United States
             Environmental Protection
             Agency
             Environmental Research
             Laboratory
             Corvallis OR 97330
EPA-600/3-79-057
May 1979
            Research and Development
&EPA
Nitrogen Dioxide

Time-Concentration
Model  to Predict
Acute  Foliar Injury

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                RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology.  Elimination  of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series  are:

      1.  Environmental  Health Effects Research
      2.  Environmental  Protection Technology
      3.  Ecological Research
      4.  Environmental  Monitoring
      5.  Socioeconomic Environmental Studies
      6.  Scientific and Technical Assessment Reports (STAR)
      7.  Interagency  Energy-Environment Research and Development
      8.  "Special" Reports
      9.  Miscellaneous Reports

This report has been assigned to the ECOLOGICAL RESEARCH series. This series
describes research on  the effects of pollution on humans, plant and animal spe-
cies, and materials. Problems are assessed for their long- and short-term influ-
ences. Investigations include formation, transport, and pathway studies to deter-
mine the fate of pollutants and their effects. This work provides the technical basis
for setting standards to minimize undesirable changes in living organisms in the
aquatic, terrestrial, and atmospheric environments.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                               EPA-600/3-79-057
                                               May 1979
    NITROGEN DIOXIDE:   TIME-CONCENTRATION MODEL
          TO PREDICT ACUTE FOLIAR INJURY
                        by
                  Walter W.  Heck
               Agricultural  Research
       Science and Education Administration
    United States Department of Agriculture and
Botany Department, North Carolina State University
               Raleigh,  N.C.   27650

                        and

                  David  T. Tingey
    Corvallis Environmental  Research Laboratory
   United States Environmental  Protection Agency
    200 S.W.  35th Street, Corvallis, OR  97330
    CORVALLIS ENVIRONMENTAL RESEARCH LABORATORY
        OFFICE OF RESEARCH AND DEVELOPMENT
       U.S.  ENVIRONMENTAL PROTECTION AGENCY
             CORVALLIS,  OREGON  97330

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                                  DISCLAIMER

     This  report  has  been  reviewed by  the Corvallis  Environmental  Research
Laboratory, U.S.  Environmental  Protection  Agency,  and approved  for publica-
tion.   Mention  of  trade names  or  commercial  products  does  not  constitute
endorsement or recommendation for use.

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                                   FOREWORD

     Effective regulatory and enforcement actions by the Environmental Protec-
tion Agency  would be  virtually  impossible without  sound scientific  data  on
pollutants  and  their   impact  on  environmental  stability  and human  health.
Responsibility for building  this  data base has  been  assigned  to  EPA's Office
of Research and Development and its 15 major field installations,  one of which
is the  Corvallis  Environmental Research Laboratory (CERL).

     The  primary  mission of  the  Coravllis Laboratory is research  on  the ef-
fects  of  environmental   pollutants  on  terrestrial,  freshwater,   and  marine
ecosystems; the behavior, effects and control  of pollutants  in lake and stream
systems; and the developmnt of predictive models on the movement of pollutants
in the  biosphere.

     This  report  contains previously  unpublished  research  results  that were
originally planned for  publication in BioScience in 1971.  This reference was
used in the 1971  Air Quality Criteria document for Nitrogen  Oxides  (Chapter 8,
ref.  8).  Data from  Taylor  was  deleted from the present  manuscript.   The au-
thors are  publishing these  results because they still  represent the best and
most extensive  dose-response information for nitrogen  dioxide  on  vegetation.
The  research  was  completed  in  1968.   The  authors  believe this  information
should be available to the scientific community.
                                       James C.  McCarty
                                       Acting Director, CERL

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                                   ABSTRACT

     An understanding of the response of plant species to specific doses of an
air pollutant or  a  group of pollutants is  essential  before air quality stan-
dards  can  be  established  in  areas  under crop  production.    Selected  plant
species were exposed  to  two nitrogen dioxide concentrations chosen to produce
threshold and  severe injury at  five time  periods ranging from  0.5  to  7 hr.
From these data  for  each species, an equation was developed  using concentra-
tion as  the  dependent  variable,  and  foliar injury  and time  as independent
variables.   The  model  allows for  the  development of  a  three-dimensional  re-
sponse  surface  within  the   limits  of the  exposure  times  and  concentrations
used.   The  model  is  useful in predicting the concentration of  nitrogen dioxide
that will produce a  given amount of injury to a specific crop during a single
12-hr day.   Research  to  date suggests  the model  may be used for other pollut-
ants and for other  plant species that show  injury following  exposure to high
ambient nitrogen  dioxide  concentrations.

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                                   CONTENTS



                                                                          Page




Foreword	             .          	     .    .    iii




Abstract .        .         ...       .      	     .      	iv




Acknowledgments  .  .       	   	     .    .  .          vi




     1.   Introduction    	       .   .       .       1




     2.   Experimental Methods and Procedures       	     .  .       4




     3.   Experimental Designs and Results ...               ...       .5




     4.   Discussion  ...                   ...            .6




References .                          ...                    .  .  .         -1

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                               ACKNOWLEDGMENTS

     The authors acknowledge the assistance of Mr.  Hans Hamann, North Carolina
State University,  in  the  statistical  analysis of  the  data.   Appreciation  is
also  extended  to Mr.   Frank Fox,  formerly  with the  National  Center  for  Air
Pollution Control,  for technical assistance in the early experimental designs.

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                                   SECTION 1

                                 INTRODUCTION

     The introduction of nitrogen dioxide as  an air pollutant was first infer-
red  in  California  when  photochemical  oxidants were shown  to  adversely affect
vegetation.   Through  the  photochemical  production  of atmospheric  oxidants,
including  peroxyacetyl   nitrate  (PAN) and  ozone,  nitrogen  dioxide  exerts  a
secondary,  though  significant  effect on  vegetation.   At ambient  concentra-
tions, the direct effects of nitrogen dioxide on vegetation are more difficult
to assess except around  localized sources.

     Glater  (1970)  stated  that increasing ambient  levels  of  nitrogen dioxide
may  have  been responsible  for some of the chronic  injury  to vegetation which
was  prevalent in the  Los  Angles Basin.   The increase of  nitrogen  oxides  was
attributed  to  the  increase  in  emissions from  motor  vehicles  whose control
devices reduced hydrocarbons and carbon monoxide but failed to reduce nitrogen
oxides.  Glater suggested  that  injury from  nitrogen dioxide  was replacing  the
PAN-type of  injury.  The symptoms discussed  by Glater,  however, were not found
by  Taylor and  Eaton (1966)  after  exposing  plants for  several  days  to  low
concentrations  of  nitrogen  dioxide.   The nitrogen dioxide  injury (reported by
Glater) is similar to that reported from low-level,  controlled ozone exposures
and/or  high   ambient  oxidant concentrations  in  eastern  urban  areas  by  the
authors of this paper  and  others.   The  responses reported by  Glater probably
are  more  related to ozone  or to pollutant  interactions than  to  the nitrogen
oxides alone.

     Direct  plant  responses to  phytotoxic  levels of  nitrogen  dioxide  can be
divided into  three broad categories:  physiological, chronic  and acute injury.
Physiological  injury  includes growth alterations,  reduced yields  (Taylor  and
Eaton,  1966) and  reduced  photosynthesis (Hill  and Bennett,  1970).   Chronic
injury  results  from intermittent  low level  exposure  over long  time periods.
Chronic  injury  produces  chlorotic and/or  other pigmented  patterns  in  leaf
tissues  and  may be  accompanied by  an  increase  in  leaf  drop  (Glater,  1970;
Thompson £t  a]_  ,  1970).   Acute  foliar injury often resembles  the  intercostal
bifacial  necrosis  associated with  the  response of plants to  sulfur dioxide.
High nitrogen dioxide concentrations produce  foliar markings  that first appear
as water-soaked areas and may develop into white, tan,  brown,  or bronze necro-
tic  lesions.   Lesions,  although normally intercostal,  are often  marginal  and
more toward  the leaf  apex.   A discoloration  of  leaves with  a  waxy appearance
has  been  reported  for  several  weed species (Benedict and Breen, 1955)   Short
exposures (measured  in  hours)  to high levels of  nitrogen  dioxide  may produce
acute symptoms  within 2  to 48 hr  after  exposure.   Two publications give good
descriptions  of nitrogen  dioxide  injury and  include  colored  plates showing
acute injury  (Taylor and MacLean, 1970; van Haut and Stratmann, 1967).

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     Investigators have reported plant responses to several time-concentration
combinations of nitrogen  dioxide,  but not for the express purpose of general-
izing  their data  to  develop  predictive  equations.   Several  reports  in  the
literature  are of  value,  however,  and  will   be  summarized.    The  threshold
concentration  for visible  injury  to  pinto  bean was  3  to 4  ppm in  an 8-hr
exposure;  a 2-hr  exposure  at  30  ppm killed  the  leaves (Middleton  et a]_. ,
1958).    A  group  of  agricultural  and horticultural  crops  exposed to  30  ppm
nitrogen dioxide  for  1  hr developed little or no injury (Czech and Nothdurft,
1952).   Exposure  of  10  weed species to 20 or 50 ppm nitrogen dioxide for 4 hr
during  midday  caused  from  zero  to medium  injury  on leaves  of well-watered
plants;  only  mustard  showed  well  defined injury  (Benedict  and  Breen,  1955).
Sixty  plant  species  were  exposed to 2.5 to 10 ppm nitrogen dioxide for 4 to 8
hr and  compared with plants exposed to  similar  levels of sulfur dioxide;  the
plants  were approximately  2.5  times  less sensitive  to  the  nitrogen  dioxide
(van Haut  and  Stratmann,  1967).   Cotton, pinto bean  and  endive  were  slightly
injured  at  1  ppm  nitrogen dioxide for 48 hr, were uninjured at 0.5 or 2.0  ppm
for  21  hr  or  at  1.0 ppm  for 12 hr,  while  3.5 ppm for 21  hr  produced slight
injury  to  cotton  and  pinto bean  and death  of  endive  leaves  (Heck,  1964).
Tobacco  was  uninjured  at  2.3 ppm for 8.7 hr; pinto bean was not injured until
exposed  for 4  hr to  10   ppm  (Taylor and Eaton,  1966).   Navel  orange  trees
continuously exposed  to  0.06,  0.12,  0.25,  0.5  and  1.0  ppm  nitrogen  dioxide
showed  extensive  chronic   injury  after 35 days at  the two  highest concentra-
tions.    Increased leaf drop and  reduced yields occurred  with  the 0.25  ppm
treatment  after 8 months  (Thompson ^t a_1_. , 1970).  Fourteen ornamental  species
and  six  citrus varieties were exposed to from 10 to 250 ppm for periods of  0.2
to 8 hr with  extensive  injury  reported  in  all plants;  young shoot  necrosis
occurred at exposures of 200 ppm for 4 to 8 hr or 250 ppm for 1 hr (Maclean et
aj_. , 1968).

     The degree of  injury to vegetation  by  nitrogen  dioxide  is  influenced by
factors  such as plant species,  stage of  plant  development,  plant environment
(temperature,  light,   humidity,  soil   moisture,  mineral   nutrition),  variable
susceptibility within species (cultivar or clone),  and the interaction of more
than one  phytotoxic  gas in the plant atmosphere (Heck, 1968).  Depending upon
the  kind  of plant and its  environment,  one  factor  may be more important than
another, but all factors must eventually be understood before adequate effects
modeling can be completed.

     Taylor and Maclean (1970)  recognized the increased sensitivity of plants
to nitrogen  dioxide  caused  by  low light intensity.   They  reported  that 2-hr
exposures of sensitive  plants  to 3 ppm nitogen dioxide under low light condi-
tions  caused  as much  injury as 6  ppm in light equivalent  to full  sunlight.
Several  reports have  shown that night exposures to nitrogen dioxide may cause
more injury  than  day exposures  (Czech and Nothdurft,  1952;  Tingey,  1969;  van
Haut and  Stratmann,  1967).  van  Haut and Stratmann  (1967)  reported  that  rye
plants  were  most  sensitive to nitrogen dioxide from  noon to 4 pm.  Oats had a
bimodal  sensitivity  to  nitrogen  dioxide with more  injury  occurring  from mid-
night to 2  am than at noon  to 2 pm.

     The report by Tingey et a_L  (1971)  is of special interest.  They exposed
six  species  to  various  mixtures  of nitrogen dioxide  and  sulfur dioxide for 4
hr   They  found  that  over  2.0  ppm  of nitrogen dioxide or 0.5  ppm  of sulfur

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dioxide  were  required  to produce  injury  when  the  gases  were  administered
separately, but  all  species  were  injured by various combinations  of  the two
gases in the concentration ranges of 0.05 to 0.25 ppm.  The relative sensitiv-
ity  of  the six  species  from  highest to  least sensitive  was  soybean,  radish,
pinto bean,  oats,  tobacco, and  tomato.  Injury developed  as a  chlorotic or
necrotic flecking on the upper leaf surface and was similar to injury produced
by ozone.

     This paper  reports  experiments  designed to more accurately predict acute
injury to  a  selected  group of plants from nitrogen dioxide exposures that are
limited  in time.   The   factors  discussed  above,  which  influence  injury re-
sponse,  have  not been  controlled  in the  design used.    The  predictive model
reported here allows  for the  prediction of concentrations of nitrogen  dioxide
that will  produce  acute  foliar  injury when the environmental  conditions are
not  known.  The  model  can be  used to suggest combinations of time and  concen-
trations of  nitrogen  dioxide  that  should  not  be  exceeded  in  the  atmosphere
without injuring specific types of vegetation.

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                                   SECTION 2

                      EXPERIMENTAL METHODS AND PROCEDURES

     Plants used  in  this  study (Tables 1 and  2)  were grown in 10 cm diameter
pots, in  a  1:1  peat-perlite mix, in charcoal-filtered greenhouses at about 27
C day and 21  C night temperatures.  Supplemental  fluorescent lighting insured
a minimum 12-hr photoperiod of 10 klux throughout the year   Relative humidity
varied  from 30 to  80%  depending on outside  conditions.   Plants  were watered
daily with  a  half strength Hoagland's nutrient solution.  Rapid growing plants
were  seeded directly into the peat-perlite potting mix; slow developing seed-
lings were  seeded  in  vermiculite and transplanted  into the  regular potting
mix.  The five ornamentals  (Table  2)  were  purchased as young  plants  from a
local  nursery  and  established  in  the  potting  mix  before  exposure.  Plants
started  directly  from  seed in the potting  mix were  overseeded and thinned to
one plant per pot  7 days after seeding.

      Plants  were  exposed  to nitrogen dioxide  in  greenhouse  exposure chambers
(Heck  et, al. , 1968) at a  young  stage  of growth   (three  to  six  fully expanded
leaves)  for  the  crop species  and when  the  ornamentals were  still  actively
growing.  One  percent  nitrogen  dioxide  was  injected  into the  chamber using a
two-stage  dilution  system and was continuously monitored with  a  Mast oxidant
meter  to insure  a  uniform concentration in  the  chamber   Chamber concentra-
tions were  determined  after Saltzman (1954) using one  to  three 5-min bubbler
samples.  The  number of  samples  varied  with  the  length of exposure.  Values
are reported as parts of nitrogen dioxide per million parts of air (ppm)2 on a
v/v basis.

     Plant  injury was assessed 2 to 3 days after  exposure when all leaves were
examined  to  determine  the percent area of each leaf, showing chlorosis and/or
necrosis.   Injury on each  leaf  was visually estimated  in  5% increments  (0 to
100%  scale),  and  an  injury  index was  computed  on  the basis  of  the average
injury to the  three  most  severely injured  leaves per plant.  The injury index
included  a  three leaf  average even  if  any  or  all   of  the leaves  showed  no
injury.    The  injury  indices  for  the  five  ornamental  plants  (Table  2)  were
based on  a visual estimation of the whole plant rather than individual  leaves.
     One ppm of nitrogen  dioxide  is equivalent to 1.9 mg/m3 of nitrogen diox-
     ide at 760 mmHg and 25 C.

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                                   SECTION 3

                        EXPERIMENTAL DESIGNS AND RESULTS

     Two experimental designs were used to study time-concentration effects of
nitrogen  dioxide on  a  group of  plants.   The first  design  was used  to help
select  times  and concentrations for the second, which was designed to develop
time-concentration response equations  for the plants studied.

     The  first  design was for  a 1-hr time period using three nitrogen dioxide
concentrations  (8,   16  and 32  ppm).   Treatments  were replicated  four times.
The  results  are  shown  as  the  average of  four replicates  per concentration
(Table  1).   The plants,  listed in order of  decreasing  sensitivity,  show the
variability  in   sensitivity  of  different plant  species  to  nitrogen  dioxide.
The  results also show the  effects of environment.  The design was purposefully
developed to  include Bel W3 tobacco in the  summer  and winter  exposures.  The
plants exposed in winter were much more resistant.

     The second  experimental  design  was used in developing time-concentration
response equations  for  a group  of plants exposed  to  nitrogen dioxide using a
time scale  of 0.5  to  7  hr.  These  equations were developed  by exposing se-
lected species to nine  different combinations of time and concentration (Table
2).  Each  time-concentration combination  was replicated on  4  successive days
using  36  observations  (plants) of  each  species  to  develop  each  equation.
Plant injury indices were assessed as previously described except for begonia,
sultana,  chrysanthemum, periwinkle  and azalea.  For  these  species  a  single
percent injury  rating was  determined  for the whole plant.   Mean plant injury
values  for  each  time-concentration  combination  of  the  design are  shown  in
Table 2.  A multiple regression model  was applied to  the plant injury indices
to develop the time-concentration response equations shown in Table 3.

     The amount of variation explained by the model,  the  coefficient  of varia-
tion (R2),  is shown  for each equation  in  Table 3.   Plants  in  this  table are
listed in order  of  their sensitivity to nitrogen dioxide,  using three suscep-
tibility groupings  (susceptible,  intermediate,  tolerant).   Examples  of calcu-
lated concentrations  for four  combinations  of percent foliar  injury  and time
are  also  shown  in   Table  3.   These  equations  and the  survey  of  literature
presented  in  the introduction  of  the  response  of plants  to  acute  doses  of
nitrogen  dioxide,  aided  in  the development  of the  susceptibility  groupings
shown in Table 4.  Values in this table are not  absolute  and  should be treated
as suggested limits  for  the given susceptibility  grouping.

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                                   SECTION 4

                                  DISCUSSION

     The interrelations of time and concentration (dose) as they affect injury
to vegetation  are  essential  for  an understanding  of air  pollution  effects.
Time-concentration  effects  have been  inadequately  studied and  are therefore
poorly  understood.    A  discussion of time-concentration  relations  should con-
sider  acute,  chronic,  and  physiological  responses.  At  this time,  there  is
insufficient literature relating the  effects of time and concentration to the
production of chronic injury, or to the reduction of growth, yield, or quality
of plant  material.   The  acute  effects of  nitrogen dioxide,  as related to a
series  of  times and concentrations,  have  not  been  widely  studied,  but the
reports discussed in the introduction along with the results presented in this
paper  have permitted the  development of estimates of concentrations that will
produce injury  to plants.

     Researchers in  the  area  of  air  pollution effects  on  vegetation  have
generally been  content  to view a plant's response  to a pollutant  or group of
pollutants in  a subjective  way.   They have preferred to  look  at  effects and
make  their  own interpretations.   In  the  biological  as  well  as the  physical
sciences, response should  be quantified whenever possible  to remove  the sub-
jective  interpretations of the investigator.  The  response of  plants to spe-
cific  times  and concentrations of  pollutants  is  subject to  quantification
through  mathematical modeling.   The  first such  model was  developed by O'Gara
(1922)  for the  relations  of dose (time x concentration)  to acute  plant injuy
from sulfur  dioxide.

     The O'Gara  equation   is  a mathematical form that  fits experimental data
obtained  from   exposures   of  relatively  short  duration   (less  than   1  day).
Guderian e_t  al.  (I960) did not believe  the O'Gara  equation would fit their
observations (derived  from  continuous  exposures over  several  hundred hours)
and suggested an exponential relationship to best describe  their data.  In the
short  time span  (1  to  12   hr),  both  equations  give  a reasonable fit to avail-
able  data.   The exponential  form  fits over  a wider  range  of time  for the
sulfur  dioxide work  reported.  Both of these equations relate time  and concen-
tration  to  a specific  percentage  injury and  thus  are  capable of developing
only a two-dimensional  model; both also require  a good estimate of a threshold
injury concentration  before they can be solved.

     Heck et a]_  (1966)  developed  a response surface showing the variation in
injury  to pinto  bean and  tobacco from  ozone exposures  as  time and concentra-
tion  varied.   Surfaces of  this type  make  apparent  the  steep  slope  that is
frequently observed  in  the injury  versus concentration  or injury  versus time
planes.  The  steep  portions  of  the  slopes indicate that relatively  slight
changes  in many  factors  (environmental, nitrogen dioxide concentration,  time,
and others)  can  cause large variations in the amount  of injury produced.

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     The models  discussed  above  give an insight  into  what  may happen under a
given  set  of circumstances.  These  relationships are  probably  universal and
could  be derived for any toxicant producing  a  definite acute-type of injury.
Relationships of this type  permit  the prediction,  with  reasonable assurance
that no  acute  injury will  occur as  long as  a certain threshold concentration
is not exceeded  for a given period of  time.

     The predictive  equation  reported  in  this paper for  nitrogen  dioxide was
first  developed  for  ozone  (Heck and Tingey,  1971).  The equation handles time
and  concentration separately and  permits  the  development  of a  three-dimen-
sional injury response surface similar to that reported by Heck e_t al.  (1966).
The  equation  treats  concentration  as  the  dependent variable  and  both injury
and time as  independent variables and is represented as:

                         C = AQ + A! I + A2/T

where  C  is  nitrogen  dioxide concentration  in ppm, I  is percent foliar injury,
T is exposure time in hours, and A , Al( and A2 are constants (partial  regres-
sion  coefficients)  which are specific for the pollutant,  plant  species, and
the  environmental  conditions used.   The equation permits  the  development  of
either  a two-dimensional  curve  or  a  three-dimensional response  surface and
eliminates  the  necessity of determining a threshold concentration  before the
equation can be  solved.   The predictive equations reported  in Table  3 elimi-
nate the necessity  for  each researcher or control official  to give a subjec-
tive interpretation  of  the  data shown in Table 2 and permit a uniform interp-
retation of  results  by  all  who  review them.   The equation can also be used  by
a researcher or control  official  to  predict the nitrogen dioxide  concentration
that could  be  in the atmosphere over a limited time  period  that  would produce
zero  or slight  injury   to  a given  variety  or  species of   plant.  The  model
indicates that  a given  dose (concentration x time) of nitrogen dioxide over a
range of times does not give constant injury.

     The experimental data presented in Table 3 were  developed from greenhouse
exposures over  several  days  in  time  and  thus include  an averaging effect  of
many environmental variables.  They  do not represent any specific combination
of environmental  conditions  tnat  would tend to make any  given plant  particu-
larly  responsive to  nitrogen dioxide.   Thus, in  some cases, plants  exposed
under  field  conditions  could be  more sensitive to nitrogen  dioxide than would
be predicted  from a  given  equation.   The  equations  do  not  consider  fluctua-
tions  in  concentration  over  a  given  time  interval or  the  effect  of  repeated
fumigations   over  either several  days  or  even several   hours  in  one  day   The
data are from short exposures and thus should not be  extrapolated to long time
periods.

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                                  REFERENCES

Benedict, H.  M.  and  W.  H.  Breen.  1955.  The Use of Weeds as a Means  of  Evalu-
     ating  Vegetation  Damage  Caused  by Air  Pollution.   Proc.  Nat.   Air  Poll.
     Symp., Pasadena, Calif.,  3rd, p. 177-190.

Czech,  M.  and W.  Nothdurft.   1952.  Investigaton of  the  Damage to  Field  and
     Horticultural   Crops  by  Chlorine,  Nitrous  and  Sulfur  Dioxide   Gases.
     (Untersuchungen uber  Schadigungen  landwirtschaftlicher und gartnerischer
     Kulturpflanzen  durch  Chlor-Nitrose-und   Schwefeldioxydgase).   Lanwirt-
     shaftliche Forschung.  Darmstadt, 4(No. l):l-36.

Glater,  R.  A.   1970.   Smog  and Plant Structure  in Los  Angeles County.   School
     of  Eng.  Applied  Sci.,  Univ.  of Calif.,  Los  Angeles,  Calif., Report  No.
     70-17.

Guderian, R.,  H.  van Haut, and H. Stratmann.   1960.  The Estimation and  Evalu-
     ation  of  the  Effects  of  Atmospheric Gas  Pollutants Upon  Vegetation.
     (Probleme  der Erfassung  und Beurteilung  von  Wirkungen gasformiger  Luft-
     verunreinigungen  auf  die  Vegetation).    Z.  Pflanzenk.  Pf1anzenschutz.
     67:257-264.

Heck, W.  W.   1964.   Plant Injury Induced by Photochemical Reaction Products of
     Propylene-Nitrogen Dioxide  Mixtures.   J.  Air  Poll. Contr. Assoc. 14:255-
     261.

Heck,  W. W.   1968.   Factors  Influencing  Expression  of  Oxidant  Damage  to
     Plants.  Ann.  Rev.  Phytopath. 6:165-188.

Heck,  W.  W.  and  D.  T.  Tingey.   1971.  Ozone:  Time-concentration  model  to
     predict  acute foliar injury.  In:  "Second  International  Clean Air Con-
     gress,   Proceedings"   (England, H.   M.  and M. T.  Berry,  eds.).   pp. 249-
     255. Academic Press, New  York,  N.Y

Heck,  W.  W. ,  J.   A.  Dunning,  and  I.  J.   Hindawi.   1966.   Ozone:   Nonlinear
     Relation of Dose and Injury in Plants.   Science 151:577-578.

Heck, W.  W. ,  J.  A.  Dunning  and H.  Johnson.   1968.   Design  of a Simple  Plant
     Exposure Chamber.   Nat. Air Poll.  Cont. Admin.  Publ.  APTD-68-6, 24 p.

Hill, A.  C.  and J.  H.  Bennett.   1970.   Inhibition  of Apparent  Photosynthesis
     by Nitrogen Oxides.  Atmos. Environ. 4:341-348.

MacLean,  D.  C. ,   D.  C.  McCune,  L.  H. Weinstein,   R.  H.  Mandl ,  and  G.  N.
     Woodruff.  1968.  Effects of Acute Hydrogen Fluoride and  Nitrogen Dioxide
     Exposures  on  Citrus  and  Ornamental Plants of Central Florida.  Environ.
     Sci  Technol.  2:444-449.

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Middleton, J.  T. ,  E.  F.  Darley,  and R.  F.  Brewer.   1958.   Damage  to Vegetation
     from Polluted Atmosphere.  J. Air Poll. Cont.  Assoc.  8:9-15.

O'Gara,  P.  J.   1922.  Sulfur  Dioxide and  Fume  Problems and  Their Solutions.
     Abst. J. Ind.  Eng. Chem. ]4:744.

Saltzmann, B.  E.   1954.    Colorimetric  Microdetermination of  Nitrogen  Dioxide
     in the Atmosphere.   Anal. Chem. 26:1949-1955.

Taylor,  0. C.  and  F.  M.  Eaton.   1966.  Suppression  of  Plant  Growth by Nitrogen
     Dioxide.  Plant Physiol. 4J_:132-135.

Taylor,  0.  C.   and D.  C.  Maclean.   1970.   Nitrogen Oxides and the Peroxyacyl
     Nitrates.  _Iri:   Recognition  of Air  Pollution Injury  to Vegetation:   A
     Pictorial  Atlas,  J.  S.  Jacobson  and  A.  C.  Hill,  eds.  Air  Pollution
     Control  Assoc., Pittsburgh,  Pennsylvania, p. E1-E14.

Thompson,  C.  R. ,   E.  G.  Hensel,  G.  Kats  and  0.  C.  Taylor.  1970.   Effects  of
     Continuous  Exposure of Navel  Oranges  to Nitrogen Dioxide.   Atmos.  Envi-
     ron. 4:349-355.

Tingey,  D.  T.   1969.  Foliar Absorption  of  Nitrogen Dioxide,  Masters  Thesis,
     Univ. of Utah, Salt  Lake City, Utah, 46 p.

Tingey,  D. T. ,  R.  A.  Reinert,  J.  A.  Dunning  and W.  W.  Heck.  1971.   Vegetation
     Injury  from  the  Interaction  of  Nitrogen  Dioxide  and  Sulfur  Dioxide.
     Phytopathology 6J_:1506-1511

van  Haut, H.  and  H.  Stratmann.   1967.   Experimental  Investigations of  the
     Effect  of Nitrogen Dioxide  on  Plant (Experimentelle Untersuchungen  uber
     die  Wirkung  von   Stickstoffdioxid  auf  Pflanzen).    Schriftenreihe  der
     Landensanstalt  flir  Immissions-und  Bodennutzungsschutz des   Landes  Nord-
     rhein-Westfalen, (Essen),  No.  7:50-70.
                                      10

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               TABLE 1.  ACUTE INJURY TO SELECTED CROPS AFTER A
                         1-HOUR EXPOSURE TO NITROGEN DIOXIDE-
                                                            a/

Plants by Name ,,
(Common, Cultivar, Scientific)-
Tomato, Roma-
(Lycopersicon esculentum, Mill.)
Wheat, Wells^
(Triticum durum, Desm. )
Soybean, Scott-
(Glycine max, (L.) Merr. )
Tobacco, Bel W3-
(Nicotiana tabacum, L. )
Bromegrass, Sac Smooth-
(Bromus i nermis , L. )
Swiss Chard, Fordhook Giant-
(Beta vulgaris L. )
Tobacco, White Gold-'7
(Nicotiana tabacum, L. )
Cotton, Acala 4-42-/
(Gossypium hirsutum, L. )

8 ppm
1

0

0

0

2

0

0

0

Injury Index (%)
16 ppm
48

47

26

23

17

11

1

0


32 ppm
100

90

100

97

97

62

70

54

Beet, Perfected Detroit-
(Beta vulgaris , L. )
Orchard Grass, Potomac-
(Dactylis glomerata, L. )
Tobacco, Bel W3-/
0
0
0
0
1
0
36
18
5

-   Plants were exposed in Cincinnati, Ohio.

-   Scientific name is given when plant is first listed.

-   Plants were exposed in August with light intensity at 2200 ft-c, tempera-
    ture 28°C, humidity 75 percent.

-   Plants were exposed in January with light intensity at 1400 ft-c, tempera-
    ture 21°C, humidity 70 percent.
                                     11

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TABLE 2.   ACUTE INJURY TO SELECTED PLANTS USED IN DEVELOPING CONCENTRATION-
          TIME RESPONSE EQUATIONS FOR NITROGEN DIOXIDE-
                                                      a/

Injury Index (%)
Plants by Name Dose-
(Common, Cultivar, Cone.
Scientific) Time
Oats, Clintland 64
(Avena sativa, L. )
Radish, Cherry Belle
(Raphanus sativus, L. )
Bromegrass, Sac Smooth
Begonia, Thousand Won-
ders, White- ,
(Begonia Rex, Putz. )
e/
Chrysanthemum, Oregon-
Chrysanthemum, sp. )
e/
Sultana, White Imp-
(Impatiens sul tani ,
Hook)
Oats, 329-80-7
Cotton, Paymaster
Wheat, Wells
Cotton, Acala 4-42
Periwinkle, Bright
Eyes- (Vinca minor, L. )
Oats, Pendek-7'
Broccoli, Calabreese
(Brassica oleracea
botryti s , L. )
Tobacco, Bel B
Tobacco, White Gold
2.5 4
5 4
0.5 1
0- 0

0- 0

0- 0
0 1


1 1

0 0


2 2
0 0
3 2
0 0
0 0

1 2
0 0


0 0
0 0
6
3
2
0

0

0
0


1

0


1
6
1
0
0

0
0


3
1
10
20
0.4
80

95

69
26


34

51


32
50
31
28
13

39
19


18
18
14
2
7
2

0

0
0


0

0


1
0
3
0
0

0
0


0
0
15
15
1
84^

90c/

50^
35


41

26


18
27
34
28
20

2
21


17
6
20
10
2
39

31

26
49


25

24


14
2
2
1
23

2
0


0
0
20
5
4
0

1

1
4


4

0


9
2
3
0
1

1
0


0
0
35
5
7
21

2

0
5


1

0


14
1
1
1
1

2
0


0
0
                                    12
                                                               continued

-------
TABLE 2 (continued)
    Plants by Name
  (Common, Cultivar,
      Scientific)
Dose^7
Cone.
Time
                                                Injury Index (%)
2.5   46    10   14    15    20   20   35
5     43    20    2    15    10    5    5
0.5   1    2   0.4    7     1     247
Tobacco, Bell W3

Tobacco, Burley 21

Corn, Pioneer 509-W
  (Zea mays, L.)

Corn, Golden Cross

Azalea, Alaska
                     e/
  (Rhododendron, sp. )-

Sorghum, Martin
  (Sorghum, sp.)

Cucumber, Long Marketer
  (Cucumi s sativus, L.)
          006    15    0     2     000

          000     80     0     000

          100     10     1      000


          000     00     0     002

          000     00     1      000
          000
                     00000
          000     00
                                 000
-   Plants were exposed in Cincinnati, Ohio.  Each value is the average of 4
    replicate plants except as noted.  Plants are listed in general order of
    sensitivity.  Scientific names are included except when already given in
    Table 1.  Equations are shown in Table 3.  Plants were exposed from July
    22 through September 20, 1968 except for wheat, oats (Pendek and 329-80)
    broccoli and cucumber which were exposed in early November

-   Dose = ppm/hrs, cone.  = ppm, time = hr.

-   Three replications per treatment.

-   Two replications per treatment.

e/
-   Ornamental plants obtained from nursery, injury indices are determined as
    whole plant values.
                                      13

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TABLE 3.   TIME-CONCENTRATION RESPONSE EQUATIONS FOR A SELECTED GROUP OF PLANTS TO NITROGEN DIOXIDE-
                                                                                                  a/
Plants by Name-7'
(common, Cultivars)
Susceptible
Oats (Clintland 64)
Radish (Cherry Belle)
Oats (329-80)
Bromegrass (Sac
Smooth)
Begonia (Thousand
Wonders White)
Chrysanthemum (Oregon)
Oats (Pendek)
Wheat (Wells)
Sultana (White Imp)
Broccoli (Calabreese)
Periwinkle (Bright
Eyes)
Intermediate
Cotton (Paymaster)
Cotton (Acala 4-42)
Tobacco (Bel B)
Tobacco (Bel W3)
Tobacco (White Gold)
Equation ,
(C = A + A! I + Ao/T)-
Q -L ^
c =
C =
C =
r> 	
C =
c =
c =
c =
c =
c =
c =
c =
c =
c =
c =
c =
1.45 + 0.
2.43 + 0.
1.75 + 0.
2.49 + 0.
2.45 + 0.
3.16 + 0.
2.79 + 0.
2.80 + 0.
3.93 + 0.
3.07 + 0.
2.92 + 0.
2.97 + 0.
3.68 + 0.
3.62 + 0.
3.65 + 0.
4.03 + 0.
13
14
15
16
15
16
14
13
13
20
23
23
22
21
18
30
I + 2.
I + 1.
I + 3.
I + 1.
I + 2.
I + 2.
I + 2.
I + 2.
I + 1.
I + 2.
I + 3.
I + 1.
I + 3.
I + 3.
I + 4.
I + 3.
39/T
02/T
24/T
90/T
99/T
14/T
88/T
94/T
73/T
94/T
02/T
94/T
15/T
98/T
40/T
56/T
d/
R2
0.76
0.83
0.56
0.71
0.63
0.72
0.50
0.52
0.67
0.53
0.55
0.58
0.50
0.38
0.31
0.40
Concentrati
I (
1-5, T=l
4.5
4.1
5.7
5.2
6.2
6.1
6.4
6.4
6.3
7.0
7.1
7.1
7.9
8.7
9.0
9.1
I=b,
2.
3.
2.
3.
3.
3.
3.
3.
4.
4.
4.
5.
5.
5.
5.
6.
ons (ppm) to produce the
in %) in T (hr)
T=8
3
2
9
5
5
7
8
8
8
5
5
3
2
2
2
0
1=50, T=l
10.3
10.5
12.5
12.4
12.9
13.3
12.7
10.2
12.2
16.0
17.4
17.4
17.8
18.1
17.1
22.6
1=50, T=8
8.3
9.6
9.7
10.7
10.3
11.4
10.2
7.7
10.7
13.4
14.8
15.7
15.1
14.6
13.2
19.5
                                                                                          continued ...

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TABLE 3 (continued)
Plants by Name-"7
(common, Cultivars)
Tolerant
Tobacco (Burley 21)
Corn (Pioneer 509-W)
Corn (Golden Cross)
Azalea (Alaska)
Sorghum (Martin)
Cucumber (Long Marketer)
Equation , d/
(C = AQ + A! I + A2/T)- R2
None
None
None
None
None
None
Concentrations (ppm) to produce the
I (in %) in T (hr)
1-5, T=l 1=5
1 of 36 plants
percent
4 of 36 plants
1 . 6 percent
1 of 36 plants
percent
1 of 36 plants
percent
0 of 36 plants
0 of 36 plants
, T=8 1=50, T=l 1=50, T=8
injured; 0.5 hr. , 26 ppm, 33
injured; all injuries were
injured; 7.0 hr, 6 ppm, 7
injured; 1.0 hr, 17 ppm, 5
injured
injured

a/
b/
    Equations were developed from exposures limited in time (0.5 - 7.0 hr) and denote acute injury symp-
    toms to the plants.  Concentrations used ranged from 1 to 20 ppm of nitrogen dioxide.   Plants are
    grouped in 3 susceptibility categories.  Specific injury averages are given in Table 2.
    Scientific  names are given in Tables 1 and 2.

-   C is nitrogen dioxide concentration in ppm;  I is percent injury; T is time in hr; and Ao, A1, and A2
    are constants (partial regression coefficients) specific for pollutant, plant species, and environ-
    mental conditions used.

-   R2, multiple correlation coefficient squared which represents the percent variation explained by the
    model.

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     TABLE 4.   PROJECTED NITROGEN DIOXIDE  CONCENTRATION  RANGES  WHICH WILL
               PRODUCE,  FOR SHORT-TERM EXPOSURES,  FIVE  PERCENT  INJURY TO

               VEGETATION GROWN UNDER SENSITIVE  CONDITIONS-7

Time
(hr)
0.5
1.0
2.0
4.0
8.0
Concentrations (ppm) Necessary to Produce Injury in Three
Susceptibility Groupings of Plants
Susceptible
6 -
4 -
3 -
2 -
2 -
10
8
7
6
5
Intermediate
9 -
7 -
6
5
4
17
14
12
10
9
Tolerant
> 16
> 13
> 11
> 9
> 8

-   The values in this table were developed  from  a  subjective  evaluation  of
    the earlier tables and references  included  in the  introduction.
                                      16

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing]
1. REPORT NO.
   EPA-600/3-79-057
                                                           3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
                                                           5. REPORT DATE
  Nitrogen  Dioxide:   Time-Concentration  Model  to Predict
       Acute  Foliar  Injury
                                                           May  1979  issuing date
                                                          6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
  Walter W.Heck
  David T.  Tingey
                                                           8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS

  Environmental Research  Laboratory--Corval1 is
  Office of Research and  Development
  U.S.  Environmental Protection Agency
  Corvallis, OR 97330
                                                          10. PROGRAM ELEMENT NO.
                                                             IAA602
                                                          1 1. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
  Same
                                                           13. TYPE OF REPORT AND PERIOD COVERED
                                                             inhouse-final
                                                           14. SPONSORING AGENCY CODE
                                                             EPA/600/02
15. SUPPLEMENTARY NOTES
16. ABSTRACT
      An experimental  design was developed  utilizing five time periods from  0.5  to 7
 hours with  two  nitrogen dioxide concentrations  at  each time period.  Concentrations
were chosen that would  produce
From these data for  each plant
concentration as the dependent
dependent variables.  The mode
                                 threshold and  severe injury at these time  periods.
                                 species, an  equation was developed utilizing
                                 variable, and  both  foliar injury and time  as  in-
                                  allows for  the  development of a three-dimensional
 response surface  within the limits of the times  and concentrations used.  The
 model should  be of practical importance in  predicting the concentration of nitrogen
 dioxide that  will  produce a given amount of injury to a specific crop during a
 single 12-hour day.   Research to date suggests the  model may be used for other
 pollutants and for other plant species that show injury following exposure to high
 ambient nitrogen  dioxide concentrations.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
 Air Pollution
 Nitrogen Dioxide
 Plants (botany)
                                              b. IDENTIFIERS/OPEN ENDED TERMS
                                              Dose-response  equations
                                              Vegetation
                                                                        c. COSATI Held/Group
06/F
18. DISTRIBUTION STATEMENT


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