Gregory L. Klunder

Portable Microcoil NMR Detection Coupled to Capillary Electrophoresis

High-efficiency separation techniques, such as capillary electrophoresis (CE), coupled to a nondestructive nuclear magnetic resonance (NMR) spectrometer offer the ability to separate, chemically identify, and provide structural information on analytes in small sample volumes. Previous CE-NMR coupled systems utilized laboratory-scale NMR magnets and spectrometers, which require very long separation capillaries. New technological developments in electronics have reduced the size of the NMR system, and small 1-2 T permanent magnets provide the possibilities of a truly portable NMR. The microcoils used in portable and laboratory-scale NMR may offer the advantage of improved mass sensitivity because the limit of detection (LOD) is proportional to the coil diameter. In this work, CE is coupled with a portable, briefcase-sized NMR system that incorporates a microcoil probe and a 1.8 T permanent magnet to measure (19)F NMR spectra. Separations of fluorinated molecules are demonstrated with stopped- and continuous-flow NMR detection. The results demonstrate that coupling CE to a portable NMR instrument is feasible and can provide a low-cost method to obtain structural information on microliter samples. An LOD of 31.8 nmol for perfluorotributylamine with a resolution of 4 ppm has been achieved with this system.

Nuclear forensics in law enforcement applications

Over the past several years, the Livermore Forensic Science Center has conducted analyses of nuclear-related samples in conjunction with domestic and international criminal investigations. Law enforcement officials have sought conventional and nuclear-forensic analyses of questioned specimens that have typically consisted of miscellaneous metal species or actinide salts. The investigated activities have included nuclear smuggling and the proliferation of alleged fissionable materials, nonradioactive hoaxes such as “Red Mercury,” and the interdiction of illegal laboratories engaged in methamphetamine synthesis.

Core-Based Intrinsic Fiber-Optic Absorption Sensor for the Detection of Volatile Organic Compounds

A core-based intrinsic fiber-optic absorption sensor has been developed and tested for the detection of volatile organic compounds. The distal ends of transmitting and receiving fibers are connected by a small cylindrical section of an optically clear silicone rubber. The silicone rubber acts both as a light pipe and as a selective membrane into which the analyte molecules can diffuse. The sensor has been used to detect volatile organics (trichloroethylene, 1,1-dichloroethylene, and benzene) in both aqueous solutions and in the vapor phase or headspace. Absorption spectra obtained in the near-infrared (near-IR) provide qualitative and quantitative information about the analyte. Water, which has strong broad-band absorption in the near-IR, is excluded from the spectra because of the hydrophobic properties of the silicone rubber. The rate-limiting step is shown to be the diffusion through the Nernstian boundary layer surrounding the sensor and not the diffusion through the silicone polymer. The rate of analyte diffusion into the sensor, as measured by the t90 values (the time required for the sensor to reach 90% of the equilibrium value), is 30 min for measurements in aqueous solutions and approximately 3 min for measurements made in the headspace. The limit of detection obtained with this sensor is approximately 1.1 ppm for trichloroethylene in an aqueous solution.

Analysis of fission products using capillary electrophoresis with on-line radioactivity detection

Capillary electrophoresis has been used to separate metal ions characteristically associated with nuclear fission. Indirect UV absorbance and on-line radioactivity detection were used simultaneously to monitor the analytes. The radioactivity detector consists of conical plastic scintillating material with the capillary passing through the center to provide a 4π detection geometry. The wide end of the cone is optically coupled to a photomultiplier tube. Transient isotachophoretic techniques were employed to stack large volumes of samples which had low specific activities. Radioactivity detection of (152)Eu and (137)Cs was achieved at the nanocurie level for 80-100 nL injections. The detector is approximately 80% efficient, enabling samples resident in the detector window for 0.1 min to be reliably assayed. The separation of (137)Cs and (137m)Ba isotopes, which are in secular equilibrium, was modeled to demonstrate the effects of the rapid decay of (137m)Ba.

Application of Visible/Near-Infrared Reflectance Spectroscopy to Uranium Ore Concentrates for Nuclear Forensic Analysis and Attribution

Uranium ore concentrates (UOCs) are produced at mining facilities from the various types of uranium-bearing ores using several processes that can include different reagents, separation procedures, and drying conditions. The final UOC products can consist of different uranium species, which are important to identify to trace interdicted samples back to their origins. Color has been used as a simple indicator; however, visual determination is subjective and no chemical information is provided. In this work, we report the application of near-infrared (NIR) spectroscopy as a non-contact, non-destructive method to rapidly analyze UOC materials for species and/or process information. Diffuse reflectance spectra from 350 to 2500 nm were measured from a number UOC samples that were also characterized by X-ray diffraction. Combination and overtone bands were used to identify the amine and hydroxyl-containing species, such as ammonium uranates or ammonium uranyl carbonate, while other uranium oxide species (e.g., uranium trioxide [UO3] and triuranium octoxide [U3O8]) exhibit absorption bands arising from crystal field effects and electronic transitions. Principal component analysis was used to classify the different UOC materials.

Collinear Photothermal Deflection Spectroscopy of Liquid Samples at Varying Temperature

The method of photothermal beam deflection was demonstrated for measuring the absorption spectrum of an aqueous Nd3+ solution at temperatures between 25°C and 90°C. Changes in the magnitude of the observed deflection can be correlated with the temperature dependence of both the absorptivity of the Nd3+ ions and the physical properties of the solvent, most notably the thermo-optic coefficient dn/dT.

Forensic Analyses of Suspect Illicit Nuclear Material

A small metal sample, alleged to be a substance that could substitute for highly enriched uranium in a nuclear weapon, was subjected to qualitative and quantitative forensic analyses using methods of materials science, radioisotopic chemistry, inorganic chemistry, and organic chemistry. The specimen was determined to be moderately pure Sc, likely derived from a uranium refining operation. Although no fissionable species or weaponization signatures were detected, the sample did exhibit some unusual properties. These anomalies included lanthanide fractionation, with concentrations of Dy, Ho, and Er elevated by factors greater than 100 over normal levels, and the presence of long, odd-chain fatty acids.

Nuclear fission product analysis using capillary separation techniques

Capillary electrophoresis has been used to separate metal ions characteristically associated with nuclear fission. Electrokinetic injections and transient isotachophoretic techniques were employed to increase sample loading and provide on-column concentration of the analyte. On-line concentration factors of approximately 700-fold have been achieved. Indirect-UV absorbance, on-line radioactivity, and indirect laser-induced fluorescence detection were used to monitor analytes of interest. The radioactivity detector consists of a plastic scintillator and photomultiplier tube with a 4π detection geometry. The efficiency was determined to be approximately 80%, enabling samples resident in the detector window for 0.1 minutes to be reliably assayed. Detection of152Eu and137Cs was achieved at the low nCi level. Indirect fluorescence was performed with quinine sulfate as the background fluorophor with α-hydroxysobutyric acid added as a complexing agent. An argon ion laser was used as the excitation source with a diode array detector. Limits of detection for La3+, Ce3+, Pr3+, Nd3+, Sm3+, and Eu3+ were determined to be in the sub — 10 ppb range (6–11 nM) with indirect laser-induced fluorescence detection.

Photothermal deflection spectroscopy of an aqueous sample in a narrow bore quartz capillary

An apparatus to perform photothermal deflection spectroscopy on liquid samples within a cylindrical capillary is described. A tunable dye laser, modulated by an optical chopper, serves as an excitation source. The resolution of a spectral absorption peak near 575 nm, of a 1×10−3 M Nd3+ aqueous solution, demonstrates the effectiveness of the system. The sample is contained within a 75 μm internal diameter quartz capillary, typical of those used for capillary electrophoresis. Across the middle of the probed section of the capillary, the magnitude of the resolved peak is 5.2×10−5 absorbance units. A helium–neon laser, focused to a 1/e2 waist diameter of 40 μm, provides an optical probe beam across the center of the sample, overlapping the excitation beam at an angle of 3°. Maximum signal-to-noise ratio is achieved with the apparatus when the excitation beam is modulated at a frequency near 205 Hz. The deflection responsivity of the probe beam at this frequency is 650 nrad per μW of absorbed excitation radiat...

Photoacoustic spectroscopy and the effect of amplified spontaneous emission.

Amplified spontaneous emission (ASE), which results from dye fluorescence, causes pulsed dye lasers to produce an output that is spectrally impure. The effect of such an output can create inaccurate analytical information, particularly in adsorption and photothermal spectroscopies. The spectral output of laser dye LD-466 has been characterized. ASE was shown to have a broad-band spectral output, 445-495 nm, and was most intense when lasing was inefficient, on the edges of the dye gain curve. A 10 -3 M Pr 3+ solution produced similar photoacoustic waveforms from lasing and ASE