\ I /
                    United States
                    Environmental Protection
                    Agency
Atmospheric Sciences
Research Laboratory
Research Triangle Park NC 27711 -
                    Research and Development
EPA/600/S3-85/012 Apr. 1985
SERA         Project  Summary

                    Methods for  Simulating
                    Gas  Phase  S02 Oxidation  in
                    Atmospheric  Models
                    James F. Meagher and Kenneth J. Olszyna
                      Two  different  approaches  are
                     presented for  simulating  gas phase
                     sulfur  dioxide  oxidation  in  at-
                     mospheric models. The first approach
                     was to  develop an  empirical relation-
                     ship based on rate data collected at
                     four coal-fired power plants during 11
                     separate studies.  Cosine  functions
                     were used to simulate annual  and
                     diurnal variations in the  oxidation rate
                     constant. The time variant rate con-
                     stant was  superimposed  on a con-
                     stant rate coefficient of  0.002 h'1 used
                     for  nonsunlight  hours.  The  model
                     predicts a maximum (solar noon) rate
                     constant of 0.0285 h'1 for mid-July.
                      The  second   approach  was  to
                     develop a kinetic  model based on data
                     obtained from  smog   chamber ex-
                     periments using  mixtures  of sulfur
                     dioxide  propene,  butane, nitrogen ox-
                     ides, and water vapor. Sulfur dioxide
                     oxidation in the gas phase was found
                     to occur by two mechanisms. At low
                     HC/NOX values hydroxyl radical addi-
                     tion to  sulfur  dioxide  predominates.
                     At  high HC/NOX values, oxidation via
                     reaction with products of the ozone-
                     olefin  reaction  dominates.  The
                     chamber data suggest  that  the  HO-
                     SO2 reaction leads mainly to the pro-
                     duction of hydroperoxyl radical  and
                     sulfuric  acid. A  previously proposed
                     mechanism for the  reaction of sulfur
                     dioxide  with Criegee   intermediates
                     was found to provide an excellent fit
                     to  the  data at  the high  HC/NOX
                     values.
                      This   Project   Summary  was
                     developed by EPA's Atmospheric
                     Sciences  Research   Laboratory,
                     Research Triangle Park, NC, to an-
nounce key findings of the research
project that is fully documented in a
separate report of the same title (see
Project Report ordering information at
back).


Introduction
  In the past decade there has been an
intensive effort to determine the rate and
the mechanism of sulfur dioxide (S02) ox-
idation in the atmosphere. Although the
oxidation is believed to be a composite of
gas and liquid phase reactions, the majori-
ty of data available are applicable to the
gas phase only. Studies of droplet oxida-
tion have only just begun and the infor-
mation for chemical  processes  in cloud
systems is sparse. The mechanism and
models discussed in this  report deal ex-
clusively with the gas phase oxidation of
SO2.
  Mathematical models that simulate S02
to sulfate conversion  in the atmosphere
fall into two general classes. The  first,
empirical  models,  are based  on  ex-
perimental data  with statistical averaging
to remove the inherent variability found in
field measurements. The  rate  is usually
assumed to be first order in S02. The sec-
ond,  kinetic  models,  are based  on a
chemical  mechanism  developed  to
describe  S02  oxidation   in  terms of
elementary  reactions. Laboratory
measured rates  of reactions are used in
mathematical expressions  that  describe
the  time  dependence  of  the  major
species.
  Empirical  models  represent  average
conditions and thus can  be expected to
fail  in  an   event  calculation.  Kinetic
schemes borrow   heavily  from   the

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smog/ozone models developed for urban
areas. The scheme may contain 50 to 150
individual  reactions and  might   be ex-
pected   to  perform  better  for  event
calculations.  The price for this capability
is considerable. Model input requirements
can be  staggering. A set of simultaneous
differential   equations,   one   for  each
species,  must be  solved at each  time
step.
   In  this  report  various empirical  and
kinetic  schemes  will  be  discussed. Al-
ternative   schemes  will   be   described.
These alternatives  have  been developed
using recent field and  laboratory  data,
much  of  which  was not  available to
previous modelers.
Empirical Model
  A  wide  variety  of schemes  for  the
parameterization of the S02 oxidation rate
constant has  been  developed in recent
years.  Techniques vary from  the use of
time invariant values for the rate constant
to ones that are allowed to vary  diurnally
and  seasonally.  These  procedures  are
based  loosely  on field  data  and often
represent best fits to monitoring  data.
  Field  studies funded  by the U.S.  En-
vironmental Protection Agency (EPA) be-
tween  1974 and 1979 have provided data
useful  in developing  parametric equations
relating  S02   gas-phase  oxidation   and
meteorological  variables.  Wilson  (1981),
for example,  has analyzed the data from
12 power plant and  smelter studies  and
obtained a linear fit to the data (excluding
the VISTTA data from the Navajo Power
Plant):
  SP/ST %  = 3.66  (average solar radia-
tion, KW/m2 (time, h )  - 0.84 where the
left-hand side of the equation represents
the percentage sulfur in paniculate form.
This relationship  is only useful if reliable
solar intensity data are available or can be
predicted.
  A more elaborate scheme was proposed
by Gillani ef al. (1981) for dry conditions.
Based  on analysis  of two  sets  of field
measurements taken in  1976,  the authors
obtained the following relationship:

     (k,)d =  (0.03 ±  0.01)(R.H.[03]0
where  (k,)d =  dry atmospheric rate con-
              stant  (% h'1)
         R  =  solar radiation (kW/m2)
         H  =  mixing height (m)
       [03]  =  background ozone con-
              centration (ppm)

The  parameterization is based on a very
limited data base and requires more input
parameters than other techniques.
  Perhaps  the most obvious feature of
field measurements for S02 oxidation rate
constants is  the variability  of the data.
Measured rate constants  range  from 0.0
to greater than 0.1 h"1, sometimes at the
same location within a period of a  few
days. There are, however, several features
of the data that provide reason for op-
timism. The most striking  of these are the
diurnal and seasonal trends.

Diurnal Variations
  The diurnal variation in the measured
S02 rate constant  has  been reported by
Husar et al. (1978), Forrest  ef al. (1981),
Gillani et al. (op. cit.  1981), and Bailey et
al.  (1982).  The maximum rate  constant
(0.02  -  0.08  rr1)  was observed  for
measurements  made  near   solar noon.
Nighttime values are generally less  than
0.005 h'1 with intermediate  values in the
morning  and  late afternoon.
  All of the studies cited above occurred
during the  summertime  and early  fall.
There is a limited data base for wintertime
studies. Meagher et al. (1978) reported no
systematic  change  (diurnal  trend)  in  a
Tennessee  Valley  Authority  (TVA)  study
during the winter of 1975-76. This marked
difference  between summer and winter
measurements  leads  to  a discussion of
seasonal  trends.

Seasonal Variations
  Altshuller (1979)  used model estimates
of  clean  tropospheric   hydroxyl  (HO),
hydroperoxyl   (H02),  and methylperoxyl
(CH302)   radical   concentrations  to
calculate the  seasonal dependence of the
homogeneous  S02 oxidation rate.   The
bulk  of  the  oxidation  was  due to the
hydroxyl  radical reaction.
  Meagher, et al.  (1983) used data  col-
lected during eight plume studies at four
coal-fired  power plants  to  demonstrate
similar annual trends. The average  rates
calculated varied from a winter low of 1.5
 x  10~3 h"1 to a  summer high of 1.3 x
10"2 h'1;  this  variation was similar to  that
predicted by Altshuller's model.

Model Description
  Conceptual  development. An alternative
parameterization  scheme for estimating
the  atmospheric  S02  oxidation rate  is
presented  here.  It is intended  that this
technique  complement  those described
previously and be used when the amount
of reliable input data are  limited.
  The model  developed is  based loosely
on  the  diurnal and annual variation  in
clear-sky,  solar   intensity.   The   basic
assumption is that the  rate constant can
be separated into a  constant value and a
component that is allowed to vary diurnal-
ly and annually.
t,i)  = k0
                        fA(i)
where k(t,i)  = diurnally and annually vary-
              ing rate  constant
          t  = time of day (solar)
          i  = Julian date
         k0  = time invariant component
              of the rate constant
       km*  = maximum value the time
              variant portion of  the rate
              constant may attain
       fA (12  +  0.5 Td)

  For a time dependent rate  constant the
average value (k) during any period of the
solar day  (tj --- > t2) is given by

                       t2
         * = (t2 -  t,)-1 J k(t,)dt
                       t,
  Substituting the proposed functionality
for k(t)i and integrating we  obtain a rela-
tionship between k~ and sine functions of
Td, t2, and t, . This equation  is of  the form  i

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R  = ko  + Mmax) • g(t,,t2).  Values  for
g(t,,t2) have been  calculated for each of
the  plume  measurement data  bases.
Estimates of  Mi)™*  have been obtained
for each study  by  plotting  R  against
g(t,,t2) and performing a least  squares fit
while forcing the line through 0.002 h'1 at
g(ti,tz) = 0. The objective of the model is
to  reproduce  average  situations  rather
than events;  thus, a single outlier was
removed from  each data set to prevent it
from unduly biasing the fit.
Annual function If All The annual variation
in  the daily  maximum  rate   constant,
kCOmax, was determined  from the  expres-
sion
M1U,  = 0.5
         [cos (2* (\  - inv»)/365)  +  1]
where im>x
occurs
Julian date on  which kn
  The seasonal trend previously described
by Meagher ef al. (op. tit. 1983), is based
on  morning  rate  measurements.  The
mean solar time for each of these is 8.4
±  0.9  a.m.  The rate  constant  was
calculated for each  of the five diurnal
studies.
  The annual maximum time variant rate
constant at solar noon Ik™*) and the date
of that  maximum (inuJ  were adjusted to
obtain the best fit to the data. The best fit
was obtained for k,™,  =  0.0265 rr1 and
imax  =  192.5.  Therefore, the  maximum
rate constant of 0.0285 rr1 is predicted for
mid-July,  20  days  after the  summer
solstice.
Model results.  A combination of the diur-
nal  and seasonal functions  provides the
following  equation for  the  pseudo  first
order rate constant.
k(i,t,Td)  = 0.002 + 0.006625
          [cos (2 T (\  - 192.5)7365)+ 1]
          . [cos(2 T (t - 12)/Td) + 1]
where k(i,t,Td) is in units of Ir1
  A linear regression analysis of all 1.03 in-
dividual  measurements from the data base
indicates that this simple model accounts
for  56% of the observed variation.
Model Limitations
  The model  proposed  is  intended to
represent average situations.  It should not
be expected to exhibit significant skill in
reproducing individual events such  as
daily values. All the field measurements of
S02  oxidation have  been made in rural
areas; past experience has shown that ur-
ban areas with their local emissions can
significantly alter  the observed rate con-
 tent. Thus, extrapolation of  these data to
urban conditions must be done with cau-
tion.

Kinetic  Models
  Many of the limitations inherent in em-
pirical models can be avoided through the
use of detailed kinetic schemes.  As the
name implies,  this approach presupposes
an  understanding  of  the   operative
mechanisms and requires rate data for all
elementary and composite reactions mak-
ing up the mechanisms.
  Calvert  and  Stockwell  (1984) reviewed
available data on, gas phase oxidation of
S02 in the atmosphere. They concluded
that hydroxyl  radical addition was the
most  important reaction in the oxidation
process.  At higher HC/NOX values  and
pollutant   concentrations   another
mechanism  becomes  equally  important.
This mechanism is poorly understood but
involves the products of the ozone-alkene
reaction.  Models  that are used for rural
assessment  could  probably ignore the
contribution   of  the   ozone-alkene
mechanism without significantly affecting
the predictions of atmospheric sulfate pro-
duction. However,  in an urban environ-
ment, both  mechanisms  should  be
included.
HO +  S02.  Most modelers  have assumed
that S02 is  an HO chain terminator and
have summarized the oxidation  by
S02 + HO
                                                             H2S04
                              If the reaction is chain terminating, then
                            model calculations predict a  high degree
                            of  nonlinearity between S02 and sulfate
                            concentrations. Also,  this  assumption
                            leads modelers to  conclude that a reduc-
                            tion in S02 would lead to an increase in
                            nitrate concentrations.
                              Recently, the S02 + HO reaction  has
                            been  studied by photolyzing mixtures of
                            nitrous acid (HONO)  in the  presence of
                            S02,  NO, N02, H20, and CO.  Extrapola-
                            tion of the data to atmospheric conditions
                            leads one to conclude the reaction can be
                            summarized in one equation thusly:
                            HO + S02 + (02, H20) ---- >
                                                       H2S04 + H02
                            and is, therefore, not chain terminating.
                              TVA  conducted smog  chamber  ex-
                            periments to evaluate the mechanistic  op-
                            tions  for  S02  oxidation.  Chamber runs
                            were  performed at constant  initial  NOX
                            and  hydrocarbon  concentrations  with
                            variable amounts of S02 (0 to 6.4 ppm).
                            Runs  were  conducted  at  low  and
                            moderate  humidities  (5%  and  40%  at
                            25°C). The overall effect of  S02 on  the
                            NO to N02 conversion and the formation
of ozone was  to slightly accelerate  the
conversion process and to increase the 03
peak concentration. The  HO steady state
concentration decreased during the runs.
Comparison between the dry and wet ex-
periments reconfirms  the observation of
other  investigators  that water vapor
enhances the  photochemical  activity in
these systems.
  The  HO concentrations for each experi-
ment were  used  to calculate  the sulfate
formation rate  using  the  rate coefficient
recommended  by Atkinson   and Lloyd
(1984)  (1.39 x  103 ppm-1  min'' at 350°K,
1 atm). These values were compared with
values  calculated by  monitoring the  rate
of aerosol volume  increase.  The agree-
ment between the two methods indicates
that under these  conditions, HO  addition
to  S02  can account for all  measured
sulfate.

Discussion
  Two  extreme mechanistic  approaches
have been used to explain sulfate  produc-
tion  following HO addition to S02.  The
first mechanism tested in  this  study was
the simple  HO chain termination.  The
reduction in  HO  steady-state  concentra-
tion predicted by this mechanism severely
inhibited  photochemical   reactivity
resulting in an extreme underestimation of
ozone formation and very slow  NO to  N02
conversion.  In  this study, reaction with
S02  represents  a significant sink for  HO
radicals (about  35% using 1.5  ppm S02).
Atkinson ef al. (1982)  had successfully
modeled Miller's  experiments  using   the
termination  mechanism because,  in  that
case,  the S02  + HO	> H2S04
reaction  represented  only a 2%  loss of
HO radicals.
  A   better  agreement  between   ex-
perimental data  and model results was  ob-
tained  when a  simplified  version of  the
reaction
  HO +  SO2	> H2SO« +  H02  (1)
proposed by Calvert and  Stockwell  was
used. This model qualitatively predicts  the
main chemical changes observed,  i.e.,  ac-
celerated  NO  to  N02  conversion,   en-
hanced O3 formation,  and the  depression
of the  HO steady state concentration with
added  S02.  The experimental  data show
that  at the  beginning of  the  experiment
the HO concentration  is insensitive to  ad-
ded S02 probably because H02 produced
in the  above reaction probably regener-
ates  HO by  reacting with NO.  The model
predicts this observation.  Near  the end of
the experiment the lack of NO inhibits  the
H02  to  HO  conversion  and  the   HO

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steady-state concentration decreases. This
mechanism, however, does  overestimate
the ozone  formation increase caused  by
S02 addition.
  It is apparent that the assumption of an
HO chain  propagation mechanism  is  a
better approximation to  the  experimental
data than  that provided  by termination.
However,  the  data  suggest  addition  ter-
mination routes are  needed. Several reac-
tions, which  may occur  in  this system,
were proposed:

       S02 +  HO	> HS03     (2)
        AH =  - 37 kcal • moM

      HS03 + 02	>  HS05     (3)
        AH =  - 16 kcal • mol'1

   HS05 + NO	> HSO,  +  N02(4)
        AH =  -25 kcal • mol'1

   HS04 + H02	> H2S04 + 02 (5)
        AH =  - 61 kcal • mol'1

  It was assumed that reactions (3) and
(4) are  very fast (k3 and kj are  greater
than 1  x 10* ppnr1  min"1). The  rate coef-
ficient ks was estimated to be in  the range
of 103 - 106 pprrr1  min"1. The addition of
these reactions  to  the  model  enhanced
the fit to the 03 data in the early stages of
the experiments, but little  improvement
was  noted in  the  prediction of  the  03
maximum.
  The overestimation of the  03  maximum
suggests the presence of additional reac-
tion(s) that consume 03 or its precursors.
A simple  reaction  that  satisfies this  re-
quirement is

    HSO«  + 03	> HS05  + 02  (6)
        AH =  - 23 kcal > mor1

By adjusting  the ratios  k,/k2 and kg/kg,
good  agreement was obtained between
model prediction and experimental data.
All rate coefficients used for the  simula-
tions are listed  in the Project Report.
  Because  this  project was intended  to
develop the capability to  predict ambient
sulfate levels, it  is of interest to compare
model  predictions with observed  values.
The  data  also allow  a comparison  be-
tween the wet and  dry experiments, i.e.,
high and  low relative humidity. At low
S02 concentrations (< 1.0 ppm)  when the
consumption  of  HO  by  S02  is small
(<10%) the  approximation  of linearity
(perfect hydroxyl propagation}  between
S02 and sulfate formation is  valid. As the
S02  concentration  increased to about 5
ppm, significant  deviation (factors  of 2 to
3) from  linearity were observed.
  The chemical  mechanism  proposed in
this  report indicates that  98.5%  of  the
time the H0-S02 reaction leads to H02
formation.  This  is  consistent  with the
conclusions of Calvert and Stockwell (op.
cit. 1984) that S02 termination of the HO
radical may not be important in the free
atmosphere. It  must be emphasized that,
although the observed HO termination is a
small fraction  of the  total  reaction,  it
significantly affects the temporal behavior
and  maximum  levels of  secondary
pollutants.
Alkene  +  O3 +  SO*
  Although the S02  + OH addition reac-
tion  can  explain the  bulk  of  the field
measurements of S02 oxidation rate, the
mechanism cannot explain nighttime S02
oxidation,  the very  high  rates  observed
near urban  areas,  or the formation of
organosulfur compounds.
  An additional pathway to sulfate forma-
tion  that has been  suggested by several
authors involves S02 oxidation  in the
presence of ozone and olefinic  hydrocar-
bons. The  mechanism of  this reaction  is
not well understood  at all. The  general
opinion is that  the  S02 oxidation occurs
via  reaction  with a product  from the
ozone-olefin  reaction.   A  reasonable
mechanism  proposed  by  Calvert  et  al.
(1978)  to explain the observed S02 oxida-
tion  in this system is

R'HC = CHR + 03	> Molozonide  (7)
     Molozonide	> R'CHO +
                        [RHCOO]*
 (8)
      [RHCOO]*	> Products    (9)

  [RHCOO]* + M	> RHCOO +  (10)
                        M
         Thermalized Criegee intermediate

  The thermalized  Criegee intermediate
can then react with S02 to produce S03
which hydrolyzes to H2S04 or with H2O to
undergo  rearrangement to  a  carboxylic
acid.
RHCOO + S02	>
(11)
                     H20
      RCHO  + S03	>  H2SO,

RHCOO + H20	>            (12)
                    RCOOH +  H20

The Criegee  intermediate can also react
with  other  atmospheric constituents as
follows:

RHCOO + NO	>RCHO + N02   (13)

RHCOO+ NO2	>RCHO + NO2  (14)

RHCOO + CO	> Products      (15)

RHCOO + RCHO	>0zonides   (16)
          Martinez  and Herron  (1981) also pro-
        posed an addition  reaction  between S02
        and the Criegee intermediate to  produce
        an organosulfur intermediate collisionally
        stabilized to a  heterocyclic  organosulfur
        species.
                       M
        RHCOO + S02 --- >              (17)
                               0 — -S = 0
        This species can then react with water to
        produce sulfuric acid:
              0-0
RCH
                            RCHO+H2SO«
                                          (18)
       To  simplify  the  kinetic  treatment  of
       aerosol  production in these systems, we
       propose an empirical representation of the
       formation process thusly:
            X0	Ox                   (19)
       RCH	0	S   =   0	>
                              S(IV) aerosol
          A steady-state  treatment -of  the in-
       termediates  in this mechanism  yields the
       following rate law for S02  oxidation:
            -d[S02]/dt = k7[03][HC].A.B     (I)
       where k7 =  rate coefficient for the ozone-
                   alkene reaction
      A = MMl/kg  + k10tM];  frac-
           tional yield of the thermal-
           ized Criegee intermediate

      B = k17[S02]/k,7[S02] +  k,2[H20]
           + k,3[NO] +  k,4[N02]; frac-
           tion of Criegee intermediates
           that react with S02
  The rate law for sulfuric acid formation
becomes:

   d[H2S04]/dt = k7[O3][HC]A.B-C   (II)

where k;,  A and B are defined above and

      C = k18[H20]/(kie[H20] +  k,9);
           fraction of the S02-Criegee
           adduct intermediates that
           are hydrolyzed to  H2S04.

Conversely, the  production  of the S(IV)
aerosols can be described  by

  d[S(IV)]/dt  = k7[03][HC]A •  B  •  D (III)

where D = ki9/(ki8 [H2O] = ki9); fraction
           of the S02-Criegee adduct
           intermediates that produce
           S(IV) aerosol

  The equation for H2S04  production rate
states that the S02 oxidation to sulfuric
acid  is a  function  of  six terms.  The im-
portance of this nonhydroxyl pathway is  (

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difficult to assess  due to the paucity of
experimental data.
  The  results of chamber runs conducted
at TVA  indicated  that all of  the  S02-
Criegee adduct  intermediates hydrolized
to sulfuric acid.  Under dry conditions (~
5%  RH) the  results  were in qualitative
agreement  with  Equations I  and II. The
competition between H20 and paniculate
formation for the adduct species (term  D
in Equation III)  predicts an  increase in
S(IV) aerosol  formation.  The dry experi-
ment was  repeated  with measurements
for total aerosol volume and analysis of
the aerosols produced for both total sulfur
content and sulfate content. The sulfate is
found  to be approximately 25 to 50% of
the total sulfur.  The results  suggest that
both sulfate and nonsulfate aerosols are
produced in an S02-NO-alkene system.
  Laboratory  experiments  during   this
study confirmed an earlier observation by
Eatough  et al. (1981) that S(IV) aerosols
formed in an 03-alkene-S02 system spon-
taneously convert to S(VI) aerosols over a
period  of days or weeks. Since most am-
bient air  filter samples  are  usually  not
analyzed for  several  weeks  after being
taken,  one would  not expect to observe
S(IV) aerosols in these samples.
Kinetic Mechanism-SO2
Oxidation
  A summary  of  the  mechanism and a
listing  of the rate parameter requirements
for modeling SO2 oxidation are presented
in the  Project Report. The entire chemical
mechanism, which draws extensively on
the work of Atkinson et al. (op. cit. 1982)
is also listed there. The mechanism in-
volves 33 individual  species and 69 reac-
tions and is obviously  too large to be in-
cluded here. The reactions and rate data
presented must be combined with a free
radical photochemical  scheme describing
atmospheric  HC-NOX  reactions.  Several
such schemes are  available (see reference
list in Project Report) and can be modified
to accommodate this mechanism.
  The mechanism  is  suitable for  both
rural and  urban situations because it has
been tested over a broad HC/NOX range.
The  hydroxyl   radical   mechanism  will
dominate  at low values  of HC/NOX  with
the  Criegee  mechanism  becoming more
important  at  the  higher  values.  From
modeling and chamber data we conclude
that, although  the relative importance  of
the two mechanisms shifts dramatically  as
the  HC concentrations inprease from 0.5
(to 3.0 ppm C,  the effect on sulfate pro-
duction is small.
Conclusions  and
Recommendations
  Two options are provided in the Project
Report for simulating S02 chemistry in at-
mospheric models. Both are intended for
gas-phase oxidation and  do  not address
cloud or precipitation  chemistry. The op-
tion  selected depends, to  a  large extent,
on available input data.
  The  empirical  model provides a  simple
alternative to the complex  kinetic models.
The  S02 rate coefficient  predictions  are
based on field measurements solely.  This
model   is  intended  to   represent  the
average situation.  It  should  not be  ex-
pected to reproduce individual events.
  The  kinetic model provides much more
insight into the  complex  chemical reac-
tions governing  SO2 oxidation  in the at-
mosphere.  When  coupled with a com-
prehensive   free  radical  photochemical
model, the recommended  scheme should
reproduce observed sulfate formation over
a wide range of NOX  and  HC concentra-
tions. This  scheme is more appropriate to
assessments  requiring estimates for  fine
temporal and spatial scales.

References
 1.  Altshuller, A. P. Model predictions of
    the rates of homogeneous oxidation
    of  sulfur dioxide to sulfate  in the at-
    mosphere.  Atmos.   Environ.   13,
    1653-1661  (1979).
2.   Atkinson,  R.,  and   A.   C.   Lloyd.
    Evaluation of kinetic and mechanistic
    data for modeling of photochemical
    smog. J. Phys. Chem. Ref. Data (in
    press) (1984).
 3.  Atkinson,  R.,  A. C.  Lloyd,  and L.
    Winges.  An  updated   chemical
    mechanism    for     hydrocar-
    bons/NOX/S02  photooxidation suit-
    able for inclusion  in atmospheric  sim-
    ulation  models. Atmos.  Environ.   16,
    1341-1355 (1982).
 4.  Bailey,  E. M., R. W. Garber, J. F.
    Meagher,  R.  J.  Bonanno, and L.
    Stockburger.  Atmospheric  oxidation
    of  flue  gases from  a  partially sulfur
    dioxide-scrubbed power  plant:  Study
    II.  TVA  Report No.  ONR/ARP-82/4
    (1982).
 5.  Calvert, J. G., F. Su,  J. W.  Bot-
    tenheim,  and   0.  P.  Strausz.
    Mechanism  of  homogeneous  oxida-
    tion  of  sulfur   dioxide  in  the
    troposphere. Atmos.  Environ.   12,
    197-226 (1978).
 6.  Calvert, J. G. and J.  R. Stockwell.
    Mechanism  and rates of  gas-phase
    oxidations  of  sulfur dioxide  and
    nitrogen oxides in  the atmosphere. In:
    Acid  Precipitation Series—Volume 3,
    S02,  NO,  and  NO2  Oxidation
    Mechanisms: Atmospheric Considera-
    tions.  John I. Teasley,  Series Editor,
    Ann Arbor Press (1984).
 7.  Eatough,  D. J., M.  L. Lee,  D. W.
    Later,  B.  E.  Richter,  N. L.  Eatough,
    and L. D. Hansen. Dimethyl sulfate in
    paniculate matter from  coal- and oil-
    fired   power  plants.  Environ.  Sci.
    Tech.  15, 1502-1510 (1981).
 8.  Forrest,  J.,  R.  W. Garber, and  L.
    Newman. Conversion rates  in power
    plant  plumes based  on  filter  pack
    data:  The  coal-fired   Cumberland
    plume. Atmos. Environ.  15, 2273-2282
    (1981).
 9.  Gillani,  N. V.,  S. Kohli, and W.  E.
    Wilson, Jr. Gas  to particle conversion
    of  sulfur  in  power plant plumes—I.
    Parameterization  of  the  conversion
    rate for dry,  moderately polluted am-
    bient conditions. Atmos. Environ. 15,
    2293-2313 (1981).
10.  Husar, R. B., D. E. Patterson, J.  D.
    Husar,  N.  V.  Gillani,  and W.  E.
    Wilson, Jr. Sulfur budget of a power
    plant  plume. Atmos.  Environ.  12,
    549-568 (1978).
11.  Martinez,  R.  I. and J. T. Herron. Gas
    phase  reaction of S02 with  a Criegee
    intermediate in the  presence of water
    vapor.  J.   Environ.   Sci.   Health,
    A16(6), 623-636  (1981).
12.  Meagher, J. F.,  E. M. Bailey, and M.
    Luria.  The seasonal variation  of the
    atmospheric S0a to SOf conversion
    rate. J. Geophys. Res.  88,  1525-1527
    (1983).
13.  Meagher, J. F., L. Stockburger,  E.
    M. Bailey, and 0. Huff.  The oxidation
    of sulfur dioxide to sulfate aerosols in
    the plume of a coal-fired power plant.
    Atmos. Environ.  12, 2197-2203 (1978).
14.  Wilson, W. E.,  Jr. Sulfate  formation
    in point source  plumes: A  review of
    recent field studies. Atmos. Environ.
    15, 2573-2581 (1981).
                                                                            *U.S.Government Printing Office: 1985 — 559-111/10823

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