Physical Chemical Characteristics of Water Author D B Walker, M L Brusseau, K Fitzsimmons

CHAPTER 3
PHYSICAL-CHEMICAL
CHARACTERISTICS OF WATER
D.B. Walker, M.L. Brusseau, and K. Fitzsimmons
Apache Reservoir, Arizona. Photo courtesy D. Walker.
24
D.B. Walker, M.L. Brusseau, and K. Fitzsimmons 25
3.1 THE WATERY PLANET
3.1.1 Distribution
Ninety seven per cent of water on the Earth is marine (salt-
water), while only 3% is freshwater (Figure 3.1). With re-
gard to the freshwater, 79% is stored in polar ice caps and
mountain glaciers, 20% is stored in aquifers or soil moisture,
and 1% is surface water (primarily lakes and rivers). An es-
timated 110,000 km3 of rain, snow, and ice falls annually on
land surfaces, and this is what replenishes fresh water re-
sources. Possible effects of global warming, combined with
continued increases in human population and economic
development are resulting in critical concern for the future Figure 3.2 The hydrologic cycle. (http://www.ec.gc.ca/water/en/
sustainability of freshwater resources. nature/prop/e_cycle.htm)
The limited supplies of surface waters and groundwa-
ter receive significant amounts of the pollutants generated
by humans. Lakes across the planet have an average reten- vulnerable to pollutants introduced directly or from surface
tion time of 100 years, meaning it takes 100 years to re- water and groundwater drainage.
place that volume of water. Rivers, on the other hand, have
a much shorter retention time. The relatively long retention
3.1.2 The Hydrologic Cycle
time in lakes highlights the danger of introducing pollutants
that will be present for a long time (i.e., they are “environ- Water covers much more of earth’s surface than does land.
mentally persistent”). The short retention time in rivers The continual movement of water across the earth due to evap-
means that pollutants are transferred rapidly to other areas oration, condensation, or precipitation is called the hydrologic
such as groundwater or oceans. The retention time of cycle (Figure 3.2). The consistency of this cycle has taken mil-
groundwater is measured in hundreds if not thousands of lennia to establish, but can be greatly altered by human activ-
years. In the groundwater environment, persistent pollu- ities including global warming, desertification, or excessive
tants may remain intact for extremely long periods because groundwater pumping. Water, in its constantly changing and
of constraints to transformation. The characteristics of various forms, has been and continues to be an important
groundwater are described in Section 3.10. Pollution of factor driving evolutionary processes in all living things.
groundwater and surface water is discussed in Chapters 17 Evaporating water moderates temperature; clouds and
and 18, respectively. water vapor protect us from various forms of radiation; and
Pollutants in the ocean may be introduced into the food precipitation spreads water to all regions of the globe, allow-
chain by filter-feeding organisms or possibly may be se- ing life to flourish from the highest peaks to the deepest
questered in cold, deep basins where they are resistant to caves. Solar energy drives evaporation from open water sur-
degradation by natural processes. Much of the world’s pop- faces as well as soil and plants. Air currents distribute this
ulation inhabits coastal areas, making oceans especially vaporized water around the globe. Cloud formation, conden-
sation, and precipitation are functions of cooling. When va-
porized, water cools to a certain temperature, condensation
occurs, and often results in precipitation to the earth’s sur-
Distribution of the World’s Water
face. Once back on the surface of the earth, whether on land
Oceans 97% ALL WATER or water, solar energy then continues the cycle. The latent
Freshwater 3%
heat of water (the energy that is required or released as wa-
ter changes states) serves to moderate global temperatures,
maintaining them in a range suitable for humans and other
Ice caps & living organisms.
Glaciers 79%
FRESHWATER Some processes involved with the hydrologic cycle aid
Accessible surface
Freshwater 1%
in purifying water of the various contaminants accumulated
Groundwater during its cycling. For instance, precipitation reaching the
20%
soil will allow weak acids absorbed from air to react with
Lakes 52% ACCESSIBLE SURFACE various minerals and neutralize the acids. Suspended sedi-
FRESHWATER
Water within living ments entrained through erosion and runoff will settle out as
organisms 1% Soil moisture 38%
Rivers 1% Water the water loses velocity in ponds or lakes. Other solids will
vapor 8%
be filtered out as water percolates through soil and vadose
Figure 3.1 Distribution of the world’s water (http://earth.rice. zones and ultimately to an aquifer. Many organic com-
edu/mtpe/hydro/hydrosphere/hot/freshwater/0water_chart.html) pounds will be degraded by bacteria in soil or sediments.
26 Chapter 3 • Physical-Chemical Characteristics of Water
Salts and other dissolved solids will be left behind as water 3.2.2 Thermal Properties
evaporates and returns to a gaseous phase or freezes into a
Water has unique thermal properties that enable it to exist in
solid phase (ice). These processes maintained water quality
three different states: vapor; solid; and liquid under environ-
of varying degrees before human impacts on the environ-
mentally relevant conditions. Changes in each phase have cer-
ment; however, the current scale of these impacts often tends
tain terminology, depending upon state changes, as described
to overwhelm the ability of natural systems to cleanse water
below:
through the hydrologic cycle. Further, we have introduced
many compounds that are resistant to normal removal or Condensation: vapor → liquid
degradation processes (Chapters 16–18). Evaporation: liquid → vapor
Freezing: liquid → solid
3.2 UNIQUE PROPERTIES OF WATER Melting: solid → liquid
Sublimation: solid → vapor
3.2.1 Structure and Polarity Frost Formation: vapor → solid
Water is an unusual molecule in that the structure of two hy- Most liquids contract with decreasing temperature.
drogen atoms and one oxygen atom provides several charac- This contraction also makes these liquids denser (i.e.,
teristics that make it a universal solvent. First is the fact that “heavier) as temperature decreases. Water is unique be-
the two hydrogen atoms, situated on one side of the oxygen cause its density increases only down to approximately
atom, carry positive charges, while the oxygen atom retains 4°C, at which point it starts to be come less dense (Figure
a negative charge (Figure 3.3). 3.4). This is important because without this unique prop-
This induced polarity allows water molecules to attract erty, icebergs and other solid forms of water would sink to
both positive and negative ions to the respective poles of the the bottom of the ocean, displacing liquid water as they did
molecule. It also causes water molecules to attract one an- so. Also, lakes and ponds would freeze from the bottom up
other. This contributes to the viscosity of water and to the with the same effect.
alignment that water molecules will take when temperatures The specific heat of water is the amount of energy re-
decrease to the point of ice formation. The fact that water be- quired to raise one gram of water, one degree C, and is usually
comes less dense in its solid state, compared to its liquid state, expressed as joules per gram-degree Celsius (J g1°C1).
is yet another unusual characteristic. Because of this, ice Specific heat values for the different phases of water are given
floats and insulates deeper water. This is critical to maintain- below.
ing deep bodies of liquid waters on Earth rather than a thin
PHASE J G1 °C1
layer of water on top of an increasingly deep bed of solid ice.
The bipolar nature of water and its attraction to other Vapor 2.02
polar compounds makes it an easy conduit for the dissolution Liquid 4.18
Solid 2.06
and transport for any number of pollutants. Because so many
materials dissolve so completely in water, their removal
from water is often difficult. The latent heat of fusion is the amount of energy re-
quired to change 1 gram of ice, at its melting point tempera-
ture, to liquid. It is considered “latent” because there is no
temperature change associated with this energy transfer,
only a change in phase. The heat of fusion for water is 333
J g1 °C1
The energy required for the phase changes of water are
given in Table 3.1.
Earth is unique because it contains the necessary
temperatures and pressures for all three states of water to
exist. Water, under the correct combination of tempera-
ture and pressure, is capable of existing in all three states
(solid, liquid, and vapor) simultaneously and in equilib-
rium. This is referred to as the triple point, where in-
finitesimally small increases or decreases in either pres-
sure or temperature will cause water to be either a liquid,
solid, or gas. Specifically, the triple point of water exists
at a temperature and pressure of 273.16 Kelvin
(0.0098°C) and 611.73 pascals (0.00603 atm) respec-
Figure 3.3 Structure and charge distribution of water. (http:// tively. Figure 3.5 shows that decreasing temperature and
faculty.uca.edu/~benw/biol/400/notes32.htm) increasing pressure causes water to pass directly from a
Figure 3.4 The density of water at varying temperatures.

(http://www.cyberlaboratory.com/library/basicsofdensity/whatisdensity.htm)
gas to a solid. At pressures higher than the triple point, in- may evaporate directly from the plant, never reaching the
creasing temperature causes solid water (ice) to transform soil. Second, it may entrain materials settled on the plant
into liquid and eventually gas (vapor). Liquid water can- surfaces. Third, by slowing the momentum and reducing the
not exist in pressures lower than the triple point and ice energy of falling rain, physical impacts on the soil and
instantaneously becomes steam with increasing tempera- resulting erosion may be reduced.
ture. This process is known as sublimation. Certain anthropogenic land use practices or natural
events can lead to decreases in interception and subsequent
increases in sediment suspended within water. Often,
3.3 MECHANICAL PROPERTIES sediment may have other pollutants attached to it thereby
polluting the water as well. Certain mining practices, if not
3.3.1 Interception, Evaporation, re-vegetated, can result in increased erosion resulting in
contamination of streams. Natural events, such as wildfires,
Infiltration, Runoff
can also result in substantial erosion and contamination of
Precipitation in a nonpolluted environment provides a fairly downstream areas (see also Chapter 16).
pure form of water. However, today precipitation may Evaporation of water is another crucial part of the
absorb pollutant gases in the environment to form acid rain hydrologic cycle. The rate of evaporation from a body of
(see also Chapter 23). Precipitation can also pick up fine
particulates that were suspended in the air. As the forms of
precipitation reach the surface, they are likely to fall upon
and be intercepted by various types of vegetation. In many
regions, much of the precipitation may settle in or on trees,
shrubs, or grasses and never actually reach the ground. In
others, the plants may slow the rate of fall of raindrops, break
them into smaller drops, or channel them more gently to the
surface. Interception leads to several factors that impact the
water and its role with later pollution events. First, the water
TABLE 3.1 Phase changes of water.
PROCESS FROM TO ENERGY GAINED OR

LOST (J g1 °C1)
Condensation Vapor Liquid 2500
Deposition Vapor Ice 2833
Evaporation Liquid Vapor 2500
Freezing Liquid Ice 333
Melting Ice Liquid 333
Figure 3.5 Phase diagram of the triple point of water. (http://
Sublimation Ice Vapor 2833
www.sv.vt.edu/classes/MSE2094_NoteBook/96ClassProj/pics/trip_pt1)
This is a major source of pollutants introduced into the envi-

ronment. The infiltration rate of water into the ground is an im-
portant measure used to determine how foundations and sewer
systems are designed, how irrigation water should be applied,
and how pollutants may migrate to a water supply.
How water runs off of surfaces is also a matter of inter-
est to hydrology, fisheries, aquatic biology, and pollution
science. Not only are pollutants entrained in flowing water,
but erosion and flooding can also occur. Studies of run off
and surface flow focus upon the amounts of soil and pollu-
tants that are transported and their eventual fate as they
arrive into lakes or streams.
3.4 THE UNIVERSAL SOLVENT
One of the most unique properties of water is its ability to

dissolve other substances. It is this ability that can lead to
large-scale landscape transformations (Figure 3.7), and the
Figure 3.6 This satellite image is of the Great Salt Lake in Utah.
This is the largest lake in the U.S. west of the Mississippi River
covering some 1,700 square miles. It is also 3 to 5 times more
saline than the world’s oceans. It is a fishless lake with only the
most saline-tolerant (“halophytic”) organisms capable of surviv-
ing. The largest organisms inhabiting its waters are species of
brine shrimp and brine flies. (http://ut.water.usgs/gov/greatsaltlake/)
water, or mass of soil, is a function of the relative humidity,

temperature, and wind speed. An important subcomponent
of evaporation is transpiration, the active transport and
evaporation of water from plants. Plants transport nutrients
in an aqueous solution and then dispose of the water through
their leaves by evaporation. As water evaporates, it leaves a
concentrated amount of compounds that were formerly dis-
solved in that water. This applies to nutrients left in plants,
as well as to pollutants that were introduced with the water.
Water that is not contained in oceans is often referred to
as “freshwater,” implying that it is not saline. This is not
always the case, and some inland waters can be much more
saline than the world’s oceans. This is especially true in arid
environments or enclosed basins that have limited or no
drainage. Often, salinity in inland waters reaches such high
levels that it supports little, if any, life. Salinity in inland
waters, and in the world’s oceans, is largely a result of evap-
oration. As water is vaporized and once again enters the
hydrologic cycle, salts accumulate on the earth’s surface,
and in lieu of adequate dilution and flushing, can often make
Figure 3.7 The Grand Canyon of the Colorado River was
water increasingly saline (Figure 3.6). formed by the dissolution and erosion of material over eons.
Precipitation that reaches the soil surface either infiltrates Historically, most of this material was deposited in the Gulf of
the ground or runs off the surface. Human uses of water also California. With the construction of large dams along the course
deliver enormous amounts of water onto soils or human-made of the Colorado River, most of this material is now deposited in
structures that can either infiltrate or contribute to run-off. storage reservoirs. (http://www.kaibab.org/tr961/lg961110.jpg)
TABLE 3.2 Examples of typical concentrations of

solutes in water. To calculate this we assume the following:
Percent parts per hundred 10 2 • Water weighs 8.33 pounds1 gallon.
Milligram mg L1 parts per million 106 • There are 7.5 gallons ft3 and this therefore weighs 62.43
Microgram g L1 parts per billion 109 pounds.
Nanogram ng L1 parts per trillion 1012
• One acre foot 43,560 ft3
• So, 43,560 ft3 62.42 pounds ft3 2,718,144 pounds
of solution.
ability to carry contaminants relatively long distances. If it • Therefore, 2,718,144 0.000023 (or 23 ppm) 62.5
were not for the various substances dissolved in water, an pounds of Na and 2,718,144 0.000035 (or 35 ppm)
organism’s cells would quickly be deprived of essential 95.1 pounds of Cl.
nutrients, salts, and gasses, leading to eventual death. The • 62.5 (Na) 95.1 (Cl) 157.7 pounds of NaCl.
dissolution of materials in water has shaped the nature of all Now that the farmer knows how much is in one acre foot,
living creatures on the planet. if the rate of water flow onto his crops is known, he can
calculate an accumulation rate. For instance, let’s say the
farmer wants to know how many tons day1 and tons year1
3.4.1 Concentration Terminology of NaCl flow onto his crops and into his soil if the flow is
held constant at 2 ft3 second1 (commonly written as cfs for
It is important to quantify the amount of material dissolved in
“cubic feet per second”).
water. Quantification require a range of values so that we can
determine high versus low concentrations for a given con- • 2.0 cfs 3600 sec hour1 24 hr day1 62.4 pounds ft3
0.000058 (58 ppm) 625 pounds NaCl day1.
stituent. The values are always expressed as a ratio of solute
to water (Table 3.2). The importance of very small concen- • 2000 pounds ton1 divided by 625 pounds 0.313 tons
trations should never be underestimated. This is especially NaCl day1.
true in toxicological studies where very small concentrations • 0.313 tons/day 365 days/year 114 tons NaCl year1.
can lead to toxic impacts on organisms (Chapter 13).
There are two major expressions in concentration ter-
minology.
– Mass/mass. An example would be parts per million 3.4.2. Oxygen and Other Gases in Water
(ppm), which equals parts of solution/parts of material
Just like terrestrial counterparts, aquatic organisms (other
106.
than anaerobic microbes) need dissolved oxygen and other
– Mass/volume. An example would be milligrams/liter
gases in order to survive. Additionally, the world’s oceans
(mg L1), which equals milligrams of dissolved
“absorb” an estimated 1/4 to 1/3 of carbon dioxide emitted by
solid(s)/liter of solution.
human activity. If it were not for the ocean’s ability to absorb
Most of the time, mg L1 and ppm will be the same carbon dioxide, an important greenhouse gas, global warm-
number. Their relationship is that the specific gravity of so- ing would proceed at an unprecedented rate (see also Chap-
lution ppm mg L1. Note that this same relationship ter 24). The amount of gas that an aqueous solution can hold
holds true when using other concentrations such as parts per is dependent upon several variables, the most important of
billion (ppb) and g L1 or parts per trillion and ng L1. which is atmospheric pressure. Simply stated, increasing
EXAMPLE CALCULATION 3.1

Using Concentration INFORMATION BOX 3.1
Knowing the concentrations of constituents in water has Examples of Why Small Numbers are Important
many utilitarian uses. For example, a farmer may want to
know how much salt will accumulate in the soil on his prop- • An AIDS virus is only 108 meters in size, or 0.00001
erty when using water where both sodium (Na) and chloride mm, yet it only takes one virus to have potentially
(Cl) concentrations are known. devastating effects on the human immune system.
• Suppose the water contained 35 ppm Cl and 23 pm Na • From Science, 20 February 1991:
(i.e., 58 ppm NaCl). “In the end, after all the antibaryons had been consumed,
• How many pounds of Na, Cl, and NaCl are contained in one odd baryon out of 10 billion was left over. It was this
an acre foot of water? (1 acre foot 1 acre of land with a tiny remnant that gave rise to all the planets, stars, and
water depth of 1 foot). galaxies.”
vegetation. During photosynthesis, plants convert CO2 into

oxygen in the process outlined below.
6CO2 12 H2O Light Energy
→ C6H12O6 6O2 6H2O (Eq. 3.2)
All natural waters also have sinks of dissolved oxygen,

which include:
Figure 3.8 The solubility of oxygen in water under different Sediment Oxygen Demand (SOD): Due to decomposition
atmospheric pressures. of organic material deposited on bottom sediments.
Biological Oxygen Demand (BOD): The oxygen required
for cellular respiration by microorganisms.
atmospheric pressure causes a greater amount of gas to go
Chemical Oxygen Demand (COD): The oxygen required
into solution at a given temperature (Figure 3.8). Generally,
for all organic compounds. Note that BOD is a subset of
increasing water temperature will result in an increased sol-
COD.
ubility of gas. This constant is otherwise known as “Henry’s
Respiration is the metabolic process by which organic
Law” and is written as:
carbon is oxidized to carbon dioxide and water with a net re-
Kc c (Eq. 3.1) lease of energy (see also Chapter 5). Aerobic respiration re-
quires, and therefore consumes, oxygen.
partial pressure of the gas in mmHg
c concentration of gas in mmoles, mL, or mg L1 at a C6H12O6 6O2 → 6CO2 6H2O energy (Eq. 3.3)
constant temp
This is, essentially, the opposite of photosynthesis. In
Kc the solubility factor, different for each gas
the absence of light, the CO2 collected by plants via photo-
The constant Kc is specific for every gas and solute at synthesis during the day, is released back into the water at
a given temperature (see also Chapter 7). There is a direct, night, resulting in a net loss of dissolved oxygen. Depending
linear relationship between the partial pressure and the upon the amount of nutrients, algae, and available light, this
concentration of gas in solution. For example, if the partial often results in large daily fluctuations in dissolved oxygen
pressure is increased by 1/4, the concentration of gas in levels known as Diel patterns (Figure 3.9).
solution is increased by 1/4 and so on. This is because the The implications of dissolved oxygen sinks and sources
number of collisions of gas molecules on the surface of the on aquatic organisms and overall water quality are crucial in
solute (water in this case) is directly proportional to in- determining whether or not a river, lake, or stream is polluted
creases or decreases in partial pressure. Since the concentra- and to what degree. If dissolved oxygen sinks are greater
tion: pressure ratio remains the same, we can predict the con- than sources for extended periods of time, it is safe to assume
centration of gas in water under differing partial pressures. some degree of contamination has occurred. Examples of an-
This relationship can be written as: thropogenic wastes that can cause dissolved oxygen impair-
ment of receiving waters are sewage (raw and treated, human
Concentration1 Concentration2
and nonhuman), agricultural runoff, slaughterhouses, and
Pressure1 Pressure2
pulp mills.
For example, 1 liter of water under 1 atmosphere of pressure,
will contain 0.0404 grams of oxygen. What will the concen-
tration of oxygen be if the partial pressure is increased to 15 3.4.3 Carbon Dioxide in Water
atmospheres? Carbon dioxide only accounts for approximately 0.033% of
C1 0.0404 g O2/1 liter solution the gases in earth’s atmosphere, yet is abundant in surface
water. The biggest reason for the abundance of carbon diox-
P1 1 atm
ide in water is due to its relatively high solubility; almost 30
P2 15 atm times that of oxygen. In the atmosphere, carbon dioxide is re-
C2 ? leased when fossil fuels are burned for human uses, and as a
.0404 g O2 C2 result of large worldwide increases in the use of fossil fuels
during the last century or so, the amount of carbon dioxide in
1 atm 15 atm
C2 (15 atm) (0.0404 g O2 per 1 liter/1 atm) the atmosphere has steadily increased. Carbon dioxide is
currently rising at a rate of approximately 1 mg L1 year1
C2 0.606 g O2
or about 40% since the beginning of the Industrial Revolu-
In any body of water, there are sources and sinks of tion. Since carbon dioxide is a major greenhouse gas,
dissolved oxygen. Sources include atmospheric re-aeration changes in global climate may have long-term environmen-
through turbulence; ripples and waves; and dams and tal consequences (Chapter 24).
waterfalls. Another potential source of dissolved oxygen is At room temperature, carbon dioxide has a solubility in
photosynthesis primarily by algae or submersed aquatic water of 90 ml3 of carbon dioxide per 100 ml3 of water.
35
Temp (C)
Diel fluctuations in oxygen and pH levels can occur
30 DO (mg/L) during the day in waters where photosynthesis is taking
place (see Figure 3.9). Algae and plants convert carbon diox-
25
ide into carbohydrates to be used in metabolic processes. In
20 very productive waters, this process can leave bicarbonate or
Levels
15 carbonate in excess, leading to increased pH levels. In the

absence of adequate light for photosynthesis, respiration
10
predominates, resulting in carbon dioxide once again being
5 restored to the water resulting in decreased pH levels.
0 Calcium carbonate, while insoluble at neutral to basic
pH levels, readily dissolves in acidic conditions. In the initial
00
30
30
30
00
30
30
00
30
00
00
00
30
00
00
30
30
14
12
15
21
23
00
03
17
18
20
02
05
06
08
11
09
12
step, carbonate acts as a base resulting in calcium ions and
Time A carbonic acid. In the next step, carbonic acid is dissociated
releasing carbon dioxide as a gas.
CaCO3 2 H → Ca2 H2CO3 (Eq. 3.7)
H2CO3 ↔ H2O CO2 (Eq. 3.8)
Rain is often slightly acidic due to the dissolution of at-

mospheric carbon dioxide. Recently, due to the burning of
fossil fuels, other gases can also be dissolved in rain result-
B ing in “acid rain.” Atmospheric pollutants responsible for
acid rain include sulfur dioxide (SO2) and nitrous oxides
Figure 3.9 Diel pattern of temperature and dissolved oxygen in
Rio de Flag, an effluent-dominated stream in Flagstaff, Arizona.
(NOx). More than 2/3 of these pollutants come from burning
A. Data was collected every 30 minutes over a 24-hour period on fossil fuels for electrical power generation, and prevailing
08/12/03. B. Profuse growth of attached algae (“periphyton”) winds can result in acid rain being deposited far from origi-
growing in the stream at the time. Photosynthesis and respiration nal source. Acid rain has far-reaching environmental conse-
by these algae likely contributed to the large swings in dissolved quences including acidification of lakes and streams, making
oxygen levels within the water over the 24-hour period. Photo them uninhabitable by aquatic life; extensive damage to
courtesy D. Walker. forests, plants, and soil; damage to building materials and
automotive finishes; and human health concerns. However
an amendment to the Clean Air Act, the Acid Rain Pro-
Carbon dioxide dissociates and exists in several forms in wa- gram, whose goal is to lower electrical power emissions of
ter. First, carbon dioxide can simply dissolve into water going the pollutants causing acid rain, shows recent evidence of
from a gas to an aqueous form. A very small portion of carbon success, and lakes, rivers, and streams have responded fa-
dioxide (less than 1%) dissolved in water is hydrated to form vorably (see also Chapters 4 and 23).
carbonic acid, (H2CO3). Equilibrium is then established In lieu of any anthropogenic acidification of rain or sur-
between the dissolved carbon dioxide and carbonic acid. face water, conditions often exist that can result in the disso-
lution of limestone:
CO2 H2O ↔ H2CO3 (Eq. 3.4)
CO2 H2O CaCO3 ↔ Ca2 2 HCO3 (Eq. 3.9)
Carbonic acid, a very weak acid, is then dissociated in
two steps. The remaining reaction is a 3-step process:
H2CO3 ↔ H HCO3 (Eq. 3.5) CaCO3 ↔ Ca 2 CO32 (Eq. 3.10)
HCO3
↔ H CO3 2
(Eq. 3.6) CO2 H2O ↔ H2CO3 (Eq. 3.11)
H2CO3 CO32 ↔ 2 HCO3 (Eq. 3.12)
As carbon dioxide is dissolved in water, equilibrium is
eventually established with the carbonate ion (CO32). Car- This reaction can result in the formation of caves when
bonate, being a largely insoluble anion, then reacts with naturally acidic rainwater reacts with a subterranean layer of
cations in the water, causing these cations to precipitate out limestone, dissolving the calcium carbonate and forming
of solution. As a result, Ca and Mg2 often precipitate as openings. As slightly acidic water reaches the cave ceiling,
carbonates. Calcium carbonate (CaCO3), otherwise known the water evaporates and carbon dioxide escapes. It is this
as limestone, has resulted in large deposits as a result of this reaction that is responsible for the many elaborate forma-
process. As limestone is once again dissolved, carbon diox- tions in cave ecosystems (Figure 3.10).
ide is released back into the atmosphere. In addition, several Total alkalinity is the total concentration of bases, usu-
aquatic organisms, such as corals and shelled creatures such ally carbonate and bicarbonate, in water and is expressed as
as clams, oysters, and scallops, are capable of converting the mg/L of calcium carbonate. Analytically, total alkalinity is
carbon dioxide in water into calcium carbonate. expressed as the amount of sulfuric acid needed to bring a so-
oxidation-reduction reactions are often referred to as redox

reactions (see also Chapter 7). Just as the transfer of hydrogen
ions determines the pH of a solution, the transfer of electrons
between species determines the redox potential of an aqueous
solution. Redox potential is also referred to as “ORP” for
oxidation-reduction potential, and is measured in volts or Eh
(1 volt 1 Eh). ORP specifically measures the tendency for a
solution to either gain or lose electrons when it is subject to
change by the introduction of a new species. A solution with a
higher ORP will have a tendency to gain electrons (i.e., oxi-
dize them) and a solution with a lower ORP will have a
tendency to lose electrons to new species (i.e., reduce them).
Whether a chemical species in solution is oxidized or
reduced has a profound influence on biogeochemical cycling
of metals, nutrients, salts, organic compounds, and so on.
Examples of redox couplings of interest to water quality
Figure 3.10 Cave formation in the Big Room, Carlsbad Caverns
National Park, New Mexico. (http://www.nps.gov/cave/home.htm)
include the following (after Cole 1994):
REDOX COUPLE VOLTS DISSOLVED O2 (MG/L)

NO3 to NO2 0.45–0.40 4.0
lution to a pH of 4.2. At this pH, the alkalinity in the solution NO2 to NO3 0.40–0.35 0.4
is “used up,” and any further addition of an acid results in Fe to Fe 0.30–0.20 0.1
drastic decreases in pH levels. Total alkalinity, by definition, SO4 to S 0.10–0.06 0.0
is the ability of a water body to neutralize acids. In other
words, it is the “buffering capacity” of a water body, and it Redox reactions have an effect on bioavailability of
is influenced by the minerals in local soils. In areas of the nutrients. For example, iron exists either as particulate and
northeastern U.S., where parent material contributes little to oxidized ferric (Fe), or the reduced and soluble ferrous
the total alkalinity in the water, the cumulative effects of acid (Fe). Phosphorous is an essential nutrient for plant and
rain have been most devastating and have extirpated aquatic animal growth and under oxidizing conditions, is bound to
life from several streams. Mining activity and pulp mills can ferric iron forming a ferro-phosphate complex that is bio-
also add to reductions in total alkalinity and subsequent logically unavailable. If pollutants enter into a water body,
decreases in pH. Stopgap measures in watersheds, lakes, or dissolved oxygen may be depleted and reducing conditions
streams where alkalinity has been depleted include such prevail. Under these reducing conditions, iron loses its
drastic actions as dropping lime from helicopters to increase normally close association with phosphorous, with the lat-
the buffering capacity for aquatic life. ter becoming biologically available for algal growth some-
times forming noxious, and potentially toxic, blooms.
Reducing conditions often prevail in the bottom of ther-
3.5 OXIDATION-REDUCTION REACTIONS mally stratified lakes and reservoirs, and phosphorous can
accumulate leading to large growths of algae when the lake
de-stratifies.
Oxidation-reduction reactions involve the transfer of elec-
Methylation of mercury (addition of CH3) also relies
trons from one atom to another. Oxidation is defined as the
upon physical-chemical characteristics such as dissolved
loss of an electron from an atom, and reduction is the gain of
oxygen, pH, and ORP. Mercury is a metal that occurs nat-
an electron from an atom.
urally in the environment and has many different chemical
Zn(s) 2 H (aq) ↔ Zn2(aq) H2(g) (Eq. 3.13) forms. Methylmercury is the form of mercury that bioaccu-
mulates (increases from one trophic level to the next by
In the above example, the oxidation number of Zn has
ingestion or absorption) and can cause mercury poisoning
changed from 0 to 2, producing Zn2, and the oxidation
in wildlife and humans. Methylation of mercury can occur
number of H has changed from 1 to 0, producing H2.
both abiotically and biotically by sulfate-reducing bacteria
In this reaction, Zn has been oxidized and H has been
(SRB’s) of the genera Desulfovibrio and Desulfotomacu-
reduced. Since Zn(s) was oxidized, it caused the reduction of
lum. SRB’s require anaerobic and reducing conditions in
H(aq) and is therefore the reducing agent. Likewise H(aq)
their environment in order to reduce sulfate to sulfide.
caused the oxidation of Zn(s), making H the oxidizing
Specifically, they use sulfate as a terminal electron accep-
agent.
tor to break down molecular hydrogen or organic matter for
Loss of electrons from one substance must simultane-
metabolism through the following processes (see also
ously be accompanied by the gain of electrons from another.
Chapter 5).
Electrons are neither created nor destroyed in chemical reac-
tions, and we can envision oxidation-reduction pairs. These 3H2SO4 C6H12O6 → 6CO2 6H2O 3S2 (Eq. 3.14)
Mercury (Hg) normally binds very tightly to organic reaches the earth’s outer atmosphere is 1.94 calories cm2
matter. The above process is the method in which mercury minute1 and is known as the solar constant. The most
can become de-coupled from organic matter and subse- common wavelength that makes it to our outer atmosphere is
quently methylated via methyl transfer from cobalamin 480nm.
(vitamin B12) to Hg2. Light wave frequency and energy are interrelated as ex-
plained by Planck’s equation, which is expressed as:
E hv (Eq. 3.15)
3.6 LIGHT IN AQUATIC ENVIRONMENTS
where:
E is the energy in a photon of light
Just as in terrestrial systems, light at the water’s surface
h is Planck’s constant of 6.6255 1034 joules
marks the beginning of photosynthesis or “primary produc-
second1
tion.” Light is the driving force behind almost all metabolic
v is the wave frequency
processes in aquatic ecosystems. Light carries heat energy to
be used in many chemical and biological processes, and can Frequency of a light wave is given by v c/
simultaneously regulate and/or damage, aquatic biota. Pollu- where:
tants, especially suspended and dissolved substances, can c is the speed of light (3 108 m/second), and
have profound effects on both the amount of light available is the wavelength
for photosynthesis and the heat energy needed for these
For example, the frequency of red light (750 nm) is calcu-
processes.
lated from
3 108 4.00 1014
3.6.1 Light Energy v 7 1
7.5 10 second wavelengths light
Light contains differing amounts of energy, depending upon
frequency and wavelength. Quantum theory states that Substituting this number into Plancks equation (E hv),
electromagnetic energy, such as light, is transmitted in 26.5 1020 joules are contained in a single photon of light.
discrete amounts or “packets” called quanta. A single Compare this with the fact that it takes 6.024 1023 photons
quanta (i.e., “quantum”) of electromagnetic energy is also just to initiate a photosynthetic reaction (otherwise known as
referred to as a photon, and the energy carried by each Avogadro’s number). Thus, it can be seen that it takes a large
photon is proportional to its frequency. The quantity of amount of light energy to perform what we would consider a
electromagnetic energy flow over time is measured as a rate, simple biological process. Photosynthetically active radiation,
i.e., quanta second1 known as the radiant flux of light. the spectrum of light needed for photosynthesis by most plants,
The arrangement of light based upon differing wave- is approximately 400 to 700 nm. Specific types of chlorophylls
lengths, frequencies, and energies is described by spectra. and accessory pigments in plants have narrowed the require-
For example, the spectrum formed by white light contains all ments of wavelength ranges. For example, chlorophyll a, a
colors and is therefore said to be continuous (Figure 3.11). photosynthesizing pigment common to all algae, absorbs light
Certain biological, chemical, and physical processes occur in two peaks, 670–680 nm and again at 435 nm.
only at specific frequencies of spectra, some of which can be
seen with the human eye and several of which cannot. Light
that is divided over a certain range of spectra is divided by 3.6.2 Light at and Below the Waters Surface
color and measured by its frequency in nanometers. Several processes can affect both the intensity and quality of
Light travels at 299,792 km second1. It takes approxi- light reaching the earth’s surface. One such process is simple
mately 400 trillion waves of red light at 750 nm to span the scattering of light by particles in the atmosphere, including
distance light travels every second. It takes almost twice as water vapor. Refraction of light occurs when the speed of
many violet waves, at 380 nm, to fill the same volume of a light changes going from one medium, such as air, into
light second. The amount of radiation emitted by the sun that another, such as water. Light can also be reflected off of a
water surface due to several factors such as the incident
angle of light, wave height and frequency, or the presence of
ice. Another factor affecting light intensity is absorption due
to the decrease in light energy by its transformation into heat.
Both atmospheric gases and water can cause absorption.
Absorption (i.e., “quenching”) of light entering a body
of water can be quantified using a vertical absorption
coefficient expressed as:
Figure 3.11 Wavelengths of light and associated spectra. ln Io ln lz

k
(http://hyperphysics.phy-astr.gsu.edu/hbase/vision/specol.html) z
where: determining total dissolved solids and/or salinity including

Io is the natural log of the initial amount of light electrical conductivity, density, light refraction, silver titra-
entering the water tion, and simple evaporation of a known volume. Each of
Iz is the natural log of light remaining at any given these methods will provide a result that can be converted to a
depth percentage, or more commonly parts per thousand, of salinity.
z is the thickness of the water in meters Open ocean seawater will vary from 33 to 35 parts per thou-
sand (ppt), while coastal waters may have less than 1 ppt.
The vertical absorption coefficient is somewhat analogous to
the coefficient of extinction, except that the latter uses the
base10 logorithm. The vertical coefficient of absorption is 3.7.2 Transport and Accumulation of Pollutants
therefore 2.3 times the coefficient of extinction. Another
The oceans tend to become the repository of many pollutants.
important variable when considering the fate of light in
Air pollution and water pollution often transport the com-
water is the total coefficient of absorption, which is the
pounds to the ocean through rain events or runoff. Histori-
sum of all factors leading to the intensity (or “extinction”) of
cally, one of the most common mindsets was that the “solution
light at any given depth. The total coefficient of absorption
to pollution is dilution.” Over time we have discovered that
can be expressed as:
even the oceans are not vast enough to handle the volume of
Iz Iokw Iokp Iokc pollutants that can be discharged by human activities. In many
cases, the effects of pollutants are so toxic that even vast dilu-
where:
tion is not effective. In other instances we have found that
kw the coefficient of absorption in pure water
filter-feeding organisms bioaccumulate toxic compounds that
kp suspended particulate matter
ascend food chains and can affect grazers and top carnivores,
kc dissolved substances
as well as humans consuming various seafoods. Mercury in
Note that kp or kc can only be determined after filtration swordfish and certain sharks is such an example.
or centrifugation. The total coefficient of absorption is
different for each body of water and is dependent upon the 3.7.3 Wave Morphology and Currents
amount of dissolved or suspended material in the water. Dis-
solved substances are normally humic or fulvic acids, tan- Waves and currents move pollutants within surface water.
nins, lignins, or anything that constitutes colored, dissolved, This is especially critical in marine systems as we attempt to
organic matter absorbing light strongly at relatively short control and/or track pollution movement. Waves are typically
wavelengths (e.g., blues and ultraviolet radiation 500 nm). the result of winds blowing across the surface of a body of
Suspended material includes fine clays, and phytoplankton, water. As the air friction pushes against the water, small
which absorb light evenly over the entire spectrum. ripples form. Continued breezes push against the sides of each
In standing water, vertical light penetration can be ripple providing additional energy. The tops of the ripples may
roughly estimated using a secchi disk which is standardized, blow off, forming whitecaps. This releases some of the
20-cm diameter, black and white, weighted disk lowered into energy, but more will continue with the bulk of the water
the water using a calibrated line. The depth at which the disk below. Continued wind energy transferred to the waves can
almost, but not quite, disappears is recorded. This is known store enormous amounts of energy. The size of a wave is a
as the secchi disk transparency expressed as Zsd. To be function of the average velocity of the wind, the period of time
comparable, this has to be done between 10 am and 2 pm on it blows, and the distance of open water across which it blows.
any given day. Secchi disk depth is often mistakenly used as a The distance over which blowing winds creates waves is
proxy for primary production (the amount of standing algal called the fetch. Waves are usually described by the period
biomass) in a water body. In reality there are many other mit- (the time between two crests passing the same point), the
igating factors besides algae that can cause either increases or wavelength (distance between two crests), and the wave
decreases in transparency. The photic zone is the volume of height (vertical distance between a trough and the next crest).
water from the surface to where 99% of the light needed for Waves are important factors in the dispersion of pollu-
photosynthesis has been extinguished. A very rough estimate tants, especially oil spills. Calm waters facilitate the recov-
of photic zone depth is anywhere from 2.7 to 3 times Zsd. ery of oil and other floating pollutants. However, in cases
where it cannot be collected, wave action can break up the
thick mats of oil and spread the material so that bacterial
3.7 OCEANS degradation can break down the organic molecules. It will
also allow the lighter fractions to volatilize.
Water motion in the oceans is a function of waves, which
3.7.1 Salts
are wind driven, and currents, which are driven by a number
The oceans are saline due to the constant input of dissolved of factors. The most important is the Coriolis effect caused by
salts leached from rocks and soils on land surfaces. These dis- the spinning of the earth (see Chapter 4). However, wind,
solved solids consist of many salts including sodium, calcium, runoff from rivers, density differences from temperature or
and magnesium salts. There are several common methods of salinity extremes, and tidal fluctuations can all drive currents.
Currents are often compared to the circulatory system of a or some other depression has been made through natural
living organism. Trade winds will power currents that trans- causes and there is adequate ground or surface water inputs to
port water and its constituents across vast distances along the fill these depressions. Reservoirs, on the other hand, are
surface. Cooling of surface waters in the high latitudes causes constructed where lakes are not in abundance and water is
cold, dense water to sink into the depths, where it flows along needed for human use. Reservoirs are often found in greater
the bottom until it upwells in lower latitudes to replace warmer abundance in arid and semi-arid regions such as in the western
surface waters that are blown away from coastlines. Tidal U.S., where large natural lakes are not abundant. The large
action will also drive currents in local situations. number of reservoirs built in arid regions often means sacri-
Currents and waves effectively mix surface waters on a ficing lotic habitats through either direct impoundment or
short time scale. Deep-water currents mix water on a much some change in water chemistry caused by impoundment.
longer time scale. Together they effectively spread pollu- Endemic aquatic organisms living in streams and rivers of the
tants to every corner of the ocean. Water motion can be western U.S. are among the most endangered species on the
effectively measured in two ways. If the motion is fairly planet due to impoundment of habitat and changes in environ-
consistent in one direction, a current meter can be used to mental conditions below large dams.
determine velocity. A more common situation is when water Some of the major differences between lakes and reser-
motion is not consistent, but varies in direction and speed in voirs are given in Table 3.3. The arrows are either increasing
three dimensions over short periods of time. In this case, a or decreasing as they relate to either lakes or reservoirs. For
better measure is to use a clod card. Clod cards consist of a example, lakes generally have a much smaller watershed
block of calcium sulfate that slowly dissolves in water. The area than reservoirs.
block is mounted on a card stock for easy attachment and
handling. Its rate of dissolution can be measured by record- 3.8.2 Trophic State
ing initial and final dry weights. These are normally used to
compare two or more environments. The clod cards can be Material within lentic systems are generally classified as
calibrated, if necessary, by placing controls in waters or either autochthonous or allochthonous in origin. Al-
tanks with known velocities of water motion. lochthonous (from the Greek, meaning “other than from the
earth or land itself”) material is everything that has been im-
ported to the lentic system from somewhere else in the wa-
3.8 LAKES AND RESERVOIRS—THE LENTIC tershed. This material can be thought of in terms of loading.
SYSTEM Autochthonous (from the Greek, meaning “of or from the
earth or land itself”) material is that which is recycled within
Lentic systems are closed ecosystems such as lakes. How- the lake or reservoir. Both sources play a role in a lentic sys-
ever, while lakes and reservoirs are relatively more “closed” tem’s trophic state.
than rivers and streams, they are far from isolated. Although The trophic status of a lake or reservoir is largely a
some lakes and reservoirs have subterranean groundwater means to communicate the ecological condition of a water
inputs, the majority of water entering them is a result of over- body. Trophic state is based upon the total weight of living
land flow; therefore, lakes and reservoirs are reflections of biological material or biomass in a water body at a specific
all processes that have occurred in the watershed up to that location and time. Time and location-specific measurements
point. Both natural and anthropogenic watershed influences can be aggregated to produce waterbody-level estimations of
can have profound effects on both water quality for human trophic state. Trophic status is not equivalent to primary
use and aquatic communities living within lentic systems. production, which is the rate of carbon fixed (usually ex-
pressed as g of C fixed day1 m3). Trophic state, being a
multidimensional phenomenon, has no single trophic indica-
3.8.1 Lentic Typology tor that adequately measures its underlying concept. Com-
There are several ways to classify lakes and reservoirs: by bining the major physical, chemical, and biological expres-
origin, ecoregion, shape and size, regimen of mixing, and sions of trophic state into a single index reduces the
stratification. Detail about every different type of lake or
reservoir is beyond the scope of this chapter, and the reader
TABLE 3.3 Comparisons of natural lakes and reservoirs.
is instead referred to any of several available limnological
texts. Rather, this section will discuss the differences be- VARIABLE NATURAL LAKES RESERVOIRS
tween two main types of lentic systems: lakes and reservoirs. Watershed
The main difference between lakes and reservoirs is that Area ↓ ↑
the former have natural origins, while the latter are manufac- Maximum
tured by humans for anthropogenic needs. Both are lentic Depth ↓ ↑
systems and therefore share some common attributes. Lakes Mean
are dominant where glaciers have scoured the landscape, as, Depth ↑ ↓
for example, around the Great Lakes. In other cases, tectonic Resident
Time ↑ ↓
activity has formed rifts, allowing for the African Rift Lakes,
TABLE 3.4 Trophic categories for lakes and reservoirs.
TROPHIC STATE CHLOROPHYLL A SECCHI DISK TOTAL P ATTRIBUTES

(g/L) DEPTH (m) (g/L)
30 0.95 8 6 Oligotrophy: Clear water, dissolved oxygen throughout
the year in the hypolimnion
30–40 0.95–2.6 8–4 6–12 Hypolimnia of shallower lakes may become anoxic
40–50 2.9–7.3 4–2 12–24 Mesotrophy: Water moderately clear; increasing
probability of hypolimnetic anoxia during the
summer.
60–60 7.3–20 2–1 24–48 Eutrophy: Problems with excessive primary production
begin. Anoxic hypolimnia in stratified lakes/
reservoirs.
60–70 20–56 0.5–1 48–96 Cyanobacteria dominate the phytoplankton. Increasing
problems with anoxia.
70 56–155 0.25–0.5 96–192 Hyper-eutrophy: Primary production limited only by
light. Dense growths of algae and/or aquatic plants.
Increasing prevalence of anoxia throughout the water
column. Fish kills possible.
80 155 0.25 192–384 Few aquatic plants or other forms of life. Sustained
periods of anoxia.
variability associated with individual indicators and pro- situation and location, while keeping in mind that trophic
vides a reasonable composite measure of trophic conditions status is just one of several aspects of the biology of the wa-
in a water body. ter body in question. Water quality, on the other hand, is a
Several trophic state indices have been devised. The se- term used to describe the condition of a water body in rela-
lection of which one to use depends upon several different tion to human needs or values. Quality is not an absolute; the
chemical and physical parameters. One of the most-used terms “good” or “poor” water quality only have meaning rel-
trophic state indices for lakes is the Carlson’s TSI (Carlson, ative to the attitude of the user. An oligotrophic lake might
1977). Especially important are the nutrients phosphorous have “good” water quality for swimming, but have “poor”
and nitrogen, both essential macronutrients for algal growth water quality for fishing. Confusion can ensue when trophic
and primary production. Other variables used include mea- state is used to infer water quality.
sures of chlorophyll a and secchi disk depth. Chlorophyll a
is a pigment common to all algae and gives a measure of
3.8.3 Density and Layering
standing biomass. Phosphorous is often the nutrient that is
most “limiting” in natural waters (although nitrogen limita- As light enters the water, different wavelengths are
tion also does occur). Carlson’s TSI relies upon three quenched exponentially (see 3.6.2). Wavelengths in the 620-
variables—chlorophyll a, secchi disk depth, and total phos- to 740-nm range are absorbed first. This range also contains
phorous—to determine trophic status of any water body that those wavelengths of light that carry the most amount of
is phosphorous-limited. In the broadest sense, trophic status heat energy. The relative density of water is temperature-
of a lake or reservoir is often divided into the categories pre- dependent. Water becomes increasingly dense down to about
sented in Table 3.4. 4°C, at which point it becomes less dense (see 3.2.2). Thus,
The advantage of a fixed boundary system is its easy differential heating leads to differential vertical layering of
application by managers and technical personnel with only the water column usually beginning in spring and early
limited limnological training. However, trophic terminology summer. The definitions of the various layers are given in
has a history of being mis-used. For example, deeming a lake Information Box 3.2. An example of thermal stratification in
as eutrophic does not automatically mean it has poor water a lake is presented in Figure 3.12.
quality. Although the concepts of water quality and trophic Interaction between the epilimnion and hypolimnion
state are related, they should not be used interchangeably. often results in the formation of autochthonous feedback
Trophic state is an absolute scale that describes the biologi- mechanisms. In almost every case, anoxia within the hy-
cal condition of a body of water. The trophic scale is a divi- polimnion mirrors epilimnetic production so that increases
sion of variables used in the definition of trophic state and is in trophic state result in increased hypolimnetic anoxia.
not subject to change because of the attitude or biases of the Prolonged anoxia within the hypolimnion often results in the
observer. An oligotrophic or a eutrophic lake has attributes prevalence of reducing conditions (see Section 3.5). Under
of production that remain constant no matter what the use of these reducing conditions, nutrients that would otherwise be
the water or where the lake is located. For the trophic state bound to material within sediments become unbound and
terms to have meaning, they must be applicable in any once again available for biological uptake. The density
0
INFORMATION BOX 3.2 Epilimnion
-5
Stratification of Lakes and Reservoirs
Depth_m
-10 Metalimnion
The uppermost layer is called the epilimnion, and is
characterized by relatively warm water where most
-15
photosynthesis occurs. Depending upon environmental Hypolimnion
conditions, it is more oxygenated than layers below it. -20
The middle layer is called the metalimnion and contains
an area known as the thermocline. The thermocline is that -25
area within the water column where the temperature
gradient is the steepest. The metalimnion is that region 15 20 25 30
surrounding the thermocline where the temperature gra- Temp ˚C
dient is steep compared to the upper and bottom layers.
Due to the temperature gradient becoming increasingly
steep within a correspondingly smaller volume of water,
the thermocline becomes an infinitesimally small plane,
whereas the metalimnion is a larger region encompass- 0
ing the mean of the greatest rate of change. The hy- Epilimnion
polimnion is the bottom layer and is colder and denser -5
than either the epilimnion or metalimnion. When a lake
Metalimnion
Depth_m
or reservoir is thermally stratified, the hypolimnion -10
becomes largely isolated from atmospheric conditions
-15
and is often referred to as being stagnant. Additionally,
the hypolimnion receives organic debris from the epil- Hypolimnion
-20
imnion, and as respiring bacteria begin the process of
decomposition of this received material, consumption of -25
dissolved oxygen (e.g., respiration) usually exceeds either
production of oxygen from photosynthesis or -30
atmospheric re-aeration. The eplimnion is often referred 0 2 4 6 8
to as the trophogenic area of lentic systems, where mix- Dissolved Oxygen DO mg/L
ing through wind and wave action as well as photosyn- Figure 3.12 Thermal stratification in Lake Pleasant, Arizona.
thesis exceeds respiration, whereas the hypolimnion is Data collected on 08/05/2003. The upper graph plots depth and
referred to as the tropholytic region, where organic temperature and the bottom graph depth and dissolved oxygen.
material is synthesized and mineralization by bacteria
occurs.
3.9 STREAMS AND RIVERS—THE LOTIC

SYSTEM
differences between the epilimnion and hypolimnion means

Lotic systems consist of running water such as rivers or
that relatively few of these nutrients are available for uptake
streams and are the great transporter of material to oceans,
by phytoplankton until the lake or reservoir de-stratifies or
lakes, and reservoirs. Rivers and streams are also vulnerable
“turns over,” which occurred when the epilimnion cools to a
to both natural and anthropogenic sources of pollution, and
temperature similar to the hypolimnion (usually during the
have a history of being used and misused.
fall). Algal “blooms” or sudden increases in biomass of al-
gae are common during this time.
Recycling of nutrients through the thermocline from
3.9.1 Stream Morphometry
the hypolimnion to the trophogenic epilimnion does occur, Stream morphometry was initiated by R.E. Horton and A.E.
although this is relatively small compared to overall nutri- Strahler in the 1940s and 50s to find suites of holistic stream
ent levels within the hypolimnion. Increases in algal properties from the measurement of various attributes. This
biomass means that more organic material is available for was designed to allow some type of classification system
transport back through the thermocline into the hy- that could be used as a communicative tool for hydrologists
polimnion, adding to anoxia and the potential release of (Figure 3.13).
more nutrients from sediments, so that a positive feedback The original idea was to develop a hierarchical classifi-
loop is established. This autochthonous cycling of nutrients cation system of stream segments. These segments were
can keep a lake or reservoir locked into a eutrophic state ordered numerically from headwaters so that individual
even after other sources of pollutants from the watershed tributaries at the headwaters were given the order of “1.”
have been reduced. The joining of two 1st order streams were given the order of
channel per unit area of drainage basin expressed as:

1 1 stream length
Drainage density (Dd)
basin area
1 Drainage density is useful numerical measure of landscape
2 1
dissection and runoff potential.
1 Rivers are often divided into relatively homogenous
units or reaches. A river has distinct chemical, physical,
2
Stream Ordering
and biological attributes, depending upon stream order and
overall size of the channel. General physical characteristics
based upon channel size are given in Table 3.5.
2
1 3.9.2 Stream Hydraulics
2 3
The flow of fluids is generally classified into two types: lam-
inar and turbulent. For laminar flow, which occurs at lower
1 velocities, the individual fluid (e.g., water) molecules move
uniformly in the direction of the mean gradient, with minimal
mixing. Conversely, at higher velocities, the fluid molecules
3 do not always move uniformly; instead, they may also cross
the paths of other molecules, mixing and forming eddies. This
Figure 3.13 Example of stream ordering. Notice that it takes 2
is refereed to as turbulent flow. The Reynolds number, a di-
stream orders of the same magnitude to increase downstream
ranking. For example, the confluence of a 2nd order and a 1st mensionless parameter, is used to characterize conditions for
order stream does not equal a third order, but the joining of which flow will be laminar or turbulent.
two 2nd order streams does. (http://www.cotf.edu/ete/modules/ The volume of water flowing in a stream at a given
waterq/streamorder.html) time is referred to as the stream discharge. Discharge has
units of volume per time (e.g., cubic meters per second). It
is calculated as: Q A * v, where Q is discharge, A is
“2” and the joining of two 2nd order streams, the order of “3,”
cross-sectional area and v is velocity. The cross-sectional
and so on.
area of the stream, which has units of length squared, is
Horton found that the ratio between number of stream
controlled by the shape and size of the channel and the
segments in one order and the next was consistently around
height of water in the channel. This latter term is often re-
three. This is called the bifurcation ratio. This ratio has
ferred to as the stream stage. The velocity (units of length
also been discovered in the rooting system of plants, the
per time) of water in a stream is controlled by the gradient
branching structure of woody plants, leaf venation, and the
(slope) of the stream and roughness of the stream channel
human circulatory system.
surfaces. Water velocities are generally not uniform across
the stream cross-section. Rather, the highest velocities
ORDER # OF SEGMENTS BIFURCATION RATIO typically occur in the center of the channel just below the
surface, and the lowest velocities occur along the channel
1 30 3.0
surfaces (where friction is greatest).
2 10 3.3
3 3 3.0
3.10 GROUNDWATER—WATER IN THE
Horton called this association the Law of Stream SUBSURFACE
Numbers, which is defined as the “morphometric relationship
observed in the number of stream segments of a particular Water in the subsurface serves as a critical resource for hu-
classification order in stream order branching.” Horton com- man consumption, both directly and indirectly (see Chapter
bined the information that he obtained to define the Laws 17). Groundwater resources serve as one of the two primary
of Stream Lengths and Basin Areas. The Law of Stream sources of potable water supply in the world (the other being
Lengths states that a geometric relationship exists between surface water). In addition, water in the soil profile supports
the numbers of stream segments in successive stream orders, plant life, upon which humans are dependent in several
whereas the Law of Basin Areas indicates that the mean ways. Water is also central to the transport and fate of con-
basin area of successively ordered streams form a linear taminants in the subsurface. We will examine the distribu-
relationship. tion and movement of groundwater in this section. The
A quantifiable measure of the morphometry of drainage impact of water flow on transport of contaminants in the sub-
networks is drainage density, which is the length of stream surface is discussed in Chapters 6 and 17.
TABLE 3.5 Properties of stream channels.
CHANNEL SIZE PHYSICAL CHARACTERISTICS ORDER

Small Cobbles ( 64 mm dia.) And boulders ( 256 mm Low
dia.) Dominate the substrate.
Pools form behind rocks or logs (step-pool
formations)
Relatively steep gradients (2° to 20°)
Banks composed of bedrock, boulders, and roots.
Highly erosional areas.
Intermediate 20–30 m max. width Intermediate
Dominated by pool-riffle-bar units
Riffles are zones of relatively shallow, rapid flow
Rapids, cascades, and glides (extended riffles) may
be prominent.
Major pool types include backwater (formed from
either obstructions in the main channel or from
periodic flooding of banks), dammed (found
upstream of boulder lies and gravel bars), and
scour (where flow converges past an
obstruction).
Large Dominated by pool-riffle sequences, bar High
formations, and meanders.
Reach gradient largely determined by valley
gradient.
Transport of sediment may increase sinuosity.
Sinuosity is defined as river length/valley length.
Braided channels may form when the river can no
longer carry its sediment load.
Increased deposition of sediment in large channels.
From Callow & Petts, 1992.
3.10.1 Water in the Subsurface

some of the water is free to move under the influence of
We can observe a cross-section of water distribution in the gravity. When this occurs, water movement would generally
subsurface by drilling a borehole or excavating a pit. A be vertically downward. If this water moves all the way to
schematic of a typical subsurface profile was presented in the water table, it serves to replenish (or recharge) ground-
Figure 2.1. The vadose zone, also known as the zone of aer- water. The capillary fringe is the region above the water
ation or unsaturated zone, represents a region extending table where water is pulled from the water table by capillary
from near the ground surface to a water table. The water forces. This zone is also called the tension-saturated zone.
table is defined as a water surface that is at atmospheric pres- The thickness of this zone is a function of grain-size distri-
sure. In the soil and vadose zones, all pores are usually not bution and varies from a few centimeters in coarse-grained
filled with water; many pores will also contain air. In such soils to a few meters in fine-grained soils. The water content
cases, the porous medium is considered to be unsaturated. in this zone ranges from saturated to partially saturated, but
Water pressure in the soil and vadose zones is less than at- fluid pressure acting on the water is less than atmospheric
mospheric pressure (P 0). The thickness of the vadose zone pressure (P 0).
varies from a meter or less in tropical regions to a few hun- The region beneath the water table is called the satu-
dred meters in arid regions, depending upon the climate rated or phreatic zone. In this zone, all pores are saturated
(e.g., precipitation), soil texture, and vegetation (see also with water and the water is held under positive pressure.
Chapter 2). Because all pores are filled with water, soil-water content is
Water stored in the soil and vadose zones is retained by equal to porosity, except when liquid organic contaminants
surface and capillary forces acting against gravitational are also present in the pore spaces (see Chapter 17). The
forces. Molecular forces hold water in a thin film around soil water in the saturated zone is usually referred to as ground-
grains. Capillary forces hold water in the small pores be- water. Water movement in the saturated zone is generally
tween soil grains. Gravity forces are not sufficient to force horizontal. Specific sections of the saturated zone, particu-
this water to percolate downward. Thus, there is very little larly those comprised of sands and gravels, are called
movement of water in the vadose zone when water contents aquifers, which are geologic units that store and transmit
are relatively low. For higher water-content conditions, significant quantities of groundwater.
3.10.2 Principles of Subsurface Water Flow overlying water. The water pressure increases with depth in
Water at any point in the subsurface possesses energy in the saturated zone. This condition occurs in all water
mechanical, thermal, and chemical forms. The energy sta- bodies—including swimming pools—which is manifested
tus of water, for example the effort required to move water by the increasing pressure one feels on their sinuses and
from one point to another, is a critical aspect of quantifying eardrums, as one swims deeper below the surface.
water flow. For groundwater flow, the contributions of The energy potentials are commonly expressed in
chemical and thermal energies to the total energy of water terms of length to simplify their use. In length terms, the
are generally relatively minor and thus are usually ignored. energy potentials are referred to as “heads.” The total
Therefore, we consider water flow through porous media to energy potential head for water is called the hydraulic
be primarily a mechanical process. Fluid flow through head; sometimes, particularly for vadose-zone applica-
porous media always occurs from regions where energy per tions, it is called the soil-water potential head. The equa-
unit mass of fluid (fluid potential) is higher, to regions tion we use to relate the hydraulic head (h) to its two parts,
where it is lower. elevation head (z) and pressure head ( ), is: h z.
From fluid mechanics, the mechanical energy of water Each head has a dimension of length (L) and is generally
at any point is composed of the kinetic energy of the fluid, expressed in meter or feet.
the potential (or elevation) energy, and the energy of fluid Hydraulic head measurements are essential pieces of
pressure. For water flow in porous media, kinetic energy is information that are required for characterizing groundwa-
generally negligible because pore-water velocities are usu- ter flow systems (i.e., direction and magnitude of flow), de-
ally small. Thus, total energy of water is considered to termining hydraulic properties of aquifers, and evaluating
consist of potential and pressure energies. the influence of pumping on water levels in a region.
The potential or elevation energy results from the Piezometers are used to measure the hydraulic head at dis-
force of gravity acting on the water. In the absence of pres- tinct points in saturated regions of the subsurface. A
sure energy considerations, water always flows from re- piezometer is a hollow tube or pipe drilled or forced into a
gions of higher elevation potential to lower. This is why profile to a specific depth. Water rises inside the tube to a
surface water flows “downhill.” Similarly, groundwater level corresponding to the pressure head at the terminus.
usually flows downward from higher elevations (under- The level to which water rises in the piezometer with ref-
neath mountain peaks) to lower elevations (underneath the erence to a datum such as sea level is the hydraulic head
valley floor). (Figure 3.14).
In the vadose zone, the pressure potential is negative, The relationship between the three head components is
indicating that energy is required to “pull” water away from illustrated in a piezometer in Figure 3.14. The value of z
the soil surfaces and small pores. In the saturated zone, the represents the distance between the measurement point in the
pressure potential is positive due to the pressure exerted by profile and a reference datum. Sea level is often taken as
Ground surface
Point of
measurement z
Sea level
Figure 3.14 Concept of hydraulic head (h), elevation head (z) and pressure head ( )
in a piezometer. The cross-hatched section at the bottoms of the tube (terminus) repre-
sents the screened interval, which allows water to flow into the piezometer. Water level
is denoted by the “” symbol. From Yolcubal et al., 2004.
No vertical Downward Upward

(1) gradient (2) gradient (3) gradient
Sea level
Figure 3.15 Three hypothetical situations for vertical hydraulic gradient water level is denoted
by the “∇” symbol. From Yolcubal et al., 2004.
the reference point where z 0, although some people use In his series of experiments, Darcy studied the relation-
the elevation of land surface as the reference datum. The ship between flow rate and the head loss between the inlet
value of represents the distance between the measurement and outlet of the column. He found that:
point and the water level in the well. The value of h 1. The flow rate is proportional to the head loss between
represents the elevation of water from the reference datum. the inlet and outlet of the column:
This basic hydraulic head relationship is essential to an un-
derstanding of groundwater flow. Water flow in porous me- Q (Ha hb)
dia always occurs from regions in which hydraulic head is
The flow rate is inversely proportional to the
higher to regions in which it is lower.
length of flow path:
Water level measurements in a network of production
or monitor wells are used to define the potentiometric (or 1
water table) surface of regional ground water. Knowledge Q
dl
of this surface is required to define hydraulic gradients and
flow directions. Data from piezometers terminating in 2. The flow rate is proportional to the cross-sectional area
depth-wise increments provide information about the verti- of the column:
cal flow direction of water in saturated regions (Figure QA
3.15). In the first (left side) diagram, the water level is
uniform, indicating no vertical flow. In the second (middle) Mathematically, these experimental results can be writ-
diagram, the water level is highest in the shallowest ten as:
piezometer and lowest in the deepest one, indicating
h

ha - hb
downward flow. The reverse is true for the third (right side) Q KA KA
l l
diagram.
where:
3.10.3 Darcy’s Law Q flow rate or discharge [L3 T1]

A cross-sectional area of the column [L2]
In 1856, a French hydraulic engineer, Henry Darcy, estab- ha, b hydraulic head [L]
lished a relationship that bears his name to this day. The dh head loss between two measurement points [L]
relationship is based on studies of water flow through dl the distance between the measurement loca-
columns of sand, similar to the schematic shown in Figure tions [L]
3.16. In Darcy’s experiment, the column is packed with sand dh/dl hydraulic gradient []
and plugged on both ends with stoppers. Water is introduced K proportionality constant or hydraulic conduc-
into the column under pressure through an inlet in the stop- tivity [L T1]
per and allowed to flow through it until all the pores are fully
saturated with water and inflow and outflow rates are equal. We can rewrite Darcy’s Law as:
Water pressures along the flow path are measured by the Q K dh
q
manometers installed at the ends of the column. A dl
ha-hb
a
dl
b hb ha
Datum
z=0
Figure 3.16 Schematic of Darcy’s experimental apparatus (original apparatus was vertically
oriented). From Yolcubal et al., 2004.
where q is called specific discharge or Darcy velocity Hydraulic conductivity has a dimension of velocity [L T1],
with units designated as [L T1]. This is an apparent velocity and is usually expressed in m s1, cm s1, or m day1 in SI
because Darcy velocity represents the total discharge over units, or ft s1, ft day1, or gal day1 ft2.
a cross-sectional area of the porous medium. Cross-sectional As indicated by the equation above, hydraulic
area includes both void and solid spaces; however, water flow conductivity depends on properties of both the fluid and
occurs only in the connected pore spaces of the cross sectional porous medium. The two fluid properties are density and dy-
area. Therefore, to determine the actual mean water velocity, namic viscosity. Intrinsic permeability is a property that in
specific discharge is divided by the porosity of the porous most cases depends solely on the physical properties of the
medium: v q/n, where v is the pore-water velocity or aver- porous medium. This relationship can be illustrated using the
age linear velocity. Pore-water velocity is always greater than expression called the Hazen approximation:
Darcy velocity.
k C(d10)2
where:
3.10.4 Hydraulic Conductivity C is a shape factor [dimensionless]
The proportionality constant in Darcy’s law, which is called d10 is the effective grain diameter [L]
hydraulic conductivity (K) or coefficient of permeability,
C is a constant that represents the packing geometry, grain
is a measure of the fluid transmitting capacity of a porous
morphology (size and shape), and grain-size distribution of
medium and is expressed as:
the porous medium. The value of C ranges between 45 for
k g clays and 140 for sand. A value of C 100 is often used as
K
an average. d10 is the diameter for which 10% (by weight) of
the sample has grain diameters smaller than that diameter, as
where:
determined by sieve analysis. The Hazen approximation is
k is the intrinsic or specific permeability [L2] applicable to sand with an effective mean diameter between
is the fluid density [M L3] 0.1 and 3.0 mm. Intrinsic permeability (k) has dimensions of
g is the acceleration due to gravity [L T2] square feet (ft2), square meter (m2), or square centimeter
is the dynamic viscosity of the fluid [M T1 L1] (cm2).
As noted above, porous-media properties that control K sands is always greater than that of clays for saturated porous
include pore size, grain-size distribution, grain geometry, media. However, in the vadose zone, this relationship may
and packing of grains. Among those properties, the influence not always hold true. For example, during drainage of a soil,
of grain size on K is dramatic, since K is linearly propor- larger pores drain first and the residual water remains in the
tional to the square of grain diameter. The larger the grain di- smaller pores. Since sand has larger pores than clay, it will
ameter, the larger is the hydraulic conductivity. For example, lose a greater proportion of water for a given suction. Conse-
hydraulic conductivity of sands ranges from 104 to 101 quently, at relatively low soil-water contents (high suctions),
cm s1, whereas the hydraulic conductivity of clays ranges most of the pores of a sand will be drained, while many for a
from 109 to 107 cm s1. The values of saturated hydraulic clay will remain saturated. Therefore, the unsaturated hy-
conductivity vary by several orders of magnitude, depending draulic conductivity of a clay unit may become greater than
on the material. The range of values of hydraulic conductiv- that of a sand unit at lower soil-water contents.
ity and intrinsic permeability for different media is illus- Hydraulic conductivity is a critical piece of informa-
trated in Figure 3.17. tion required for evaluating aquifer performance, charac-
In the vadose zone, hydraulic conductivity is not only a terizing contaminated sites for remediation, and determin-
function of fluid and media properties, but also the soil-water ing the fate and transport of contaminant plumes in
content (), and is described by the following equation: subsurface environments. For example, for water manage-
ment issues, one needs to know the hydraulic conductivity
K() K kr()
to calculate the water-transmitting and storage capacities of
where: the aquifers. For remediation applications, knowledge of K
distribution of contaminated soils is necessary for calculat-
K() is the unsaturated hydraulic conductivity
ing plume velocity and travel time, to determine if the
K is the saturated hydraulic conductivity
plume may reach a downgradient location of concern. Hy-
kr() is the relative permeability or relative hydraulic
draulic conductivity can be measured in the laboratory as
conductivity
well as in the field. Laboratory measurements are per-
Relative permeability is a dimensionless number that formed on either disturbed or undisturbed samples that are
ranges between 0 and 1. The kr() term equals 1 when all the collected in the field. Laboratory measurements are rela-
pores are fully saturated with water, and equals 0 when the tively inexpensive, quick, and easy to make compared to
porous medium is dry. Unsaturated hydraulic conductivity is field measurements. They are often used to obtain an initial
always lower than saturated hydraulic conductivity. characterization of a site before on-site characterization is
Unsaturated hydraulic conductivity is a function of soil- initiated. However, measurements made for a sample rep-
water content. As the soil-water content decreases, so does resent that specific volume of media. A single sample will
K(). In fact, a small drop in the soil-water content of a porous rarely provide an accurate representation of the field be-
medium, depending upon its texture, may result in a dramatic cause of the heterogeneity inherent to the subsurface.
decrease (e.g., 103,106) in the unsaturated hydraulic conduc- Thus, a large number of samples would usually be required
tivity. As we discussed earlier, the hydraulic conductivity of to characterize the hydraulic conductivity distribution
Figure 3.17 Hydraulic conductivity and permeability at saturation. (Adapted from Klute, A., and
Dirksen, C. [1982] Methods of Soil Analysis. Part I— Physical and mineralogical methods. Soil Science
Society of America, Madison, WI).
present at the site. Thus, field tests, while more expensive, political boundaries. Natural physical, chemical, and biolog-
are generally preferred to characterize large sites. ical processes within watersheds provide civilization-
sustaining benefits when functioning properly. Unfortu-
nately, the same civilization to which watersheds provide
3.11 A WATERSHED APPROACH these benefits is often the source of impairment and disrup-
tion of natural processes within them. Acknowledging this
Strictly defined, a watershed is a bound hydrologic unit where fact while understanding that political boundaries do exist is
all drainages flow to a common water source. Referring back a necessary prerequisite toward cooperative management of
to the section on stream order, we can see that a watershed en- the world’s most precious natural resource.
compasses all stream orders from beginning to end. No matter While water within watersheds follows the physico-
where one goes on the earth (excluding the oceans), that per- chemical “laws” previously described in this chapter, water-
son would be in a distinct watershed. Watersheds are usually shed management is equal parts hydrology and social sci-
delineated by sharp gradients and precipitation or snowmelt ence. Watershed management acknowledges that humans
flows along one side of the gradient or the other, depending are a part of, not separated from, watershed processes and
upon local topography and natural hydrology. functioning. Watershed management, as a component of
Increasingly, resource managers are using watersheds ecosystem management, tries to unify communities, man-
as the unit of measure for management and delineation pur- agers, water quality experts, and as many stakeholders as
poses on a landscape scale. In hydrologic terms, it makes possible, with the overall goal of increasing or sustaining
perfect sense to focus management efforts in these terms, be- water quality over large geographic areas for the common
cause a land use activity in one part of a watershed often has good of not only affected communities, but also of the wa-
an effect on downstream areas. The more traditional ap- tershed itself.
proach of addressing specific sources of pollution in a spe- This ideology is far from revolutionary, and perhaps the
cific area has been successful in addressing problems that are best definition of a watershed was by the geologist, explorer,
readily noticeable; however, this approach has met with lim- and teacher John Wesley Powell, who stated over 100 years
ited success in addressing the chronic and subtle stressors ago that:
that often contribute to impairment within a watershed. A “A watershed is that area of land, a bounded hydrologic
watershed framework is better able to capture these subtle system within which all living things are inextricably linked
changes over time. by their common water course and where, as humans set-
It’s important to understand that watersheds, and the or- tled, simple logic demanded that they become part of a
ganisms they contain, pay no attention to human-imposed community.”
QUESTIONS AND PROBLEMS
1. A. Determine pressure head ( ), elevation head (z), and hy- Well 2. The elevation at the ground surface is 115 m;
draulic head (h) for both wells. the measured water level in the well is 50 meters below
B. Calculate the hydraulic gradient. the ground surface. The well casing length is 80 m.
C. Does groundwater flow from well #1 to #2, or from #2 to #1? 2. Why is hydraulic conductivity a function of the fluid as well as
the porous medium? Is the conductivity for water greater than or
less than that for air (for a given porous medium)?
3. Water has been described as a universal solvent. Describe three
Well #2
Well #1
properties of water that account for its ability to dissolve so
many types of compounds.
4. Describe some physical, chemical, and biological characteris-
tics within the epilimnion and hypolimnion of a thermally strat-
ified lake.
5. For the temperatures and pressures given below, determine if
water will be in a solid, liquid, or gaseous state (or some combi-
nation thereof).
a. 219 ATM and 0.0000098°C
Datum (mean sea level) b. 100 ATM and 100°C
c. 1 ATM and 373°C
The horizontal distance between the wells is 250 meters. d. 0.006 ATM and 0.01°C
Well 1: The elevation at the ground surface is 100 m;
the measured water level in the well is 40 meters below
the ground surface. The well casing length is 60 m.
REFERENCES AND ADDITIONAL READING
Birge E.A. (1898) Plankton studies on Lake Mendota II. The crus- Mitsch W., and J.G. Gosselink. (1993) Wetlands, 2nd ed. Van
tacea of the plankton from July, 1894, to December, 1896. Trans. Nostrand Reinhold, New York, New York. 722 pp.
Wis. Acad. Sci. Arts Lett. 11:274–448. Reynolds O. (1883) An experimental investigation of the circum-
Brezonik P.L. (1994) Chemical Kinetics and Process Dynamics in stances which determine whether the motion of water shall be di-
Aquatic Systems. Lewis-CRC Press, Boca Raton, Florida. 754 pp. rect or sinuous, and of the law of resistance in parallel channels.
Callow P. and Petts G.E. (1992) The Rivers Handbook. Vol. 1. Royal Society, Phil. Trans.
Blackwell Sci. Publ., Cambridge. 526 p. Schlesinger W.H. (1991) Biogeochemistry: An Analysis of Global
Carlson R.E. (1977) A trophic state index for lakes. J. Limnol Change. Academic Press, Orlando, Florida.
Ocean. 22:361–369. Streeter H.W. and Phelps E.B. (1925) A study of the pollution and
Clesceri L.S., Greenberg A.E. and Eaton A.D. eds. (1999) Stan- natural purification of the Ohio River. III. Factors concerned in
dard Methods for the Examination of Water and Wastewater. 20th the phenomena of oxidation and reaeration. U.S. Public Health
Ed. American Public Health Association, Washington, DC. Serv. Public Health Bull. 146.
Swain E.B., Engstrom D.R., Brigham M.E., Henning T.A. and
Cole G.A. (1994) Textbook of Limnology. 4th ed. Waveland Press
Brezonik P.L. (1992) Increasing rates of atmospheric mercury
Inc., Prospect Heights, Illinois.
deposition in midcontinental North America. Science
Edmondson W.T. (1994) What is limnology? In Limnology Now: 257:784–787.
A Paradigm of Planetary Problems, R. Margalef, ed. Elsevier,
van der Leeden F., Troise F.L. and Todd D.K. (199) The Water
New York, New York.
Encyclopedia. Lewis Pubs. Chelsea, Michigan.
Frey D.G. (1963) Wisconsin: The Birge and Juday years. Chapter
Vannote R.L., Minshall G.W., Cummins K.W., Sedell J.R. and
1 in Limnology in North America, D.G. Frey, ed. University of
Cushing C.E. (1980) The river continuum concept. Can. J. Fish.
Wisconsin Press, Madison, Wisconsin. 734 pp.
Aquat. Sci. 37:130–137.
Horton R.E. (1931) The field, scope, and status of the science of
Vollenweider R.A. (1975) Input-output models with special refer-
hydrology. pp. 189–202 in Reports and Papers, Hydrology,
ence to the phosphorous loading concept in limnology. Schweiz.
Trans. AGU. National Research Council, Washington, DC. Z. Hydrol. 37:53–84.
Hutchinson G.E. (1957) A Treatise on Limnology, Vol. I. John Wetzel R.G. and Likens G.E. (1991) Limnological Analyses.
Wiley & Sons, New York. Springer-Verlag, New York, New York.
Hynes H.B.N. (1970) The Ecology of Running Waters. University Williams J.E., Wood C.A. and Dombeck M.P. eds. (1997) Water-
of Toronto Press, Toronto. shed Restoration: Principles and Practices. American Fisheries
Kelly C.A., Rudd J.W.M., Hesslein R.H., Schindler D.W., Dillon Society, Bethesda, Maryland.
P.J., Driscoll C.T., Gherini S.A. and Hecky R.E. (1988) Prediction Yolcubal I., Brusseau M.L., Artiola J.F., Wierenga P. and Wilson
of biological acid neutralization in acid sensitive lakes. Biogeo- L.G. (2004). Environmental physical properties and processes. In
chemistry 3:129–140. Environmental Monitoring and Characterization (J.F. Artiola, I.L.
Klute A. and Dirkson C. (1982) Methods of Soil Analysis. Part I— Pepper, and M. Brusseau, eds.). Elsevier Academic Press, San
Physical and mineralogical methods. Soil Science Society of Diego, California. pp. 207–237.
America, Madison, Wisconsin.

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CHAPTER 3

D.B. Walker, M.L. Brusseau, and K. Fitzsimmons

Apache Reservoir, Arizona. Photo courtesy D. Walker.

3.1 THE WATERY PLANET

Figure 3.4 The density of water at varying temperatures.

TABLE 3.1 Phase changes of water.

PROCESS FROM TO ENERGY GAINED OR

This is a major source of pollutants introduced into the envi-

3.4 THE UNIVERSAL SOLVENT

One of the most unique properties of water is its ability to

water, or mass of soil, is a function of the relative humidity,

TABLE 3.2 Examples of typical concentrations of

EXAMPLE CALCULATION 3.1

vegetation. During photosynthesis, plants convert CO2 into

All natural waters also have sinks of dissolved oxygen,

15 carbonate in excess, leading to increased pH levels. In the

H2CO3 ↔ H2O CO2 (Eq. 3.8)

Rain is often slightly acidic due to the dissolution of at-

oxidation-reduction reactions are often referred to as redox

REDOX COUPLE VOLTS DISSOLVED O2 (MG/L)

Figure 3.11 Wavelengths of light and associated spectra. ln Io ln lz

where: determining total dissolved solids and/or salinity including

TABLE 3.4 Trophic categories for lakes and reservoirs.

TROPHIC STATE CHLOROPHYLL A SECCHI DISK TOTAL P ATTRIBUTES

3.9 STREAMS AND RIVERS—THE LOTIC

differences between the epilimnion and hypolimnion means

channel per unit area of drainage basin expressed as:

TABLE 3.5 Properties of stream channels.

CHANNEL SIZE PHYSICAL CHARACTERISTICS ORDER

3.10.1 Water in the Subsurface

No vertical Downward Upward

3.10.3 Darcy’s Law Q flow rate or discharge [L3 T1]

QUESTIONS AND PROBLEMS

REFERENCES AND ADDITIONAL READING

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