C H A P T E R

1
The State of the Atmosphere

1.1 INTRODUCTION
Discussions about air pollution often begin with the
composition of the atmosphere. In particular, the discus-
sion often focuses on how a particular part of the tropo-
sphere or stratosphere deviates in quality from a norm.
Popular perceptions of air pollution are driven largely by
fear. After all, the most notorious air pollution events
have often been associated with dramatic atmospheric vi-
suals, such as smoke billowing from industrial stacks into
the air, smog hangingover large cities, deadtrees from acid
rain, and disasters with plumes of contaminants reaching
upward and outward into the troposphere, the lowest at-
mospheric layer where humans and other organisms
reside. Other mental pictures have been more abstract,
yet just as dramatic, e.g. increasing levels of greenhouse
gases in the troposphere or the so-called “hole” in the
ozone layer higher up in atmosphere, the stratosphere.
Like many perceptions, those of the atmosphere are
frequently correct, but incomplete. For example, the at-
mosphere is studied at every scale from planetary to mo-
lecular. The portion of atmosphere influencing a single
cell organism may be a few cubic nanometers in volume,
whereas the atmosphere influencing and being influ-
enced by biome shift is planetary in scale, with pollution
encompassing many cubic kilometers. Indeed, much of a
human being’s exposure to air pollutants occurs in
comparatively small parcels of the atmosphere, espe-
cially in the home. These small compartments, known
as microenvironments, are indeed subdivisions of the at-
mosphere. In fact, humans are frequently exposed at
highest rates to many of the most harmful air pollutants
in what is known as a “personal cloud”.1
respectively), argon (Ar), and carbon dioxide (CO 2).
Chemically, Ar is inert (nonreactive) since it is a noble
gas. The other three compounds are also very stable
and nonreactive under most atmospheric conditions of
temperature and pressure, so they remain very stable
components of the atmosphere. Approximately 99% of
the mass of the atmosphere lies within 50 kilometers
(km) of the earth’s surface, i.e. in the troposphere and
stratosphere. This is where the air pollution occurs.
The earth’s atmospheric temperature varies with
altitude (Figure 1.1), as does the density of the sub-
stances comprising the atmosphere.2 The earth is
warmed when incoming solar radiation is absorbed at or
near the earth’s surface and reradiated at longer elec-
tromagnetic wavelengths (infrared). In general, the air
grows progressively less dense with increasing altitude
moving upward from the troposphere through the
stratosphere and the chemosphere to the ionosphere.
In the upper reaches of the ionosphere, the gaseous
molecules are few and far between as compared with
the troposphere.

1.2 PHYSICAL AND CHEMICAL

PROPERTIES OF THE ATMOSPHERE

By dry volume, 99.997% of the atmosphere consists of

four gases, molecular nitrogen and oxygen (N 2 and O2, FIGURE 1.1 Temperature profile of the earth’s atmosphere.

Fundamentals of Air Pollution 3

http://dx.doi.org/10.1016/B978-0-12-401733-7.00001-3 Copyright © 2014 Elsevier Inc. All rights reserved.
4 1. THE STATE OF THE ATMOSPHERE

The ionosphere and chemosphere are of interest to TABLE 1.1 Gaseous Composition of the Atmosphere
space scientists because they must be traversed by space (Dry, Unpolluted Air)
vehicles en route to or from the moon or the planets, and ppm (vol.) mg mL3
they are also regions in which satellites travel in the
earth’s orbit. These regions are also of interest to com- Nitrogen 780,000 8.95 × 108
munications scientists because of their influence on ra- Oxygen 209,400 2.74 × 108
dio communications. However, these layers are of
Water e e
interest to air pollution scientists primarily because of
their absorption and scattering of solar energy, which in- Argon 9300 1.52 × 107
fluence the amount and spectral distribution of solar en- Carbon dioxide 315 5.67 × 105
ergy and cosmic rays reaching the stratosphere and the
Neon 18 1.49 × 104
troposphere.
The stratosphere is of interest to aeronautical scien- Helium 5.2 8.50 × 102
tists because it is traversed by airplanes; to communica- Methane 1.0e1.2 6.56e7.87 × 102
tions scientists because of radio and television
Krypton 1.0 3.43 × 103
communications; and to air pollution scientists because
global transport of pollution, particularly the debris of Nitrous oxide 0.5 9.00 × 102
aboveground nuclear testing atomic bomb tests and vol- Hydrogen 0.5 4.13 × 101
canic eruptions, occurs in this region and because ab-
Xenon 0.08 4.29 × 102
sorption and scattering of solar energy also occur
there. The lower portion of this region contains the Organic vapors c. 0.02 e
stratospheric ozone layer, which absorbs harmful ultra-
violet (UV) solar radiation. This layer may also be
undergoing modifications by long-term accumulation gas phase fraction of those substances that would be
of chlorofluorocarbons (CFCs) and other gases released liquids under most environmental conditions, espe-
at the earth’s surface or by high-altitude aircraft. cially commonly found temperatures and pressure.
The troposphere is the region in which we live and is This is the subject matter of thermodynamics, the
the primary focus of this book; however, we will discuss study of the relationships among properties of matter
stratospheric ozone formation and destruction in some and the changes that occur to these properties. A
detail in Chapter 11. change in physical state may result spontaneously or
from interactions with other materials. Thermody-
namics concerns itself with the thermal systems,
1.2.1 Tropospheric Composition
including ecosystems and organic systems in humans,
Gaseous composition of the so-called “unpolluted” especially how these systems work. In thermody-
tropospheric air is given in Table 1.1. Unpolluted air is namics, a system is simply a sector or region in space
a conception, i.e. the composition of the air without hu- or some parcel that has at least one substance that is
man influence. There is really no place on the planet that ordered into phases.
presently meets this criterion. Even at the most remote The phase diagram in Figure 1.2 is an example of the
locations at sea, at the poles, and in the deserts and phases that are available in this ordering. The more gen-
mountains, the air contains pollutants, albeit at eral understanding of scientists and technicians is that a
extremely low concentrations. “system” is a method of organization, e.g. from smaller
Note that the gaseous concentrations are mean values to larger aggregations. At a basic thermodynamic level,
for the atmosphere and do not actually exist as reported systems are a means for understanding how matter and
in the table in any region of the atmosphere, especially energy move and change within a parcel of matter.
near the earth’s surface. The atmosphere is more com- Matter in the solid phase has a fixed volume and
plex than a dry mixture of permanent gases. It has other shape. Solid substances’ component particles (i.e. atoms,
constituentsdespecially varying concentrations of molecules, or ions) are confined and fixed into place.
water vapor and other vapors (e.g. organic liquids), as Liquids maintain a fixed volume, but their shape
well as liquid and solid phase constituents (aerosols or changes to fit their container. Liquid particles are denser
particulate matter (PM) held in suspension). than those of the vapor of the same substance (e.g. liquid
The distinction between gases and vapors is often water versus water vapor), but move freely. Gases have
academic. However, in this book, as in many environ- both variable volume and shape, filling the container.
mental texts and handbooks, the difference has to Gas particles are neither close together nor fixed in
do with how substances are partitioned among envi- place. Plasmas have a substantial number of ions and
ronmental compartments. In this case, vapors are the free electrons, along with neutral atoms. Like gases,

I. FOUNDATIONS OF AIR POLLUTION

 1.2 PHYSICAL AND CHEMICAL PROPERTIES OF THE ATMOSPHERE
Supercritical
Solid
Solid
Sodli d fluid
Pcritical
Critical
point
Liquid
Liquid
Li
iqqudid
Pressure
Vapor
Vapor
Temperature Tcritical
FIGURE 1.2 Phase diagram for a hypothetical substance. All of
the polygons shown in the diagram will exist, but their shapes and
slopes of the polygon sides and points of phase changes will differ. The
vaporeliquid boundary line temperature is the boiling point and the
pressure is the vapor pressure. The line between the vapor and solid
phases is known as the sublimation point (i.e. a phase change from
solid to gas, or gas to solid, without first becoming a liquid). The
liquidesolid boundary line temperature is freezing and melting point.
Cpressure and Ctemperature are the pressure and temperature, respectively,
of a fluid at its critical point; i.e. the point at which a gas cannot be
liquefied by an increase of pressure.
plasmas have no definite volume or shape since the ions
and electrons move freely.
Air pollution terminology generally breaks matter
down into two phases, particulate and gas. Particulates
and aerosols are generally synonymous terms in air
pollution literature, i.e. liquid and solid phase. They
are distinguished from gases and vapors.a
For air pollutants, gases are distinguished from va-
pors in that they exist entirely within the vapor phase
of Figure 1.2 under environmental conditions, i.e. not
under extremely high pressure and extremely low tem-
perature. That is, gases are those that would be in the
physical gaseous state under conditions ranging from
the arctic temperatures to the largest pressures found
in the atmosphere.
At higher orders important to air pollution, systems
include the “ecosystem” and the “organism” ordering
systems. These consist of physical phases and order.
For example, ecosystems ordering systems include pro-
ducereconsumeredecomposer, predatoreprey, and
individualeassociationecommunity. Ordering within
organisms includes celletissueeorganesystem.
a
Although the plasma is the most common state of matter in the universe, plasmas are not often mentioned in air pollution. Perhaps
they should be since fires are plasmas, which are a major source of pollutants. Lightning produces plasmas, a major source of nitrogen
exchange between the earth’s surface and the atmosphere. The upper portion (85e600 km altitude) of the atmosphere, i.e. the
ionosphere, is the plasma resulting from solar radiation.
I. FOUNDATIONS OF AIR POLLUTION
5
Thermodynamic systems are classified into two major
types: closed and open. Both exist and are important in
the environment. A closed system does not allow mate-
rial to enter or leave the system (engineers refer to a
closed system as a “control mass”). The open system al-
lows material to enter and leave the systems (such a sys-
tem is known as a control volume).
Another thermodynamic concept is that of the
“property”. As will be covered in more detail in Section
1.4 discussions of fluid properties of contaminants, a
property is some trait or attribute that can be used to
describe a system and to differentiate that system from
the others. A property must be able to be stated at a spe-
cific time independently of its value at any other time
and unconstrained by the process that induced the con-
dition (state). An intensive property is independent of
the system’s mass (such as pressure and temperature).
An extensive property is proportional to the mass of
the system (such as density or volume). Dividing the
value of an extensive property by the system’s mass
gives a “specific property”, such as specific heat, specific
volume, or specific gravity.
The thermodynamic term for the description of the
change of a system from one state (e.g. equilibrium) to
another is known as a “process”. Processes may be revers-
ible or irreversible; they may be adiabatic (no gain or loss
of heat, so all energy transfers occur through work inter-
actions) or non-adiabatic (See Chapter 2). Other processes
include isometric (constant volume), isothermal (constant
temperature), isobaric (constant pressure), isentropic
(constant entropy), and isenthalpic (constant enthalpy).
This discussion introduces the concept of phase parti-
tioning, which is covered in detail in Chapter 18. Parti-
tioning simply means the substance will exist in one or
more physical phases. An important partitioning coeffi-
cient for air pollution is Henry’s Law, which states that
the partial pressure of a compound can be related to
its equilibrium concentration in a dilute aqueous solu-
tion through a constant of proportionality. In other
words, a varying number of molecules will find their
way into the air, even though most of the molecules
remain in the water, i.e. dissolved in water. Even a small
amount of partitioning can account for large amounts of
vapor phase compounds in the atmosphere.
One of the earth’s nicknames is the “water planet”, so
the predominant vapor in the air is, not surprisingly, wa-
ter vapor. In the atmosphere, above their temperature of
condensation, vapor molecules act just like permanent
gas molecules in the air. Below its condensation
6 1. THE STATE OF THE ATMOSPHERE

TABLE 1.2 Gaseous Composition of the Atmosphere (Wet Basis; TABLE 1.3 Conversion Factors between Volume and Mass Units
Unpolluted Air) of Concentration (25 ○C, 760 mmHg)

ppm (vol.) mg mL3 To Convert from

8
Nitrogen 756,500 8.67 × 10 ppm (vol.) mg mL3 to ppm
8 to mg mL3, (vol.), multiply
Oxygen 202,900 2.65 × 10 Pollutant multiply by by (3 10L3)
7
Water 31,200 2.30 × 10 Ammonia (NH3) 695 1.44
7
Argon 9000 1.47 × 10 Carbon dioxide 1800 0.56
5
Carbon dioxide 305 5.49 × 10 Carbon monoxide 1150 0.87
4
Neon 17.4 1.44 × 10 Chlorine 2900 0.34
2
Helium 5.0 8.25 × 10 Ethylene 1150 0.87
2
Methane 0.97e1.16 6.35e7.63 × 10 Hydrogen chloride 1490 0.67
3
Krypton 0.97 3.32 × 10 Hydrogen fluoride 820 1.22
2
Nitrous oxide 0.49 8.73 × 10 Hydrogen sulfide 1390 0.72
1
Hydrogen 0.49 4.00 × 10 Methane (carbon) 655 1.53
2
Xenon 0.08 4.17 × 10 Nitrogen dioxide 1880 0.53
Organic vapors c. 0.02 e Nitric oxide 1230 0.81
Ozone 1960 0.51
temperature, if the air is saturated, water changes from
vapor to liquid. This phenomenon gives rise to fog or Peroxyacetyl nitrate 4950 0.20
mist in the air and condensed liquid water on cool sur- Sulfur dioxide 2620 0.38
faces exposed to air. The quantity of water vapor in the
air varies greatly from almost complete dryness to
supersaturation, i.e. between 0 and 4% by weight (see
Table 1.2). If Table 1.1 is compiled on a wet air basis at where MW equals molecular weight (g mol —1). For
a time when the water vapor concentration is 31,200 con- venience, conversion units for common
parts by volume per million parts by volume of wet air pollutants are shown in Table 1.3. The rationale for
(Table 1.2), the concentration of condensable organic va- Eqn (1.1) is dis- cussed in Section 1.4.1.
pors is seen to be so low compared to that of water vapor Extra care must be taken for conversions of pollutant
that for all practical purposes the difference between wet classes. For example, the units of the air pollutant,
air and dry air is its water vapor content. nitrogen dioxide (NO2), can be converted using
Gaseous composition in Tables 1.1 and 1.2 is expressed Eqn (1.1). However, when addressing smog and ozone
as parts per million by volumedppm (vol.) or ppmV. in the troposphere, the oxides of nitrogen, not NO 2 spe-
(When a concentration is expressed simply as ppm, it is cifically, are the major concern. The concentrations of
unclear whether a volume or weight basis is intended.) NO2 and nitric oxide (NO) are commonly expressed
To avoid confusion caused by different units, air pollutant in ppm (vol.) and expressed as a sum, known as
concentrations in this book are generally expressed as mi- “NOx”. Thus, the conversion from ppm (vol.) to
crograms per cubic meter of air (mg m—3) at an environ- mg m—3 must be carried out separately for NO2 and
mental temperature (e.g. 20 ○ or 25 ○C) and 760 mmHg, NO before the two species are added together.
i.e. in metric units. To convert from units of ppm (vol.)
to mg m—3, it is assumed that the ideal gas law is accurate
under ambient conditions. A generalized formula for the 1.3 ATMOSPHERIC CHEMICAL
conversion at 25 ○ C and 760 mmHg is: CONCENTRATIONS
1 l pollutant
1 ppm ðvol:Þ pollutant ¼ As mentioned, molecular nitrogen (N2), molecular
106 l air
oxygen (O2), water (H2O), argon (Ar), and carbon diox-
ð1 l=22:4Þ× MW × 106 mg × g m—1 (1.1) ide (CO2) make up most of the atmosphere (Tables 1.1
¼ and 1.2). Most other compounds and substances exist
106 l × 298 K=273 K × 10—3 m3 × l— 1
only in trace amounts. Note that of the remaining most
¼ 40:9 × MW mg m—3 abundant gases by volume, all but two are also quite
reactive; the exceptions being hydrogen (H2) and nitrous
oxide (N2O). Neon (Ne), helium (He), krypton (Kr), and

I. FOUNDATIONS OF AIR POLLUTION

 1.3 ATMOSPHERIC CHEMICAL CONCENTRATIONS
xenon (Xe) are noble gases; and methane (CH 4) is quite
stable under atmospheric conditions.
Hydrogen is highly reactive, but exists only in trace
amounts in the lower troposphere. Its relative abun-
dance, i.e. seventh most abundant gas in dry air, is
mainly because of the high energy conditions in the
upper atmosphere (altitude > 500 km), where the solar
radiation dissociates molecules of H2O, CH4, and H2,
producing H atoms. Since concentrations of H 2O and
CH4 molecules are highly variable in the atmosphere,
the amount of H produced in this manner is also highly
variable. Incidentally, the same is true for ozone (O 3)
which is also produced photochemically in the upper
atmosphere (15e50 km altitude) and why there is a
distinctive O3 layer in the stratosphere. This is also the
reason that atomic oxygen, which is almost nonexistent
in the lower layers, is also much more abundant in the
upper atmosphere.3
It should be noted from a mass balance perspective
that nitrogen (N) and oxygen (O) exist in numerous
chemical compounds in the atmosphere. As will be dis-
cussed in detail in Chapter 22, nitrogen’s compounds
include a number of air pollutants, especially nitrogen
dioxide (NO2), and many essential compounds, e.g.
nitrates, nitrites, and ammonia. However, N 2 is the
dominant atmospheric N-constituent, i.e. 3.9 × 1018
I. FOUNDATIONS OF AIR POLLUTION
7
kilograms (kg) being six orders of magnitude larger
than the second, N2O. The movement to and from the at-
mosphere, i.e. flux, of N in its many species is massive.
The flux of N2 between the earth’s surface and the atmo-
sphere is about 1011 kg annually.3
Oxygen is a part of myriad compounds, including
most organic compounds. Photosynthesis provides
most of the atmospheric O2, predominant from terres-
trial plants and aquatic microbes, especially phyto-
plankton (see Figure 1.3).3 Using light energy from
incoming solar radiation, photosynthesis converts vapor
phase CO2 and water into solid phase carbohydrates
and O2. Although there are numerous intermediate
steps, the reaction is summarized as:
CO2 D H2O D sunlight / CH2O D O2 (1.2)
In the upper altitudes, water vapor and N 2O undergo
photodissociation via UV solar radiation, additional O 2
is formed providing between 1 and 2 percent of atmo-
spheric oxygen.
Respiration is the chemical counterpart to photosyn-
thesis, i.e. the transport of O2 from the atmosphere into
cells and the transport of CO2 away from cells into the
atmosphere. Respiration is the process by which organ-
isms use O2 for energy and to build cells, with CO2 as the
FIGURE 1.3 Photosynthesis and respiration
processes in a tree. Note that there are several sites
at which O2, H2O, and CO2 are exchanged, both
above and below ground. Although photosynthesis
is the dominant process for plant life, there is also
respiration (i.e. dark respiration) in the absence of
sunlight. (For color version of this figure, the reader
is referred to the online version of this book.)
Adapted from: Kamath R, Rentz JA, Schnoor JL, Alvarez
PJJ. Phytoremediation of hydrocarbon-contaminated
soils: principles and applications. Stud Surf Sci Catal
2004;151:447e78.
8 1. THE STATE OF THE ATMOSPHERE
waste product. Conversely, air breathing organisms
come in many forms, but the basic respiration chemistry
is similar. Humans and other mammals, as well as birds,
reptiles for their entire lives, and amphibians for parts of
their lives use lungs to exchange the O 2 in the air
mixture. Fish similarly use gills to exchange the O 2 in
the water mixture (i.e. dissolved oxygen). Other organ-
isms in air and water use similar mechanisms to extract
O2 for respiration. The only exceptions are the anaerobic
organisms, which use electron acceptors other than O 2.
These electron acceptors include sulfate ðSO2— 4 Þ, nitrate
ðNO—3 Þ, sulfur (S), and fumarate (HO2CCH]CHCO2H).
Carbon (C) is the distinguishing element for organic
compounds, i.e. those with CeC and/or HeC bonds,
but it is also part of many inorganic compounds,
including CO2 and carbon monoxide (CO). Organic
compounds include those that comprise cells in organ-
isms and other biochemical substances. Carbon is a ma-
jor constituent of many air pollutants, including CO, PM
in various forms, as well as many of the most toxic air
pollutants, e.g. dioxins, polychlorinated biphenyls
(PCBs), and many pesticides. Of recent interest are
greenhouse gases, of which, most are carbon com-
pounds, e.g. CO2, CH4, and chlorofluorocarbons
(HCHs). Thus, C, O, N, and H are the principal elements
involved in air pollution.
Several of the abundant compounds in the atmo-
sphere are greenhouse gases, most notably CO 2, CH4,
and N2O. Indeed, H2O is also a greenhouse gas since, by
definition, it traps heat in the atmosphere. That is, the
portion of the incoming solar radiation that is reradi-
ated as infrared wavelengths is either trapped by green-
house gases or is allowed to leave the atmosphere. In
particular, as the most abundant greenhouse gas, CO 2
has been the focus of much recent interest in both scien-
tific communities and the public at large. The amount
has steadily increased in recent decades (see Figure 1.4).
Methane (CH4), the most abundant organic molecule
in the atmosphere, also increased in concentration
dramatically after the industrial revolution, but is no
longer increasing. It is produced from anaerobic pro-
cesses. These include agriculture, e.g. livestock and
rice paddies; landfills; fossil fuel extraction and gas dis-
tribution; and biomass burning.3 These anthropogenic
sources produce about the same amounts of CH 4 as nat-
ural sources, which include reduced, anoxic portions of
wetlands and portions of ecosystems undergoing
organic decomposition. CH4 is a much more potent
greenhouse gas than CO2, absorbing 22 times energy
per unit mass. However, at about nine years, its atmo-
spheric residence could be far less than that of CO 2,
which is estimated to range between 5 and 100 years
(see Table 1.4). No unique lifetime can be defined for
CO2 given the varying rates of uptake by different
I. FOUNDATIONS OF AIR POLLUTION
FIGURE 1.4 Monthly mean atmospheric carbon dioxide con-
centrations (ppm by volume) at Mauna Loa Observatory, Hawaii. The
CO2 data (red curve) are presented as the mole fraction in dry air, on
Mauna Loa constitute the longest record of direct measurements in the
atmosphere. The black curve represents the seasonally corrected data.
Data are reported as a dry mole fraction defined as the number of
molecules of CO2 divided by the number of molecules of dry air
multiplied by one million (ppm). (For interpretation of the references
to color in this figure legend, the reader is referred to the online version
of this book.) National Oceanic and Atmospheric Administration. Trends
in atmospheric carbon dioxide. http://www.esrl.noaa.gov/gmd/ccgg/
trends/; 2013 [accessed 23.09.13].
production and removal processes and exchanges occur-
ring between the atmosphere, ocean, and land surfaces.
More than 90% of the degradation of methane is by
oxidation, mainly by reactions with the hydroxyl radical
in the stratosphere which accounts for more than 90% of
methane loss. The equilibria and fate of CO 2, CH4, and
other carbon compounds are discussed in detail in
Chapter 21.
It is important to note that the gases listed in the tables
vary in concentration throughout the atmosphere. Each
gas mixes in the air at different altitudes, i.e. they have
unique mixing ratios (see Figure 1.5). The mixing ratio
is the number density of the gas divided by number den-
sity of all gases in dry air. Only N2 and the noble gases
have nearly constant mixing ratios below 100 km, given
their chemical stability. Since most CH4 and N2O are
destroyed at the stratosphere, their mixing ratios start
decreasing at about 20 km altitude. The mixing ratio of
water vapor, with a highly temperature-dependent con-
centration, decreases sharply with altitude and
decreasing temperatures in the troposphere. The strato-
spheric O3 layer is also apparent at 35 km from Figure 1.5.
The trace amounts of thousands of compounds in the
atmosphere include both essential compounds and air
pollutants. The physics, chemistry, and biology of these
substances comprise the bulk of scientific interest in air
pollution.
 1.3 ATMOSPHERIC CHEMICAL CONCENTRATIONS 9
TABLE 1.4 Approximate Concentrations (ppb) and Rate of Concentration Change (ppb year—1) of Select Greenhouse Gases That Are
Affected by Human Activities

CFC-11 HFC-23 CF4

CO2 CH4 N2O (Chlorofluorocarbon-11) (Hydrofluorocarbon-23) (Perfluoro methane)
5
Preindustrial concentration 2.8 × 10 700 270 0 0 4.0 × 10—2
5
Concentration in 1998 3.7 × 10 1745 314 0.27 14 8.0 × 10—2
Rate of concentration changex 1.5 × 106* 7.0* 0.8 —1.4 × 10—3 5.5 × 10—4 1.0 × 10—3
4
Atmospheric lifetime (years) 5 to 200{ 12k 114k 45 260 >5.0 × 10

* Rate has fluctuated between 0.9 and 2.8 ppm/year for CO 2 and between 0 and 13 ppb/year for CH4 over the period 1990e1999.
x
Rate is calculated over the period 1990e1999.
{
No single lifetime can be defined for CO2 because of the different rates of uptake by different removal processes.
k
This lifetime incorporates the indirect effect of the gas on its own residence time.
Source: Folland CK, Karl TR, Christy JR, Clarke RA, Gruza GV, Jouzel J, et al. Observed climate variability and change. In: Houghton JT, Ding Y, Griggs DJ, Noguer M, van der
Linden PJ, Dai X, et al., editors. Climate change 2001: the scientific basis. Contribution of working group I to the third assessment report of the intergovernmental panel on climate
change. Cambridge (United Kingdom) and New York (NY): Cambridge University Press; 2001.

Essential compounds include micronutrients needed
by plant life and other organisms in the ecosystems.
However, even essential substances can become pollut-
ants in the wrong concentrations. Thus, expression of
chemical concentration is crucial to understanding at-
mospheric science generally and the fundamentals of
air pollution specifically.
Constituents of air are expressed as densities. Many
earth and atmospheric science texts and references
express the larger constituents (i.e. N2, O2, and H2O)
in percent volume of air. Thus, this is a unitless expres-
sion, i.e. volume of constituent per volume of air. How-
ever, smaller air constituents, including all air
pollutants, are expressed either as a number density,
i.e. molecules per unit volume, such as molecules cm —
3
; or as a mass density, such as mg m—3. An example of a
number density expression of an air pollutant would be
1.2 × 1012 formaldehyde (CH2O) molecules per cm3 ¼
1.2 × 1018 molecules per m3.
Unitless density (e.g. parts per billion [ppb]) and
mass density are the most common expressions of air
pollutant concentration. A number density can be con-
verted to mass density by the use of gram molecular
weight (mole) per volume. Avogadro’s constant, the
number of constituent particles (molecules or atoms), in-
forms us about the number of moles. That is, 1 mole
(mol) of any particle contains 6.022 × 1023 molecules.
Thus, since we know the number density of formalde-
hyde, we can find its mass density from its number of
moles per volume:
Σ Σ
1:2 × 1018 CH2O molecules per m3 O6:022
× 1023 moleculesz2 × 10—6 mol m—3
Therefore, the number density can be converted to a
mass density. In this case, the number density of
1.2 × 1012 formaldehyde (CH2O) molecules per cm3
is the same as the mass density 2 × 10—6 mol m—3 or
2 micromoles (mmol) per cublic meter.
The 2 mmol formaldehyde per m3 of air can be con-
verted to the more common units of mg m—3. The atomic
mass of carbon (C) is 12, hydrogen (H) is 1, and oxygen
(O) is 16, so the atomic mass of CH2O is 30. Thus, 1 mol
CH2O ¼ 30 g ¼ 3 × 10—5 mg.
Since 1 mmol ¼ 10—6 mol, then 2 mmol formalde-
hyde ¼ 2 × 30 × 10—6 g ¼ 6 × 10—5 g ¼ 60 mg. Expressed
as a mass density, 2 mmol per m CH 3
2 O in air is the
same as a chemical concentration of 60 mg m—3.
Mass

FIGURE 1.5 Atmospheric mixing ratios for ozone and

abundant atmospheric gases, other than molecular nitro-
gen and noble gases (given they are well mixed up to 100-
km altitude). With permission from Goody RS. Nat Med.
1995 Jun;1(6):519e520.

I. FOUNDATIONS OF AIR POLLUTION

10 1. THE STATE OF THE ATMOSPHERE
density is more commonly used than number density to
express air pollutant concentrations. However, the
expression of mass density is highly variable, especially
with regard to standards and regulations. Even in the
same standards, different units are used (e.g. ppb and
mg m—3).
1.3.1 Chemical Concentration
The chemical concentrations in Tables 1.2 and 1.3
are mean atmospheric concentrations. Concentration
can be expressed as combinations of mass and volume,
usually volume per volume or mass per volume. Note
that the tables include at the bottom what would
appear to be a small amount of compounds under
the classification of “organic vapors”. Actually, this
seemingly small group of compounds comprises a
very large amount of air pollutants. It includes any
compound with at least one carbon-to-carbon or
carbon-to-hydrogen bond that emits molecules into
the atmosphere. These molecules are emitted as vapors.
Generally, the higher the vapor pressure of a substance,
the more of the molecules of that substance finds its
way to the atmosphere. This exchange among solid,
liquid, and gas phases, including vaporization, is dis-
cussed in detail in Chapter 18.
Indeed, formaldehyde would be included among
the organic vapors that in total comprise about
0.02 ppm. However, formaldehyde concentrations are
highly variable, depending on the unique environ-
mental conditions where it exists. There is both spatial
and temporal variability, such as the differences in
ambient concentrations in various urban areas and sea-
sonal differences in the same urban area (Figure 1.6).
For example, formaldehyde concentrations in urban
areas are generally higher in summer; whereas, the
concentrations of benzene, another organic vapor,
are generally higher in the winter (Figure 1.7).
Atmospheric concentrations can vary even more in
different microenvironments than in the ambient air
(see Table 1.5).
Formaldehyde is not unique. All other organic vapor
concentrations also vary significantly in different parts
of the atmosphere; as do inorganic compounds, for
that matter. Thus, although the total amount of sub-
stances under the category “organic vapors” is some-
what constant on a global atmospheric scale, it is
highly variable in the ambient air (e.g. much higher con-
centrations near a wood processing facility) and even
more variable between ambient and indoor air, as indi-
cated in Table 1.5.
The variability in chemical concentrations can be
even greater among various types of indoor environ-
ments. For example, the two types of homes listed in
Table 1.5 have very different mean and maximum
I. FOUNDATIONS OF AIR POLLUTION
concentrations, with manufactured homes much higher
than conventional homes. This likely indicates that man-
ufactured homes include sources of formaldehyde that
are greater than those of conventional homes, e.g. higher
ratios of formaldehyde-containing building materials to
non-formaldehyde-containing materials in manufac-
tured homes. It may also be the result of smaller air ex-
change rates in manufactured homes.
Some microenvironments contain concentrations of
compounds that are several orders of magnitude
higher than these mean values. For example, work-
place microenvironments may contain levels far higher
than atmospheric means and even higher than those
found in highly polluted urban air; especially if air
pollution control devices are not deployed. Thus, the
concentration of an air pollutant that is expected and
permitted will vary according to the protection needed
in ambient air and various personal and workplace
microenvironments (see Figure 1.8). This type of figure
is used frequently in this text, especially in Chapter 7.
It is quite useful in comparing allowable amounts of
toxic air pollutants.
Higher concentrations of air pollutants are often
permitted in workplace environments than in the gen-
eral environment. This is because workplace environ-
ments often require personal protection equipment
(PPE), which is enforced by occupational regulatory
agencies. In addition, exposures in workplace environ-
ments are generally much shorter in duration and
frequency, e.g. 8 h per day, five days per week for
30 years, compared to general exposures, e.g. 24 h per
day, seven days per week for a lifetime. Thus, both the
cancer and minimum risk level (MRL) are much lower
than the occupational levels on the right-hand side of
Figure 1.8. The MRL is an estimate of the daily human
exposure to a hazardous substance that is likely to be
without appreciable risk of adverse noncancer health
effects over a specified duration of exposure. 4
The recommended or regulated amount of exposure
to air pollutants varies by scenario and activity. In the
United States, the Occupational Safety and Health
Administration’s (OSHA) workplace exposure standard
is the permissible exposure limit (PEL) for each air
pollutant. The PEL is set to protect workers day in and
day out for their entire career, i.e. a long-term exposure.
There are three types of PELs:
1. The Time-Weighted Average (TWA) is the average
employee exposure over a time period that a person is
expected to work. This is usually 8 h, so the 8-h TWA is
very commonly used. It is based on the measurements
taken near or on the worker, i.e. personal exposure.
The measured pollutant concentration may exceed the
TWA value at times during the 8-h period but the 8-h
average concentration must be below the PEL.

Average seasonal concentration (µg/m3)
1.3 ATMOSPHERIC CHEMICAL CONCENTRATIONS 11
4.5 FIGURE 1.6 Measured concentrations of form-
aldehyde in several urban areas during four sea-
4 sons of the year 2005. APMI, Allen Park, Detroit, MI;
3.5 AZFL, Azalea Park, St. Petersburg, FL; BAPR, Bar-
celona, Puerto Rico; BTUT, Bountiful, UT; CANC,
3 Candor, NC; CANJ, Camden, NJ; CHNJ, Chester, NJ;
CUSD, Custer, SD; DITN, Dickson, TN; ELNJ, Eliz-
2.5
abeth, NJ; ETAL, East Thomas, Birmingham, AL;
2 FLFL, Davie, FL; GAFL, Gandy in Tampa, FL;
GRMS, Grenada, MS; INDEM, Gary, IN; ITCMI,
1.5 Sault Sainte Marie, MI; LDTN, Loudon, TN; MAWI,
Madison, WI; MIMN, Minneapolis, MN; MUTX,
1
Murchison Middle School in Austin, TX; NBAL,
0.5 North Birmingham, AL; NBNJ, New Brunswick, NJ;
ORFL, Winter Park, FL; PCOK, Site 1 in Ponca City,
0 OK; PGMS, Pascagoula, MS; PITX, Pickle Research

GPCO
CUSD
BAPR

MUTX
ITCMI

MIMN
CHNJ

MAWI
CANJ

DEMI

LDTN
BTUT

ETAL
APMI

ELNJ
DITN
Center, Austin, TX; POOK, Site 2 in Ponca City, OK;
PVAL, Providence, RI; RRTX, Round Rock, TX;
Monitoring site RTPNC, Research Triangle Park, NC; SFSD, Sioux
Falls, SD; SIAL, Sloss Industries, Birmingham, AL;
Spring Summer Autumn Winter SJPR, San Juan, Puerto Rico; SMFL, Simmons Park in
Tampa, FL; SPIL, Schiller Park in Chicago, IL; TRTX,
Travis High School in Austin, TX; TUMS, Tupelo,
Average seasonal concentration (µg/m3)

8 MS; WETX, Webberville Road in Austin, TX. (For

color version of this figure, the reader is referred to
7
the online version of this book.) U.S. Environmental
6 Protection Agency. 2005 Urban Air Toxics Monitoring
Program (UATMP). Final report. Report No. EPA-454/
5 R-07-001; 2006.

0
PVAL

SPIL
SJPR

YDSP
NBIL

YFMI
NBNJ

PCOK

SFSD

TRTX

TUMS
PITX

POOK

RRTX

WETX
S4MO

Monitoring site
Spring Summer Autumn Winter

2. The Ceiling Limit (PEL-C) is the maximum allowable the National Institute of Occupational Safety and Health
concentration, not an average. Thus, any exceedence (NIOSH) publishes air quality limits for substances to
is considered a violation of the PEL, even for a very provide guidance on safe worker exposures. The recom-
short time. mendations can also come from professional and scien-
3. The Short-Term Exposure Limit (STEL) is the tific associations. For example, the American Conference
concentration that must not be exceeded when of Governmental Industrial Hygienists publishes occu-
averaged over a specified short period of time pational exposure guidelines, i.e. the threshold limit
(usually 15 min). When there is an STEL for a values (TLV). Both, the TLV and Recommended Expo-
substance, exposure still must never exceed the sure Level (REL) are advisory, but the PEL is a legal
PEL-C or the 8-h TWA. requirement that carries penalties when exceeded.
NIOSH publishes four types of exposure recommen-
The majority of air pollutants with PELs have a pub-
dations, structured similarly to the PELs:
lished TWA value. Some air pollutants also have ceiling
or short-term exposure limits (STELs). Others have ceil- 1. The REL-TWA: 8-hour time-weighted average
ings and STELs instead of TWA values. concentration.
The science behind recommended levels of work- 2. The REL-TWA: 15-min time-weighted average
place exposure comes from governmental research; e.g. concentration.

I. FOUNDATIONS OF AIR POLLUTION

12 1. THE STATE OF THE ATMOSPHERE

FIGURE 1.7 Measured concentrations of benzene 35

Average seasonal concentration (µg/m3)

INDEM Summer
in several urban areas during four seasons of the year Concentration is
193.41 µg/m3
2005. APMI, Allen Park, Detroit, MI; AZFL, Azalea Park, 30
St. Petersburg, FL; BAPR, Barcelona, Puerto Rico; BTUT,
Bountiful, UT; CANC, Candor, NC; CANJ, Camden, NJ; 25
CHNJ, Chester, NJ; CUSD, Custer, SD; DITN, Dickson,
TN; ELNJ, Elizabeth, NJ; ETAL, East Thomas, Birming- 20
ham, AL; FLFL, Davie, FL; GAFL, Gandy in Tampa, FL;
GRMS, Grenada, MS; INDEM, Gary, IN; ITCMI, Sault 15
Sainte Marie, MI; LDTN, Loudon, TN; MAWI, Madison,
WI; MIMN, Minneapolis, MN; MUTX, Murchison Mid- 10
dle School in Austin, TX; NBAL, North Birmingham, AL;
NBNJ, New Brunswick, NJ; ORFL, Winter Park, FL; 5
PCOK, Site 1 in Ponca City, OK; PGMS, Pascagoula, MS;
PITX, Pickle Research Center, Austin, TX; POOK, Site 2 0

INDEM
AZFL

DEMI

GAFL
APMI

ETAL
CANJ

GPCO

MAWI

MIMN
CANC

CHNJ

DITN

ELNJ
CUSD
BAPR

BTUT

LDTN

MUTX
in Ponca City, OK; PVAL, Providence, RI; RRTX, Round
Rock, TX; RTPNC, Research Triangle Park, NC; SFSD,
Sioux Falls, SD; SIAL, Sloss Industries, Birmingham, AL; Monitoring site
SJPR, San Juan, Puerto Rico; SMFL, Simmons Park in
Spring Summer Autumn Winter
Tampa, FL; SPIL, Schiller Park in Chicago, IL; TRTX,
Travis High School in Austin, TX; TUMS, Tupelo, MS;
Average seasonal concentration (µg/m3)
WETX, Webberville Road in Austin, TX; YDSP, El Paso, 35
SPIL Summer
TX; YFMI, Yellow Freight in Detroit, MI. (For color Concentration is
53.82 µg/m3
version of this figure, the reader is referred to the online 30
version of this book.) U.S. Environmental Protection
Agency. 2005 Urban Air Toxics Monitoring Program 25
(UATMP). Final report. Report No. EPA-454/R-07-001;
2006. 20

15

10

0
NBIL

ORFL

SIAL

SMFL

SPIL
PVAL

SKFL

SYFL
NBNJ

RTPNC

SFSD

SJPR

TRTX
PITX

RRTX

S4MO

TUMS

WETX
Monitoring site

Spring Summer Autumn Winter

3. REL-C: Ceiling concentrationdnot to be exceeded.

TABLE 1.5 Formaldehyde Concentrations Measured at Various 4. IDHL: 30-min concentration that is Immediately
Locations in California Dangerous to Life and Health.
Meandmg mL3 Maximumdmg mL3 Table 1.6 shows the PELs and RELs for some impor-
Location (ppb) (ppb) tant workplace air pollutants.
Conventional homes 11.3 (9.1) 38.8 (31.3)
1.3.2 Concentration Unit Example
Manufactured homes 45 (36.3) 282 (227)
Public & commercial 16 (12.9) 32 (25.8)
The REL-TWA concentration of for ammonia (NH3) is
buildings 25 ppm. The ceiling REL is 5 ppm for hydrogen chloride
(HCl). The ammonia TLV is also 25 ppm. The PEL-TWA
Industrial plant 16 (12.9) 32 (25.8)
for ammonia is 50 ppm, and the ceiling PEL for HCl is
School 26.2 (21.1) 121.5 (98.0) 5 ppm, the same as its REL. For ammonia, the time for
In-vehicle (Sacramento) 9.3 (7.5) 18.5 (14.9) which the concentration is averaged is often 8 h (i.e. 8-
h TWA), but the TWA can also be calculated for
In-vehicle (Los Angeles) 15.3 (12.3) 23.6 (19.0)
extended work periods, e.g. a 10-h TWA, or for short-
Outdoor 3.6 (2.9) 14.3 (11.5) term exposures.
Source: California Office of Environmental Health Hazard Assessment. Formaldehyde.
Suppose that a work area is monitored to show an 8-h
Prioritization of toxic air contaminants. Children’s Environmental Health Act. http:// TWA NH3 concentration of 23 mg m—3 and 3 mg m—3 for
oehha.ca.gov/air/toxic_contaminants/pdf_zip/formaldehyde_final.pdf; 2001 [accessed HCl. Are the workplace concentrations meeting NIOSH
20.09.13].
and OSHA recommendations?
I. FOUNDATIONS OF AIR POLLUTION
 1.3 ATMOSPHERIC CHEMICAL CONCENTRATIONS 13

Regulatory, advisory
Health numbersa
numbersb
1000
LC50 (mice) (400 mg m–3)
LC50 (rats) (203 mg m–3)

100
NIOSH IDLH (25 mg m–3)
AIHA ERPG-2 (12 mg m–3)
10

Concentration (mg m–3)

AIHA ERPG-1 (1.2 mg m–3)
OSHA PEL (0.9 mg m–3)
1
ACGIH STEL (0.4 mg m–3)

0.1
NIOSH REL
(0.02 mg m–3)
ATSDR chronic MRL
0.01
(0.004 mg m–3)

0.001
Cancer risk level
1 in a million risk
(8  10 mg m )
0.0001

0.00001

FIGURE 1.8 Health data for inhalation exposure to formaldehyde as of 1999. To convert concentrations in air (at 25 ○C) from ppm to mg m—3:
mg m—3 ¼ (ppm) × (molecular weight of the compound)/(24.45). For formaldehyde: 1 ppm ¼ 1.23 mg m—3. AIHA ERPG, American Industrial
Hygiene Association’s emergency response planning guidelines. ERPG 1 is the maximum airborne concentration below which it is believed nearly all
individuals could be exposed up to 1 h without experiencing other than mild transient adverse health effects or perceiving a clearly defined
objectionable odor; ERPG 2 is the maximum airborne concentration below which it is believed nearly all individuals could be e xposed up to 1 h
without experiencing or developing irreversible or other serious health effects that could impair their abilities to take protective action. ACGIH STEL:
American Conference of Governmental and Industrial Hygienists’ short-term exposure limit expressed as a time-weighted average exposure; the
concentration of a substance which should not be exceeded at any time during a workday; LC50 (Lethal Concentration-50): A calculated concentration
of a chemical in air to which exposure for a specific length of time is expected to cause death in 50% of a defined experimen tal animal pop-
ulationdthis is a common expression of acute hazard; NIOSH IDLH: National Institute of Occupational Safety and Health’s immediately dangerous
to life or health limit; NIOSH recommended exposure limit to ensure that a worker can escape from an exposure condition that is likely to cause death
or immediate or delayed permanent adverse health effects or prevent escape from the environment; NIOSH REL: NIOSH’s recommended exposure
limit; NIOSH recommended exposure limit for an 8- or 10-h time-weighted average exposure and/or ceiling; OSHA PEL: Occupational Safety and
Health Administration’s permissible exposure limit expressed as a time-weighted average; the concentration of a substance to which most workers
can be exposed without adverse effect averaged over a normal 8 h workday or a 40 h workweek aHealth numbers are toxicological values derived
from animal testing or risk assessments developed by the U.S government. bRegulatory values have been incorporated in U.S. government regu-
lations, whereas advisory values are non-regulatory, but based on advice from the U.S. government or other groups as advice. OSHA numbers are
regulatory, whereas NIOSH, ACGIH, and AIHA numbers are advisory. 5e11(For color version of this figure, the reader is referred to the online version
of this book.) U.S. Environmental Protection Agency. Formaldehyde. http://www.epa.gov/ttnatw01/hlthef/formalde.html; 2013 [accessed 21.09.13].

From Table 1.3, the conversion factor if mg m—3 is
known is 1.44 × 10—3 for NH3 and 0.67 × 10—3 for HCl.
23 mg ¼ 23;000 mg:
23;000 mg m—3 × 1:44 × 10—3 ¼ 33:12 ppm NH3:
This means that the readings are higher than the REL,
but lower than the PEL (50 ppm). Although the PEL is
not being violated, there may still be concern, since it ex-
ceeds the recommended levels. Due diligence would call
for finding ways to reduce the workplace concentrations
to be closer to the REL and TLV.
For HCl, applying the 0.67 conversion factor gives:
3 mg ¼ 3000 mg:
3000 mg m—3 × 0:67 ×
Given that 2 ppm < 5 ppm, would OSHA deem that
this facility is not violating the PEL standard of 5 ppm if
this area requires workers to be present? Note that
Table 1.6 indicates that HCl is not a TWA PEL, but
is a C-PEL. The C-PEL cannot be exceeded, even
instantaneously. Thus, the average HCl concentration
is not the appropriate measure. The actual measure-
ments would have to be used instead to determine
compliance with the C-PEL. Let us assume that
the monitor provides 5-min intervals of data and
that during the sampling period there were 15 in-
tervals above 5 ppm. The peak concentration measured
was 20 mg m—3:
20 mg ¼ 20;000 mg:
10—3 ¼ 2 ppm: 20;000 mg m—3 × 0:67 × 10—3 ¼ 13:4 ppm:

I. FOUNDATIONS OF AIR POLLUTION

14 1. THE STATE OF THE ATMOSPHERE

TABLE 1.6 U.S. Permissible Exposure Levels (PELs) and Recommended Exposure Levels (RELs) for Selected Workplace Air Pollutants

Air Pollutant Permissible Exposure Level Recommended Exposure Level

Acetaldehyde TWA 200 ppm (360 mg m—3) Treated as a carcinogen*

Careful consideration given to reducing exposures to nine
related aldehydes
Acetone TWA 1000 ppm (2400 mg m—3) TWA 250 ppm (590 mg m—3)

Acrolein TWA 0.1 ppm (0.25 mg m—3) TWA 0.1 ppm (0.25 mg m—3) ST 0.3 ppm (0.8 mg m —3)
Careful consideration given to reducing exposures to nine
related aldehydes
Ammonia TWA 50 ppm (35 mg m—3) TWA 25 ppm (18 mg m—3) ST 35 ppm (27 mg m—3)
n-Butane None TWA 800 ppm (1900 mg m—3)

2-Butanone TWA 200 ppm (590 mg m—3) TWA 200 ppm (590 mg m—3) ST 300 ppm (885 mg m—3)
Chlorine C 1 ppm (3 mg m—3) C 0.5 ppm (1.45 mg m—3) (15 min)
Chlorine dioxide TWA 0.1 ppm (0.3 mg m—3) TWA 0.1 ppm (0.3 mg m—3) ST 0.3 ppm (0.9 mg m—3)
Diethyl phthalate None TWA 5 mg m—3

Ethyl benzene TWA 100 ppm (435 mg m—3) TWA 100 ppm (435 mg m—3) ST 125 ppm (545 mg m—3)
Formaldehyde TWA 0.75 ppm (0.9 mg m—3) NIOSH Potential Occupational Carcinogen. RELs for
ST 2 ppm (2.5 mg m—3) asbestos, formaldehyde, benzene, and ethylene oxide are
quantitative values based primarily on analytical limits of
detection or technological feasibility. C 0.1 ppm (0.1 mg m—3)
(15 min)
Gasoline None Treated as a carcinogen*
n-Heptane TWA 500 ppm (2000 mg m—3) TWA 85 ppm (350 mg m—3) C 440 ppm (1800 mg m—3)
(15 min)

n- Hexane
Hydrogen bromide
Hydrogen chloride
Hydrogen fluoride
Hydrogen sulfide
Isobutane
Hg vapor
Mercury (organo) alkyl
compounds (as Hg)
TWA 500 ppm (1800 mg m—3) TWA 50 ppm (180 mg m—3)
TWA 3 ppm (10 mg m—3) 3 ppm (10 mg m—3)
C 5 ppm (7 mg m—3) C 5 ppm (7 mg m—3)
TWA 3 ppm TWA 3 ppm (2.5 mg m—3) C 6 ppm (5 mg m—3) (15 min)
C 20 ppm 50 ppm (10-min C 10 ppm (15 mg m—3) (10 min)
maximum peak)
None TWA 800 ppm (1900 mg m—3)
TWA 0.1 mg m—3 Hg vapor: TWA 0.05 mg m—3 (skin)
Other: C 0.1 mg m—3 (skin)
TWA 0.01 mg m—3 C 0.04 mg m—3 TWA 0.01 mg m—3 ST 0.03 mg m—3 (skin)

Methyl alcohol
Methyl chloride
Methyl chloroform
TWA 200 ppm (260 mg m—3)
TWA 100 ppm C 200 ppm
300 ppm (5-min maximum peak
in any 3 h)
TWA 350 ppm (1900 mg m—3)
TWA 200 ppm (260 mg m—3) ST 250 ppm (325 mg m—3) (skin)
Treated as a carcinogen*
C 350 ppm (1900 mg m—3) (15 min)
Along with 1,1-dichloroethane, ethyl chloride,
pentachloroethane, and 1,1,1,2-tetrachloroethane should be
treated in the workplace with caution because of their
structural similarity to the four chloroethanes shown to be
carcinogenic in animals

Naphthalene None TWA 0.040 mg m—3 (0.005 ppm) C 0.170 mg m—3 (0.020 ppm)
(10 min)
Nitric acid TWA 2 ppm (5 mg m—3) TWA 2 ppm (5 mg m—3) ST 4 ppm (10 mg m—3)

I. FOUNDATIONS OF AIR POLLUTION

 1.3 ATMOSPHERIC CHEMICAL CONCENTRATIONS 15
TABLE 1.6 U.S. Permissible Exposure Levels (PELs) and Recommended Exposure Levels (RELs) for Selected Workplace Air
Pollutantsdcont’d
Air Pollutant Permissible Exposure Level Recommended Exposure Level

Nitrogen dioxide C 5 ppm (9 mg m—3) ST 1 ppm (1.8 mg m—3)

Octane TWA 500 ppm (2350 mg m—3) TWA 75 ppm (350 mg m—3) C 385 ppm (1800 mg m—3)
(15 min)
Ozone TWA 0.1 ppm (0.2 mg m—3) C 0.1 ppm (0.2 mg m—3)
Sodium hydroxide TWA 2 mg m—3 C 2 mg m—3

Styrene TWA 100 ppm C 200 ppm TWA 50 ppm (215 mg m—3) ST 100 ppm (425 mg m—3)
600 ppm (5-min maximum peak
in any 3 h)
Sulfur dioxide TWA 5 ppm (13 mg m—3) TWA 2 ppm (5 mg m—3) ST 5 ppm (13 mg m—3)
Tetrachloroethylene TWA 100 ppm C 200 ppm (for Treated as a carcinogen*
5 min in any 3-h period), with a
maximum peak of 300 ppm
Titanium dioxide TWA 15 mg m—3 Treated as a carcinogen*
Toluene TWA 200 ppm C 300 ppm TWA 100 ppm (375 mg m—3) ST 150 ppm (560 mg m—3)
500 ppm (10-min maximum peak)
1,2,3-Trimethylbenzene None TWA 25 ppm (125 mg m—3)
1,2,4-Trimethylbenzene None TWA 25 ppm (125 mg m—3)
1,3,5-Trimethylbenzene None TWA 25 ppm (125 mg m—3)
Vinyl acetate None C 4 ppm (15 mg m—3) (15 min)
Vinyl bromide None Treated as a carcinogen*
Vinyl chloride TWA 1 ppm C 5 ppm (15 min) Treated as a carcinogen*

Welding fumes None Treated as a carcinogen*

—3
o- Xylene TWA 100 ppm (435 mg m ) TWA 100 ppm (435 mg m—3) ST 150 ppm (655 mg m—3)
m-Xylene TWA 100 ppm (435 mg m—3) TWA 100 ppm (435 mg m—3) ST 150 ppm (655 mg m—3)
p-Xylene TWA 100 ppm (435 mg m—3) TWA 100 ppm (435 mg m—3) ST 150 ppm (655 mg m—3)
Zinc chloride fume TWA 1 mg m—3 TWA 1 mg m—3 ST 2 mg m—3

Zinc oxide TWA 5 mg m—3 (fume) Dust: TWA 5 mg m—3 C 15 mg m—3

TWA 15 mg m—3 (total dust) Fume: TWA 5 mg m—3 ST 10 mg m—3
TWA 5 mg m—3 (respirable dust)

* For these substances, NIOSH will project a no-effect exposure, as well as exposure levels at which there may be residual risks. This policy applies to all workplace hazards,
including carcinogens, and is responsive to Section 20(a)(3) of the Occupational Safety and Health Act of 1970, which charges NIOSH to “.describe exposure levels that are safe
for various periods of employment, including but not limited to the exposure levels at which no employee will suffer impaired health or functional capacities or diminished life
expectancy as a result of his work experience.”
TWA, time-weighted average; C, ceiling concentration; ST, short-term exposure level (STEL), ppm, parts per million; mg m —3, milligram per cubic meter.
Source: National Institute of Occupational Safety and Health. NIOSH pocket guide to chemical hazards. http://www.cdc.gov/niosh/npg/pgintrod.html; 2013 [accessed 09.09.13].

Sometimes, industrial operations can be conducted
entirely within a sealed area, e.g. using robots. However,
several industrial operations may require work in higher
workplace exposures. This is permitted if the workers
wear appropriate PPE, especially respirators.
Assigned protection factors (APFs) are published
by OSHA.12 An APF defines the level of respiratory pro-
tection expected to be provided by a respirator or class
of respirators. The APFs range from 5 to 10,000 (see
Table 1.7). Similarly, the maximum use concentration
(MUC) is the highest atmospheric concentration of a
hazardous substance from which a worker would be
expected to be protected when wearing the respirator.
The relationship between the MUC and APF informs
the decision on the type of respirator needed:
MUC ¼ PEL × APF (1.3)
If the phase of concernof HCl is a vapor, Table 1.7(B) de-
scribes the appropriate respirator. Several respirators
equipped with appropriate gas/vapor cartridges would

I. FOUNDATIONS OF AIR POLLUTION

16 1. THE STATE OF THE ATMOSPHERE

TABLE 1.7 Assigned Protection Factors for Particulate (A) and Gas/Vapor (B) Respirators

Assigned
Protection
Factor Respirator Type
A. PARTICULATE RESPIRATORS
5 • Quarter mask respirator
10 • Any air-purifying elastomeric half-mask respirator equipped with appropriate type of particulate filter (filter medium must
provide protection against the particulate in question).
• Appropriate filtering facepiece respirator filter medium must provide protection against the particulate in question; APF of
10 can only be achieved if the respirator is qualitatively or quantitatively fit tested on individual workers.
• Any air-purifying full facepiece respirator equipped with appropriate type of particulate filter (filter medium must provide
protection against the particulate in question).
• Any negative pressure (demand) supplied-air respirator equipped with a half-mask.
25 • Any powered air-purifying respirator equipped with a hood or helmet and a high-efficiency (HEPA) filter.
• Any continuous flow supplied-air respirator equipped with a hood or helmet.

50 • Any air-purifying full facepiece respirator equipped with N-100, R-100, or P-100 filter(s).
• Any powered air-purifying respirator equipped with a tight-fitting facepiece (half- or full facepiece) and a high-efficiency
filter.
• Any negative pressure (demand) supplied-air respirator equipped with a full facepiece.
• Any continuous flow supplied-air respirator equipped with a tight-fitting facepiece (half or full facepiece).
• Any negative pressure (demand) self-contained respirator equipped with a full facepiece.
1000 • Any pressure-demand supplied-air respirator equipped with a half-mask.
2000 • Any pressure-demand supplied-air respirator equipped with a full facepiece.
10,000 • Any pressure-demand self-contained respirator equipped with a full facepiece.
• Any pressure-demand supplied-air respirator equipped with a full facepiece in combination with an auxiliary pressure-
demand self-contained breathing apparatus.
B. GAS/VAPOR RESPIRATORS
10 • Any air-purifying half-mask respirator equipped with appropriate gas/vapor cartridges (select a cartridge/canister certified
to be used for the specific class of chemicals or the specific gas/vapor found in the workplace).
• Any negative pressure (demand) supplied-air respirator equipped with a half mask.
25 • Any powered air-purifying respirator with a loose-fitting hood or helmet equipped with appropriate gas/vapor cartridges
(select a cartridge/canister certified to be used for the specific class of chemicals or the specific gas/vapor found in the
workplace).
• Any continuous flow supplied-air respirator equipped with a hood or helmet.
50 • Any air-purifying full facepiece respirator equipped with appropriate gas/vapor cartridges2 or gas mask (canister
respirator) (select a cartridge/canister certified to be used for the specific class of chemicals or the specific gas/vapor found
in the workplace).
• Any powered air-purifying respirator equipped with a tight-fitting facepiece (half or full facepiece) and appropriate
gas/vapor cartridges or canisters (select a cartridge/canister certified to be used for the specific class of chemicals or the
specific gas/vapor found in the workplace).
• Any negative pressure (demand) supplied-air respirator equipped with a full facepiece.
• Any continuous flow supplied-air respirator equipped with a tight-fitting facepiece (half or full facepiece).
• Any negative pressure (demand) self-contained respirator equipped with a full facepiece.
1000 • Any pressure-demand supplied-air respirator equipped with a half-mask.

2000 • Any pressure-demand supplied-air respirator equipped with a full facepiece.

10,000 • Any pressure-demand self-contained respirator equipped with a full facepiece.
• Any pressure-demand supplied-air respirator equipped with a full facepiece in combination with an auxiliary
pressure-demand self-contained breathing apparatus.

Source: Centers for Disease Control and Prevention. National Institute for Occupational Safety and Health. NIOSH Respirator Selection Logic. DHHS (NIOSH) Publication
No. 2005-100; 2004.

I. FOUNDATIONS OF AIR POLLUTION

 1.4 FLUID PROPERTIES AND DYNAMICS
provide an APF of 10. That is, MUC ¼ 5 × 10 ¼ 50 ppm. If
the measured 13.4 ppm peak concentration represents the
highest HCl levels expected in this workplace, respirators
providing an APF of 10 should be sufficient protection, if
worn and used properly.
Monitoring must continue; but let us assume that the
equipment being used does not display ppm units, but
gives units of mg m—3. Since the peak (ceiling PEL) con-
centration not to be exceeded using the APF 10 respi-
rator is 50 ppm, what is this in units of mg m—3?
Returning to Table 1.3, the conversion factor for HCl to
use when ppm is known is 1490:
1490 × 50 ¼ 74;500 mg m—3 ¼ 74:5 mg m—3
If concentrations begin to approach 70 mg a m —3,
more protective respirator may be needed (e.g. the
supplied-air respirator with an APF of 1000 would be
much more protective).
To ensure that the unit conversions for NH 3 and HCl
are correct, the molecular weight (MW) of each can be
inserted in to Eqn (1.1):
33.12 ppm NH3 ¼ 33.12 × [40.9 × MW] mg m—3
33.12 ppm NH3 ¼ 33.12 × [40.9 × 17.0] mgm—3
33.12 ppm NH3 ¼ 23,028 mg m—3
13.4 ppm HCl ¼ 13.4 × [40.9 × MW] mg m—3
13.4 ppm HCl ¼ 13.4 × [40.9 × 36.5] mg m—3
13.4 ppm HCl ¼ 20,004 mg m—3
Both unit conversions are within rounding error at
three significant figures.
1.4 FLUID PROPERTIES AND DYNAMICS
Gases and liquids are fluids. Since the air is a
mixture of gases, with varying amounts of suspended
liquids and solids, it posseses fluid properties. b In addi-
tion to the complex and changing chemical composition
of the atmosphere, the air’s fluid properties and
dynamics must be understood at various scales, from
the movement of air masses at a global scale to the
movement of contaminants and essential nutrients
among and within an organism’s cells. Air is the most
prominent fluid when considering air pollutants, but it
is not the only fluid involved in air pollution. Water is
arguably equally important for numerous reasons,
including as a component of the atmosphere and as
the transport and transformation medium of bodily
fluids during intake, adsorption, metabolism, distribu-
tion, and excretion of air pollutants and their byprod-
ucts within an organism. Many other fluids are
b
Even solids can be fluids at a very large scale. For example, in plate tectonics and other expansive geological processes, solid rock will
flow, albeit very slowly.
I. FOUNDATIONS OF AIR POLLUTION
17
important to air pollution. Indeed, the pollutants them-
selves are often fluids under environmental conditions,
e.g. alcohols, solvents, and oils.
The first law of motion states that every object in a
state of uniform motion tends to remain in that state of
motion unless an external force is applied to it, i.e.
inertia. The most common external force that changes
the state of uniform motion is friction.
The second law of motion describes the relationship
between an object’s mass m, its acceleration a, and the
applied force:
F ¼ ma (1.4)
Acceleration and force are vectors; wherein the direc-
tion of the force vector is the same as the direction of the
acceleration vector. For example, if the mass of the
pollutant, the mass of the fluid where it resides (i.e. air
mass), and applied force (e.g. generated by the wind)
are known, then the acceleration of a particle can be
calculated, as well as the acceleration of the entire plume
from one point to another.
The third law of motion states that for every action
there is an equal and opposite reaction. Like the first
law, this means that movements are dynamic and
actions taken to change the velocity or direction of a
pollutant (e.g. baffles, vents, and barriers) will be met
with resistance and will result in changes in flow and di-
rection of the pollutants. This comes into play when
designing pollution control equipment.
The laws of chemistry remind us that what we put
into a reaction always leads to a specific product.
Thus, science tells us that so long as we understand
the variables and parameters of any system, the
outcome is predictable. This is obviously not
completely possible when designing air pollution con-
trol equipment, for example, but lessons learned from
successes and failures in previous designs lead to
improved control technologies. There are numerous
ways to identify, characterize, and analyze air pollution
and to determine how the exposure to a pollutant has
led and can lead to health and environmental impacts.
Accurate descriptions of fluid properties and fluid
dynamics are an essential part of this.
1.4.1 Atmospheric Fluid Properties
Air pollution involves fluids. The term “fluid” in-
cludes all liquids and gases. A liquid is a form of matter
that is composed of molecules that move freely among
themselves without separating from each other. A gas
is a form of matter that is composed of molecules that
18 1. THE STATE OF THE ATMOSPHERE
move freely and are infinitely able to occupy the space in
which they are contained at a constant temperature. En-
gineers define a fluid as a substance that will deform
continuously upon the application of a shear stress; i.e.
a stress in which the material on one side of a surface
pushes on the material on the other side of the surface
with a force parallel to the surface.
The medium itself, i.e. air, is a fluid. So are some of the
pollutants (gases like carbon monoxide, vapors like
benzene, and liquid aerosols). Also, water is a key fluid,
such as its vapor phase (e.g. clouds, fog, and steam) and
its liquid phase (e.g. droplets, surface and groundwater
interactions with the atmosphere). Indeed, many other
fluids must be considered to describe air pollution fully,
notably after exposure, blood, lipids, and other bodily
fluids transport air pollutants and their metabolites
within organisms.
As mentioned, fluids are either liquid or gaseous.
Fluid properties, along with fluid dynamics determine
the extent and severity of a disaster. For example, con-
taminant’s fluid properties will determine how soluble
it will be in water droplets that are transported and
deposited differently from air pollutants having lower
aqueous solubility. A substance that is insoluble in water
is often quite soluble in fats, meaning that exposures will
lead to buildup in lipids. If a chemical is easily absorbed,
the hazard may be higher.
The fluid properties of an agent, whether chemical or
biological (e.g. bacteria and viruses), determine where
the agent is likely to be found in the environment after
release (e.g. in the air as a vapor, sorbed to a particle, dis-
solved in water, or accumulated in biota).
As science becomes less reductionist and more sys-
tematic, certain long-held boundaries between disci-
plines are becoming blurred. For example, physical
transport is not only a function of the mechanics of
fluids, but it is also a chemical process, such as when
and under what conditions transport and chemical
transformation processes become a steady state or
nearly steady state, e.g. sequestration and storage in
the environment. Thus, transport and transformation
of air pollutants depends on the characteristics of envi-
ronmental fluids.
FIGURE 1.9 Classification of fluids based on
continuum fluid mechanics. Research and Educa-
tion Association. The essentials of fluid mechanics
and dynamics I. Piscataway (NJ): REA; 1987.
Laminar
Compressible Incompressible
I. FOUNDATIONS OF AIR POLLUTION
Fluids can be classified according to observable phys-
ical characteristics of flow fields. A continuum fluids
mechanics classification is shown in Figure 1.9. Laminar
flow is in layers, while turbulent flow has random move-
ments of fluid particles in all directions. In incompress-
ible flow, the variations in density are assumed to be
constant, while the compressible flow has density varia-
tions, which must be included in flow calculations.
Viscous flows must account for viscosity while inviscid
flows assume viscosity is zero.
The time rate of change of a fluid particle’s position in
space is the fluid velocity (V). This is a vector field quan-
tity. Speed (V) is the magnitude of the vector velocity V
at any given point in the fluid, and average speed ðVÞ is
the mean fluid speed through a control volume’s sur-
face. Therefore, velocity is a vector quantity (magnitude
and direction), while speed is a scalar quantity (magni-
tude only). The standard units of velocity and speed
are meter per second (m s—1).
Velocity is important in determining pollution prop-
erties and mechanisms, such as mixing rates after an
effluent is discharged to a stream, how rapidly an
aquifer will become contaminated, and the ability of
liners to slow the movement of leachate from a landfill
toward the groundwater. The distinction between veloc-
ity and speed is seldom made, even in technical
discussions.
Another important fluid property is pressure. A force
per unit area is pressure (p):
F
p¼ (1.5)
A
So, p is a type of stress that is exerted uniformly in all
the directions. It is common to use pressure instead of
force to describe the factors that influence the behavior
of fluids. The standard unit of p is the pascal (Pa),
which is equal to 1 N m—2. The preferred pressure
unit in this book is the kilopascal (kPa), since the stan-
dard metric unit of pressure is the pascal, which is quite
small.
Potential and kinetic energy discussions must
consider the fluid acceleration due to gravity. In many
ways, it seems that acceleration was a major reason for
Continuum fluid mechanics
Viscous Inviscid
Compressible Incompressible
Turbulent
Compressible Incompressible
 1.4 FLUID PROPERTIES AND DYNAMICS
Isaac Newton’s need to develop the calculus. 13 Known
as the mathematics of change, calculus is the mathemat-
ical means of describing acceleration and addressed
Newton’s need to express mathematically his new law
of motion. Acceleration is the time rate of change in
the velocity of a fluid particle. In terms of calculus, it is
a second derivative. That is, it is the derivative of the
velocity function. And a derivative of a function is itself
a function, giving its rate of change. This explains why
the second derivative must be a function showing the
rate of change of the rate of change, which is readily
apparent from the units of acceleration: length per
time per time (m s—2).
Unfortunately, in the United States and some other
countries, pollution rules, regulations, and standards
are not used consistently and uniformly. For example,
the regulations for ozone (O3) are expressed volumetri-
cally in parts per billion, but aerosols are usually mass
per volume. Since volume is directly proportional and
temperature indirectly proportional to density (com-
bined gas law), some assumptions must be made before
converting volumetric units (ppm, volume) to concen-
tration units (mg m—3). Unless otherwise stated, the first
simplifying assumption is that the ideal gas law is ex-
pected to apply to environmental conditions in this
book:
pV ¼ nR0 T (1.6)
where n is the number of moles and R0 is the gas con-
stant, R0 ¼ 8.315 J K—1 mol—1.
An ideal gas is one in which the atoms or molecules
are moving randomly and not interacting with one
another. Under environmental conditions, e.g. standard
temperature and pressure, most gases in the atmosphere
behave like ideal gases. However, at decreasing temper-
atures and pressures, gases begin to deviate from ideal
behavior, especially due to molecular size (i.e. less space
between molecules means the ratio of molecule to void
space increases) and intermolecular forces (i.e. the ratio
of kinetic energy to intermolecular forces decreases).
Since the density (r) of a fluid is its mass per unit vol-
ume (e.g. mg m—3), the density of an ideal gas is found
using the gas constant specific to that molecule and
applying the ideal gas law:
r ¼ pðRTÞ—1 (1.7)
where,
p ¼ gas pressure
R ¼ specific gas constant
T ¼ absolute temperature.
The specific gas constant must be known to calculate
the gas density. For example, the R for air is
287 J kg—1 K—1. The specific gas constant for methane
(RCH4) is 518 J kg—1 K—1.
I. FOUNDATIONS OF AIR POLLUTION
19
Applying these assumptions, at 25 ○C and 760 mmHg,
ppb (vol.) can be converted to mg m—3:
1 l pollutant
1 ppb ðvol:Þ pollutant ¼
109 l air
ð1 l=22:4Þ× MW × 109 mg × g m—1 (1.8)
¼
109 l × 298 K=273 K × 10—3 × l—1
¼ 4:09 × 104 MW mg m—3
where MWequals the molecular weight. Thus, Equations
1.1 and 1.8 can be used to convert any molecule volu-
metric concentration to mass per volume concentration.
Several airpollutantsare consideredasclassesorcollec-
tions of compounds (e.g. coke oven emissions, oxides of
sulfur, and oxides of nitrogen). Thus, it is important to
keep in mind that a published concentration will often
beanaverage ortotal. To becompletelycorrect, eachchem-
ical speciesmust be convertedseparately, since the density
of each compound in the group differs. For example, it is a
common practice to add concentrations of nitrogen diox-
ide and nitric oxide in ppm (vol.) and express the sum as
“oxides of nitrogen”. In metric units, conversion from
ppm (vol.) to mg m—3 must be calculated separately for ni-
trogen dioxide and nitric oxide prior to addition.
Density is a very important fluid property for any air
pollution situation. If a pollutant is very dense, such as
a heavy particle, it will stay aloft for a much shorter
time and distance than will a lighter particle of the
same shape and size. For first responders, the density in
part determines the response. For example, whether a
burning substance is of greater or lesser density than wa-
ter will be one of the factors on how to extinguish the fire.
If the substance is less dense than water, the water will
likely settle below the layer of water, making water a
poor choice for fighting the fire. So, any flammable liquid
with a density less than water (see Table 1.8), such as ben-
zene or acetone, will require fire-extinguishing sub-
stances other than water. For substances heavier than
water, like carbon disulfide, water may be a good choice.
The reciprocal of a substance’s density is known as its
specific volume (y). This is the volume occupied by a
unit mass of a fluid. The units of y are reciprocal density
units (m3 kg—1). Stated mathematically, this is:
y ¼ r—1 (1.9)
The weight of a fluid per unit volume is known as the
specific weight (g). Scientists and engineers sometimes
use the term interchangeably with density. Geoscientists
frequently refer to a substance’s specific weight. A sub-
stance’s g is not an absolute fluid property as it depends
upon the fluid itself and the local gravitational force:
g ¼ gp (1.10)
20 1. THE STATE OF THE ATMOSPHERE

TABLE 1.8 Densities of Some Important Environmental Fluids TABLE 1.9 Surface Tension (Contact with Air)
of Selected Environmental Fluids
Density (kg mL3) at 20 ○ C
Fluid unless Otherwise Noted Surface Tension, s
Fluid (N mL1 at 20 ○C)
Air at standard temperature 1.29
0 ○C and
and pressure (STP) ¼ Acetone 0.0236
101.3 N m—2
Benzene 0.0289
Air at 21 ○C 1.20
Ethanol 0.0236
Ammonia 602
Glycerin 0.0631
Diethyl ether 740
Kerosene 0.0260
Ethanol 790
Mercury 0.472
Acetone 791
n-Octane 0.0270
Gasoline 700
Tetrachloromethane 0.0236
Kerosene 820
Toluene 0.0285
Turpentine 870
Water 0.0728
Benzene 879
Pure water 1000
Seawater 1025 E is expressed in units of pressure (e.g. kPa). Water’s
Carbon disulfide 1274
E ¼ 2.2 × 106 kPa at 20 ○C.
Surface tension effects occur at liquid surfaces (inter-
Chloroform 1489 faces of liquideliquid, liquidegas, liquidesolid). Sur-
Tetrachloromethane (carbon 1595 face tension, s, is the force in the liquid surface normal
tetrachloride) to a line of unit length drawn on the surface. Surface ten-
Lead (Pb) 11,340 sion decreases with temperature and varies depending
on the contact fluid. Surface tension is involved in capil-
Mercury (Hg) 13,600
lary rise and drop. Water has a very high s value
(0.0728 N m—1 at 20 ○C). Of the environmental fluids,
only mercury has a higher s (see Table 1.9). The high sur-
face tension creates a type of skin on a free surface,
Specific weight units are the same as those for den- which is how an object that is denser than water (e.g. a
sity, e.g. kg m—3. Specific weight is not often used by steel needle) can “float” on a still water surface. It is
air pollution practitioners and researchers, but it the reason insects can sit comfortably on water surfaces.
can be an important property when characterizing fugi- Surface tension is somewhat dependent upon the gas
tive dust and for source apportionment. For example, a that is in contact with the free surface. If not indicated,
particle’s specific weight may be a way to distinguish it is usually assumed that the gas is air.
dust from soil erosion or surface mining or from other The composition and fluid properties of the atmo-
sources. sphere provide the setting and context for the discussion
The fractional change in a fluid’s volume per unit of air pollution. The following chapters consider various
change in pressure at constant temperature is the fluid’s ways of characterizing air pollution and air pollutants,
coefficient of compressibility. Any fluid can be com- beginning with the physical processes at work in the at-
pressed in response to the application of pressure (p). mosphere, followed by discussions of society’s expecta-
For example, water’s compressibility at 1 atm is tions of scientists and professionals who must apply
4.9 × 10—5 atm—1. This compares to the lesser compress- scientific principles to address air pollution.
ibility of mercury (3.9 × 10—6 atm—1) and the greater
compressibility of hydrogen (1.6 × 10—3 atm—1). A QUESTIONS
fluid’s bulk modulus, E, is a function of stress and strain
on the fluid, and is a description of its compressibility, 1. What is the mixing ratio? What advantage is there to
and is defined according to the fluid volume (V): using this as opposed to concentrations of gases in
stress dp the atmosphere?
E¼ ¼— (1.11) 2. Explain why the mixing ratio below 100 km altitude
strain dV=V in the atmosphere is highly variable for most
1

I. FOUNDATIONS OF AIR POLLUTION

 QUESTIONS
substances other than molecular nitrogen and the
noble gases.
3. Why do the mixing ratios for methane and nitrous
oxide decrease beginning at about 20 km of altitude?
4. What is a standard atmosphere?
5. What is air density?
6. What is density of air at 1 atm and 20 ○C? How about
in the Nevada desert in summer, if the atmospheric
pressure is 0.92 atm and T ¼ 40 ○C?
7. If the number density of benzene in a garage is
2.4 ×1018 molecules per m3, what is the mass
density in mmol? In mg m—3?
8. Give some possible reasons for the differences in
formaldehyde concentrations shown in Figure 1.6
and benzene concentrations in Figure 1.7?
9. Assume the average weight of a passenger vehicle
is 1800 kg and the average gas mileage is 10 km L —
1
, and that gasoline weighs an average of 0.7 kg L —
1
, with 85% of this weight as carbon. Does the
average vehicle emit its own weight in CO2 each
year?
10. Using the data from the previous question, if there
are 1 billion vehicles in the world, estimate the
annual global carbon emissions from vehicles. Give
your answer in tons, tonnes, and teragrams.
11. If the average vehicle lowers its emissions of NO x
(i.e. NO + NO2) from 17 to 0.64 kg year—1 and
volatile organic compounds from 35 to 1 kg year —1,
how would the global emissions of these
compounds change? What effect might this have on
smog?
12. What would the answers to the three previous
questions be if the average gas mileage were 15 and
25 km L—1? Based on these calculations, make a
statement about the relationship between air
pollution and efficiency.
13. Why might formaldehyde concentrations be
higher in manufactured homes versus conventional
homes, such as the data shown in Table 1.5? How
might time since construction affect these data?
14. Explain why the bars for acute toxicity (LC50) are so
much taller than those for chronic toxicity (MRL and
cancer risk) in Figure 1.8.
15. At 25 ○C and 760 mmHg, express 15 ppm benzene,
180 ppb ozone and 500 ppm of sulfuric acid in
mg m—3.
16. What may cause the above calculations of benzene
and sulfuric acid to be incorrect?
17. Explain why a first responder needs to know the
density of substances that may be in a building?
Why do the different densities between air and those
of carbon disulfide and ammonia matter for a first
responder?
18. How is the formation of CO2 different in respiration
versus combustion?
I. FOUNDATIONS OF AIR POLLUTION
21
19. A 200 scfm gas stream from the ground consisting of
60% by volume methane and 40% carbon dioxide is
to be treated by an incinerator. The gas is to be
burned with 20% excess air at 980 ○ C. Find the
stoichiometric amount of air required, the total
auxiliary air required, the total influent gas flow rate
to the incinerator, and the total emission rate from
the incinerator. What could be a likely source of this
gas stream? In the real-world, what else is likely to
be in this gas stream?
20. Why do concentrations of H2O vapor and CO2 vary
so much in the atmosphere compared to most other
substances?
21. Name two atmospheric gases that absorb incoming
(shortwave) solar radiation.
22. Name two gases that absorb outgoing thermal
(infrared) radiation.
23. Why does such a small amount of the atmosphere’s
gases not drift off into space?
24. Which principal atmospheric gas changes the most
in concentration with altitude?
25. Describe the major changes in temperature profile in
the troposphere and stratosphere. Explain.
26. What is the spectral range of thermal radiation?
27. At what spectral range is the atmosphere
transparent to IR energy (i.e. heating)?
28. Define atmospheric pressure.
29. What causes the fluid dynamics (i.e. movement of
air) in the atmosphere?
30. What are the major sources of CH4 and CO2 in the
environment? How do these two compounds relate
to each other?
31. Why has the preindustrial concentration of N 2O
changed so little as of 1998 compared to that of
methane and carbon dioxide?
32. What were the sources of perfluoromethane before
the industrial revolution? Why has it doubled since
then?
33. What are some of the possible air pollutants that can
be released by confined animal feeding operations?
What can be done to address them?
34. Why was asbestos used so commonly in the
twentieth century?
References
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eogtrain.nsf/DisplayView/SI_409_0-5?OpenDocument; 2007.
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Boulder, Colorado: Earth System Research Laboratory. National
Atmospheric and Oceanic Administration; 2009.
22 1. THE STATE OF THE ATMOSPHERE
4. Agency for Toxic Substances and Disease Registry. Toxicological
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National Institute for Occupational Safety and Health (NIOSH).
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13. Newton actually co-invented the calculus with Wilhelm Leibniz in
the 17th century. Both are credited with devising the symbolism
and the system of rules for computing derivatives and integrals,
but their notation and emphases differed. A debate rages on
who did what first, but both of these giants had good reason to
revise the language of science; i.e. mathematics, to explain motion.