Peroxyacetyl Nitrate (Pan) : Historical Perspective
Peroxyacetyl Nitrate (Pan) : Historical Perspective
Peroxyacetyl Nitrate (Pan) : Historical Perspective
January 14-19,2001
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1.3 PEROXYACETYL NITRATE (PAN): HISTORICAL PERSPECTIVE
Further studies initiated in 1958 identified PAN as CH3C0 + Oz + NOZ + PAN (8)
a key compound causing the bronzing of leaves of
petunias and other susceptible plants. These studies, Similarly, NOS radical has been used to produce PAN,
done with O. Clifton Taylor at the UCR Horticulture with NOS being generated by dark reaction of nitrogen
Department (Taylor et al., 1960), led to the use of gas dioxide and ozone (Gaffney et al., 1989).
chromatographic separation of PAN from the
photochemica! reaction mixture. Further These methods require photochemical apparatus
characterization showed that PAN is a potent eye and chromatographic or distillation equipment to
irritant. This collaboration between chemists and plant separate the PAN for instrument calibration or
pathologists led to the observation that PAN and laboratory study. The fact that PAN can considered a
some of its analogs are 10-50 times more toxic than mixed anhydride of peracetic acid and nitric acid
ozone to plants. Indeed, PAN, hydrogen peroxide, (Roberts, 1990) led Hendry and co-workers to use the
and nitrogen dioxide were identified in the first air strong acid nitration of peroxyacetic acid in aqueous
pollution criteria documents, but they were later solution to synthesize PAN, followed by the
omitted from the Clean Air Act of 1970 because of extraction into a normal alkane solvent (Gaffney
dit7iculties in measuring and synthesizing standards et al., 1989). Gaffney and co-workers modified the
at that time. This important collaboration at the UCR procedure to overcome potential safety hazards of
Statewide Air Pollution Research Center was one of working with PAN dissolved in a high-volatility solvent
the first to begin interdisciplinary work on air quality and recommended that n-tridecane be used for high-
purity PAN and derivative synthesis (Gaffney etal., found in the Los Angeles air shed (Tuazon et al.,
1984), 1978; Hanst et al., 1982). However, the infrared
instruments of the early 1960s were clearly not
Over the years, advances in the synthesis of capable of routine monitoring of PAN. With the
PANs have led to improvements in analytical invention of the electron capture detector (ECD) by
procedures and in determinations of the chemical and James Lovelock, Ellis Darley and co-workers in 1963
physical properties of PANs. Noteworthy are studies developed a method for PAN analysis that has been
of Karen Darnall and James N. Pitts, Jr., who used used since then quite successfully (Darley et al.,
PAN canister samples obtained from Edgar Stephens 1963). Many others have used a similar approach that
to produce high-concentration PAN samples in employs a nonpolar column to separate PANs from
deuterated chloroform and methylene chloride. These the various other ECD-sensitive gases (oxygen,
studies led to the understanding that PAN is highly Freons, organic nitrates, etc.) (Roberts, 1990). Used
soluble in nonpolar solvents. These researchers used in the 1960s and 1970s to monitor PAN in the air in
nuclear magnetic resonance (NMR) to study the the Riverside area, this method found very high
liquid-phase ‘reactions of this novel oxidant with values of the phytotoxin (20-50 ppb). In 1974, James
olefins; studies examining alcohols etc. followed Lovelock and Stewart Penkett used a similar analysis
(Gaffney et al., 1989: Roberts, 1990). system to measure PAN off the coast of England,
observing a level of 2 ppb and alerting the community
Key structural information was obtained by to PAN’s ubiquity (Lovelock and Penkett, 1974).
Stephens and by Nicksic and colleagues, who
observed products of base hydrolysis that helped to Calibration of the above instruments was usually
confirm the PAN structure (Nicksic et al., 1966). Later accomplished by using base hydrolysis to yield
studies with ammonia and amines that showed the acetate and nitrite. These methods had some
formation of oxygen, HONO, and acetamides difficulties, and thermal decomposition to NOZ and
supported these observations (Wendschuh et al., direct measurement with a chemiluminescent nitrogen
1973), oxides monitor have seen more use in recent years
(Roberts, 1990).
The very simple ultraviolet absorption spectrum
of PAN observed by Stephens was confirmed by Other approaches were examined in the mid-
Senum, Lee, and Gaffney at Brookhaven National 1980s, when Iuminol chemiluminescence was
Laboratory in the early 1980s (Gaffney et al., 1989; observed to occur with PAN, as well as with NOZ. Two
Roberts, 1990). Recent reexamination of the data led groups, Gaffney’s at Los Alamos and Stedman’s at
to the conclusion that the PAN molecule is not readily the University of Denver, demonstrated in 1986 that
photolyzed at altitudes below 5-7 km. In 1984, Tim chromatography works for this application. Stedman
Wellington, Roger Atkinson, and Arthur Wirier at UCR published the method in 1988, documenting a five-
showed the reaction rates with OH to be quite slow. minute analysis for PAN with a packed column
The aqueous-phase solubilities of PAN were examined (Burkhardt et al., 1988). Gaffney and Marley reported
by Yin-Nan Lee of Brookhaven and found to be 3-5 M a modification of this method that employs fast
atm”l; these results were confirmed by Chester capillary chromatography to obtain 30-second time
Spicer’s group at Battelle Columbus Laboratory resolution for PAN and its analogs and also gives
(Gaffney et al., 1989; Roberts, 1990). measurements of NOZ (Gaffney et al., 1998).
In the meantime, PAN was observed by Stephens Mass spectrometry of PAN was first reported by
and others to decompose thermally to form methyl Ron Steer,--Karen-Damall, and James N. Pitts, Jr., in
nitrate, carbon dioxide, and other minor products. electron impact mode in 1969. The chemical ionization
What has been determined is that PAN is in thermal spectrum was reported in 1976 by Chris Pate, Jerry
equilibfiunlwith NOZ and the peroxyacetyl radical and Sprung, and Pitts, who used one of the first Finnigan
that this equilibrium is strongly temperature gas chromatograph-mass spectrometer systems
dependent (Gaffney et al., 1989; Robetis, 1990; equipped with this capability. Because of its very
Finlayson-Pitis and Pitts, 2000). At the cold large ECD cross section, the negative-ion mass
temperatures found at higher altitudes and in spectrometric sensitivity for PAN is quite high. This
wintertime PAN is quite stable, while at lower altitudes was predicted in 1989 to be a reasonable approach
in the summertime PAN has a fairly short lifetime that (Gaffney et al., 1989), and it has been pursued in
depends on the ratio of NO to NOZ and the recent years by Chester Spicer of Battelle Columbus
abundance of HOZ radicals, which can remove the and by Hiroshi Tanimoto and Hajime Akimoto in
peroxyacetyl radical. Hanwant Singh was the first to Japan.
point out that PAN could act as a means of
transporting NOZ over very long distances and Because of its rather undistinctive ultraviolet
therefore was a globally important molecule and not spectrum, direct ultraviolet absorption spectroscopy
just an urban air pollutant (Singh, 1987). has not been used for PAN analyses. NMR has been
used for laboratory studies of PAN, and that method,
The first measurements of PAN were made in the along with circular internal reflectance infrared
laboratory by using long-path infrared techniques that spectroscopes, may be important in future studies of
worked reasonably well at the higher concentrations PANs in solution.
5. FUTURE NEEDS - PANS, PERACIDS, chemical toxicity and radiative behavior of these
PEROXIDES, NITRATES compounds needs to be evaluated. A number of
research groups, notably Paul Shepson’s at Purdue
Since the initial work at the Franklin Institute in University (Roberts, 1990), are beginning to explore
Philadelphia and the original observation of PANs in the organic nitrates in detail by using methods
Los Angeles photochemical smog, PANs have been mentioned above.
measured in every corner of the world (Gaffney et al.,
1989; Roberts, 1990). Measured PANs include the Peroxy nitrates might play important roles in the
commonest (PAN), as well as peroxypropionyl nitrate transport of NOZ under cold conditions:
(PPN) and peroxybutyryl nitrate (PBN). Other PANs
deemed important include those derived from isoprene ROZ+ N02 e R02N02 (11)
oxidation (MPAN) and aromatics (PBzN) (Gaffney
et al., 1989; Roberts, 1990). These species were first examined by Edward Edney,
John Spence, and Philip Hanst at the
PANs are strongly connected with peracids by U.S. Environmental Protection Agency laboratories.
the following reactions in low-NO conditions: Because of their short lifetimes at room temperature,
the compounds were assumed not to act as key
PAN + RCO-00 + NOZ (9) storage modes in the lower atmosphere (Edney et al.,
1979). However, at middle latitudes in the wintertime
RCO-00 + H02 + RCO-OOH + 02 (lo) they may have lifetimes that approach days, and, like
PAN (depending upon NO, HOZ and NOZ levels), they
The peracids are known to be produced in rural might be reformed to actively transport NOZ and also
air masses, where NO levels allow the buildup of HOZ tie up peroxy radicals that would lead to ozone
However, methods for measurement of these species, formation.
along with other organic peroxides, need to be given
serious examination, especially as we begin to control The PANs are known to be quite sensitive to
NO. emission levels to reduce the urban and regional walls in laboratory studies and therefore are likely to
ozone problems. react on aerosol surfaces. PANs are very soluble in
nonpolar organics and indeed may undergo important
The PAN levels in urban U.S. regions like the Los oxidation reactions on soot surfaces, leading to the
Angeles air basin and surrounding air shed have formation of oxidized and nitrated polynuclear
dropped significantly in recent years. Levels are aromatic hydrocarbons potentially having high
rarely observed above 5 ppb, a tenfold reduction mutagenicity (Finlayson-Pitis and Pitts, 2000).
compared to the 1960s and 1970s. However, in other
areas of the world, PANs can also be produced in We have known about these fascinating
large quantities if NO. levels and the reactive molecules for over 40 years, but our fundamental
hydrocarbon species leading to PAN and ozone understanding and ability to measure PANs is just
formation are not controlled. Indeed, in Mexico City now beginning to expand. Interestingly, many
we recently measured total PANs of 40 ppb by gas physical chemists are beginning to explore the
chromatography with ECD (Gaffney et al., 1999). unusual properties of these highly energetic
molecules.
Another concern is that the production of PANs
from aldehydes is a direct process, as noted in the The future of PAN chemistry, opened to us by
early synthetic procedures. The use of oxygenated Edgar Stephens and his colleagues, looks bright, and
fuels that lead to increased emissions of aldehydes its further exploration should lead us to a much better
or aldehyde precursors such as ethanol or methyl-f- understanding of the key oxidation reactions
butyl ether should continue to be accompanied by occurring in the troposphere.
assessment for PANs and other oxidants (Gaffney
et al,, 1997; Gaffney et al., 1999). In addition, the 6. ACKNOWLEDGMENTS
potential for long-range transport of PANs on
continental scales and for PANs to function as a This work was supported by the U.S. Department
source of regional ozone should not be forgotten of Energy, Office of Science, Office of Biological and
\S$~_I, 1987; Gaffney et al., 1993; Gaffney et al., Environmental Research, Atmospheric Chemistv
. Program. We wish to dedicate this paper to the late
Dr. Edgar Stephens and to Dr. James Lovelock,
The PANs are indicators of peroxy radical activity whose pioneering work on PANs continues to serve
and are indicative of the potential importance of as an inspiration to workers in the field who are
organic nitrates. PAN decomposition is known to lead developing new, faster methods for analysis of this
to methyl nitrate formation, which is fairly stable in important class of pollutants. Realizing that this is a
the atmosphere. The nighttime thermal decomposition brief document, by necessity we will certainly not give
of methyl nitrate may be an important source of credit to all who are deserving. Our apologies to any
radicals for the oxidation of NO to NOZ and for the pioneers in the measurement and study of PANs
formation of HONO. Our understanding of the whom we have not mentioned in this work.
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