Detection of Chemical/Biological Agents and Simulants A new detector for chemical and biological ... more Detection of Chemical/Biological Agents and Simulants A new detector for chemical and biological agents is being developed for the U. S. Army under the Chemical and Biological Mass Spectrometer Block II program. The CBMS Block II is designed to optimize detection of both chemical and biological agents through the use of direct sampling inlets [I], a multi- ported sampling valve and a turbo- based vacuum system to support chemical ionization. Unit mass resolution using air as the buffer gas [2] has been obtained using this design. Software to control the instrument and to analyze the data generated from the instrument has also been newly developed. Detection of chemical agents can be accomplished. using the CBMS Block II design via one of two inlets - a l/ I 6'' stainless steel sample line -Chemical Warfare Air (CW Air) or a ground probe with enclosed capillary currently in use by the US Army - CW Ground. The Block II design is capable of both electron ionization and chemical ionization. Ethanol is being used as the Cl reagent based on a study indicating best performance for the Biological Warfare (BW) detection task (31). Data showing good signal to noise for 500 pg of methyl salicylate injected into the CW Air inlet, 50 ng of dimethylmethylphosphonate exposed to the CW Ground probe and 5 ng of methyl stearate analyzed using the pyrolyzer inlet were presented. Biological agents are sampled using a ''bio-concentrator'' unit that is designed to concentrate particles in the low micron range. Particles are collected in the bottom of a quartz pyrolyzer tube. An automated injector is being developed to deliver approximately 2 pL of a methylating reagent, tetramethylamonium- hydroxide to 'the collected particles. Pyrolysis occurs by rapid heating to ca. 55OOC. Biological agents are then characterized by their fatty acid methyl ester profiles and by other biomarkers. A library of ETOH- Cl/ pyrolysis MS data of microorganisms used for a recently published study [3] has been expanded with additional bacteria and fungi. These spectra were acquired on a Finnigan Magnum ion trap using helium buffer gas. A new database of Cl spectra of microorganisms is planned using the CBMS Block II instrument and air as the buffer gas. Using the current database, the fatty acid composition of the organisms was compared using the percentage of the ion current attributable to fatty acids. The data presented suggest promising rules for discrimination of these organisms. Strain, growth media and vegetative state do contribute to some of the distributions observed in the data. However, the data distributions observed in the current study only reflect our experience to date and do not fully represent the variability that might be expected in practice: Acquisition of MS/ MS spectra has begun (using He and air buffer gas) of the protonated molecular ion of a variety of fatty acids and for a number of ions nominally assigned as fatty acids from microorganisms. These spectra will be used to help verify fatty acid .
Microbially influenced corrosion of pipeline steels is an economically important problem. Microbe... more Microbially influenced corrosion of pipeline steels is an economically important problem. Microbes form tubercles which block fluid flow and can facilitate localized corrosion leading to through-wall penetrations. Microbes of diverse physiological types and metabolic potentialities have been recovered from fresh tubercles or under-deposit corrosion and have been characterized. In tests utilizing sterilizable flow-through systems containing pipeline steel coupons, corrosion rates
The technique of laser-induced breakdown spectroscopy (LIBS) to detect elements for a variety of ... more The technique of laser-induced breakdown spectroscopy (LIBS) to detect elements for a variety of homeland security applications such as nuclear materials identification and inventory,and forensic applications has been demonstrated. For nuclear materials applications, we detected and profiled metals in coatings that were used to encapsulate nuclear fuel. Multivariate analysis has been successfully employed in the quantification of elements present in
Page 1. Biological Agent Detection and Identification by the Block II Chemical Biological Mass Sp... more Page 1. Biological Agent Detection and Identification by the Block II Chemical Biological Mass Spectrometer Wayne H. Griest, Marcus B. Wise, Kevin J. Hart, Stephen A. Lammert, Cyril V. Thompson, and Arpad A. Vass Chemical ...
Biomedical Vibrational Spectroscopy and Biohazard Detection Technologies, 2004
Surface-enhanced Raman scattering (SERS) spectra of chemical agent simulants such as dimethyl met... more Surface-enhanced Raman scattering (SERS) spectra of chemical agent simulants such as dimethyl methylphonate (DMMP), pinacolyl methylphosphonate (PMP), diethyl phosphoramidate (DEPA), and 2-chloroethyl ethylsulfide (CEES), and biological agent simulants such as bacillus globigii (BG), erwinia herbicola (EH), and bacillus thuringiensis (BT) were obtained from silver oxide film-deposited substrates. Thin AgO films ranging in thickness from 50 nm to 250 nm were
Advanced Environmental, Chemical, and Biological Sensing Technologies II, 2004
An integrated multi-functional biochip based on integrated circuit complementary metal oxide semi... more An integrated multi-functional biochip based on integrated circuit complementary metal oxide semiconductor (CMOS) sensor array for use in medical diagnostics and pathogen detection has been described. The usefulness and potential of the biochip as a rapid, inexpensive screening tool for detection of bioenvironmental pathogens will be demonstrated. Detection of aerosolized spores was achieved by coupling the miniature system to a
This study, conducted at the University of Tennessee's Anthropological Research Facility (AR... more This study, conducted at the University of Tennessee's Anthropological Research Facility (ARF), describes the development of the Decompositional Odor Analysis (D.O.A.) Database and seeks to establish the chemical basis for canine's scenting ability when detecting human remains. This database is composed of chemicals that are liberated during the decompositional process from buried human remains. This 'living' database currently spans the first year and a half of burial, providing identification, chemical trends and semi-quantitation of chemicals liberated below, above and at the surface of 1.5 - 2.5 ft graves for three individuals (two males and one female). A fourth male individual (buried in 1990) was also sampled to provide possible 'endpoint' information. In-ground, in-corpse thermocouples provided temperature information which can be used to correlate accumulated degree days (ADDs) to surface decompositional events and indicated an approximate 12 h...
This study, conducted at the University of Tennessee&... more This study, conducted at the University of Tennessee's Anthropological Research Facility (ARF), describes the establishment of the Decompositional Odor Analysis (DOA) Database for the purpose of developing a man-portable, chemical sensor capable of detecting clandestine burial sites of human remains, thereby mimicking canine olfaction. This "living" database currently spans the first year and a half of burial, providing identification, chemical trends and semi-quantitation of chemicals liberated below, above and at the surface of graves 1.5 to 3.5 ft deep (0.45 to 1.0 m) for four individuals. Triple sorbent traps (TSTs) were used to collect air samples in the field and revealed eight major classes of chemicals containing 424 specific volatile compounds associated with burial decomposition. This research is the first step toward identification of an "odor signature" unique to human decomposition with projected ramifications on cadaver dog training procedures and in the development of field portable analytical instruments which can be used to locate human remains buried in shallow graves.
The ability to differentiate microorganisms using pyrolysision trap mass spectrometry was demonst... more The ability to differentiate microorganisms using pyrolysision trap mass spectrometry was demonstrated for five Gram-negative disease-causing organisms: Brucella melitensis, Brucella suis, Vibrio cholera, Yersinia pestis, and Francisella tularensis. Bacterial profiles were generated for gamma-irradiated bacterial samples using pyrolytic methylation and compared for electron ionization and chemical ionization using several liquid reagents with increasing proton affinities. Electron ionization combined with pyrolysis caused extensive fragmentation, resulting in a high abundance of lower mass ions and diminishing the diagnostic value of the technique for compound identification and bacterial profiling. Chemical ionization reduced the amount of fragmentation due to ionization while enhancing the molecular ion region of the fatty acids. As the proton affinity of the reagent increased, the protonated molecular ions of the fatty acids became the predominant ions observed in the mass spectrum. As a result, chemical ionization was shown to be more effective than electron ionization in bacterial profiling. Whereas the bacteria could be distinguished at the Genera level using electron ionization, further differentiation to the subspecies level was possible using chemical ionization. The greatest separation among the five test organisms, in terms of Euclidean distances, was obtained using ethanol as the chemical ionization reagent and using pooled masses representing specific fatty acid biomarkers rather than total ion profiles.
Description/Abstract The technique of laser-induced breakdown spectroscopy (LIBS) to detect eleme... more Description/Abstract The technique of laser-induced breakdown spectroscopy (LIBS) to detect elements for a variety of homeland security applications such as nuclear materials identification and inventory, and forensic applications has been demonstrated. For nuclear materials applications, we detected and profiled metals in coatings that were used to encapsulate nuclear fuel. Multivariate analysis has been successfully employed in the quantification of elements present in treated wood and engineered wood composites. ...
Detection of Chemical/Biological Agents and Simulants A new detector for chemical and biological ... more Detection of Chemical/Biological Agents and Simulants A new detector for chemical and biological agents is being developed for the U. S. Army under the Chemical and Biological Mass Spectrometer Block II program. The CBMS Block II is designed to optimize detection of both chemical and biological agents through the use of direct sampling inlets [I], a multi- ported sampling valve and a turbo- based vacuum system to support chemical ionization. Unit mass resolution using air as the buffer gas [2] has been obtained using this design. Software to control the instrument and to analyze the data generated from the instrument has also been newly developed. Detection of chemical agents can be accomplished. using the CBMS Block II design via one of two inlets - a l/ I 6'' stainless steel sample line -Chemical Warfare Air (CW Air) or a ground probe with enclosed capillary currently in use by the US Army - CW Ground. The Block II design is capable of both electron ionization and chemical ionization. Ethanol is being used as the Cl reagent based on a study indicating best performance for the Biological Warfare (BW) detection task (31). Data showing good signal to noise for 500 pg of methyl salicylate injected into the CW Air inlet, 50 ng of dimethylmethylphosphonate exposed to the CW Ground probe and 5 ng of methyl stearate analyzed using the pyrolyzer inlet were presented. Biological agents are sampled using a ''bio-concentrator'' unit that is designed to concentrate particles in the low micron range. Particles are collected in the bottom of a quartz pyrolyzer tube. An automated injector is being developed to deliver approximately 2 pL of a methylating reagent, tetramethylamonium- hydroxide to 'the collected particles. Pyrolysis occurs by rapid heating to ca. 55OOC. Biological agents are then characterized by their fatty acid methyl ester profiles and by other biomarkers. A library of ETOH- Cl/ pyrolysis MS data of microorganisms used for a recently published study [3] has been expanded with additional bacteria and fungi. These spectra were acquired on a Finnigan Magnum ion trap using helium buffer gas. A new database of Cl spectra of microorganisms is planned using the CBMS Block II instrument and air as the buffer gas. Using the current database, the fatty acid composition of the organisms was compared using the percentage of the ion current attributable to fatty acids. The data presented suggest promising rules for discrimination of these organisms. Strain, growth media and vegetative state do contribute to some of the distributions observed in the data. However, the data distributions observed in the current study only reflect our experience to date and do not fully represent the variability that might be expected in practice: Acquisition of MS/ MS spectra has begun (using He and air buffer gas) of the protonated molecular ion of a variety of fatty acids and for a number of ions nominally assigned as fatty acids from microorganisms. These spectra will be used to help verify fatty acid .
Microbially influenced corrosion of pipeline steels is an economically important problem. Microbe... more Microbially influenced corrosion of pipeline steels is an economically important problem. Microbes form tubercles which block fluid flow and can facilitate localized corrosion leading to through-wall penetrations. Microbes of diverse physiological types and metabolic potentialities have been recovered from fresh tubercles or under-deposit corrosion and have been characterized. In tests utilizing sterilizable flow-through systems containing pipeline steel coupons, corrosion rates
The technique of laser-induced breakdown spectroscopy (LIBS) to detect elements for a variety of ... more The technique of laser-induced breakdown spectroscopy (LIBS) to detect elements for a variety of homeland security applications such as nuclear materials identification and inventory,and forensic applications has been demonstrated. For nuclear materials applications, we detected and profiled metals in coatings that were used to encapsulate nuclear fuel. Multivariate analysis has been successfully employed in the quantification of elements present in
Page 1. Biological Agent Detection and Identification by the Block II Chemical Biological Mass Sp... more Page 1. Biological Agent Detection and Identification by the Block II Chemical Biological Mass Spectrometer Wayne H. Griest, Marcus B. Wise, Kevin J. Hart, Stephen A. Lammert, Cyril V. Thompson, and Arpad A. Vass Chemical ...
Biomedical Vibrational Spectroscopy and Biohazard Detection Technologies, 2004
Surface-enhanced Raman scattering (SERS) spectra of chemical agent simulants such as dimethyl met... more Surface-enhanced Raman scattering (SERS) spectra of chemical agent simulants such as dimethyl methylphonate (DMMP), pinacolyl methylphosphonate (PMP), diethyl phosphoramidate (DEPA), and 2-chloroethyl ethylsulfide (CEES), and biological agent simulants such as bacillus globigii (BG), erwinia herbicola (EH), and bacillus thuringiensis (BT) were obtained from silver oxide film-deposited substrates. Thin AgO films ranging in thickness from 50 nm to 250 nm were
Advanced Environmental, Chemical, and Biological Sensing Technologies II, 2004
An integrated multi-functional biochip based on integrated circuit complementary metal oxide semi... more An integrated multi-functional biochip based on integrated circuit complementary metal oxide semiconductor (CMOS) sensor array for use in medical diagnostics and pathogen detection has been described. The usefulness and potential of the biochip as a rapid, inexpensive screening tool for detection of bioenvironmental pathogens will be demonstrated. Detection of aerosolized spores was achieved by coupling the miniature system to a
This study, conducted at the University of Tennessee's Anthropological Research Facility (AR... more This study, conducted at the University of Tennessee's Anthropological Research Facility (ARF), describes the development of the Decompositional Odor Analysis (D.O.A.) Database and seeks to establish the chemical basis for canine's scenting ability when detecting human remains. This database is composed of chemicals that are liberated during the decompositional process from buried human remains. This 'living' database currently spans the first year and a half of burial, providing identification, chemical trends and semi-quantitation of chemicals liberated below, above and at the surface of 1.5 - 2.5 ft graves for three individuals (two males and one female). A fourth male individual (buried in 1990) was also sampled to provide possible 'endpoint' information. In-ground, in-corpse thermocouples provided temperature information which can be used to correlate accumulated degree days (ADDs) to surface decompositional events and indicated an approximate 12 h...
This study, conducted at the University of Tennessee&... more This study, conducted at the University of Tennessee's Anthropological Research Facility (ARF), describes the establishment of the Decompositional Odor Analysis (DOA) Database for the purpose of developing a man-portable, chemical sensor capable of detecting clandestine burial sites of human remains, thereby mimicking canine olfaction. This "living" database currently spans the first year and a half of burial, providing identification, chemical trends and semi-quantitation of chemicals liberated below, above and at the surface of graves 1.5 to 3.5 ft deep (0.45 to 1.0 m) for four individuals. Triple sorbent traps (TSTs) were used to collect air samples in the field and revealed eight major classes of chemicals containing 424 specific volatile compounds associated with burial decomposition. This research is the first step toward identification of an "odor signature" unique to human decomposition with projected ramifications on cadaver dog training procedures and in the development of field portable analytical instruments which can be used to locate human remains buried in shallow graves.
The ability to differentiate microorganisms using pyrolysision trap mass spectrometry was demonst... more The ability to differentiate microorganisms using pyrolysision trap mass spectrometry was demonstrated for five Gram-negative disease-causing organisms: Brucella melitensis, Brucella suis, Vibrio cholera, Yersinia pestis, and Francisella tularensis. Bacterial profiles were generated for gamma-irradiated bacterial samples using pyrolytic methylation and compared for electron ionization and chemical ionization using several liquid reagents with increasing proton affinities. Electron ionization combined with pyrolysis caused extensive fragmentation, resulting in a high abundance of lower mass ions and diminishing the diagnostic value of the technique for compound identification and bacterial profiling. Chemical ionization reduced the amount of fragmentation due to ionization while enhancing the molecular ion region of the fatty acids. As the proton affinity of the reagent increased, the protonated molecular ions of the fatty acids became the predominant ions observed in the mass spectrum. As a result, chemical ionization was shown to be more effective than electron ionization in bacterial profiling. Whereas the bacteria could be distinguished at the Genera level using electron ionization, further differentiation to the subspecies level was possible using chemical ionization. The greatest separation among the five test organisms, in terms of Euclidean distances, was obtained using ethanol as the chemical ionization reagent and using pooled masses representing specific fatty acid biomarkers rather than total ion profiles.
Description/Abstract The technique of laser-induced breakdown spectroscopy (LIBS) to detect eleme... more Description/Abstract The technique of laser-induced breakdown spectroscopy (LIBS) to detect elements for a variety of homeland security applications such as nuclear materials identification and inventory, and forensic applications has been demonstrated. For nuclear materials applications, we detected and profiled metals in coatings that were used to encapsulate nuclear fuel. Multivariate analysis has been successfully employed in the quantification of elements present in treated wood and engineered wood composites. ...
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