previously been measured. The 229Th massic activity was measured by direct comparison with SRM 4328C using 4παβ liquid scintillation counting, NaI counting, and standard addition liquid scintillation counting. The massic activity was confirmed by isotope dilution alpha spectrometry measurements. The calculated 229Th half-life is (7825 ± 87) years (k = 2), which is shorter than the three most recent half-life determinations but is consistent with these values within uncertainties.

Comparison of tritiated-water standards by liquid scintillation for calibration of a new Standard Reference Material®

A new National Institute of Standards and Technology (NIST) tritiated-water ((3)H-labeled oxidane) standard was prepared and calibrated. It is the 17th in a series of linked standards since 1954 and will be disseminated as Standard Reference Material® SRM 4927G, having a massic activity of 544.2kBqg(-1), with an expanded (k=2) relative standard uncertainty of 0.96%, at a Reference Time of 1200 EST, 1 May 2015. The calibration is based on relative liquid scintillation (LS) measurements using quench-varied efficiency tracing with two previous 1999 issues, viz., SRM 4927F and 4926E. Measurement comparisons were also made with respect to a 1994 tritiated-water French national standard and to a tritiated-water solution measured by 19 laboratories as part of an international measurement comparison organized by the Bureau International des Poids et Mesures (BIPM) in 2009. Confirmatory measurements for the massic activity of both SRM 4927F and 4927G by a triple-to-double coincidence ratio (TDCR) technique were also made.