Atmospheric Environment

Dr.rer.nat Doni Prakasa E. Putra

Principal of Environmental Geochemistry – Nelson Eby
Structure & Composition
of Earth Atmosphere

Figure 8-1. The U. S. Standard Atmosphere, 1976. Note the various

temperature reversals, which act as thermal lids on the lower parts of
the atmosphere. In the troposphere, gases are well mixed. From
Neiburger et al. (1982).
Ta ble 8-1. A verage co mposition of the earth’s at mos phere to a height of 25 k m

Gas Volu me % Source Variability

N2 7 8.08 biologic permanent
O2 2 0.95 biologic permanent

Ar 0.93 rad iogenic permanent

Ne 0.00 18 interior permanent

He 0.00 05 rad iogenic escap ing

Xe 0.00 0009 interior permanent
H 2O 0 to 4 evaporation variable
CO 2 0.03 6 biologic, industrial increasing
CH 4 0.00 017 biologic increasing
N 2O 0.00 003 biologic, industrial increasing

O3 0.00 0004 photochemical variable

 E = σT-4 (Stefan-Boltzmann Law)
E Energy emmited in Wm-2
T Temperature of the radiator in K
σ Stefan-Boltzmann constant 5.670 x 10-8 Wm-2K-4

λm = αT-1
λm Wavelength of maximum energy
α Wien displacement law constant (2.898 x 10-3 mK)

Figure 8-2. Schematic representation of the variation in total energy emitted per unit
wavelength as a function of temperature for a perfect radiator. With increasing
temperature the total amount of energy increases and the wavelength of maximum
energy decreases.
Figure 8-3. Absorptivity of various atmospheric gases, and the atmosphere as a whole, as a function of
wavelength. From Fleagle and Businger (1963).
Figure 8-4. Incoming (shortwave) and outgoing (longwave) radiation as a function of
latitude. The crossover occurs at ~40o. At lower latitudes there is a heat excess, at higher
latitudes a heat deficit.
 Air Pollution

The presence in the atmosphere of substances that are

toxic, irritant, or otherwise harmful to man or damaging to
vegetation, animals, or property

Primary Pollutant  direct products of combustion and

evaporation (particulates, VOCs, CO, CO2, Sox and NOx)
Secondary Pollutant  formed in the atmosphere by reaction
with the primary pollutants
 Air Pollution
Ta ble 8-2. Classificati on of air pollutants

Major Class Subclass Examples

Inorganic gases O xides of nitrogen N 2 O, NO, NO 2

O xides of sulfur SO 2 , SO 3

O xides of carbon CO, CO 2

Other inorganics O 3 , H 2 S, HF, NH 3 , Cl2 , Rn

Organic gases Hydro carbons M ethane (CH 4), butane (C4 H 10), octane (C8 H 18 ),
ben zene ( C6H 6 ), acetylene (C2 H 2), ethylene (C2H 4 )
Ald ehydes and ketones For maldehyde, acetone

Other organics Chlo rofluorocarbons, PAHs, alcohols, organic acids

Particulates Solids Fu me, dust, smoke, ash, carbon soot, lead, asbestos
Liquids M ist, spray, oil, grease, acids
 Greenhouse gases

Figure 8-7. Increase in greenhouse gases since 1750. CFCs (as represented by CFC11) are entirely of
anthropogenic origin and don’t become significant until after 1950. Besides their role as greenhouse gases, CFCs
are also important in the breakdown of ozone. From Berner and Berner (1996).
Table 8-5. D ata for greenhouse g ases

Positive Relative Global

radiative % total instantaneous W arming
Concentration fo rcing radiative Lifetime radiative forcing Potential
Gas 1990 (pp mv) (W m-2) forcing (y) (molecular basis) (100 y)

CO 2 354 1.5 61 50 - 200 1 1

CH 4 1.72 0.42 17 12 43 21

H 2 O strat - 0.14 6
N2 O 0.310 0.1 4 120 250 310
CF C-11 0.00028 0.06 2 2.5 65 15,000 3,400
CF C-12 0.00048 4 0.14 6 130 19,000 7,100
Other CFCs 0.08 5 3.5

Total 2.45 100.0

CF C substitutes
HFC-23 264 650
HFC-152a 1.5 140
CF 4 50,000 6,500
C6 F1 4 3,20 0 7,400
Figure 8-8. Mean monthly concentrations of CO2 at Mauna Loa, Hawaii. From Berner and Berner (1996).
Figure 8-10. Variation in methane abundance from 1841 to 1996. The fitted curve is a sixth-order polynomial. Data
from Etheridge et al. (1994) and IPCC (1996).
Ta ble 8-7. Sources an d sinks for at mos pheric methane

Source or Sink CH 4 (1 0 12 g C y-1) % total

Sources
Natural

Wetlands 86 22.5
Ter mites 15 3.9

Oceans 8 2.1

Lakes 4 1.0
Methane hydrates 4 1.0

Total natural 117 30.5

Anthrop ogenic

Energy pro duction/use 69 18.0

Enteric fermentation 63 16.4
Rice 45 11.8

Ani mal wastes 20 5.2

Land fills 29 7.6
Bio mass burning 21 5.5
Do mestic sewage 19 5.0
Total anthrop ogenic 266 69.5
Total for sources 383

Sinks

At mospheric remo val 353 88.2

Remo val by soils 23 5.8

At mosphere 24 6.0

Total for sinks 400

Figure 8-11. Variations in temperature, CO2, and CH4
concentrations in Antarctica during the past 240,000 years. From
Lorius et al. (1993).
Figure 8-12. Surface temperature of the
Pacific Ocean based on oxygen isotope
ratios. From THE BLUE PLANET, 2nd
Edition by B. J. Skinner, S. C. Porter
and D. B. Botkin. Copyright 1999. This
material is used by permission of John
Wiley & Sons, Inc.
 Aerosols
Ta ble 8-3. Sources of aerosols an d contri butions of natural versus anthro pogenic Solid particles or
sources liquid droplets
Natural Anthropo genic
Source (1 0 12 g y -1) (1 0 12 g y -1)
with size < 20
Soil and rock dust 3 000 - 4000 ?
μm in radius
Sea salt 1 700 - 4700

Biogenic 100 - 500

Bio mass burning (so ot) 6 - 11 36 - 15 4

Volcanic 15 - 90
Direct emissions - fuel, incinerato rs, industry 15 - 90

Gaseo us emissions

Sulfate fro m biogenic DM S 51

Sulfate fro m volcanic SO 2 18 - 27

Sulfate fro m fossil fuel 105

Nitrate fro m NO x 62 128
A mmoniu m fro m NH 3 28 37

Biogenic hydro carbons 20 - 15 0

Anthropogenic hydrocarbons 100

Total 5 000 - 9619 421 - 614

Figure 8-24. Sources of atmospheric particulates. Arrows with dashed lines indicate that there is a gaseous
emission associated with the source.
 Smogs

Combination of smoke and fog  hazy and irritating air

Table 8-4. Ty pes of smogs an d their characteristics

Characteristic Industrial Photochemical

First occurrence London Los Angeles

Principal pollutants SO x O 3 , NO x, HC, CO, free radicals

Principal sources Industrial and household fuel co mbustion M otor vehicle fuel co mbustio n
Effect on hu mans Lung and throat irritation Eye and respiratory irritation

Effect on co mpounds Reducing O xidizing

Ti me of worst events Winter months in the early morning Su mmer months around midd ay
Ta ble 8-1 0. S ou rces of in di vidu al ions in rain water

Ion
Na+ Sea salt
M arine inputs
Soil dust
Origin

Terrestria l inputs Pollution inputs

Bio mass burning
Rainwater
Mg 2+

K+
Sea salt

Sea salt
Soil dust

Biogenic aerosols
Bio mass burning

Bio mass burning

Chemistry
Soil dust Fertilizer

Ca2 + Sea salt Soil dust Ce ment manufacture

Fuel burning
Bio mass burning

H+ Gas reaction Gas reaction Fuel burning

Cl - Sea salt None Ind ustrial H Cl

2
SO 4 Sea salt DM S, H 2S, etc., fro m Bio mass burning
DM S fro m biological biological decay
decay Volcano es
Soil dust


NO 3 N 2 plus lightning NO 2 fro m biological d ecay Auto e missions
N 2 plus lightning Fossil fuels
Bio mass burning
Fertilizer


NH 4 NH 3 fro m biologic al NH 3 fro m bacterial de cay N H 3 fe rtilizers
activity Hu man, ani mal waste
dec o mposition
(Co mbustion)

3
PO 4 Biogenic aerosols a dsorbed Soil dust Bio mass burning
on sea salt Fertilizer


HC O 3 C O 2 in air C O 2 in air None
Soil dust

SiO 2 , Al, Fe None Soil dust Land c le aring

Ta ble 8 -11. W eigh t ratios of m ajor ions in s ea water relati ve to C l-- or N a++

Ion Weight ratio to Cl - Weight ratio to Na+

Cl- 1.0 0 1.80

Na + 0.5 6 1.00

M g 2+ 0.0 7 0.12
2
SO 4 0.1 4 0.25

Ca2+ 0.0 2 0.04

K+ 0.0 2 0.04
Figure 8-17. Average Cl- concentration (mg L-1) of rainwater for the United States from July 1995 to June 1996.
From Berner and Berner (1996).
Figure 8-18. Average Cl-/Na+ weight ratio of rainwater for the United States from July 1995 to June 1956. From
Berner and Berner (1996).
Ta ble 8-12. P ri mary as s ociations for r ain water

Origin Association
Marine Cl - Na - Mg - SO 4

So il Al - Fe - Si - Ca - (K, Mg, Na)

Biological N O 3 - NH 4 - SO 4 - K

Bio mass burning N O 3 - NH 4 - P - K - SO 4 - (Ca, Na, Mg)

Industrial p ollution SO 4 - NO 3 - Cl

Fertilizers K - PO 4 - NH 4 - NO 3
 Gaseous Species

Figure 8-19. Global SO2 produced by the burning of fossil Figure 8-20. Global NOx produced by the burning of fossil
fuel, 1940 to 1986, in Tg SO2-S y-1. (1 Tg = 106 metric tons = fuel, 1970 to 1986, in Tg Nox-N y-1. From Berner and
1012 g). From Berner and Berner (1996). Berner (1996).

The presence in the atmosphere of substances that are

toxic, irritant, or otherwise harmful to man or damaging to
vegetation, animals, or property
Figure 8-21. Generalized isoconcentration contours for SO42- (in mg L-1) for atmospheric precipitation over the
contiguous United States in 1995. Source of data is the NADP. From Langmuir (1997).
Figure 8-22. Generalized isoconcentration contours for NO3- (in mg L-1) for atmospheric precipitation over the contiguous
United States in 1995. Source of data is the NADP. From Langmuir (1997).
T able 8-13. C on cen tration (mg L-1
-1
) of selecte d s pecies in rain water

Excess
- 2 2  2 
Lo cation Cl SO 4 SO 4 NO 3 SO 4 / NO 3 Reference

Hawaii 9.63 1.92 0.57 0.2 2.9 1

N. Atlantic 5.3 1.2 0.61 0.2 3.1 2

Bermuda 6.2 1.74 0.88 0.34 2.6 3

Poker Flat, Alaska 0.09 0.25 0.24 0.12 2.8 3

New Jersey Pine
2.82 5.09 4.70 0.39 12.0 4
Barrens
Hubbard Brook, New
0.22 2.08 2.05 1.46 1.4 5
Hampshire
Bishop, California 0.64 2.26 2.17 1.03 2.1 6
Figure 8-23. Average pH for precipitation in 1955-1956 and 1972-1973 for the northeastern United States and
Canada and in 1980 for the contiguous United States and Canada. From Langmuir (1997).
Ta ble 8 -14. Ele men tal c om pos ition of th e con tin en tal crus t

Concentration (pp m) Co ncentration (p p m)

Element Upper crust Bulk crust Element Upper crust Bulk Crust

Al 80,400 84,1 00 Se 0.05 0.05

Fe 35,000 70,7 00 Mo 1.5 1.0

Sc 11 30 Ag 0.050 0.08 0

Ti 3000 54 00 Cd 0.098 0.09 8

V 60 2 30 Sn 5.5 2.5

Cr 35 1 85 Sb 0.2 0.2

Mn 600 14 00 W 2.0 1.0

Co 10 29 Au 0.0018 0.00 3

Ni 20 1 05 Pb 20 8.0

Cu 25 75 Th 10.7 3.5

Zn 71 80 U 2.8 0.91

As 1.5 1.0
 Source Identification and
Apportionment
Enrichment factor
(X /RE)particulates
EF =
crust
Where:
X element (X /RE)crust
RE reference element
EF a factor of 3 indicate the element has come from the crust, either
directly as windblown soil or indirectly from coal fly ash

Noncrustal component
Xnoncrustal = Xtotal REp (X / RE)crust
EXAMPLE

An aerosol contains 1000 ppm Al and 7 ppm Cr. Calculate

the enrichment factor and noncrustal concentration of Cr
using bulk crust for normalization!
 Figure 2-25. Theoretical two-
component logarithmic plots
for (a) crustal/marine and (b)
crustal/pollution components.
From Rahn (1999).

X = Xcrust + Xmarine + Xpollution

X = Al(X/Al)crust + Na(X/Na)marine + Se(X/Se)pollution