ch qp ter

II ,-r\
I l r c , r i r s e h r t a t l t e ,l i k c t l r t \ \ ' : t l c rw c t l r i r l k .i t I l ( ( ( s s . t n
to lif-e.As rvith water. we want to bc assurcclthlrt thc air rvill
r1()tcallse us hamr. We exoect tO brcathe "clcatr ltir.
NROUALITY

l.:"
 I I.l l{eteorolo$-v and,\ir itlovernent

tsut what cxxctl)' is clean air? This question is iust as difficult to answer a9
delining what is clc:rn water. Recall from Chapter 8 that manl'para';neters are
necded to clescribe the quality of water, and that cnly with the selec'ive and
iudicious usc of tl'rcsc parameters is it possible to describe what is mcant b.v
rvater qualit'r. Recall also that water qualitf is a relative temr anci that it is
unrealistic to ask fbr irll water to be pure H2O, ancl that in many' cases suclt as
in streams ancl lekcs pure \\,ater would actuall_vbe unacceptable.
fur anulogons situation exists with air quality. Pure air is a mixture of
g : t s c s u. l t i r ' l t ( ' ( ) n t ; l i r ) s

. 78.0% nitrogen
. 2O.l,k ox.yg,en
. 0.9% argon
. 0.03% carbot.tclioxicle
. 0.002% ncon
. 0.(XX)512"
helium

and so on. But such ail is nclt found in nature and is of interest onlv as a
refercnce , such as pure I{2O would be.
If this is pLrre air, then it may be useful to deline as pollutants those
materials (gases, liquid, or solid) that, when added to pure air at sufficienti,v
high concentrations, will cause adverse effects. For example , sulftrr compounds
emitted into the irtmosphere reduce the pH of rain and result in acidic rivers
and lakes, causing rvidespread damage. This is clearly unacceptable, and the
sulfirr compouncls can bc without much argument classi{ied as air polltltants.
Yet the problem is not so casily settled, since some sulftlr may be emitted from
natural sourccs such as volcanos and l-rot sprilgs. Sulfur cannot therefore be
classilieclas a pollutant without specifving its sources.
Furthcr, the pollutants emitted into the atmosphere must travel through
the atmosphere to rcach people, animals, plants, or things to have an eff'ect.
Vhereas in \\'ater pollution this caffiage of pollutants is by u'ater currents. in
air pollution wind is thc means for transport of pollutants.
In this chapter some basic meteorologf is discussedfirst to illustrate how
the transport and dispersion of pollutants takes place . Then the methocls of air-
qr.ralitymcasurement are discussed,followed bv a discussion of the sources and
effects of some major air pollutants. Finally, some air pollution law is introduced
to show ho$' the government can influence the attainmcnt of qualin' irir.

I 1.1 o Nleteorolog-vand Air Movement

-l'hc
carth's lltmosphere can be divided into easiivrecognizable strata,depcnding
on the temperatllre profile. Figure 11-1 shon's a fi'pical tempcrattrre prolilc
fcrr four major la1'crs.Thc troposphere, rvhere most ol or.rr \veather occtlrs,
-l'hc
rirnges from about 5 km at the poles to about 18 km at tl-rc cquat()r.
 ';:','-q
ll ..Ur Qrralin'
.:

100

BO
Altitude
(k')
60

40

20

0
t00 200 300 400
Temperoture{"k)
,'
F I G U R EI l - I T h ee o r t h ' so t m o s p h e r e .

tcmpcrature hcre decreases with altitude. More than g0g,nof thc air is within
this well-mixed layer. orr top of the troposphere is a la1,cr of air wherc the
tempe rature profile is inverted, and in tl-risstratosphere little mixing takes place.
P()liutants that migrate up to the stratosphere can st:r)' thcrc fcrr man\,
),cars.
The stratosphere has a high ozone concentration, ancl thr: ozonc aclsorbsthe
sur-r'sshortwave ultraviolet radiation. Above the stratosphere are two more
la1'ers,the mesosphere and the thermosphere, wl-rich cont:rin or-rlr.about 0.1%
of tl-reair.
other than the problems of global warming and stratospheric ozone deple-
tion. air pollution problems occur in the troposphere. Poih.rtantsin the tropo-
sphere, u'hether produced naturally (such as terpenes in pine fbrests) or emitted
from human activities (such as smoke from po\\'er plants) arc movccl b1, air
curr(]nts, which we commcnly call wind. Meteorologists iclcntil,r'nranl' diffcrcnt
kinds of winds, ranging from global wind patterns causecl b1. the difrerential
r'varming and cooling of the earth as it rotates uncler the slln. to local wincls
caused by differential temperatures between lancl and $,aler masses. A sea
breeze. for example, is a wind caused by the progressive wamring of the land
cluring a sunny day. The temperature of a large wlter bocll' such :rs an ocean
or large lake cloes not change as rapidly during the ciav, ancj thc air over the
rvarm land mass rises, creating a low-pressure area tou.arcl $'hich air coming
horizontally over the cooler large w:rter bod1, flows.
vind not only moves the poll'tants horizontaliv, l)ut it also causcs the
pollutlnts to disperse, reducing the polh-rtantconccnrration s.itl-rclistanceasra],
Iiom thc source. The amount of dispcrsion is directl,v related to thc stabiliry of
the air, or horv much vertical air movement is taking place . The stabilitv of the
atmosprhercis best explained using an ideal parccl of air.
As an im:rginary parcel of air rises in the eanh's atm'sphere. it cxperiences
I I .l \le teorokrgv ancl Air Ilovemcnt

1{)\\'cr:rndkrrver pressurefrom surntunding air molecules and thus expands.

-fhrs
cxpansion lowers the temperaturc of tl-reair parcel. Ideally a rising parcel
Lrlair cools at about 1"C/100 m or 5.4"F',r1000 ft (or warms nt l"C/100 m if it
ir corrrirrg down). This warming or cooling is termed the drn udiabatic lttpsa
,z//e. (Rccall from Chapter 6 that adiabutic is a term denoting no heat transfer
\uch ils bctlvccn the air parcel and the srlrrounding air.) 1'he acliabatic laltsc
nrte is irrdcpcndcnt of prevailing atmosphcric tempcraturcs.'l'he 1'Cll(X) nr
rtlu,a)ls l-rolcls(for dry air), regardless of the actual temperxtrlre at var.i()us
clevations. When there is moisture in thc air the lapsc rate becomes the tlel
tdiabalic lctpserate because the er.aporation and condensation of n'ater inflrr-
cttces the temperlttlrc of the air parcel. This is an unncccss:rn. complication
firr the purpose of the following argumcnt and a ntoisturc-fiec atmospltcrc
is assumed.
Tlre :rctual temperature-elevation mcasurcments are callcd pret:ttilitrg
Idpse rates ancl can be classified as shown in Figurc 11-2. A supenrrliabrttic
lapse rate, also called a sf,"onglapse rat..e,occurs whe n the atntosplteric tcmpcr;r,
ture drops more than 1"C/100 m. A subctcliabatic lapse rate, tls<.tcalled a ztledA?
lapse rlte, is characterized by drop tlf less than l'Ci 10O m. A special r:asc of
the weak lapse rate is the inuersion, a conclition that has rvarmer uir ulrove
colder air.

100

f
I
Elevotion
lml

T 1aa T

-Temperoture ('C)+
a
FIGURE I I -2 Prevoiling
ond dry odioboticlopserotes.

During a supcradiabatic lapse rate the atmosphcric contlition.s are unsta-

blc; a subacliabaticand especiallyan inversion characrerizesa stablc atntosphere.
-I'his
can be demonstrated by depicting a parcel of air ar 500 m (sce l.'igurc
11-3). If the temperature at 500 m is 20"C. dr-rringa superadiabatic condition
the temperature at grolrnd level might be 30'C and at 1000 m it might be 1OoC.
\otc that this represents a change of more than 1"C/100 m.
If the parcel of air at 500 m and 20'C is moved uprr,-arclto 1000 m, rvhar
s'oulcl be its temperature?Remember that assumingaclabatic condirion. the
ltarcel r.r'ouldcooi 1"C/100 m. The temperatlrre of tl.reparcel ar I000 m is rhus
5'(. less tlran 20'C or 15oC.Thepreuailing temperarure(thc air surrounding --
thc parcel), horvever, is i0"C. and rhc air ltercel finds irsetf si.rrrounrlecl br'
coolcr uir'.Will it rise or fall? Obviousll , it will rise. since nlrnr.rir rirrs. \\'e
=-;ffi
ll Air Quality
-
>-*---
\
it\

/)
E ,--u
(r5')
c
o
E 5oo --.d-
(--,^-r^
20')
o

r0 rs 20 25 30
l e m p e r o r u r el L ,

A . S u p e r o d i o b o t i c c o n d i i i o n s (unstoble)

r 000 [-
E
c
l \
l
/@\
o
t--
( 20')
o
o 'S S
U i \\
\\
\\i. /

r0 15 2A 25
T e m p e r o i u r(e' C )
B. Subodiobo'c ondio
r rs {stoble)

c ds u b o d i o -
F I G U R Et I - 3 A p o r c eol f o i r m o v i n gi n r h eo t m o s p h e r seu; p e r o d i o b o toi n
botic prevoiling Iopse rotes.

is
then conclucle that once a parcel of air rrnder supcradiebatic cot]ditions
tli:placed upward. it keeps on going
similarly, if a parcel of air under super:rdilbltic conditittns is displaced
- (50(l m x [1/100 m]) -
downward, sa-vto ground level, the air parcel i: l()'C
25"C. ft finds the air around it a warm l0'C .rnd thus the cooler air parcel
i,f it could .upcrudiabf,tic conditions also
would iust as soon keep going dow-n
t'r ':c rnstabilin'. Supcradiabatic
pfomote the downward air m,rvement. adding
are characterized by a great deel ':: rclrcal air movement and
"tmosphetes and
turbulence, Since any upward or dorr'nrr.ard mO\.C:...::.:te nds to c()ntinue
not be damPened out.
'--::i -l Vf f\' stable sYstem.
The subadiabatic prevailing lapse rate is br c'--:'
< , -:: ::-.J. .1t 20oC. A tYPical
Consideragain,as in Figurc.il-1, a parcel of air r:
'l , . - : . J1 9 ' C a t 1 0 0 0 m .
subadiabaticsystem has a ground level temperetu:r : -
gg'r 'r < , : ^< (-. Ilut, hnding
If the parcel is displaced to 1000 m. it svill
it s'ill tall ngi': - : . : - . : : . f ,) i r l t o f o r i g i n .
thc :rir around it a warmer 10'C,
parcel were brought to grou''r : : : ; i . 1 1 .i 1r t 1 12 5 ' t . .
Sirnilarly, if the air
it rr":: ' --1 -: .. - i()() rr Thus
ancl hnding itself surrounded by 21"C air'
' .r - . . ( l 1 l (l l t . t l l t l i s
tIrcstrbacliabatics-vstemwouldtendtodampen
charactcrized by a limited vertical mixing'
'i
].1 \icteorolo!r- aird'\ir -\.ii-rr.'ernelt
ffi-
Thc move mcnt of ph-rmes fronr sntokestacksis governcd bt' the lapse rate
into rvhich the\':rre cmitted. as illustratcd bv Example 11.1.

lr.I

Problem A stack 100 m tall emits a plume at l() (-. The prcr';Lilinglapserates
are shorvn in Figure 1l-4. How high will the' pluntc ri.c (tssunting pcrt'ect
acliabatic cor-rclitions)?

?
: 200
C

eo
o
U
r00

0
19 20 2l 22
Temperoiure
{'C)
a
F I G U R EI l - 4 A typicop
l r e v o i l i n lgo p s er o t e

Solution N'lte that the prevailing lapse rate is subadiabatic to 2(X) m and an
inversion exists above 200 m. The smoke at 2A'C linds itsclf surrounclcd bv
colder (1f1.5'(.)air. and rises. As it rises, it cools. so that at 200 m it is 19 (
At atrout 22O nr. the surrounding air is at the same temperature as thc sntoke
fubout 18.-'C) and thc smoke cea-ses to risc.
a

An inversion is en er-treme subadiabatic condition, and the vertical air

movement rvitlrin an inr-ersion is aknost nil. Some inversions, calledsttbsidertt'e
inuersiotts, are due to the movement of a large warm air mass over cooler air.
Sr-rchinversions. n'pical in Los Angeles, last for several days and are resltonsible
for the serious air pollution episodes. A more common n,pe of inversion is the
radiatictrt inuersiort. caused bl the thermal raciiationof hcat to the atmosph('rc
from thc earth. Durinfa the night, as the earth cools, the air close to the ground
loses heat, thr:s causing an inr.crsion @igure 1i-5). fire polltrtior-rernrttcrl
during the nigl'rt is caught under this lid and does not esc:rpe until thc c:rrrh
warms sufficicntly to break the inversion.
In addition to inversions,seriousair pollution episodcslrc ulnro:t :rln ur.
'I'hese
accompaniecl bv firgs. tinv droplets of u'ater are clctrinrcntri in r$ () \\ .1\\.
" *WE it -ir QurC!t-r'

I
c

E
o
o
o
u

i
-Temperoiure-+
a
FIGURE I l-5 Atmospheric
inversioncousedby thermolrodiotion.

In the fust place, fog makes it possible to converr SO, to H,SO1.Second, fog
sits in valleys and prevents the sun from warming thc valley floor ancl breaking
invcrsions, often prolonging air pollution episoclcs.

11.2 I Major Air Pollutants

11.2.1 Particulates

Particulate pollutants can be classilieciby several means.

o Dust is clefined as solid particles that are

o. entrained by process gases directlr. fi0m lhe rnaterial being
hanciledor processed.e.g., coal. ash, and cement;
b. direct offspring of a parent material unclergoing a mechanical
operation, e.9., sawdust from r.voodworking;
c. entfained materials used in a mechanical operation. e.g., sand
from sandblasting.
. Dusts from grain elevators and coal-cleanir-rgplants t,vpifi. the last
class of particulate. Dust consists of relatively large particles. Ce-
ment dust, for example, is about 100 g. in ciiameter. (In air-pollu-
tion control parlance, a micrometer (pm) is often referred to as a
rnicron (p,). This usage is adopred here.)

. Afume is also a solid particle, frequenrh' a metallic oxide.

formed by the condensation of r.apors bv sublimation, distillation,
calcination, or chemical reaction processes. Examples of ftlmes
are zinc and lead oxide resulting fronr the condcnsatkrn and oxi-
dation of metal volatilized in a higl-r-tcmperaturcprocress.1'he par-
ticles in fumes are quite small. *'ith ciiantctersfrom 0.03 to 0.3 rr.
i i.2 Nlajor Air Pollutants

. An entrained liquid particle formed by the conclensation of a va_

por and perl.rapsby chemical reaction is called ?rmist. N{istsWoi_
cally range fron.r 0.5 to 3.0 p, in diametcr.
' stntke is made up of entrainccl solicl particles fcrrmeclas a result
of incomplete combustion of carbonaccous materials. Although
hydrocarbons, organic acids, sulfur oxides, and nitrogen oxicles
are also proc|-rccd in combustion processes,or-rlythe solicl pani_
cles resr.rltingfrom the incomplete combustion of c:rrbonaceous
materials are callecl smoke. snrokc lrarticlcs ha'e cliametcrs from
0.05 to approximately I g,.
. Finaily, ^ spra! is a liqr.ridparticle lbrrnccl bv rhe eromizarion of a
parcnt liquid. Sprays settlc out under gravifi,.

Approximate size ranges of the various t_vpesof air p.ll'tants are sho*'n
Figure I 1-6.

:T
-€ l:

Goses

l-
00001 000t .oot .ol .1 I l0
P o r t i c l es i z e ( m i c r o n s )
a .'A -
FIGURE I I -6 Definitionof oir pollutonts
by size.
i

l
11.2.2 Nleasurement of Particulates
I

The measurement cf particulates is historicalh' donc using tl-rebigb-uolume

{
sa?npler (or "hi-vol"). The high-volume samplcr (FigLrre I I _7) operates much
like a vacuum cleaner by simply forcing more than -l(rax)cubic mcters (70,000
ft3) of air through a filter in 2.1 hours. The anirlr-sisi: qravimerric; the filter is
weig,hcclbeforc and after. and the cljffert.nccir rltr .rnrt trl:rrcscollccted.
f
The air flow is measured b1'a small flo*' mcrcr. u:r,rlll' ca|brated in cubic
feet of air per minute. Because the filter gcts dinr tluring the 24 hours of
operation, less air goes through the lilter during thc i.rrrcr purt of tl-retest than
in the beginning and the air floq' firusr 1[]s1sfe1cbc rr.tcusurecl at both the starr
and end crf the test period and the valucs avcragcd.

ll.2

I)roblern A clean hlter is found to tleigh IO.OOg. \ficr 2+ hours in a hi-r.ol.

the filter plus dust weighs 1 0 . 1 0 g . T l . r c a i r' flou' :rt rlte start ancl encl of the
ll r\ir Qualitl'

test is 60 ancl 40 ftrlrninute, rcspecrivcl),. .What is

the particrilxte concentr:l-
tkrn?

Solutiorr

\\'ci.qhtof rl'rcpurriculutes(clust).. (10 l0 _ l0.t){))g x

l(\(,lL.g/g,
-O. l x l0,,g.g
,\r'crageair florv : (60 + 1U/2 - 59 lril'ri'

Tcrtalair throtrgh thc filrer.- 50 ltrlnrin x 60 nrin/hr. x

24l.tr/dltt. x I clav
- 7 2 , ( X ) 0f t r

: 7 2 . 0 0 0t i j x 2 8 . J x

- 2031Jnrr

Total suspcndeclpaniculates - (0.1 x 10., : +9 pg/m'

tr-g)/2038

F I G U R EI l - 7 H i - v o sl o m p l e r
I L2 Nlzrior;\ir Pollutants

The particulate concentration measureclin this manner is often referredi

to as total suspendeclparticulates (TSP) to ilifferentiate it fro:,'r othcr measure-
ments of particulatcs.
Another rvidely used mcasure ol paniculatcs in the environmental healtl-r
area is of respirable particulates, or thosc particulates that would be respired
into lungs. Thcsc :rre generally dehnecl as being less than 0.1 ir in sizc, ar-rclthe
'llhc
nleasurements are with stackecllilters. first filter removes onll' particulates
> 0.3 p, and the seconcl filter, havir-rgsmaller spaces,removes the small respirrr-
ble particulatcs.
The EPA has also recoguized that the measllrement of particulates can be
badll' skeu.ed if a few really large particles happen to fall into tl.resampler. To
get around this problem, they now measrlrc particles smaller than 10 pr,onll'.
Desigr-ratedsymbolically as PM,u,for "particulate matter less than 10 microns,"
this mcasure is r-rsedin the ambient air qualiq' standards.
Woodburning stoves are apparcntly pafticularl)' effcctive emitte rs of small
particulates, of the PM,n variery. In one C)regoncir,v,the concentration of PM,u
concentrations reached above 700 pg/mt, *4rcrpas the r-rationalambient air
clualiq.'standard (see below) is only 150 ptg/mi. Cities where the atmospl.reric
conditions prevent tl-re dispersal of u,'ood smoke havc been forced to pass
woodburning bans during nights wher.rthe conditions could lead to high panicu-
latc levels in the atmosphere.
Interestingly, no continuous particulatc measuring devices have yet been
developed and accepted. The problen, of cotrrse,is that the measurement must
bc gravimetric, and it is dillicult to construct a dcvice that continuously weighs
minute quantities of dust. Some indirect devices are used for estimating particu-
lates, the nrost notable being the nepbelonteter. which actuall_vmeasures light
scatter, the assumption being that an atmosphere that contains particulates
aiso scatters light. Unfortunately, clifl'erent sizes of particulates scatter light
differently and atmospheric moisturc (fog) also interferes with tire passageof
light, but this should not be measured as particulates.

11.2.3 GaseousPollutants

In the context of air pollutkrn cor-r1rol,gaseous polllrtants include substances

that are gases at normal temperature :rnd pre ssureas*'ell asvapors of substances
that are liquid or solid at normal tefirpcr.rturc and pressure. Among the gaseous
pollutants of greatest importance in ternrs of prcscnt knowledge are carbon
monoxide, hydrocarbons, hydrogen strlfide, nitrogen oxides. ozone and other
oxidants. and sulfur oxides. Carbon dkrxidc should bc added to this list bccause
'fhese
ol its potential effect on climate. ancl other gaseous air pollutants are
listeclir-rTabie 1 1- 1. Pollutant concentrxtions rlrc commonh'exDre ssedasmicro-
tr:rln: l)cr ctrbicmeter ( pg/nr1l.

1 1 2 . 4 ) l e a s u r e r n e not i G i t s c s

\\ lrilc the r.rnitsclf p:rrticulate measurcrrcllt arc cor-rsistenth'in tcrms of micro-

!rilnls per cubic r-nctcr, thc cxpresskrrr of tlie aonccntration of gasescan be as
 II lir Qualitv

ProPerties oJ SigniJicartceas Ait

Narnt litnnttln It/tporldrrce I'r'tlltttctrtt

dioxide
Sulfur SOz Colorlessgos, intense Domoge to proPertY,
chokingodor, highly heolth,ond vege-
solublein woter to
form sulfurous ocid
H2SO3
Sulfurtrioxide SO, Solublein woter to form Highlycorrosive
sulfuricocid H2SOa
Hydrogensulfide H,S Rottenegg odor ot low Highlypoisonous
concentrottons,
odorlessot high con-
centrotions
Nitrousoxide N,O Colorlessgos, usedos inerl.Not pro
Relotively
corriergos in oerosol ducedin combustion
bottles
Nitric oxide NO Colorless gos Producedduring high-
temperoture, high-
pressure, combus-
tion. Oxidizesto
NO,
Nitrogendioxide NOt Brownto orongegos Mojor componentin
the formotionof pho-
tochemicolsmog
Corbon monoxide CO Colorlessond odorless Productof incomplete
c o m b u s t i o nP.o i -
50nous
Corbon dioxide COz Colorlessond odorless Formedduringcom-
pletecombustion.
Greenhouse gos
I I.2 NlajorAir Pollutants

Properties of Signi"r',cance as Ait'

Intportonce Pollutant

Highlyreoctive Domogeto vegetotion

ond property.Pro-
duced moinlyduring
the formotionof pho-
tochemicolsmog
Somehydrocorbons
ore emifiedfromouto-
mobilesond indus-
tries;othersore
formedin fhe otmo-
sphere
Greenhouse gos
Depleiesozone in up-
per ofmosphere

either parts pcr million (ppm) on volume to volume basis or as micrograms

per cubic meter. l'he conversion from one to the other is

,l1 x 1000
Film': x ppm
A5

where ,44: molecular weight of the gas. This equation is applicable for concli-
tions of 1 atmosphere and25"C. For I atmosphere and 0"C (273.K), the consrant
becomes 22.4.

il.3

Problem A stack gas contains carbon monoxide (CO) at a concentration of

lO% l>y volume. \What is the concenrration of CO in pg/m.? (Assume 25"L end
I atmosphere pressure.)

Solution Since 1%by volume is 10,000 ppm, l09i bv r-olumc is 100,000 ppn-r.
\ i n c c t l t c m o l c c u l a rw e i g l r t o f C ( ) i s 2 8 . t l r e c r ) n ( . ( . l l l r : r t i oi n m i ( r ( ) i l r : l m \l ) e r
clibic meter is

28 x 1000 - 1 1 . 1x l O " p g l r n r
x 100,000
2L5
a
ll ;\ir Qualitl'

'l'he
earliest gas-mcasurementtechniques almost all irrvolve the use of a
btlbbler, shown in Figure 1l-8. The gas is literally bubblccl through the liquid,'
rvhich either reacts chemicalll' with the gas of interest or into rvhich the gas
is clissolvcd.Wet chemical tcchniques are then trscclto t-neasrlrethe concentra-
tion of thc rras.

Diffuser

a
FIGURE I I -8 A typicolbubblerfor meosuringgoseousoir pollutonts.

A simple (but now seldom usecl)br-rbblcrtcchnicNe for measuring SO2is

to bubble air through hydrogen peroxicle, so that thc lolkrwing rcaction occurs:

SO2+HrOr+H,SC),
'Ihe
amount of sulfuric acid formccl can be dete rn-rincclby titrating the solution
r.vith a base of known stfength.
One of the better third-generatior-lmethocls of nreasuring SO, is thc colori-
mctric pararosaniline method, in which SO, is bubblecl into a liqriid containing
tetrachloromercurate (TCM). The S(), and T(,1,1conrbine to fbrnl :r stablc com-
1rlcx.P:rrarosanilineis then addeclto this contplex. r.r'itlrwhicl-r it f<rrmsa cokrred
solution. I'he amount of color is proportional to thc S(), in thc soh-rtion,and
the color is mcasured with a spcctrophotontctcr. (Scc (lhaptcr 6 fbr amntonia
l]lcasurcmcnt-anothcr cxample of a colorirtrctric tcchni(Fle).
 '-'__--_-}
t
\
I L2 }la.ior '\ir Pollutants

11.2.5 N,leasurementof Smoke

Air pollutkrn has historicallv been associatedwith smoke-the clerker the smoke,
thc more llollution. We now of course know tl'ratthis isn't nccessarilvtrue ,
l)ut l'l'lxn),regulutiOtts(e.g., fbr municipal incinerators) are still \\'rittcn on tht:
basis of smoke clensitl'.
Thc clcnsity of smoke has firr many .veirrsbccrr measurcclon the Rirryle-_
trtnrttr scale, cleviseclin tlre late 1800s b1' Nlaxmiliun l{inglcmrLnn,l Frenclt
DmfCsGr of enginecring, mnning from 0 tirr rvhitc or tnulsl)xrent sntokc to 5
firr totally black opaque smoke. The test is concluctcclb1,holclinga carclsuch
as shorvn in Figure l 1- 9 and comparing the blacknessof thc curclto the smoke.
A flirly clark smoke is thus said to bc "Ringlemrnn.l," lirr cxarlplc.

FFFFFFM
ffi
hfrtrt-t1
ffi
ffi-fl
rit-1-1-t1 1-1
Frffi-fi--1

No.0 No. I No. 2

( o l lw h i t e ) (209i,block){ 4 0 7 .b l o c k l
FFf,*EM -
ffi
ffi
ffi ffi I
No. 3 No. 4 No. 5
{ 6 0 % b l o c k )( 8 0 % b l o c k ) l o l i b l o c k l
a
F I G U R EI I - 9 T h eR i n g l e m o nsnc o l e

1 1 . 2 . 6 Visibility
C)nc of the obvious effects of air pollutants is the recluctior-rin visibilitl'. Loss
of visibilify is often defined as the condition uhen. in bright clevlight, it is just
possible to iclentiS' a large obiect such as a bLrilcling.or at nigl-tt.to bc able to
see a moderately bright light. This is of course a Yaguc dcfinition of Yisibility,
but it is useftl, especially for dehning the limits ol t isibilin .
'
Reductions in visibility can occur due to natur:rl air "polltrtants srtch as
tcrpenes ftom pine trees (that's wh\- thc Smokel }{Ountains are snlokey) or
firrm human-produced emissions. Many cor-rstituentscan cause :lttcnuateclvisi-
bilin'. such as water droplets (fog) and gascs (NO,). but tl.re most effective
rccluction in visibility is by small particulates. Particulatcsreclucevisihiliry both
bl aclsorbing the light and by scattering the light. In the first case, thc liUht
does not enter the eye of the viewer, and in the sccortcl cxsc the scattcrilrg
reduces the contrastbetween light and dark objects.\lethematiclLll\-, the change
rn the intensitl. of a :rn obiect illuminated b1-a bcailt ol- intcrlsit\'1. a clistancc
.i 1i'()nlthc observer. is attenuated as
dI -ol
clx
 &*
i4i:

II Air Qualitl,
i{
wherc 1 - intensity of the light beam as viewed by the observer
.r : clistance from thc observer
(, : constant that takes into account thc atmospheric condition, often
called the extinction coefJicient

Intcgratccl, this ccltr:rtionrcacls

II\ : -ox
'n
\;/

rvherc1.l-istlreintensiwofthebeamwhenthedistlnccxapp:rllcl]cszcrtl.
'Whcn
tl-rcligi-rtintensity is recluced to about 2Yoof t]neunattcnuxtcd light,
rhis is rhe lower limit of visibility for most people. If this value is substituted
ir.rrhe above equarion, the distance r is then the limit of visibility, ./-", or

ln(0.02) : -rtLr

1.9
Lr: -

As a rougir approximation,'the extinction coefflcient is dircctl)' and linearl-v

proportional to the concentration of particulates (for atmospheres c()ntainir-lg
lcss rhan 70% moisture). An approximate expression for visibility is then

1.2 x lOj
Lr--T

rvhere .1.r : the limit of visibility, km

C : thc concentration of particulates, plg/m'
'lhe
coustant 1,2 x 10r takcs into account the conversion fhctor if /-u is in
kilomcters ancl (,'is micrograms per cubic meter. Remembcr that this is an
approximate relationship and shoulcl be used only for atmosphcres \!ith less
-,t'tu
ttttn ntoislurc.l

I 1.3 o Sources and Effects of Air Pollution

Unwantcd constituents in air, or air pollution, can have a clctrimental effect on
human health. on the health of other cfeatufes, on the valuc of property, and
on the qualiry of life . Some of the pollutants of human healtl] conccrn are
irrrmccl and emittecl through natural proccsses.For example, naturalll.occurring
particulates inch.rclcpollen grains, fungus spores, salt spral', smokc particles
fronr firrest lires. ancl clust from volcanic eruptions. (laseotts pollutants l'rom
natural sources inclttcle carbon monoxicle as a breakdorvn Prodtlct irl thc dcgre-
tlatio;r of ircrnoglobir].hydrocarbons in the form of tcrpcncs fr'rnl pitrc trecs'
hvclrogcn sr-rlficlcresrrlting from the breakclown of c1'steineatrd <lther sulfttr"
containing :rnrino acicls by bacterial action, nitrogcn oxidcs. atlcl tnethane.

L.
r11 Sourcesand Dft'ectsof Air Pollution

People-madesources of pollutants can be conveniently classi-fiedasstatk)n-

a4' combustion, transportation, industrial process, ancl solid-waste disposal
'I'hc
sources. principal pollutant emissions from stationary combustion pro-
cesses are particulate polh.rtants, as fly ash and smoke, and sulfur and nitro-
gen oxides. Sr-rlfuroxide emissions are, of course, a function of the amount of
sulfur present in the fucl. Thus, combustion of coal ancl oil, both of u'l-rich
contain appreciablc amounts of sulfur, yields significant quantities of sulfur
oxide.
Much of the knowledge of the effects of air pollution on peoplc comes
from the study of acute uir pollution episodcs. The two most fhflous cpisocles
occurred in Donora, Pennsylvania, and in London, England. In both episocles,
the pollutants affected a spccilic segment of the public-tl.rosc individuals
already sr.rfferingfrom diseasesof the cardiorespiratory system. Anothe r obscn-a-
tion of great importance is that it was not possible to blame the adverse effects
on any one pollutant. This observation puzzled the investig.rtors (industrial
hygiene expcrts), who were accustomed to studying industrial problems ttr
'l'oda\',
which one cor,rld usually relate health effects to a specihc pollutant.
after many years of study, we believe that the health problen-rs dr,rring thc
episodes were attributable to the combined action of a particulatc matter (solid
or liquid particles) and sulfur dioxide, a gas.No one pollutant by itself, ho*'evcr,
could have been responsible.
Except for these episodes, scientists have little informatiorr from s'hich
to evaluate the health effects of air pollution. Laboratory studies rvith anir-ttals
are of some help, but thc step from a fat to a person (anatomicalll' speaking)
is quite large.
Four of thc most difficult problems in relating air pollutior-r to health :tre
unanswered questions concerning: (l) the existence of thresholcis. (2) the
total body burdcn of pollutants, (3) the time versus dosage problern, and i+;
synergistic effccts of various combinations of pollutants.

Threshold. The existence of a threshold in health effects of pollutants has

been debated for many years. As discussed in Chapter l, there are sevcral
dose-response curves possible for a dose of a speci,ficpollutant (e.g.. carbor-t
monoxide) and the response (e.g., reduction in the blood's or1'gen-carning
capacitl'). One possibiliry is that there will be no effect on human nretabolisnt
until a critical concentration (the threshold) is reached. HoweYcr. some pollut-
ants can producc a detectable response for any finite concentration. Nor cltr
these cun'es have to be linear. In air pollution, the most likely closc-response
relationship for many pollutants is nonlinear, without an identifiable thrcshold
but also a minimal response up to a higher concentration, at which point the
response becomes severe. Tl-re problem is that for most polh-rtantsthc shapcs
of these curves afe unknown.

Totol Body Burden. Not the entire dose of pollutants comcs from air. fror
example, although a person breathes in about 5O p.g/day of leacl. the dailr-
intake of lead from water ancl food is about 300 l-tg/daS'.In the sctting r.ri rLrr
qualitv strnclarclsfirr lead it must therefore be recognized that most Of thc lcacl
intake is from food and water.
 .. .t
:
!i
ll Air Quality

V_e1susDoiqgg. N{ost pollutants require time to react, and the time

,firyr-e
oi contact is as important as the level. Thc' best example of this is the effect
of carbon monoxide. as illustrated in Figure l1-10. co.-reduces the oxygen-
carrying capacin.of thc blood b,vcombining with the hemogkrbin and forming
carboxvhemoglobin At abotrt 60% carborlthemoglobin concentration' death
rcsults from lack of oIvgcrl. The effects of CO at sublethal concentfations are
usuallv reversible. llccause of the time-fesponsc problem, ambient air quality
standlrcls urc sct ilt ntlximum allowable concentfations fbr a given time

r00
Deoth 500 mg/rn3
50 9q'lq -
N
.= Vomit
j
o
20
I O Om o / m 3
Heodoche
'o E t0
s 50 m3
o 5
ri 20 m3
o

.1
1 l0 100
time(hr)
Exposure
e
FIGURE l l-lO Effectof corbon monoxideon heolth.(Adoptedfrom W. Agnew,
Proceedings 4302, 153, 1968.)
of the RoyolSociety,

Svneroism. Svnergism is defined as an effect that is greater than the sum

:-
ciithe-pani. For example, black lung diseasein coal miners occurs only when
the miner is also a cigarette smoker. Coal mining b-vitsclf, or cigarette smoking
br. itself, will not cause black lung, but the synergistic action of the two puts
miners who smoke at high risk.
Tl.re maior target of air pollutants is the respiratory system, pictured in
Figure 1 I - I 1. Air (and entrained pollutants) enter the body through the throat
and nasal cavities and pass to the lungs through the trachea. In the lungs, the
air mor-es through bronchial tubes to the alveoli, small air sacks in which the
glastransfer takes place. Pollutants afe either absorbed into the bloodstream or
mor-cd out of the lungs by tiny hair cells called cilia, which afe continually
s$'eeping mucus up into the throat' The respiratory system can be damaged
bv both particulate and gaseous pollutants.
in rhe upper respiratory
Particles grearef than 0.1 g, will usually be car.rgl.tt
s).steman<Iswept or.rtby the cilia. Howevef, particles le ss thar-r0.1 pcin diameter
can move into the alveoli. where there are no cilia, and thcv can stay there for
a long time and cause d.amageto the lung. Droplcts of H,SO1and lead particles
rcprescnt the most serious forms of particulate matter in xir'
 'bo.n
I 1.3 Sourcesand Effects of Air Pollution
:ncv
Ltion
cnnt
ends
Adenoids
nary
tonsils
tillns
Tongue r the
Epiglottis
Lorynx
Ir o c n e o com-
510ns
Iy as
Ribs
pera-
Bronchus ever,
as an
clude
;sions
:arbu-

'mod-

Bronchiol ant is
Bronchiole cilio
rce of
Alveolus il/aste.
rning,
olume
Itants.
:arbon
FIGUREI I - I I of theAmericonLungAssociotion.)
system.{Courtesy
Therespirotory
rbons,

The effects of carbon monoxide are potentially deadll'. Human hemoglo-

bin (Hb) has a carbon monoxide affinity 210 times greater than its afirnity for
ox,vgen,and thus CO combines readily with hemoglobin to form carbox)'hemo- i been
globin (COHb). The formation of COHb feduces the hemoglobin ar-ailableto nviron-
carry oxygen, and this can cause death by asph)'xiation mit its
Ozone (Or) in the atmosphere is an eye irritant and can cause damage to rble ms
materials such as rubber in automobile tires. Ozone is usuall,va part of ufban
air :rnd photochemical smog. )end so
A number of diseasesare thought to be causally related to air pollution, litored.
including lung cancer, emphysema, and asthna. There is overwhelming evi- cluding
dence that air pollution can increase the risk of these diseases,especiall,vwhen {siness,
ricd s_ynergistically to cigafette smoking, yet the actual causc-:tnd-cffectrelation-
eathing
rhip is not medically pfoven. It is incorrect to asseft that aif poilution, no
nretter how bad (or cigafettes, for that matter), cause lung c1lncer or other
:c:pirltory cliseases.
Sulfur dioxide is pefhaps the mosr insidious air pollutant. lt acts as an
rrrirlnt ancl restricts air flow an(l slows the action of the cilia. Silce it is highly
s1;luble. it sl-rould be readily rcmoved b-V the mttcus nlembr11ne,bttt studies
har-c shos'n that it can invade the deep reaches of tfre lung b1' first adsorbing
ll Air Quality

onto tinY particles, thcn using this tfansport to fcach the deep lung-a classic
case of syncrgistic action.
'I'he
amount Of sulfur Oxicle producecl can be calculatcd if the sulfur
content of the fuel is known, as thc fbllowing example illustratcs.

Problern During a two-wcckl()tlg nlaior air polltrtiol episoclc it-tLonclon in

1952, tn estirnated 25,000 metric tolls of coal rv:rs burnecl tl-rtt l-raclan average
sulftrr content of about 1%. "I'hc mixing clepth (hcight o1 tl-tc itlr-crsion ll1'cr or
citp over the ciry, which preventecl thc pollutallts fiom escallitrg) was about
150 m, over an areaof 1200 kmr. lf initiall)'there was no SC),in the atmosphere
(a conscrvatlve assumption). $.hat is the cxpected SO'l conccntration at the
cnd of two rveeks-i

Solution LIse the "box mociel" for calctrlating the col-lccntfirtk)n. That is,
consicler the volume over Lonclon a black box, ancl tlse the well-w'orn matcfials
balance equation:
-l
I reteof So, Iratc of S(l,l Irateof sorl
Ia ccu u u u fm]: I t^ ]- L otrl' l
- [ r " , . ' . , i : < l I' - | r ' r t c , , f s o I'
I PR()Dl CEI)I L( ONstMED,I
-I'he
rate of SO2 out \\'as zero, since nothing escaped from under thrs haze
boocl. T:rle rate producecl and consumcd is als<-rassurned to be zero if it is
assumedthat suifur oxiclc was not creatcd gr clestroyedin thc atn-rosphere.The
rate of SO, concentration increasing in the box is constant, or

I rateof So, I -- -o+o-o

Iaccur.tul-raol [ ' * ' , i i t " ' ]
dA
dt

A - Ao't kt

where ,4 : the mass of SO,.

The sulfur emitted is calculated as : 25,000 metric tons of coal burned
per weck x o.o4 - 1000 metric tolls of sulfur emitted pcr rveck. Sulfur has
an atomic weight of 32 and sr-rlfurdioxicie has a molecular rveight of 64. The
s u l f u r d i o x i c l c e m i t t c d p e r w c c k i s ( 6 ' i l - 1 2x) 1 0 0 0 - 2 0 0 0 r n c t r i c t o n s p e r w c e k .
If the initial concentration. ,'1,1,is ltssttmed to bc zero,

2000 (tonsh.eek) x 2 n'ccks - 1000 metric tons of SO,

accumrtlated in the atmosllhere over Lonclott

I 1.3 Sourcesand Effects of Air Pollution

The volume into which this is mixed is

150m x 1200km'zx 106m2/km':180,000x 106m3

The concentration of SO, at the end of two weeks shoulcl have been

4000 metric tons x 106g/metric ton x 106pg,/g

= 22'OOOlt'g'/m.
180,000 x 106mr

The actual peak concentration of SO, during the 1952 London episode was less
than 2000 pg/m3. Yet the calculation above shows more than l0 times that
value. Where did all the SO2go? The answer lies in the assumption used in the
calculation that no SO, was consumed. In fact, there is a continuous scavenging
of SO2from the atmosphere by contact with buildings, vegetation, wildlife, and
human beings. Most important, sulfur oxides seem to be a major constituent
of poody buffered precipitation, more commonly known as acid rain.

,|.3.,|
I Sulfur and Nitrogen Oxides and Acid Rain

One way in which SO, is removed from the atmosphere is the formation of
acid rain. Normal, uncontaminated rain has a pH of about 5.6, but acid rain
can be as low as pH 2 or er.en below. Acid rain formation is a complex process,
and the dynamics are not fully understood. In its simplest terms, SO, is emitted
from the combustion of fuels containing sulfur, the reaction being

hrar
5+(J,--'-.-..-'--'-5(J,

SOr+o:99!soo
SO3+H2O+H2SOa

HrSOl is of course sulfuric acid. Sulfur oxides do not literally produce sulfuric
acid in the clouds, but the idea is the same. The precipitation from air containing
high concentrations of sulfur oxides is poorly buffered and readily drops its pH.
Nitrogen oxides, emitted mostly from automobile exhaust, but also from
any other high-temperature combustion, contribute to the acid mix in the
atmosphere. The chemical reactions that apparently occur with nitrogen are

N2 + O? ----------+
2NO

NO+01+NOz*Oz

NO2+Or+H2O+2HNO3+O'

where HNO, is of course nitric acid.

The effect of acid rain has been devastating. Hundreds of lakes in North
America and Scandinaviahave become so acidic that they no longer can support
fislr lif'e. In a recent stud1. of Norwegian lakes, more than 7O% of the lakes
lt Air Qualit-v

having a pH of less than 4.5 containecl no fish, wl]iie nearll'all lakcs rvith a pH
of 5.5 ancl above conrainecl fish. The krrv pII not onh' afTectsfish directlr-, but
contributes to the releasc of potentially toxic metals sttch as aluminum, tl-tus
m a g n i f y i n gt l r c p r o b l en r .
In North Amcrica, acicl rain has alrc:rd1'wiped out irll fish anclmany plants
i1 50% of the high motrr-rtein lakcs in thc Aclirttucllcks.Thc pl1 in manv of thest:
lakes has re:rchccl strch lcvcls ol :tciclit. as to rcplllcc the nlltivc platrts with
acicl-tolerant t-uatsof ltlg,ec.
'l'he
clepositiolt of atfnosphcric acicl on fieshwatcr xqtlatic s.Vstems
r
promptecl EPA to suggest a limit of from 10 to 20 kg S(1. Pcr hcctarc l)cr ,vcar.
If "Newton's law of air pollution" is trsccl (what goes tlp lntrst conrc clown). it
is easy to see thtrt thc amount oi'sulfirric ancl nitric oxidcs emitted is vlstlv
gfeater than this lin-rit. Fof cxample, iust fbr the statc of Ohio alonc, the total
a n n u a l c m i s s i o n s r l r e 2 . ,xi t 0 ( ' m c t r i c t o n s o f S O ,1 l e r 1 ' e a lrf.a l l t h i s i s c o n v c r t e d
to SOI: and is clcposited ot-t thc stirte of Ohio, the t()txl would bc -160 kg pcr
hectare pcr t'ear.'
But t.tot all of this sulfur falls on thc folks in Ohio, and much of it is
exportccl bv the atmospherc to places f;rr away. Similar calculations for the
sulfur emissions for the northeastefn United Statcs indicates that thc fatc of
sulfur emission is .l to 5 times greater than the rate of deposition. Whcrc docs
it rll go?
The Canadianshave a ready and compelling answer. Thel'have for many
vcer: blamed the Llnited Stateslbr the fbrmation of most of the acid rain that
inrldcs acrossthe bordcr. Similarly,much of the problem in Scandinavil cln
ltc trrccd to the use of tall stacks in Great Britain and the log'land crlttntrics of
contincnrel ELrrope. For 1'earsBritish industry simplv built taller ancltallcr stacks
r\ r nrcthod of air pollution control, reclucing the immcdiatc ground level
c()ncentration.but emitting the samc pollutants into the l'righeratmosphere.
l'l'rc eir qualin' in the United Kingclom improved, but at thc expcnse of ecid
rein in othcr parts of Europe.
Pollution across political boundaries is a particularll' difficult rcgulatory
problcm. The big stick of police power is no longer availablc. \\rh-vs/:oz1d thc
[.K sorn'about aciclrain in Scandinavia? Why sbotrld the Germansclean up
rhc Rhinc bcfore it flows through The Nctherlands? rJfll'rysltttt.tld Israel sttlp
teking, nrore than its share of watcr out of the Dead Sea, q'hich it supposedll'
:h:rrc: s'itlr .lorclan?Laws are no longer uSeftil, and threatcnecl fctaliatioll is
unlrkclr. \\'l-rut fbrces are there to cncourage these countries ttl clo thc right
thine-i Is thcrc such a thing as "international ethics"?

Smog
11.3.2 Photocl-rernical

- { . n i n t l ) ( ) r r . u t t u 1 - r p r o a c ht o c l a s s i h c a t i o n o f a i r p o l l u t e n t s i s t h l t t o 1 - 1 r l ' i l / r r l n ' l l . t c l
set'rttrtlrtn prtlltttttttts. A primaq'pollutant is defincd as onc thllt is ernittecl as
suc6 to thc lrtnrosphere. s'hereas sccondary pollutants lrc ltctttallr' procluccd
in tltc etr]1tr:ltltcrc lt\. chcnrical rcactions. Thc comltOt-tcllts o1'lttttonl(lbilc cx-
'fl-tc
hur.rst are llufticulxrlv important in tl'rc fbm-ratiot-t o1 scconclan' polllttltrlts.
I 1.3 Sorrrcesnnd Effects of Air Pollutiott

of secondary
well-knorvn ancl mttch ctiscusseclLos Angelcs smog is a case
Tablc ll-2 lists in simplificd form some of the keY
pollutant formation.
rcactions in thc formation of photocl-remical smog

'a

+ Light

+Oz
Moleculor
oxygen
+NO NOz + Oz
+HC HCO"
Hydro- Rodicol
corbon
+Oz HCO3"
Rodicol
+HC Aldehydes,ketones,Ptc.
+NO HCO? + NO2
Rodicol
O: + HCO?
nitroles
PeroxyocetYl

formed in the
The reactton sequence illustrates how nitrogen oxides
conbusti0nofgasolincandotherftrelsan<lemittecltotheatmosphereareacted
emitted as such from
r4ron bv sunlight to vielcl ozone (O,), a compound not
pollutant. ozone in turn reacts with
soufces anclhence consrclereda secondary
compounds that includes aldeh,vdes. organic
hydrocarbons to fbnn a series of
The atmosphere can be viewed as a huge reaction
acicls,anclepoxy compouncls.
vesselrvlreretnne$.c()mpoundsarebeingformedwhilet;tlrersarebeingde-
stroyed.
Figure 1 1 - 12
The formation tlf photochemical smog is a dynamic process
thc components vary
is an illustration of how the conccntrations of some of
Note that as the moming rush hour begins the NO levels
ct-rring thc clav.
increase,followctlquicklyb,vNOr'Asthelatterreactswithsunligl.rt'Otand
otheroxi(lantsareproduced.Tlrelrydrocarbonlevelsinrilarlyincreasesatthe
beginning of the day ancl then drops off in the evening'
a mystery fof
The reactions involvecl in photochemical smog remaincd
high ozone levels As
rnanj' -vears.Particularly baffling was the formation of
:ecrrf'romthefirstthreereactionsinTablell-2,foreverymoleofNO'reacting
NOt is created from
r() nllke atomic oxvgen and hence ozollc, one mole of
All of thesc rcactions are fast so thal if these arc the
rcirction \\'ith the ozonc.
to
()ull' rertcttolls occtlrrllrla in photochemic:rl snog, it should be imp<lssible
c()llcclltrJtio's build
brrilri Lr' high .z.ne lcriels.Ho*', then. c'ulcl tirc ozottc
t o s 1 1 ql 1 l t i u . l r l c r c l s - a
II ,\ir Qrralitl'

1c
o

e
C
o
- / \.i
3 NO.
/
.\
i\

I Norztrr\,' i

\2 6 12 612
midnighl noon P.M. midnight
a
F I G U R EI l - 1 2 l o gd u r i n go s u n n y2 4 ' h o u rp e r i o d .
F o r m o t i oonf p h o t o c h e m i csom

( ) n ( . x n s w e ri s t l r a t N O ( ' n t e f si n t ( )o r h ( ' r r c x c ( i o n s c. t p c t i . i l l l s ri t h v a r i t - r t t s
hvclrocarbon rxclicals,ancl thus allows excess ozone to accumulate in the atmo-
sphere (the 7rh reaction in ]'able 1 I - 2). In addition, some hYdrocarbon radicals
rcact with molecular oxygen and also produce ozone'
'I'lie
chemistry of photochemical smog is still not clearlv ttuderstood This
r.vas$,itncssecl b-V the atiempt to reduce h-vclrocafbon cnlissions to contfol
used
ozone lcvcls. The thir-rking was that if HC is not aylihtrle. ther O, n-ill be
tO oxiclize NC)to NO., thus using the available ozone . Unlirrtrrnitelv, this control
strategl. rvas a failurc, ancl the answef seems to be that all primarl polltttants
involvecl in photochemical smog formation lnust bc controllecl'

I 1.3.3 Ozone DePletion

()zone (o,) is an eye irfitant at usual urban levels, but ufban ozone should not
the
bc confusecl with stratospheric ozone which occurs 7 to 10 miles above
(lhlo-
e.irth's Srtrface. Stratospheric ozone acts aSan ttltraviolet radiation shield.
(rfluorocarbclns (CFCs), emitted mostlY from rcfrigerati()11Lrrlit\end spral'cans,
as
can appxfently alter this shield and increase the risk of skin c:lncef as well
change global ccology in unpredictable w:r1.s, itlclucling contribttting to
global warming.
Tu,o of the most impoftant CFCs are tfichlofofltlofomethane, cFCl,, and
clicl-rlorodifluofomethane,CF-2Clr, both of which afe ine ft irnd nonw:rter soluble,
'fhe,v
and therefore do not wash out of the atmospl'rere. drift into the uppef
atmosirhefe and are eventually destrol,ed by shonr"'ave solar racliation,releasing
'fhe
chlorine. which can react with ozone. cleplction of ozone can allow the
rultr:rviolctracliation to p2rssthrough r-rnimpcdccl,ancl this clttt l-t:tvcil serlotls
potcntial cff'ect On the ir-rcidenceof skin c21ncef.whilc basking in the sun is
r-rotu go,,cl iclca in the lirst plaCe. cloing so n'hcn thc ozone laYcr is ttot effcctir-e
in screciling Ottt rnttch of thc ultravitllct raYsis cvcll lll()rc risk\ '
1 I.3 Sources ancl EtTectsof Air Polhltiou

.l.3.4
I Global \\rarming
Thc earth acts as a reflcctor to the sun's rays, receiving tl-reradiation from the
sun, rcflecting some of it into spacc (callecl atbedrl, and aclsorbing the rcsr,
only to reracliate this into space as heat. In cffect tl're earth acts :ls a \\,1rvc
converter, recciving the high-cnergy, high-freqr.rencr.radiation fronr the slr]
and converting most of it into low-energy, low-frcclr.rencyhcat to be racliatecl
back into spacc. In this manncr, thc eafth maintains a balancc of tcmpcrattrre,
so that

ttr
I energyfiom rhc snn | _ | .n..gy retliate,d.back,,,.1rr..l
LtNJLolrl']
unfortunately, some gases such as methane (cIIr) and carbrn clioxicle
(CC)) adsorb radiation at wavelengths approximatell, the same as thc I'reat
racliation tn'ing to lind its way back to space. Becausc the racliation is aclsorbecl
in the atmosphere b1.these gases,the temperature of the atrnosphere iucrc:rscs,
heating the eartl-r.The system works exactll. like a greenhousc in that light
energy (shortwave, high-fieqr.rencyradiation) passes tlrrough the grcenhouse
glass, but tl-relong-wavelength, low-frequency heat radiation is preventcd from
escaping. The gasesthat adsorb the heat eneffry radiation are propcrly referrecl
to as greenbouse geses since they in effect causc the earth to heat up just like
a greenhouse.
Altirough it is fairly easy to measure the concentrations ol' greenhouse
gasessuch as CO2, CHr, and NrO, and to show that the levels of these sascs
have been increasing dr.rring the past 50 years. it is another mxtter to argllc
fiom empirical evidence that the earth's temperatrlrc is actuallr incrcasing.
'fhe
temperature of the earth undergoes continual change. rvitl-r fluctuation
frequencies ranging from a few years to thousands of years. Er-cn if it wcre
possible to measure accurately the earth's temperature, there r,,rruld be ncr
proof that the change is being caused by the higher concentrarion of the
greenhouse gases.
I'here seems to be growing consensus. l-rou..cvcr,that cvcr-rthougl-rit is
not possible to prove without doubt that global warn-ringis occurrin!], the nct
eff'ect can be so devastating to the earth that it woulcl be impmclent to sin"rply
sit back and wait for the irrefutable proof. 81' tl-ren the change coulcl Lrc so
immense thar rhe effect might be irreversible.
The most remarkable thing about global temperature ntight bc that it has
been so constant over millions of years. Somehow the eartl-rhas been able to
develop the thermal conditions suitable for the creation ar-rdsupport of life.
speculating on this idea, James Lovelock suggestcd the Gaia hrpothesis, that
I
the earth is actualll' a single entity* (mother nature), q'l-rich lives mucl'r like an1.
other crcature and has to adapt to changing conclitiorrs as u,cll us to ligl-rt off
cliscases.' Iite name Gaia comes from the Greek namc lirr tl'rc nr.rrtr-rring
gocldcss. sonre Gaians h:rve interpreted this notion in its broaclcst and most
carth
I
spiritual sense. taking the vielv that tl-rccarth rcallv is one organisnr.albeit ar-r
rtnusualone. and it has manv of the characteristicsof other orgenisnrs.()thcrs
II Air Quality

(ir-rcluclingJames Lovel<lck,who has been a little en-rbarrasscdabout this Gaia

br-rsincss)sce the hvpothesis as nothing but a feeclback-rcsporrsc moclcl and
do not ascribc mysticism to it.
Ilut suppose humans are simply one part of a wholc living organism, the
cxrth, much like brain cells are a part of the ar-rimal.If this is trLle, the n it nrakes
's
no scnsc to clestro)'one own bocly, anclthercfore it makes no scllsc lirr hr.rmans
to clestroy thc rcst of thc creatures that co-inhabit the earth. To think of tl-rc
carth as a living organism suggestsa spiritual rather th:rn a scientific ap1'rroach,
especiallvi1 it is taken literally.
If rve accept this notion, some interesting extensiolls cillr restrlt. ()ne
coulcl spcculatc (irnd this is pure whimsy!) that the earth (C;aia)is still clevekrping
and is goir-rgthrougir adolescent stages.Most notably, it h:rs not scttlecl on the
carbon balirnce. Millions of years ago, most of the carbon on eartl-rusecl to bc
ill the atmospherc as carbon dioxide, and thc prepondcrance of (.O, Irromotecl
tl-re rlcvclopment of plants. But as the plants grew, the)' soon sturtecl to rob
'l'his
thc atmosphere of carbon dioxide, replacing it with ox).gen. changc in
atmospheric gasespromoted the growth of animals, whicl-r convertecl the ox_r'.
gen back to carbon clioxide, once again seeking a balance. Unfrrrtunatcl_v,Gaia
nr:rclcu rnistakc and clid not count on the animals d1.ingin such hugc numbcrs,
trappir.rgthe carbon in deep geologic deposits, which eventr-rallybecame coal,
oil. ancl natural gas.
How to get this carbon out? What is needed is some semi-intelligent being
rr ith opposable digits. So Gaia invented humans! It can thercforc be :rrgued
that our sole purpose on earth is to dig up the carbon dcposits as rapidly as
1-rossiblc and to liberate the carbon dioxide. This is the long-sought-for"meaning
'
oi lifc.
Lrnfortunately, Gaia again messed up and did not count on the humans
bcconring so grrolitrc and destructive, and especially clid not collnt on humans
-l'l-re
invcnting nuclear power, which eliminates their sole purpose for existing.
shecr numbers of humans (especially if they are not going to dig trprthe c:rrbon)
bccome a problem, much as a pathogenic bacterium causes an infection in an
orglnism. It is not a coincidence that the growth of the l-rumanpopulation on
carth is not at all unlike the growth of cancer cells in a malignancl'.
So next (iaia has to limit the number of humans, and sl-rervill do so by
der-eloping antihumatics" (as in antibiotics), which will kill ofT a si-rfficicnt
numbcr of humans and once again bring the earth to a propcr balance. The
increase in highh' rcsistant strains of bacteria and vimses ma1' be the flrst
indications of a general culling of the human population.
Ihe application of the Gaia hypothesis to environmental ethics leads to
existentialism-the notion that life is meaningless (except as a.burner of f<rssil
fucl) and that onc should not concern oneself rvith the environment. Grim stuf1.

I I .3.5 Other Sourcesof Air Pollutzrnts

Nitrogen oxicles are fbrmed b,v the thcrmal lixation of atmosphcric nitrogcn in
high-tcmpcratllre. processes. Accordingly, ah-nost any combr.rstion oper:rtion
rvill produce nitric oxide (NO). Other.polhrtants of.interest from combustion I
J
I I . 3 Sourcesnnd Eftects of Air Pollution

processcs are sttlfttr clxicles,organic acids. aldellr-des. ammonia. ancl c:rrbolr

'l'hc
monoxicle. amount of c:rrbon mOnoxidc cmitted relatcs to the clhcicrlcl-
of the combustion operation, that is, a more eflicier-rtcombustiort opefatiorl
will 6xiclize more of the carbon pfesent to carbon dioxide , redttciug the enlotlllt
of carbon mt>noxiclc emitted. Tl-rc quantity of sulfur oxides emittcd tlepencls
entirel)' on the tmount of sulfur in the fuel. Of the ftrels tlsed in stationan'
coml)ustion, coal contains the largestfraction of sulfur while natural gas contrtins
practically r-rosulfirr. As an added advantage,the particulate emissions from tht:
conlbustion of natrtral gas are almost nil.
'Irans;rortation
sources, particulafly automobiles using the internal com-
bustign cngine, constitutc a maior sonrce of air pollution. Particulate entissittt-ts
fiom the automobile include smoke and lead particles, the lattef usually as
l-ralogenatcclcompounds. Smoke emissions. as in any other combttstion opera-
tion, afe cftleto the incomplete combustion of carbonaceousmaterial. l{owcver,
leacl emissions relate directly to the addition of tetractllyl lead to the ilel as an
antiknock compouncl. Gaseouspollutants from transpoftation Sourcesinclucle
carbon monoxide, nitrogen oxides, and hydrocarbons. Hydfocarbon emissions
result fiont incomplete combustion and evaporation from the crankcase, carbu-
r c t o r . l n d g a s o l i n ct a t l k .
Pollutant emissions from inclustrial processes reflect the ingenufty of mod-
em industrial technology. Thus, nearly every imaginable form of pollutant is
emitted in some quantify b-v some industrial operation.
Although solicl waste disposal operations need not be a ma.ior source o1
air pollutants, many communities still permit backyard burning of solid waste.
other comrnur-lities use incinefators for solid-waste management. Burniug,
rvhethcr in the backyarcl or in incinerators, iS an attempt to reduce thc volume
of waste , but may produce instead a variettt of difficult-to-control pollutants'
Inefhcient systems conffibute to many undesirable odors, as weli as cafbon
monoxicle, small amounts of nitfogen oxides, organic acids, h-vdrocarbons,
aldchl'clcs, and smoke.

.l.3.6
1 IndoorAir

A stickt. problem for thc Environmental Protection Agency (EPA) has been
ctxrtr<il of incloor air quality. Does EPA's mandate include the indoor environ-
ment. and sh<tr.ridit in effect become a health agency, or should it limit its
concefn to outdoor air? Pragmatically, if EPA does not address thc prohlems
of ir-rcloorair, no other federal agency seems ready to do so.
Incloor air quality is of importance to health simplv because we spend so
mr.rchtime indoors ancl the quality of the air we breathe is seldom monitored.
Cgntaminatecl indoor air can cause any number of health problems, including
c\'e irritation, headache, nausea, sneezing, dermatitis, heartburn. drowsiness,
'I'hese
:rnclmlnv othci slmptoms. problems can arise as a resrtlt tlf breathing
ir:rrnrfirl oollutants such as
. lsbcstos-fiom fireproofir-rgand r-invl floors
. (.elbon monoxide-from smoking. space hcaters,stovcs
. Formalcleh-vdc-from carpets, ceiling tile , paneling
w II '\ir Qualitl'

. Particulates-from smoking, Iireplaces, dusting

. Nitrogen oxides-from kerosene stoves, gas stoves
. Ozone-from photocopying m:rchincs
. Radon-diffused fr<tm the soil
. Sulfur clioxide-from kerosenc heaters
. Volatile organics-from smoking, paints, solve,rts, cooking
Although thc air exchange and cleaning in oflice buildings aud man\'trparrments
is controlled, private residencesusually depencl on natural venlilariotr to provide
air exchange.
Most l-rousesue in fact poorly sealcd, and air leakage takcs placc at many
locations including through doors and windows, exhaust vents, ancl chimneys.
In warmer weather some homes of course have forced ventilation. with rvl-role
house fans or individual window fans.
In calculating the ventilation of any enclosure such as :r home or office,
engineers use the concept of air change, defined as
Ll
n--
V
where .4 : number of air changes per hour, hr I
q- flow rate, m3lhr
volume of enclosure. m3

ll.5

Problem A small room is to be used for a copy machine, and there is concern
that the ozone level may be too high unless the room is ventilated. 'l'he volume
of the room is 700 ft3, and it is recommended that the numbcr of air chanscs
per hour be 30. What flow of air must the fan deliver?

Solution From the above equation,

fan air handling capacity : 30/hr x 700 ftr : 21 000 Ftrlhr

The emission of indoor air pollutants can be handih' anallzccl using the
"black box" technique, mainly becausean enclosure literalll,is a box. Pollutants
are emitted within the box and are completely and idcally mixed. while clean
air is brought in and contaminated air is flushed out. The matcrials balance in
terms of the pollutants is

I rateof I [ ,",. or I f ."t. ,',r I

-
i potlutants | : I potlutanrs| | ponutantsI
L A C C T ]MU T A T
L ED rN
I I Lour i
f ,at.,,f I I r .r r ( .( ,rI
-l p o l l u t a n t s| | p o l l t r t . r r r rI .
PRODUCET)I , ( )\sl \lr:t)
I | |
I 1.3 Sourccsand Effectsof Air Pollution

If steaclystate is assumed, then the first term is zero. The second temr can be
assumed zero if the incoming air is clean, and since the pollutants are not
consumed, the last term drops out. Hence,
- 0
0 - 0 lrate OUT] + [rate PRODUCED]

l'hc rate ol'pollutants leaving is equal ttr

Q: CAV

rvl-rerc Q : rirtc tlf pollutant leaving the room, mg/hr

(,' : concentration of pollutants in the room, mg/mr
A - ir change rate, number per/hour
I volume of tlte enclosure,m'

Thc ratc of pollutants being produced is called the source strengtlt, s,

of pollutants emitted per hour. The conccntration of
expresseclas n-rilligran-rs
the polhrtant in the room and in the exiting air is
6 : g/(AV)

il.6

Problem smokers in a room (10 ft x 10 ft x 8 ft) are smoking so thirt there

is on avcrage one cigafette burning at all times. If the emission ratc of a cigarette
is 86 mg/hr of CO, and if the venti-lation is 0.2 change per hour, what is the
level of CO in the room?

Solution

C : (86 mglhr)/(800 ft1 x 0.2/hr) : 0-537 mg/ft! :: " .:

'Ilrisconverts to19,OOO
1tg/m3.Isthisaconcentrationthatwouldlleof cgncern?
(Refer to Figure 1l-10, on page 338.)

If the pollutant is decaying or being removed by adhering to surfaces.

,,CONSUMED" teffn cannot be assumed to be zero. 'fhe decaY or
thcn the
removal of the pollutant can be assumed to be flrst order, or pfoportional to
the concentfation in the enclosure. Similarly, if the ventilation air is not pe rfectl,v
clean and contains some of the pollutant, the "IN" term cannot be zcro. The
steady-stateequation then must read
-
0 : lrate IN] - lrateOUT] + [rate PRODUCED] frate CONSIIMED]

O--C,"4V-CAV+S-KCV

of

,\/t'+ c,,A
1+K
II Air Qualitl'

whcre (,I rmbicnt air quality, air usecl for ventilation' mg/n-rl
4 - air change rate, per hour
I '
volurne of enclosure
concentfation in the enck)sure, or exhltrtst c()llcclltrltti()n,
mg/mr
sortrce stfength, mg/hr
rate of clecay constant, Per hour

ot]c of thL. most insiclious indoor air pollut:rnts is sccontlan' smrlke trom
smoking cigarettes ancl pipes. Most of the particulates in lt cig:trettc are cmittcd
int() thc room rvitl]ottt being inhalecl by the smoker, ancl thcse arc thcll inhalcd
of
b-v cr-enone elsc in the room. cigarette smoke also contains l-righ amounts
co. anctu,hen scveral persons are smoking in a roont, the co level can become
higl-renough to affect performance. One of the smallest roonts wc commonly
(,o level in
live in is ollr car, and cigarette smokers can signifrcantly affect thc
a cer. Sntokers exhale high levels of CC) even rvhen thel' afe not smoking. and
this hes beer-rblamed for the "sleepy driver syndrome" in commutef cafs.
_\nother impoftant and troublesome indoor llir ptllltttrnt is rttdttn,ir natu-
rall| cI-rlitteclgas entering homes through the basenlcnt, well wltcr, and even
buildir-rgmaterials. Radon and its radioactive daughters afe'I'he part of the natural
clecaYchain beginning with uranium and ending with lead. decay products
of redon-ltolonilm, lead, and bismuth-are easil-vinhalecl and c:rn reaclilylind
rhcir $-uv into lungs. The most important health eff'ect of radon thereiore rs
lung cancer. Raclon control is discussed further in Chapter 14'
-l'hcre
are no effective means of correlating the it-rl-ralationof radon gas
lund inciclence of lung cancef, and all studies depend on \rell' high exposure
ftrres strch as to uranium miners. Retatively speaking, however, the risk of radon
in thc home is considerable when compared to other potcntial sources of
c:lncef. Because radon is a carcinogen, thefe is no threshold, and therefore
rherc is no "safe level" of radon in the home. Nevertheless, the EI'A suggests
thet resiclenrsliving in homes that contain 4 pci/L (pico Curies per liter) due
r() r:rclon should consicler taking corrective action, and at 8 pci/L, such action
is rccommended. Mitigating action usually involves the sealing of the basement
end othcr soil contact areas, and the ventilation of basements to prevent the
nrdou ges from seeping upstairs into the living quafiers'
It is estimated that the risk of contfacting lung cancer due to living for
-()
\.cars ili a house containing 1.5 pCi/L is about 0.3 perccnt.i This is a high
risk sr'licn comparecl to other regulated carcinogcns, which arc in the range of
1 x 10 ' percent. Raclon exposure in fact ranks as the llrst potential problem
ir-rEPA s list of problem areas,with an €xpectation of bctrvcen 5000 and 20'000
Iung cancers annually from exposure to radon and its progeny in homes'
Although this may seem to repfesent a major problcm, tl-rerisk of harm
b}' raclon still pales when compared to the voluntary risks u'e routincl)'impose
on ourselves, such as clriving cars, drinking alcohol, ancl snloking. In fact, living
lll of onc's life in a homc with between l0 anct20 pCi/L rcpresentsan cquivalent
ri:k ol :rttoking,oltc 1'lackof cig,arettcspcr dar '
 1l 4 .\ir Qualitl' Standards

1 1. 4 A i r Q t r a l i n 'S t a r r d a r d s

IIistOricallr,,locltl commttnities havc been afiaid to enact strict ilir polltttion

orclinanccs ftlr fbar of clrivilg arva.vindustry. While there are cheaprcretlcl less
rcstrictir.elocttiot"ls.inclustrialplants could threaten to leavc town' taking nrrrch-
ncedecl jol)s \\,ith tltcnt. Ir-rthe {initecl states. 1;nly t?deral legislatiorl has bceu
ablc to prcvcnt this t1'pc of blackmail.
Ilnt cverr with the pfesent federal legislation, inclustn'has the option to
nror.c "oflilxrre ." tO the Caribbean or to Latin Amcrica, whcre pollution-control
rcgulations lrre llot as stringent. This seems to be a clearly unethical trend,
trxltsporting pollution to other countries less able t() resist sttch contaminatton'
However, thc United States grew rich in part bccause we were able to
prodr-rccbettcr products at cheaper prices, ancl one reason the cost was low
wus ltecausc \^.e cliclnot bother s'ith pollution control. Thc water and air were
{iec. ancl thcre rv:ts "so muclt of it" that it m:rde little sense to clcan up. Nature
seemed to clo a prcttv good iob by itself.
No\\, countries considerablY poorer than the tlnited Statesare saying that
thc1, n'oulcl like to beconle iust as wealthl' and would like to tlsc their water
ancl air thc same way-that is, pollute it. They welcome American industry
that pfomiscs to buiki plants in their countries and decline to implement strict
pollution rcgttlations.
\\'hat should be the ethical stance of American industry in this case?If
in(lustn'cleclines to lnvest in the poorer countries, these countries are deprived
9f income arrclbenefits, and the gap befwee n poof and rich natitlns will increase'
lf. ho$'evcr. industn,invests in these countries and builds manufactufing facili-
ties. inclustn, must have some advantage such as minimal pollution-contfol
will
regulariOns to rnake it worth their rvhile, ancl hence the air and water
be po[utect to what we would consider unacceptable levels. what cthical
responsibilitr., if anl'. does industry have to implement American polltttion-
such
control stanclarclsfor facilities located in countries that do not rcquire
strict staualards?

I I .4..l '\ir Qualitl' Legislation in the United States

'fhc
histon. o1 air qualiq' standards has been long and often tumultuous. At
first. all air pollutir n was rhought of as smoke pollution, and the first legislation
gove rning smoke r.as p:rssedin Los Angeles in 1905. Los Ajrgelcs sits in a basin
of
that is frcc[lentl1, covered b,v a thermal inversion, ancl even from the days
rose only to a set
the (l()nquistaclors,it was evident that smoke from campfrres
lcvel ancl rcmainecl there.
Rr 19.f1. the number of automobiles in Los At]geles hld increased to
This
$,here the| rvere experiencing the world's tirst photochemical smog.
phenonrdton was thought at first to be due to incltlstries, ancl r'rnique to I-os
.\ngclcs. [1 rOOkmauv 1'earsfirr both of these m_vthsto be cxprlsed. Angelenos
 jE
+
ll '\ir Quality'

simpll'clicl not want to bclieve tl-ratthcir r-r-nrch-beloved cars were the cause of
sucl] putricl air. It becanrc obviotrs that sr>rncthinllhaclto be clonc about automo-
bile emisskrns, but tl-risrn,ls a'classic uphill battlc fbr scicntists and rcgulators.
'l'he
automobile lobbr', wl-rich inclucles the autontobilc manufacturers, the oil
industry. ancl thc pcople who wantccl clteap personal transportation, engaged
in a now-notorious campaign of foot-ch'ugging, dcnial, ancl even obfuscation.
Thel' lattncirecl public rclations ancl loblt-ving cxntp:tigns to prevent or slow
clorvn an1,taml)cring rvith cars or firels. Wltcn it finalll' became evident to all
that smog in l.os fuigelcs wes indced due mristlv to internal-combustior-rengines,
the inchlstn' insistcd tl-rat tltis was a spccial case firr Los Ar-rgeles,and that
rlational legislatior-rwas not ncccssar\'. l)hotochentical smog coulcl not happen
:rny'wherc else, thcy' claimecl.
Finaiiy, as it became cvident that ltoth (.llifornia and tl-re United States
were about to pass "tcchnology-driving" legislation restricting auto emissions,
the American auto industry bemo:rneci their inabilit_vto mect these goals and
warncd that cars would bccome undrir.ablc. Nluch Of tl-reirbombast was blunted
u'hen Honda camc out witl-r a vel-riclc that not onlv met all of the stringent
exharlst requirements, but also got 40 nliles to a gallon of gasl
Ihe 1963 Clcan Air Act, a major piecc of legislation that for the {irst time
anywhere set both emission and ambicnt air qualiq' limits, rvas passed in great
part due to the effbrts ()f Senator Edmund Muskie of Maine. The act required
the fcdcral government to set ambient air quality standards frtr seven maior air
pollutants. Thcsc wcre not implemcntecl until 1970, ancl tlte states were given
until 1975 to meet them. So as not to clrag out rhis gt1lesome tale, suffice it to
sav that many states have 1'et to meet thcsc stanclards,and the city of Los
Algclcs ma_vhave to go to extreme lne asrlresto recluce its photochemical smog.
The 1990 amendments to the Clean Air Act acl.l more than 180 hazardous
materiais (n<rw known a.sair toxics) to the ambient air qualify standards and
requires signilicant cuts in the emission of sulfur anclnitrogen oxides, precursors
of acicl rain. The act also extends the deaclline for trreeting the ambient ozone
standard until the year 2007-rvhich n.rakesit 4.1,vearssince the original 1963
Clean Air Act!

11.4.2 Flmissionand Ambient Air

Quality Standards
The cmission standardsare rcgulated (anclfbr tire most part set) by the individual
state air quality ofhces. As an example of an emission standard, an incinerator
might not be allowed to excccd emissions of X p.g/m' of particulates at a
specified CO2minimum level. The latter is.ngcessarysince particulate concentra-
tions can be recluced b1' simply diluting with exceis air. But since air contains
negligible CO,, thc minirnurn C01 level pre\.enrs cmission standard attainment
bv simple dilutior.r.
'fhe
EPA also has the authority to sct n:ltional enrission performance
stanclarclslirl hazar<lor.rs :rir pollutar-rts.Thc list of 1>ollutantsis growing daily,
:tr-tcl<rncea lrollr.rtentis listed, thc EPA can ct.rfrrrccthe emission standards for
I I.4 Air Quality Standards

largcr facilitics. At present, listed are chemicals such as asbestos, benzene,

ct',ryleneglycol, methanol, phenol, styrcne, vin1.lchloriclc, and l-rurrdredsmore.
,The second type of air quality stanclarclsltarallel the stream standardsin
water quaiity. These standards specify the minimum clualiq' of ambient air.
Included in thcse standarclsare particulates, sulftlr oxicle, carbon monoxide,
pl-rotochemical oxidants, l-r1'clrocarbons,nitrogcn oxides, and lead. As data be-
comc available, other standarclsrvill be cler.cloped.
The ambient air quality stanclardsarc of trvo kincls:primary and scconclary.
Primary standards are intendecl to rel:rte to human hcaltl-r,u4tereas secondary
standards addrcss such problems ls corrosion, animal heirlth, r,isibilin'. and so
'Iablc
on. 1l-3 is a listing of the present ltational ambient air qualitr.stan-
clercls(NAAQS).

Prirnary Standard ,Secondarl, Slandard

Pollutdnt (pg/rn';t e.,,9/m.)
Porticulotemofierlessihon
10 p, in diometer
24-houroveroge 150 t50
onnuolgeometricmecn 50 50
Sulfurdioxide
3-hourmoximum r 300
24-houroveroge 365 60
onnuolgeometricmeon 80 260
Nikogen oxides
onnuolgeometricmeon 100 100
Cqrbon monoxide
I -hourmoximum 10,000 r 0,000
8-hourmoximum 40,000 40,000
Ozone
'I-hour
moximum 210 210
Hydrocorbons
3-hourmoximum 160 160
leod
quorterlyorithmeticmeon 1.5 1.5

Areas in the United Stateswhere tire national ambient air qualiw standards
are exceeded more than once or fwice a year for an1. of the pollutants are
knorvn as non-attainment areas fo r those pollutants. In such areas,air pollution
control programs must be initiated to bring the area back into compliance, and
industries contcmplating expansion must show l-rov.thcy can improve the air
qr.ralirvbv reducing emissions.In some areas,either automobiles will be required
to change fuels to reduce emissions or travel festrictions on the use of private
alrtomobileswill bc initiated. Sincethe internal-combustilrnenginc is the single
Iargestcontributor of air pollution, a rcplaccment tirat useshvclrogen or electric-
itt'rvould be a significantcontribution to cleancr :rir.
 II Air Quality

Abbreviations
a

A - air change pcr hour p - pollutant cnlissionfiom an ent:lo-

C : concentratk)n, p{,€alnrJ sttrc. mg/hr
K : decly constant, per hour .9 '- sottrcc stlcrlgth' ptg/hr
q - air flow rate, t-nr/hr I' - r"<>ltttttc.
nt1

Problems
'fhc
I l-l A 1974 car is clrivenan 2lverageof 1000 milcs/nronth. EI)A 19'4 emissi,rrr
sLrndards are 3.1 g,/mi fbr FIC ancl 30 g/mi of CO.
o. How much CO ancl H(l woulcl be emittcC dtrring the lcar?
b. How long woulcl it takc to exccccl a lethal collccntrlrtion ttf CO in rl conmoll
double-car garage, 20 x 2i x 7 ft1

11-2 A2.5% level of co in hemoglobin (coHb) has been shop'n to cause impairment
in time-interval discrimination. The level of CO on crowclcd ciq' streets some-
times hits l0 pcglmr.Air approximate relationsl.ripbetrvcen CO anclCOIIb (after
prolonged exPosure) is

COHb(%) : 0.5 + [0.16 x 10(C() concentratiorl in pg,/m')l

o. What level of COHb would a traflic co1'rbe strbjected to during a working
day directing trafic on a cit)' streeti/
b. Might this affect the cop's attitucle-l(See Figurc I 1- 10.)

I l-3 Photochemical smog is a serious problem in manY large cities.

o. Drav' a graph showing the concentration of NO, NOz, HC, and C)r, in tht-'
Los Angeles area during a sunn)', 561rggv dat.
b. Draw another graph sh'wing how thc samc cun'cs appeaf .n :r cloucly
day. Explain the difference.
c. The onlr- fcasible rva_vof reclucing the fornration of photochctnical smog
in Los Angeles seemsto be to prcvent automobilesfrom entering the cit).
Draw the same curr'es as thc-v might appear t all cars werc banned from
LA stfeets.
d. lVould this ever happen? Wlry or why not?

11-4 Give three examples of s-vnergismirt air pollution.

I I -5 If SO, is so soluble in water, l]ow can it get to tl-rcclecper reaciles of thc iung
without hrst clissolvingin the muctts'l
'l -6 g. The initial
I A hi-vol clearrfiltcr $'eighs 1t1.0g anclthe cliltr. liltcr rrcighs 113.6
and tinal :rir flo5.s lrre 7O :tnd +O itr/nlilt.
 II l'roblems
*i
o. What volumc of air wcnt thror.rgh thc filtr:r in 2,1 l-rorrrs?

l1-7
b. I7hat was thc concentration of p.irticulatcsin tltc airi,

A higl'r-volumesampler dr;ru,s air in at :rn ilverxge rilrc r)f ?0 firlmin. If the

II
partictrlate readir.rgis 2(X) g,g/mi, rvh:rt n'as the rveight of the dust on the filter?

I l-B Rcsearchantl rcpolt on olle of the classic:rlair pollution cltisodcss1rchas Meuse

Valley. I-onclon. or L)onora.

I 1-9 rVhat does Ringlcmann 5 tell xru about a smoke bcing cmirtcclfront a chimney?
'l'he
1l-]0 data fbr a l.ri-volare as firllows:

Clean filtcr: 20.0 g

Dirtl.filter: 20.5 g
Initial air fkrw: 70 ftilrnin
Final air flow: 50 ftjlmin
Tin-re:24 hours
o. What volume of air wirs put through the tilter'i (Answer in cubic feet.)
b. How is the air flow in a hivol measured?
c. What is the weigl.rt of the particulates collecrecl?
d. If half of the collected particulates are {10 /r, does this air meet national
ambient air quality standards?

I l-'l I If the primary ambient air quality standard for nitrogcn oxides (as Nor) is 100
pg/m', wl-rat is this in ppnr? (Assr-rme25'C and 1 atmosphcre pressure.)

11-12 The concentration of carbon monoxicle in a smoke-lillecl room can reach as

high as 500 ppm.
o. Wl-ratis this in p,g/mr? (Assume 1 atmosphcre and 2i'C.)
'Wl-rat
b. eff'ect would this have on people n'ho are sitting around having a
political discussion for 4 hours?

ll-13 Figure 11-13 shows schematicallythe global Av(:ragecnergy flow between

space, the atmosphere, and the earth's surface. 'I'he units in this ligure are in
watts pef squafe meter of surface area.
o. Using spacc, the atmosphere, ancl the carth as black boxes, check if the
numbers represent valid balances.
b. Suppose the earth experiencecl the eruption of scveral iarge volcanos,
spewing dust into the atmosphere. Horv might these numbers change, and
what eflect would such an event have or-rthc e:rrth's temperature?
c. Since most of thc greenhouse gasesarc emittecl fron-rindustrialized nations
in the northerh hemisphere, *'hat reasoning might tl-redirector of an cnvi-
ronmental pfotection agency in an equatorial cor.rntrl.pfesent to argue for
the ctlrtailment of gre enhousc gas emissiorrs?Write x short raclio commen-
tan' fbr thc environntental protection agencv clirector, one that ire could
read fbr thc National Public Raclio in thc Llnited States. Remember that
7
il Air Qualitl'

-r \- t-
,-\-/..,
/t\
I n c o m i n gs o l o r
r o d i o t i o n{ 3 4 3 )
o.
-o I
It -
N
c o >l.o tl
o o i@
o
a 4a c ;tp
o o nt6 4H
- o f
ld-
E d f
o Elo
o 6 -o ol.-
<ls E
o o
o o
I o O
I o ot!
I o E
o Almosphere
I I (vl o
+ N
= t E o_
E E E .o
o o oj
o -! o
E c OO
o
c o o E-
o o
o
_j
c
,s
3
-!. 9 o o

o o
6

a
r
FIGURE I l-13, Glol?l o.ve,roge energyfrows.Unitsore wottsper squoremeterof
surfoceoreo. {AdoptedfrorirJ. Horte, t'onsider sph"riro,lirl,
.l985.) *, Koufmonn,
M e n l oP o r k ,C A "

emotionarism wilr not win nearly the public sr-rpport that

a solid cthicar
argument will.
11-1 4 Awood-burni^gstoveoperatesfor4hoursrnaroonlmeasuring
5 x j x 2.5
meters, with a ventilation of 0.5 air changes per hour. The
CO level reaches 5
mglmr and remains there. Assume that the ventilation
air has negtigible CO
and that CO does not decay.
o. At what rate does the stove emit CO?
b. If thisstoveisusedinasmallhutmeasuringZx
3 x Jmeters,what
would be the CO concentration in the hut?
c. Is burning wood any better environmentalry than using
naturar gas or oil?
Anaryze the use of wo.d as alternative energy for heating based
on pre sumed
environmental impact and cost.
ll-]5 The cEo of a prominent environmental consulting Iirm,
steven Fisher of
Brown & caldwell, is quotecr as saying, "we have to rearize
that ail of the s,ork
in the environmental area is realll' being clone becausc of .fhat
fear. in turn
leads to public pressure, legislation, and then enforcement
of tl.ratlegislation.,,s
Fear of what? f)o you think he is right? If so, is this fcar $.ell
fbundecl?If
not' what is clriving cnvironmental legislation and cnfbrccmcnt?
Consider these
cluestions in light of the history of air pollution conrrol legislation
in the United
 II Problems

States,and write a onel)age discussion ol why you think this legislation was
passed ancl whv it is taking EI)A so long to enforce the regulations.
I I- I6 The rate of coal excavation is clecreasingby about 1.2% per year, whilc rhc use
of oil and gas is increasing by about )% per year. Estimate horv long it will takc
to double the rate of carbon emissions.
'Ihe
11-17 particulate concentration in an urban atmosphereis 16Opg,/nr.
o. What woulcl be the visibilify at the airport?
b. Suppose the measurement \tras made early in the morning when thc atmo-
'Would
sphere was 90% saturated with moisture. the visibilin' havc been
lower or higher then?
'l
l-]8 A pilot reports that the visibilit,v ar rhe airporr is 3 miles.
o. If it is a dry day, what might be the concentration of the particulates in
this city?
b. Does this concentration exceed the National ,{mbient Air Qualifi'Standards
for particulates?
I I -.|96 Metals are frequently coated with thin films of light hydrocarbon oil ro prevent
oxidation of the raw metal feedstock during shipping and storage. Thc opera-
tions is accomplished by immersing the metal pieces in a vapor and having
the solvent condense on the surface. Unfortunately, about 9O% <tf the solvent
eventually escapesinto the atmosphcrc.
At one timc, trichlorethylene (ICE) was the mosr v'idcl1' used solvent
'I'CE,
for degreasing and metal cleaning. however, is a n"rajorcontributor to
photochemical smog, acting as one of the hydrocarbons that rcacts l-itl'r nitric
oxides, thereby allo*.ing high concentrations of ozone to build up. h-r tl-re
past few years 1,1,l-trichloroethanc (TCA) has been substitutecl for TCE. The
substitution is not without problems, however, since TCA has potential for
both stratospheric ozone depletion ancl global warming. The follon'ing table
illustrates a comparison of TCE and TCA relative to their environmental effects.

SmogFormotion GlobolWorming Ozone Depletion

Potentiol Potentiol Poientiol
per Ton per Ton per Ton

TCE 350 6.9 n e gl i gi b l e

TCA 3 390 r000
'ICE,
The increasingly stringent regulation of a photochemically reactive chlori-
nated solvent, encouraged industry to convert to TCA. The results indicate that
while TCE plays a relatively minor role in photochemical smog formation, its
contribution to global warming and to the depletion of stratospheric ozone is
relatively significant. A dilemma arises from the conJlicting criteria used in
choosing a solr.ent.For instance. shoulcl we replacc a photochcmicallv reactive
solvent that breaks down easily in the troposphere with a solvent that is persis-
tent and makes its wa)' up into thc str:rtosphere'iOnce therc, thc solvent will
absorb infrared radiation anclcontribute to global warming or rclcase a chlorinc
atom. which l.hen panicipatcs in thc catall'tic destruction of the ozonc laver.
 II Air Qualit-v

Write a one-page paper outlining your criteria for making the cleciskrn
'l'CA.
Lrctwcen TCts and You may wish to look back in Chapter I to remi:,d
_vourselfof the various ways engineers make decisions.

Endnotes
a
'I'lris
1. disctrssicrrris based in pirn on R. D. Ross, ed.,Air Pollution antl lrtchtst4,,Ya.rt
Nostrand Reinholcl, New York (1972), and K. Wark, and C. F. W'.l.rner.Air Pollutiott,
I{arper & Ron-. New York (1981).
2. Stcphen Schrvartz, "Acid Deposition: Unraveling a Regional Phenomenon," Science
2.i3 (FebrLtan' 1989).
3. .JanresLovclock, Gaia: A New Look at Life on Eanh, Oxford llniv. Press, New
York. (1979).
.1. A. ..i"ero,"'fhe Indoor Radon Story," Technology Review Qanuaq' 1986r.
5. Quotecl in "The Environmental Age," Engineering News Record, 2282i:22 (June
1992).
'fhis
6. problem is based on a similar problem in David Allen, N. Bakshani, and Kirsten
Sinclair Rosselot, Pollution Preuention: Homework and Design Problems ftn- Engi-
,rcering Curricula, American Institute of Chemical Engineers and other societies
t l99l). Used*ith permission.