Development of a technique for mercury speciation and quantification using gas chromatography/mass spectrometry

One element of concern to DOE is mercury. Mercury was used extensively at the DOE facilities in Oak Ridge, Tennessee from 1950 to 1963 in the process of making lithium deuteride, a component of nuclear weapons. Although both the inorganic and organometallic forms of mercury are toxic to humans, the organic compounds are often more toxic. Since the toxicity of mercury is a function of its chemical form, an understanding of the interactions between commercially discharged mercury, naturally occurring mercury, and the environment in which they are present is vital. In this report, the authors have been investigating gas chromatography/mass spectrometry (GC/MS) for the analysis of both the organometallic and inorganic forms of mercury in the same environmental sample (e.g., solutions, soils, and sludges). Although gas chromatography is the classical technique for analyzing organic molecules, (e.g., organometallic compounds) little has been done on the analysis of inorganic compounds. In a previous publication, the authors described how a solid phase microextraction (SPME) fiber could be used to sample organomercurials from aqueous samples. An alkylation reaction was then carried out to transform chemically mercury nitrate into dimethylmercury; subsequent GC/MS analysis of this compound permitted quantification of the inorganic constituent. Subsequently, several different alkylation reagents have been synthesized that methylate any inorganic mercury compound to methylmercury iodide. Here, the authors report results on alkylation reaction time and the effect of pH on the population of the product

A fieldable instrument for waterborne radionuclide detection

In monitoring effluent leaving its sites, US DOE assays for alpha- emitting radionuclides (U, transuranics) to ensure compliance with regulatory limits. Because alpha emissions can only by detected over a short range in water ({approximately}40{mu}m), the conventional approach is to collect samples for processing in a central laboratory; a time-consuming and cost procedure ensues to separate and measure the radionuclides. Because of the sporadic nature of sampling processes, there is the possibility that a release may go undetected. We are addressing this issue by a developing a real-time, field- deployable instrument which incorporates a proprietary film that selectively binds radionuclides from dilute aqueous samples. By combining the film with an appropriate alpha spectrometer, we have developed a fieldable system that can operate as an autonomous monitor in a batch or continuous manner. Laboratory results to date have been encouraging. Positive identification of U and Pu has been made by resolving the energy spectrum of emitted alphas. Sensitivity for U is at the 10 part per trillion level (15 femtocuries per liter)

Electronic Aroma Detection Technology for Forensic and Law Enforcement Applications

A major problem hindering criminal investigations is the lack of appropriate tools for proper crime scene investigations. Often locating important pieces of evidence means relying on the ability of trained detection canines. Development of analytical technology to uncover and analyze evidence, potentially at the scene, could serve to expedite criminal investigations, searches, and court proceedings. To address this problem, a new technology based on gas sensor arrays was investigated for its applicability to forensic and law enforcement problems. The technology employs an array of sensors that respond to volatile chemical components yielding a characteristic `fingerprint` pattern representative of the vapor- phase composition of a sample. Sample aromas can be analyzed and identified using artificial neural networks that are trained on known aroma patterns. Several candidate applications based on known technological needs of the forensic and law enforcement communities have been investigated. These applications have included the detection of aromas emanating from cadavers to aid in determining time since death, drug detection for deterring the manufacture, sale, and use of drugs of abuse, and the analysis of fire debris for accelerant identification. The results to date for these applications have been extremely promising and demonstrate the potential applicability of this technology for forensic use

Evaluation of the uranium double spike technique for environmental monitoring

Use of a uranium double spike in analysis of environmental samples showed that a {sup 235}U enrichment of 1% ({sup 235}U/{sup 238}U = 0.00732) can be distinguished from natural ({sup 235}U/{sup 238}U = 0.00725). Experiments performed jointly at Los Alamos National Laboratory (LANL) and Oak Ridge National Laboratory (ORNL) used a carefully calibrated double spike of {sup 233}U and {sup 236}U to obtain much better precision than is possible using conventional analytical techniques. A variety of different sampling media (vegetation and swipes) showed that, provided sufficient care is exercised in choice of sample type, relative standard deviations of less than {+-} 0.5% can be routinely obtained. This ability, unavailable without use of the double spike, has enormous potential significance in the detection of undeclared nuclear facilities

Analysis of accelerants and fire debris using aroma detection technology

The purpose of this work was to investigate the utility of electronic aroma detection technologies for the detection and identification of accelerant residues in suspected arson debris. Through the analysis of known accelerant residues, a trained neural network was developed for classifying suspected arson samples. Three unknown fire debris samples were classified using this neural network. The item corresponding to diesel fuel was correctly identified every time. For the other two items, wide variations in sample concentration and excessive water content, producing high sample humidities, were shown to influence the sensor response. Sorbent sampling prior to aroma detection was demonstrated to reduce these problems and to allow proper neural network classification of the remaining items corresponding to kerosene and gasoline

A glow discharge ion source with Fourier transform ion cyclotron resonance mass spectrometric detection

AbstractA glow discharge (GD) ion source has been coupled to a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer using a four-element electrostatic lens to accelerate and focus ions generated external to the instrument's high magnetic field into its analyzer cell. Like other GD mass spectrometers, GD-FT-ICR can provide a quantitative measure of bulk analyte concentration with good precision and accuracy. Although detection limits currently attainable are several orders of magnitude higher than the commercially available magnetic sector-based instrument, GD-FT-ICR holds promise for ultrahigh resolving power elemental mass analysis. Several schemes are proposed to lower the detection limits of the technique while still providing high enough resolution to resolve isobaric interferences

Recent trends in inorganic mass spectrometry

The field of inorganic mass spectrometry has seen substantial change in the author`s professional lifetime (over 30 years). Techniques in their infancy 30 years ago have matured; some have almost disappeared. New and previously unthought of techniques have come into being; some of these, such as ICP-MS, are reasonably mature now, while others have some distance to go before they can be so considered. Most of these new areas provide fertile fields for researchers, both in the development of new analytical techniques and by allowing fundamental studies to be undertaken that were previously difficult, impossible, or completely unforeseen. As full coverage of the field is manifestly impossible within the framework of this paper, only those areas with which the author has personal contact will be discussed. Most of the work originated in his own laboratory, but that of other laboratories is covered where it seemed appropriate

<title>Electronic aroma detection technology for forensic and law enforcement applications</title>

A major problem hindering criminal investigations is the lack of appropriate tools for proper crime scene investigations. Often locating important pieces of evidence means relying on the ability of trained detection canines. Development of analytical technology to uncover and analyze evidence, potentially at the scene, could serve to expedite criminal investigations, searches, and court proceedings. To address this problem, a new technology based on gas sensor arrays was investigated for its applicability to forensic and law enforcement problems. The technology employs an array of sensors that respond to volatile chemical components yielding a characteristic `fingerprint` pattern representative of the vapor- phase composition of a sample. Sample aromas can be analyzed and identified using artificial neural networks that are trained on known aroma patterns. Several candidate applications based on known technological needs of the forensic and law enforcement communities have been investigated. These applications have included the detection of aromas emanating from cadavers to aid in determining time since death, drug detection for deterring the manufacture, sale, and use of drugs of abuse, and the analysis of fire debris for accelerant identification. The results to date for these applications have been extremely promising and demonstrate the potential applicability of this technology for forensic use