C H A P T E R

20
The Hydrologic Cycle

20.1 THE WATER PLANET
In Chapters 1, 2, and 9, several fluid properties are
introduced. These apply to all fluids at all macroscopic
scales, including those important for air pollution,
especially air and water. In Chapter 27, these and other
physical properties are applied to the processes and
mechanisms in the atmosphere to employ models to
predict how air pollutants will move in the tropo-
sphere, i.e. the lowest layer in which humans and
other biota live.
pollutants. The atmosphere holds about the same
amount of water as the relatively small quantity of water
in living organisms (0.0055% of total; 0.04% of fresh-
water) compared to the 96.5% in the oceans (see Table
20.1). However, the atmosphere accounts for much of
water’s activity on earth, from weather systems to
nutrient cycling (see Chapter 22) to pollutant transfor-
mation (e.g. hydrolysis) and pollutant transport (e.g.
wet and dry deposition).

H H
20.2 THE WATER MOLECULE
O

Water is an amazing molecule (see Figure 20.1). Its

features shape the earth’s surface, e.g. the fact that
due to its configuration it expands substantially as it δ–
freezes or sublimates (i.e. change of state from gas to
solid). This molecular configuration also makes for
the solvent characteristics of water. The water mole-
cule’s oxygen and two hydrogen atoms are aligned so δ+ Hydrogen bonds
that there is a slightly negative charge at the oxygen
end and a slightly positive charge at the hydrogen H

end. Since in chemistry “like dissolves like”, polar sub-

stances have an affinity to become dissolved in water,
O
and nonpolar substances resist being dissolved in wa-
ter. The hydrogen atoms form an angle of 105
with H
the oxygen atom. The asymmetry of the water molecule
leads to a dipole moment (see the discussion in the next
session) in the symmetry plane pointed toward the
more positive hydrogen atoms. Thus, the highly polar
H2O readily dissolves other polar compounds.
The interactions of air and water occur throughout
the hydrosphere, i.e. the discontinuous stratum that
holds the earth’s water, including groundwater beneath
the surface, surface water, water in soil and biota, and
moisture in the atmosphere. The fluid properties of air FIGURE 20.1 Configuration of the water molecule, showing the
and water combine in the hydrosphere, not only to electronegativity (d) at each end. The hydrogen atoms form an angle of
make weather, but also to move and transform air 105
with the oxygen atom.

Fundamentals of Air Pollution 491

http://dx.doi.org/10.1016/B978-0-12-401733-7.00020-7 Copyright © 2014 Elsevier Inc. All rights reserved.
492 20. THE HYDROLOGIC CYCLE

TABLE 20.1 Estimation of Water Volume in the Hydrosphere potential air pollutants in clouds and soil water, or the
release and the biota’s uptake of water from the atmo-
Water Volume Percentage of Percentage of
sphere (see Figure 20.2).
Water Source (3 1000 km3) Freshwater Total Water
Air pollution is impacted by and affects the water cy-
Oceans, seas, & 1,338,000 e 96.5 cle. For example, air pollution is directly affected when
bays hydrolysis occurs in water droplets suspended in the at-
Ice caps, 24,064 68.6 1.74 mosphere, which is an important type of reaction that
glaciers, & degrades air pollutants. In addition, air pollution
permanent snow changes the water cycle by adding particulate matter
Groundwater 23,400 e 1.7 (PM) on which water condenses. The water droplet is
Fresh 10,530 30.1 0.76
the site for much of the physical and chemical activities
in the atmosphere, given that the PM in the atmosphere
Saline 12,870 e 0.93 can have cores of sulfates and nitrates, with aerody-
Ground ice & 300 0.86 0.022 namic diameters <1 mm.
permafrost These aerosols can be removed from the atmosphere
Lakes 176.4 e 0.013 by several processes. “Rain out” occurs when the parti-
cles serve as condensation nuclei that lead to the forma-
Fresh 91 0.26 0.007
tion of clouds. The particles are then precipitated if the
Saline 85.4 e 0.007 droplets grow to sufficient size to fall as raindrops.
Soil moisture 16.5 0.05 0.001 Another mechanism, known as “washout”, also in-
volves rain, but the particles in air are captured by rain-
Atmosphere 12.9 0.04 0.001
drops falling through the air. Both mechanisms
Swamp water 11.5 0.03 0.0008 contribute to “acid rain”, which results in the sulfate
Rivers 2.1 0.006 0.0002 and nitrate particles reaching lakes and streams, and
increasing their acidity.
Biological water 1.1 0.003 0.0001
Both homogeneous and heterogeneous reactions
Source: U.S. Geological Survey. The world’s water. http://ga.water.usgs.gov/edu/ occur in the atmosphere. If the reaction only occurs in
earthwherewater.html; 2013 [accessed 01.11.13].
the gas phase, the reaction is homogeneous. If the
reaction involves an interface with a surface of an aerosol
20.3 THE HYDROSPHERE or within a liquid droplet, it is heterogeneous. Certain
chemical species of S and N have sufficient aqueous sol-
The entire hydrosphere is involved in air pollution, ubility to be dissolved by the droplet. These liquid-phase
whether it is exchange of pollutants between ground compounds are already acidic (e.g. including concentra-
and surface waters and the atmosphere, the storage of tions of sulfuric acid [H2SO4], nitric acid [H2NO3], and

FIGURE 20.2 The hydrological (water) cy-

cle. (For color version of this figure, the reader is
referred to the online version of this book.) U.S.
Geological Survey. Summary of the water cycle.
http://ga.water.usgs.gov/edu/watercyclesummary.
html; 2013 [accessed 01.11.13].

IV. BIOGEOCHEMISTRY OF AIR POLLUTANTS


carbonic acid [H2CO3*])a before washout. Thus, the wa-
ter droplet plays a key role in both dry and wet deposi-
tion of pollutants that lead to acidic conditions in soils
and surface waters (see Figure 20.3).
The ultimate change in pH in the hydrosphere
brought on by acid rain is buffered to varying degrees
by soils and surface waters, depending on the ionic
strength of the soil water and surface water. These buff-
ering processes are discussed in Chapter 21.
Air pollution also indirectly affects the hydrosphere
when it changes climate. Humans and other creatures
live in a very small optimal range of water, which is a
balance of precipitation, evaporation, and other sources
and sinks of water (see Figure 20.4). Increases in ambient
15
Temperature (°C)
10
Air
Water
1980 1985 1990 1995 2000
Year
FIGURE 20.4 Lake Superior water temperatures (1979e2006): the
recent large jump in summer water temperature could be associated
with the recent reduction in ice cover. (For color version of this figure,
the reader is referred to the online version of this book.) Adapted from:
Ref. 1.
a
The asterisk (*) in H2CO3 indicates that this actually occurs as an equilibrium among the acid and ions, especially carbonate and
bicarbonate. See Chapter 21.
IV. BIOGEOCHEMISTRY OF AIR POLLUTANTS
20.3 THE HYDROSPHERE 493
FIGURE 20.3 Precipitation-weighted mean pH
in wet deposition for the year 2012. (For color version
of this figure, the reader is referred to the online
version of this book.) National Atmospheric Deposition
Program. National Atmospheric Deposition Program
2012 Annual Summary. NADP Data Report 2013-01.
Illinois State Water Survey: University of Illinois at
UrbanaeChampaign; 2013.
temperatures increase evaporation rates into the atmo-
sphere. Warmer air holds more water than cooler air,
so some areas will gain water, sometimes in excess
(e.g. experience regional increases in flooding). The
increased evaporation rates can also increase desiccation
of soils and biota in the water loss areas (see Figure 20.5).
These and other changes threaten the delicate balances
within the optimal ranges of the water regimes.
The total amount of water in the hydrosphere will
remain relatively the same, but the relative locations of
the water could change substantially with changes in
climate. For example, water may move from impounded
surface waters to the atmosphere, which will change
rain and other precipitation patterns, including hurri-
canes and other storm systems.
2005
FIGURE 20.5 Drought trends in the United States. Hatching
indicating a significant trend. (For color version of this figure, the
reader is referred to the online version of this book.) Adapted from:
Ref. 2.
494
20.3.1 Air Pollution’s Indirect Effects
on the Hydrosphere
A reasonable hypothesis is that any average global
temperature increases due to increased atmospheric
concentrations of global greenhouse gases will lead to
some increase in the rate and amount of melting of po-
lar ice and glaciers.2 The net effect of this change of state
of water would be a rise in sea level, as well as other
large water bodies, e.g. the Great Lakes in North Amer-
ica (see Figure 20.4). If the rise is substantial it could be
associated with displacing human populations (e.g. is-
landers and coastal dwellers). It could also greatly
impact coastal ecosystems with biota that is not
completely submerged for at least part of the year.
Another indirect result would be the contamination of
many coastal and near-coastal water supplies by salt
water (e.g. ground water recharged by tidal rivers and
estuaries).
The density difference between fresh and salt water
is presenting a slowly unfolding public health problem
for people living in coastal communities, as well as an
environmental problem for marine and estuarine eco-
systems. Salt water contains a significantly greater
mass of ions than does freshwater (see Table 20.2).
The denser saline water can wedge beneath freshwaters
and pollute surface waters and groundwater (see
Figure 20.6). This phenomenon, known as saltwater
intrusion, can significantly alter an ecosystem’s struc-
ture and function, and threaten freshwater organisms.
It can also pose a huge challenge to coastal commu-
nities which depend on aquifers for their water supply.
The freshwater Everglades, e.g. recharge the Biscayne
aquifer, a natural underground layer that collects water.
TABLE 20.2 Important General Ionic Composition Classifica-
tions of Freshwaters and Marine Waters
Composition River Water
pH 6e8
Ca2þ 4  105 M
Cl 2  104 M
HCO 1  104 M
3
Kþ 6  105 M
Mg2þ 2  104 M
Naþ 4  104 M
SO2
4 1  104 M
M ¼ molarity (moles per liter solution).
Sources: Hunter KA, Kim JP, Reid MR. Factors influencing the inorganic speciation of
trace metal cations in freshwaters. Mar Freshwater Res 1999;50:367e72; and Schwar-
zenbach RR, Gschwend PM, Imboden DM. Environmental organic chemistry. New York
(NY): Wiley Interscience; 1993.
IV. BIOGEOCHEMISTRY OF AIR POLLUTANTS
20. THE HYDROLOGIC CYCLE
Direction of flow of ions Salt water intrusion
of freshwater Flux
Sa ltdge
we
Tidal
Tidal Estuary Marine
river system
FIGURE 20.6 Saltwater intrusion into a freshwater system. This
denser salt water submerges under the lighter freshwater system. The
same phenomenon can occur in coastal aquifers.
The Biscayne aquifer is the primary water supply to the
Florida Keys.
The effect in South Florida could be doubly trouble-
some. In addition to the type of saltwater intrusion
shown in Figure 20.6, the rising sea level could sub-
merge low-lying areas of the Everglades (see
Figure 20.7), increasing the salinity in portions of the
aquifer. In addition, the rising sea water could force salty
waters upstream into coastal areas, thus threatening sur-
face water supplies. Similar problems could also occur
in Northeastern US aquifers that are recharged by fresh
portions of streams that are vulnerable to increased
salinity during severe droughts.3 Indeed, similar
groundwateresurface wateresea water interactions
could be affected across the globe.
Salinity of water is a relative term. The values in
Table 20.2 are at best averages and target concentrations.
Actually, salinity is the concentration of total dissolved
solids (TDS). Indeed, in the United States, the drinking
water standard for TDS is a “secondary” or nuisance
standard, which is 500 mg l1. Note that the classifica-
tions using two dominant ions, Naþ and Cl, differ by
three orders of magnitude between “fresh” and “saline”
waters. Consider the hypothetical example in Figure 20.8
of these ionic strengths (indicated by TDS) before and
Salt Water after saltwater intrusion. Although the water near the wa-
8
ter supply is not “salt water”, nor does it currently violate
the secondary drinking water standard, the ionic concen-
1  102 M trations are cause for concern and serve as a warning that
6  101 M the trend is likely to be toward even higher salinity.
2  103 M
The foregoing discussion illustrates how an indirect
air pollution effect (atmospheric warming from emis-
1  102 M sions of greenhouse gases) can have hydrospheric im-
5  102 M pacts (warming and sea level rise) that lead to another
5  101 M
form of pollution (freshwater contamination). The inter-
connectedness of the atmosphere, hydrosphere, and
3  102 M biosphere are complex and extensive (see Figure 20.9).
A small change in one small part of the spheres can
lead to unanticipated outcomes. Put within a chaos
perspective, the hydrosphere has many features that
are sensitive to initial conditions.
 20.4 SCALE AND COMPLEXITY OF WATER CYCLES 495
FIGURE 20.7 Elevation and aquifer locations
Palm Beach in southern Florida. Although a small part of the
Lake aquifer is beneath salty mangrove area, most of it is
Okoochobee
recharged by the freshwater Everglades, rendering
the area vulnerable to saltwater intrusion and
increased salinity of both surface and groundwater
sources of drinking water. (For color version of this
figure, the reader is referred to the online version of
this book.) U.S. Environmental Protection Agency.
Saving Florida’s vanishing shores. http://www.epa.gov/
Ft. Lauderdale
climatechange/Downloads/impacts-adaptation/saving_
FL.pdf; 2002 [accessed 01.11.13].

Miami

Land Elevaon of Southern Florida

< 5 feet
50 miles
5 - 11 feet

> 11.5 feet

Mangroves Florida
N Bay
Biscayne Aquifer

Marathon

Key West

(A) Year 2003

100 20.3.2 Extremes

Well
Water quality can be adversely affected by either
200
extreme of water availability. For example, water quality
may suffer as a result of climate change in areas experi-
300
encing increases in rainfall as a result of heavier and
400 more frequent precipitation events. In addition to the
500
Coast damage and safety hazards of a flood, more intensive
precipitation events harm water infrastructures, e.g.
sewer systems and wastewater treatment plants are
(B) Year 2013 not designed to handle the increased volumes of water,
300 leading to greater numbers of pass-through of untreated
sewage, and the concomitant health effects this brings.
Well
These events also overwhelm storm water sewers,
increasing nutrient loadings to surface waters (see
400 Chapter 22). This causes problems, such as eutrophica-
tion and fish kills due to the oxygen demand of the
500
organic material and nutrients.1
Coast

FIGURE 20.8 Hypothetical isopleths of total dissolved solid (TDS) 20.4 SCALE AND COMPLEXITY OF
concentration (milligrams per liter) in groundwater (e.g. 30 m depth). WATER CYCLES
Note that the isopleths in A are widened compared to B. The increases
in TDS concentrations over the decade indicate saltwater intrusion and
potential contamination at the drinking water well site. (For color Myriad processes are involved in environmental sys-
version of this figure, the reader is referred to the online version of this tems, with water playing vital roles in most of them. The
book.) previous discussion has focused on the planetary

IV. BIOGEOCHEMISTRY OF AIR POLLUTANTS

496 20. THE HYDROLOGIC CYCLE

FIGURE 20.9 Potential impacts of climate

change of the hydrologic cycle. (For color version of
this figure, the reader is referred to the online
version of this book.) Ref. 2.

cycling of water, i.e. throughout the hydrosphere. How- (A) Source of water
ever, water cycling takes place at all levels, each of which (e.g. river, lake,
is important to air pollution. groundwater; or from
a public water
Water plays a large role in climate. Microclimatolog-
supply)
ical changes can occur due to the release of heated
plumes from combustion facilities and vehicles. Ex- Thermoelectric water usage
Pretreatment
changes between the atmosphere and other media, e.g. (to meet water Water for: Cooling
soil and sediment, create sinks and sources of energy. quality
• Boilers
requirements
Heat reservoirs in terrestrial and aquatic systems for boiler water
• Boiler blowdown
and other • Stack cleaning
receive added heat, which is released in ways that can sensitive needs)
alter habitats (e.g. changes to freezeethaw cycles, sea- Wastewater
sonal variations, and selectivity of certain soil bacteria Treatment
of used water
genera).
Water cycling is closely tied to energy cycling and bal-
ances. Some of these watereenergy relationships are Outfall

obvious and direct, e.g. the thermal inversions that

ΔT1
lead to urban air pollution are the result of differences
in heat energy in water vapor at various layers in the
troposphere. Some of the watereenergy relationships
are more subtle and indirect, such as the transfer of en-
ergy between trophic states in an ecosystem, which re-
lies in part on energy and water exchanges among
biotic tissue and abiotic substrates (e.g. photosynthesis
using aqueous-phase phosphorous compounds to trans-
+……
fer energy). ΔT1 +
Watereenergy cycling is also important in anthropo- ΔT2
+….
River ∑T = ΔT1 + ...ΔTn
genic systems and is part of a design of pollution control
equipment selection and application. For example, at the Mil 5 10 15 20 25
facility scale, water and energy are often addressed
together, such as the management of water and energy FIGURE 20.10 Difference in cumulative heat contribution to a
at a factory or power plant. Managing water is a simul- river from electric generating plants using a once-through cooling
taneous process with managing energy. Indeed, system (A) versus the same plants using a cooling water return system
(B). The cumulatively added heat is greatly reduced with the closed
mismanagement of water systems at the facility level water return systems compared to the once-through cooling systems
can involve trade-offs between types of pollution. The (hypothetical scenario). (For color version of this figure, the reader is
first law of thermodynamics requires, e.g. that allowing referred to the online version of this book.) Ref. 4a.

IV. BIOGEOCHEMISTRY OF AIR POLLUTANTS

 20.4 SCALE AND COMPLEXITY OF WATER CYCLES 497

(B) Source of water

FIGURE 20.10 (Continued)
(e.g. river, lake, groundwater;
or from a public water
supply)

Thermoelectric Water Usage

Pretreatment Recycled
(to meet water Water for: water from
quality Cooling systems
• Boilers cooling
requirements for where water does not
• Boiler ponds and
boiler water and blowdown directly contact heat
towers
other sensitive • Stack cleaning sources, i.e. stays
needs) enclosed in piping
(known as
“noncontact cooling)
Wastewater
Treatment of treatment
used water

Clean water
Returned
water

+……

River
∑T = ↓

Mile 50 100 150 200 250

heated water to be released in any amount, even the
permitted level, would increase the overall temperature
of the receiving stream.
The watereenergy exchanges will also scale up-
wardly. That is, heat can initiate cumulative environ-
mental impacts, such as the heat exchange and
balances were changing conditions of receiving water
bodies.4a,4b Up to the 1970s, every power plant along
the major rivers of the United States was releasing
heated water to a stream (see Figure 20.10). This meant
that the incremental effect of all the permitted releases
led to a cumulative increase in the temperature. In the
late 1970s, once-through cooling, i.e. letting water pass
through turbines and then discharging to adjacent
streams, was no longer allowed in US waters
(Figure 20.10(A)). Other cooling systems, e.g. cooling
towers and cooling lakes, had to be installed and oper-
ated, which meant power plant water systems became
more closed, both from a fluid dynamics and thermody-
namic perspective (Figure 20.10(B)).
The heat from boilers and other industry-scale oper-
ations is going to be exchanged. This is a consideration
in both air pollution and water pollution control deci-
sions. Facility design determines in large part where
the energy goes (see Figure 20.11). In fact, an air
pollution control and heat control design can directly
affect dissolved oxygen (DO) content of the receiving
water since temperature is directly proportional to DO
content. The DO is a limiting factor of the type of fish
communities that can be supported by a water body
(see Tables 20.3 and 20.4). The resulting net increase in
heat may directly stress the biotic integrity of a surface
water ecosystem, e.g. fish species vary in their ability
to tolerate higher temperatures, meaning that the less
tolerant, higher value fish will be inordinately
threatened.

IV. BIOGEOCHEMISTRY OF AIR POLLUTANTS

498 20. THE HYDROLOGIC CYCLE

FIGURE 20.11 Adverse effects in the real Heat Emission to

world usually result from a combination of atmosphere
conditions. In this example, both energy and
Industry scale
matter must be considered in the control of air
pollution. The control of matter leaving the Heat
combustion unit (upper left-hand side) must be Combustion unit
optimized with the transfer of energy (middle).
The added heat results in an abiotic response (i.e. Flue gas
Air pollution
decreased dissolved oxygen (DO) concentrations control
Ash
in the water), which leads to biotic processes that
Heat
either increase or decrease DO and increase the Residue
toxic responses (e.g. low DO and increase in handling
metal bioavailability). (For color version of this Solids Water
figure, the reader is referred to the online version
of this book.) Adapted from: Ref. 4a.

Treated solids
Heat added to
surface water

Decreasing Increasing
Algal
DO DO
photosynthesis

Oxidation
Bacterial Algal of metals
metabolism metabolism

Toxicity to
anaerobes
Decreasing
DO

Reduction of
metals Nutrition to
microbes
Toxicity
to aerobes

Toxicity to
higher
organisms

The increased temperature can also increase the
aqueous solubility of substances that are toxic to organ-
isms. For example, greater concentrations of mercury
and other toxic metals will occur with elevated temper-
atures (see Chapter 23). The lower DO concentrations
will lead to a reduced environment where the metals
and compounds will form sulfides and other com-
pounds that can be toxic to aquatic life. Thus, the change
in temperature, the resulting decrease in DO and
increasing metal concentrations, and the synergistic
impact of combining the hypoxic water and reduced
metal compounds are a cascade of harm to the stream’s
ecosystems (see Figure 20.3).
Biota also plays a role in the heat-initiated effect.
Combined abiotic and biotic responses occur. Notably,
the growth and metabolism of the bacteria results in
even more rapidly decreasing DO levels. Algae both
consume DO for metabolism and produce DO by photo-
synthesis. The increase in temperature increases their
aqueous solubility and the decrease in DO is accompa-
nied by redox changes, e.g. formation of reduced metal
species, such as metal sulfides. This is also being medi-
ated by the bacteria, some of which will begin reducing
the metals as the oxygen levels drop (reduced conditions
in the water and sediment). However, the opposite is
true in the more oxidized regions, i.e. the metals are
forming oxides. The increase in the metal compounds
combined with the reduced DO, combined with the
increased temperatures can act synergistically to make
the conditions toxic for higher animals, e.g. a fish kill.
The initiating abiotic effect (i.e. increased tempera-
ture) results in an increased microbial population. The
associated decline in DO, however, is a net decline be-
tween photosynthetic and nonphotosynthetic microbes.

IV. BIOGEOCHEMISTRY OF AIR POLLUTANTS

 20.4 SCALE AND COMPLEXITY OF WATER CYCLES 499
The growth and metabolism of the bacteria result in more oxidized regions, i.e. the metals are forming ox-
decreasing the DO levels, but the growth of the algae ides. The increase in the metal compounds combined
both consume DO for metabolism and produce DO by with the reduced DO, combined with the increased
photosynthesis. temperatures can act synergistically to make the condi-
Meanwhile a combined abiotic and biotic response tions toxic for higher animals, e.g. a fish kill.5 Predicting
occurs with the metals. The increase in temperature in- the likelihood of ecosystem change and adverse events
creases their aqueous solubility and the decrease in like fish kills can be quite complicated, with many fac-
DO is accompanied by redox changes, e.g. formation tors that either mitigate or exacerbate the outcome (see
of reduced metal species, such as metal sulfides. These Figure 20.12). The increase in metal concentrations in
changes can increase the exposure of human popula- water not only increases the potential exposure to total
tions to toxic substances. The increase in temperature metal mass, but may also transform the metals into
in Figure 20.11, e.g. leads to increased solubility of chemical species with much higher bioavailability,
metals. This is also being mediated by the bacteria, which increases the dose and body burden of the
some of which will begin reducing the metals as the metals (e.g. methyl mercury in fish ingested by
oxygen levels drop (reduced conditions in the water humans).
and sediment). However, the opposite is true in the At the cellular scale, numerous processes and ex-
changes occur among and within the environmental
compartments (see Figure 20.13); as well as those at
TABLE 20.3 Relationship between Water Temperature and the interface between the organism and the environ-
Maximum Dissolved Oxygen (DO) Concentration ment. The gill-water exchanges by fish, e.g. are
in Water (at 1 atm)
analogous to the lung-air exchanges in air-breathing
Temperature Dissolved Temperature Dissolved animals.
(
C) Oxygen (mg lL1) (
C) Oxygen (mg lL1) Transfer of matter via fluids is a key part of the bio-
accumulation process in a multiphase system (water,
0 14.60 23 8.56
sediment, particles, and biota), as represented by the
1 14.19 24 8.40 gill6 and the lung. The mechanisms include (1) water
2 13.81 25 8.24
3 13.44 26 8.09
4 13.09 27 7.95 TABLE 20.4 Normal Temperature Tolerances of Aquatic
Organisms
5 12.75 28 7.81
Range in Minimum
6 12.43 29 7.67 Temperature Dissolved
7 12.12 30 7.54 Tolerance Oxygen
Organism Taxonomy (
C) (mg lL1)
8 11.83 31 7.41
Trout Salma, Oncorhynchus, 5e20 6.5
9 11.55 32 7.28 and Salvelinus spp.
10 11.27 33 7.16 Smallmouth Micropterus dolomieu 5e28 6.5
11 11.01 34 7.16 bass

12 10.76 35 6.93 Caddisfly Brachycentrus spp. 10e25 4.0

larvae
13 10.52 36 6.82
Mayfly Ephemerella invaria 10e25 4.0
14 10.29 37 6.71 larvae
15 10.07 38 6.61 Stonefly Pteronarcys spp. 10e25 4.0
larvae
16 9.85 39 6.51
Catfish Order Siluriformes 20e25 2.5
17 9.65 40 6.41
Carp Cyprinus spp. 10e25 2.0
18 9.45 41 6.41
Water Notonecta spp. 10e25 2.0
19 9.26 42 6.22 boatmen
20 9.07 43 6.13 Mosquito Family 10e25 1.0
21 8.90 44 6.04 larvae Culicidae

22 8.72 45 5.95 Source: Ref. 4a; and Vernier Corporation. Computer 19: dissolved oxygen in water.
http://www2.vernier.com/sample_labs/BWV-19-COMP-dissolved_oxygen.pdf; 2009
Sources: Ref. 4a; 4b. [accessed 19.10.09].

IV. BIOGEOCHEMISTRY OF AIR POLLUTANTS

500 20. THE HYDROLOGIC CYCLE

FIGURE 20.12 Environmental transport pathways can be affected by net heat gain. Compounds (nutrients, contaminants), microbes, and
energy (e.g. heat) follow the path through the environment indicated by arrows. The residence time within any of the boxes is affected by con-
ditions, including temperature. (For color version of this figure, the reader is referred to the online version of this book.) Adapted from: Vallero DA,
Reckhow KH, Gronewold AD. Application of multimedia models for human and ecological exposure analysis. International conference on environmental
epidemiology and exposure. Durham (NC); October 17, 2007. Graphic adapted from U.S. Environmental Protection Agency.

FIGURE 20.13 Transport and transformation phenom- Vapor phase

ena in a water system. The transformation processes,
Atmospheric
including dissociation and degradation to form metabolites deposition
and degradation products (B, C, and D), simultaneously Volatilization
consist of both abiotic (e.g. hydrolysis and photolysis) and
biotic (i.e. biodegradation). The parent compound A and its
reaction products include molecular diffusion (usually only Aqueous phase
important in quiescent systems, e.g. sediment layers) and
advective processes. (For color version of this figure, the
reader is referred to the online version of this book.) Adapted Dissociation &
from: Lyman WJ. Transport and transformation processes e chapter B+C degradation
15. In: Rand G, editor. Fundamentals of aquatic toxicology: effects,
environmental fate, and risk assessment. 2nd ed. Washington (DC):
Taylor & Francis; 1995. Sorption

A in
Biotransformation + Suspended solids Desorption
solution
& complexation

Precipitation
A–D
Dissolution Sedimentation

Resuspension Scour & bed

transport
Parent compound
A
Diffusion

IV. BIOGEOCHEMISTRY OF AIR POLLUTANTS

 QUESTIONS
flow across membrane; (2) blood flow within organism;
(3) chemical flux across membrane; (4) binding and
release from serum proteins; (5) sorption/desorption
to blood cells; (6) chemical mass transfer from blood to
tissues by perfusion; (7) complexation to and decom-
plexation from organic carbon in a particulate phase;
(8) sorption to and desorption from coarse particulate
solids, in addition to internal diffusion within the
particles.
Water is integral and essential to biomass growth,
which can be expressed as energy content and flow
(e.g. kilocalories per fish and kilocalories per day).7ae7c
Factors that lead to healthy human and ecological com-
munities must account for atmospheric exchanges of
mass and energy. The direct and indirect impacts can
be dramatic.
The next chapters consider the cycling of important
elements from a biogeochemical perspective. The
cycling of these substances occurs predominantly via
two fluids, water and air, at most scales, but predom-
inately by three fluids at the organism scale, i.e. air,
water, and blood. Organisms may be seen as micro-
cosms of mass and energy cycling, regardless of scale.
Indeed, cycling depends on the dynamics of water, air,
and other fluids, whether among biomes or at the
cellular level.
QUESTIONS
1. How does particulate matter affect the earth’s
hydrological cycle?
2. Explain the atmosphere-hydrosphere interfaces and
interactions in the formation and distribution of
acidic deposition.
3. Explain the atmosphere-hydrosphere interfaces and
interactions in the formation and distribution of
ozone-depleting substances.
4. How does the water cycle affect the formation of
tropospheric ozone and smog?
5. What is a biome shift? How might the hydrological
cycle change and be changed by such shifts from
climate change? Describe these changes in terms of
physics, chemistry and biology.
6. DDT is found in a people’s blood in the Arctic.
Explain the role of the water cycle in this finding.
7. In spring 1999, scientists discovered a brownish
pollution haze layer of aerosol over the Indian Ocean.
IV. BIOGEOCHEMISTRY OF AIR POLLUTANTS
501
The formation of the haze layer is a seasonal
phenomenon facilitated by an extended dry season,
which prevents the removal of pollution from the
atmosphere through rainfall. What is the role of the
water cycle in this phenomenon and how might the
water cycle be affected by such events?
8. From the perspective of pollutant transport and
uptake by organisms, compare the physics and
biology of the gill versus the lung. Why would this be
important in a book about air pollution?
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