**OAK RIDGE NATIONAL LABORATORY**

Chemical Sciences Division

**Sampling, Ionization, and Energy Transfer Phenomena in Mass
Spectrometry**

*Gary J. Van Berkel, Douglas C. Duckworth, Douglas E. Goeringer, and
Peter J. Todd*

*Science:* The goal of this research program is to advance the knowledge
of diverse and complex chemistry with and within mass spectrometry.
These investigations involve research aimed at elucidating a fundamental
understanding of the processes comprising the framework of mass
spectrometry and exploiting its multidimensional capabilities for
chemical analysis and characterization. Multiple chemical disciplines
are brought to bear along research avenues including electron-transfer
chemistry, correlation of gas- and condensed-phase chemistry, surface
chemistry, mechanisms and energetics of ion processes, and metal-ligand
complex chemistry. The knowledge gained from such research enables
existing mass spectrometric analysis and characterization methods to be
enhanced and ultimately transcended, which at the same time affords mass
spectrometry the capability of providing new types of fundamental
information, thus benefiting the varied aspects of the DOE mission,
including National Security and Counter Terrorism.

Many current and certainly future detection systems deployed for nuclear
nonproliferation, explosives or chemical, or biological weapons
detection are or will be mass-spectrometry based, and thus will benefit
from past and expected future fundamental principles elucidated in this
program. For example, this BES funded research has for a number of years
included the investigation of the chemical and physical principles
governing the small, mobile, and relatively inexpensive mass analyzers
known as the quadrupole ion traps. Today's commercial ion trap
instruments incorporate many features that stem from the findings of the
ORNL research funded by BES. The international reputation of ORNL as a
center of expertise in ion trap research was one of the important
factors in the selection of ORNL by the US Army Soldier and Biological
Chemical Command to be the lead contractor in the Block II Chemical
Biological Mass Spectrometer (CBMS) program. This 5-year, \$45M program
is developing, demonstrating and delivering to the Army the first
integrated instrument capable of detecting and identifying both chemical
and biological warfare agents on the battlefield. The heart of the CBMS
is an ion trap mass spectrometer that incorporates many of the
improvements realized from fundamental research. ORNL is now working to
leverage this technology further to antiterrorism applications.

*Relevance to Counter Terrorism:* Four nearly three decades, this same
BES research program has provided a fundamental understanding of
ionization processes and mass analysis of ultra-trace quantities of
nuclear materials. This knowledge has resulted in precise and sensitive
mass spectrometric techniques that are employed worldwide in support of
the Nuclear Nonproliferation Treaty. Because of its sensitivity, these
mass spectrometric techniques are the mainstay in nuclear forensic
applications. Recent BES sponsored activities in electrochemically
modulated separations (for mass spectrometry) have resulted in improved
means of separating and concentrating U and Pu from complex matrices.
Understanding the mechanism(s) of the U and Pu accumulation continues to
be an area of ongoing BES investigations, yet the application is already
being developed in a \$1.2M project recently funded project by the
Office of Nonproliferation Research and Engineering (NA-22).