Appendix

B1

Chemistry of Atmospheric Reactions of VOCs Leading to Smog

Figure B1-7 Presence of VOCs Leads to Aldehydes, and Ozone

F. REACTIONS AND REMOVAL OF

FREE RADICALS
It is true that additional VOCs always produce more ozone,
but it is not true that additional NOx always produces more
ozone!
When VOCs (or BVOCs) are present along with NOx,
they react to form radicals which either consume NO or
convert NO to NO2, which causes O3 levels to increase. But
sometimes that's not so.

Figure B1-8 Ozone Formation is a Time and VOC Dependent

Phenomena

Environmental regulation of the mass of VOC

emissions may be totally ineffective in controlling
ozone formation in the troposphere, if the mass
emission of NOx is not also controlled14, and
those VOCs which are more reactive to produce
ozone are not recognized for that characteristic
and treated accordingly. To date, latter hasn't
happened at the US Federal level (Chapter 6.4.6).
Environmental conditions can dominate the outcome.
Temperature, illumination intensity, and frequencies
are obvious variables, but the humidity (aerosols) and
particle content of the air can strongly also affect
outcomes.

HO* radicals are a major (and in many cases the

only) ingredient causing most VOCs (or BVOCs) to
react (Equations B1-7 and B1-8). If a VOC reacts in
a way which initiates the production of HO* radicals
(or produces a product which does), that would
enhance the rate of ozone formation by all VOCs
present.
Alternatively, if radical termination processes take place
(Equations B1-14 [producing PAN]) and B1-16
[producing nitric acid]) when a VOC reacts with NOx, it
will cause all VOCs to react more slowly and form less
ozone15.

At sufciently low levels of NOx, the formation of ozone

is limited because there is not enough NOx to participate in
the reaction pathway of Equations B1-9 through B1-14.
At somewhat increased levels of NOx, ozone formation
from VOCs increases through the same pathway.
But at much higher levels of NOx there is a diminution
of the rate of ozone production from VOCs because
reaction of HO* with NOx is an important radical
terminating process (Equation B1-16 to produce nitric
acid), as is formation of PAN from NO2 (Equation
B1-16, Figure B1-9).

14

This is especially important because of the massive amounts of

uncontrollable biogenic (Box 6.4) emissions of VOC. If the emissions of
NOx were not present to be co-reactants, emissions of BVOCs would not
have the deleterious effect they do.
Biogenic reactions are subject to the same environmental stimuli as
are VOCs and produce similar outcomes. A topical reference is
Atkinson R, Arey J. Gas-phase Tropospheric Chemistry of Biogenic
Volatile Organic Compounds: a Review., Atmospheric Environment.
2003;37(Suppl.2):197e219.

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15

In rare but recognized cases, reduced ozone from other VOCs may be
more than enough to counter the ozone formed from the VOCs direct
reactions. In such cases the VOC would have a negative incremental
reactivity in the presence of NOxdaddition of NOx producing less
ozone. Two obvious examples are nitric oxide and nitrogen dioxide. But
other examples are methyl iodide and tert-butyl amine.