WATERAS A SUBSTANCE
1. The Characteristics of Water D. Density Relationships
A. Molecular Structure
and Properties
B. Isotopic Content of Water
C. Specific Heat
I. THE CHARACTERISTICSOF WATER
Water is the essence of life on earth and totally
domina tes the chemical composition of all organisms.
The ubiquity of water in biota, as the fulcrum of bio-
chemical metabolism, rests on its unique physical and
chemical praperties.
The characteristics of water regula te lake metabo-
lism. The unique thermal-density properties, high
specific heat, and liquid - solid characteristics of water
allow the formation of a stratified enviranment that
controls extensively the chemical and biotic properties
of lakes. Water pravides a tempered milieu in which
extreme fluctuations in water availability and tempera-
tures are ameliorated relative to conditions faced by
biota in aerial life. Coupled with a relatively high
degree of viscosity, these characteristics ha ve enabled
biota to develop many adaptations that imprave sus-
tained praductivity.
A. MoIecuIar Structure and Properties
The unique properties of water center upon its
atomic structure and bonding and the unusual associa-
tion of water molecules in solid, liquid, and gaseous
phases. In equilibrium, the nuclei of a water molecule
form an isosceles triangle, with a slightly obtuse bond
angle of 104.5° at the oxygen nucleus (Eisenberg and
Kauzmann, 1969). The bond length from the center
of the oxygen atom to that of each hydrogen atom is
0.96 X 10-8 cm. The nuclei of the molecules are in a
E. Viscosity-Density Relationships
F. Surface Tension
n. Surnrnary
continual state of vibration. As the molecule resonates,
an electrical dipole moment occurs, such that a com-
plex wave function results in a valence electron density
pattern in which electro n density is highest near the
atoms and aIong the bonds (Fig. 2-1). The electronic
charge of the molecule is not restricted to the planar
configuration depicted, but is distributed in multiple di-
rections.
Although most (ea. 56%) water molecules have
balanced va lances, excitation and ionization do occur.
The most common ionized state is characterized by
removal of one of the hydragen atoms, which is
charged positively and is functioning essentially as a
proton. Higher ionization potentials (energy needed to
remove electrons fram the molecule) are needed to
reach further ionization states of water and occur less
frequently. The weak coulombic characteristics of the
bonding of hydrogen atoms to the weakly electronega-
tive oxygen atom result in both ionized and covalent
sta tes that simultaneously maintain the integrity of
water. Water is nearly the only known compound that
possesses these characteristics.
The density properties of water that are so
germane to limnology and life in water result fram the
aggregation and bonding characteristics of the water
molecules. It is instructive to look first at the structure
of ice, whose physicaI properties are understood better
than those of liquid water. Every oxygen atom is at the
center of a tetrahedran formed by four oxygen atoms,
each about 2.76 X 10-8 cm distant (Eisenberg and
Kauzmann, 1969; Horne, 1972). Every water molecule
9
 10 2. Wateras a Substance
FIGURE 2-1 Contour map of the electronic charge distribution of
the water molecule in the plane of the nuclei (positions indicated by
crosses). Contours increase in value of atomic units (au) (1 au =
67 e- per nm3) from the outermost contour in steps of 2 X Ion, 4 X
Ion, 8 X Ion. The smallest contour value is 0.002, with n increasing
in steps of unity to yield a maximum value of 20. (Unpublished figure
courtesy of Dr. R. F. W. Bader, Department of Chemistry, McMaster
University.)
is hydrogen-bonded to its four nearest neighbors; its
O-H bonds are directed toward lone pairs of elec-
trons on two of these adjacent molecules and form two
O-H-O hydrogen bonds. In turn, each of its lone
pairs is directed toward an 0- H bond on one of the
other adjacent molecules and forms two O-H-O
hydrogen bonds. This arrangement leads to an open
lattice in which intermolecular cohesion is great
(Fig. 2-2). This structure results in both parallel and
perpendicular voids among the molecules and creates
an open tetrahedral structure that permits ice to float
upon liquid water.
Molecules in liquid water near O°C experience
about 1011 to 1012 reorientational and translational
movements per second, whereas ice molecules near O°C
experience only about 105 to 106 movements per sec-
ond. Increasing the temperature of water increases the
rate of reorientations and molecular displacements and
results in decreased viscosity, decreased molecular re-
laxation times, and increased rates of self-diffusion. By
virtue of their dipolar nature, water molecules interact
to form quasi-stable polymers.
We have viewed here water molecules as diffu-
sionally averaged structures both in vibrational time
and in space between molecules. However, variations
in temperature change the intermolecular distances.
Thermal increases result in increased agitation of the
molecules, which distorts and breaks down the hydro-
FIGURE 2-2 A diagrammatic representation of an ice crystal show-
ing the van der Waals radii of the atoms and open voids between the
aggregated molecules. (From Pimental, G. c., and McClellan, A. L.:
The Hydrogen Bond. San Francisco, W. H. Freeman and Co., copy-
right @ 1960.)
gen-bonded networks. As the ice melts, increased
bond dislocation and rupture occur, which disrupt
and fill in the open spaces of the ice lattice structure.
The result is an increase in density, and this effect pre-
dominates and reaches a maximum at 4°C. As water
is heated above 4°C, intermolecular vibrations in-
crease in amplitude and increase interatomic dis-
tances. The result is expansion of the liquid and de-
creased density. It is a characteristic of water that
minimum volume, hence maximum density of water,
occurs at 3.98°C. At this point, competition between
the negative configurational contribution of hydrogen
bonding and its positive vibrational contribution is
maximized.
B. Isotopic Contentof Water
Known isotopes of hydrogen are lH, 2H or D (deu-
terium), and 3H (tritium). Tritium is radioactive, with a
half-life of 12.5 years, sufficiently short that after its
decay to 3He, most of which is lost from the atmos-
phere into space, concentrations of tritium in unconta-
minated natural water are very low (approximately 1
3H atom per 1018 lH atoms) and do not accumulate.
Six isotopes of oxygen are known: 140, 150, 160, 170,
180, and 190. The isotopes 140, 150, and 190 are

radioactive but are short-lived and do not occur signifi-
cantly in natural water. The precise isotopic content of
natural water depends on the origin of the sample but,
within limits of variation, the abundances of H2180,
HpO, and HD160 are 0.20, 0.04, and 0.03 mole per-
cent, respectively (Eisenberg and Kauzmann, 1969).
Other isotopic combinations are exceedingly rare in
natural water (Hutchinson, 1957).
Changes in the ratios of these isotopes in com-
pounds and in remains of organisms formed within a
lake over geological time permit an estimation of pale-
otemperatures. The technique is based on the tempera-
ture dependence of fractionation of the oxygen isotopes
in the carbon dioxide-water-carbonate system (Stuiver,
1968). During slow precipitation of the carbonate, the
temperature of the solution is reflected in the ratio of
180 to 160 in the carbonates of sediments and mollusks.
The ratio of oxygen isotopes in the precipitated carbon-
ates depends not only on the temperature but also on
the ratio of 180 to 160 isotopes in the water in which
carbonate is formed. The measured difference in the ra-
tio of 180 to 160 isotopes between a carbonate fossil
and a contemporaneous sample is the result of changes
in both temperature and composition of water isotopes.
Before paleotemperature determinations can be made,
an estimate of the changes in ratio of oxygen isotopes of
the water is needed. This measurement is more difficult
to make in lakes, where variations over time are greater
than in the oceans. However, estimates can be made
with reasonable precision.
C. Specific Heat
Specific heat1 of liquid water is very high (1.0) and
is exceeded only by a few substances, such as liquid
ammonia (1.23), liquid hydrogen (3.4), and lithium at
high temperatures. Other substances of the biosphere,
such as many rocks, have much lower specific heats
(approximately 0.2). The high specific heat of water, as
well as a high latent heat of evaporation (see below), is
a function of the relatively large amounts of heat en-
ergy required to disrupt the hydrogen bonding of liquid
water molecules.
These heat-requiring and heat-retaining properties
of water provide a much more stable environment than
is found in terrestrial situations. Fluctuations in water
temperature occur very gradually. Daily and seasonal
extremes in temperature are small in comparison to
those of aerial habitats. The high specific heat of water
can also have profound effects on climatic conditions
of adjacent air and land masses. This thermal inertia of
1Specific heat is the amount of heat in calories that is required to
raise the temperature l°C of 1 g mass of a substance.
1. The Characterjstjcs of Water 11
the hydrosphere (Hutchinson, 1957) occurs on both
large and small scales, in relation to the volume of wa-
ter bodies. Examples are many. The warm Gulf Stream
currents of the Atlantic Ocean increase the prevailing
temperatures and improve the climate of Western
Europe. The prevailing air movements across the Lau-
rentian Great Lakes moderate the climate of Michigan
and other states adjacent to and east of the lakes
(Leighly, 1942). Milder winters with higher precipita-
tion rates are found in these areas than in the interiors
of continents, beca use the water masses cool and yield
heat to the air more slowly than do land masses. Simi-
larly, areas adjacent to large water mas ses experience
moist, cool summer periods. Fall fogs are common over
and adjacent to lakes and large rivers, where water
vapor from evaporation of the warm lake or river
water condenses and stagnates in the cold overlying air.
That the lake or river "is steaming" is the description
of this phenomenon in common parlance.
The specific heat (thermal capacity) of ice below
O°C is about half (0.5 g~1 °C-1) that of water and de-
creases progressively at temperatures below O°c. The
amount of heat required, however, to change ice to
liquid water is large (latent heat of melting = 79.72
cal g-l) and is very much larger for disruption of hy-
drogen bonding in evaporation of water (latent heat of
evaporation = 540 cal g-l) or for direct sublimation of
ice to water vapor (latent heat of sublimation = 679
cal g-I). Conversely but similarly, a large amount of
heat must be lost for the fusion of molecules of O°C
water to ice (latent heat of fusion = 79.72 cal g-I).
Because of these properties, large energy inputs are re-
quired to melt ice in the spring, and large energy losses
are required in order to form ice cover in the winter.
D. Density Relationships
The entire physical and chemical dynamics of lakes
and reservoirs and resultant metabolism within them
are regulated to a very great extent by differences in
density. Throughout the remaining chapters of this
book, we will refer repeatedly to the fundamental im-
portance of the unique density properties of water.
The density or specific gravity of pure ice at O°C is
0.9168 g ml-\ about 8.5% lighter than that of liquid
water at O°C (0.99987). The density of water increases
to a maximum of 1.0000 at 3.98°C, beyond which mol-
ecular expansion and decreasing density occur at a pro-
gressively increasing rate (Fig. 2-3). The density differ-
ences are small but highly significant. It is important to
examine the difference in density between water at a
given temperature and water at a temperature 1°C
lower, referred to as the density difference per degree
lowering (Vallentyne, 1957). The magnitudes of this
12 2. Water as a Substance

TEMPERATURE 'c DENSITY DIFFERENCE x 10YoC LDWERING

-5 o +5 lO 15 20 25 30 O 10 20 30 40
1.00000

0.99900

0.99800

~ 0.99700
(/)
Z
~ 0.99600

0.99500

f-J
-"-

density difference for water of different temperatures
are shown on the right side of Figure 2-3. The density
difference per degree lowering increases markedly as
the temperature goes above or below 4°C. Physical
work is required to mix fluids of differing density, for
example, when mixing cream into milk, and the
amount of energy input required is proportional to the
difference in density. The amount of work required to
mix layered water masses between 29 and 30°C is 40
times, and between 24 and 25°C 30 times, that required
for the same masses of water between 4 and 5°C.
Density also increases with increasing concentra-
tions of dissolved salts in an approximately linear fash-
ion (Table 2-1). The salinity of most inland waters is
within a range of 0.01 and 1.0 g liter-!, and usually
between 0.1 and 0.5 g liter-l. Inorganic salinity of
highly saline lakes can commonly exceeds 60 g liter-l
and exhibits great seasonal variations (e.g., Rawson and
Moore, 1944; International Association of Limnology,
1959; Wetzel, 1964; Eugster and Hardie, 1978;
TABLE2-1 Approximate Changes in the Density
(g mi 1)of Water with Salt Content
~
Salinity (parts per thousand, %0) Density (at 4°C)
o 1.00000
1 1.00085
2 1.00169
3 1.00251
10 1.00818
35 (mean, seawater) 1.02822
After Ruttner (1963).
Hammer, 1990; Williams, 1996). In most lakes, how-
ever, salinity is very low and varies less than 0.1 g liter-l
spatially and seasonally. Salinity-induced variations
in density may be small, but they cannot be ignored.
Under certain conditions of lake stratification, inorganic
salts can accumulate temporarily or permanently (d.
Chap. 6).
Salinity also decreases the temperature of maxi-
mum density of water at arate of approximately 0.2°C
g-l liter-l(%o) increase. The temperature of maximum
density of sea water (mean 35 g liter-l) is -3.52°C,
which does not occur at surface pressures and is below
the freezing point (-1.91 °C). In most fresh waters,
however, changes in the maximum density of water
from salinity are very smal!.
Hydrostatic pressure can be sufficient to compress
water and thereby lower the temperature of maximum
density. Pressure increases 1 atmosphere per 10m of
depth. The temperature of maximum density decreases
about 0.1 °C per 100 m of depth (Stf0m, 1945). In very
deep lakes, temperatures below 4°C are found to be
partially, but not totally, related to the relatively high
pressures encountered at great depth (Eklund, 1963,
1965; Johnson, 1964, 1966; Bjerke et al., 1979).
E. Viscosity- Density Relationships
The density of water is 775 times greater than
that of air at standard temperature and pressure (O°C,
760 mm Hg). The high density of water makes aquatic
organisms relatively buoyant against gravitational pull
and consequently reduces the amount of energy that
an organism must expend to support or maintain its
 1. The Characteristics oi Water 13

position in the water. Reduction of supporting tissue
has occurred in many freshwater animals, particularly
among the lower invertebrates, but these adaptations
are particularly conspicuous among aquatic vascular
plants. Truly submersed angiosperms are good exam-
pIes; these plants are almost totally limited to fresh
water s and have immigrated and adapted to aquatic
conditions relatively recently. Modifications have led to
marked reductions in vascular tissues, particularly by
reduction of the extent of lignification of the xylem and
supporting elements, and most of the vascular strands
are condensed into a weakly developed central cylinder.
Supportive tissues of these hydrophytes develop
strongly only in those plants or plant parts that are
adapted to aerial existence as surface-floating or emer-
gent forms.
Water viscosity decreases as temperature increases.
Water viscosity doubles as the temperature is lowered
from 25 to O°c. The viscosity of water offers approxi-
mately 100 times more frictional resistance to a moving
organism or particle than air does and is dependent
upon the surface exposure area, the speed, and the tem-
perature and chemical composition of the fluido As will
be discussed further on, organisms with locomotion
must expend considerable energy to overcome changes
in viscosity. Sinking rates and distribution of passive
organisms, such as planktonic algae or sedimenting
particles, are influenced by density-related changes in
viscosity.
F. Surface Tension
The quasi-polymeric bonding properties of liquid
water molecules discussed earlier are disturbed at the
interface with air. At the interface plane, the molecular
attractions are unbalanced and exert an inward adhe-
sion to the liquid phase. The result is an interface sur-
face or film under tension. The surface tension at the
air-water interface of pure water is higher than that
for any other liquid except mercury. Surface tension de-
creases with increasing temperature and increases
slightly with dissolved salts (Table 2-2).
The surface tension of water is reduced markedly
by the addition of dissolved organic compounds. This
phenomenon is seen in aquatic habitats wherever dis-
solved organic matter concentrates (Table 2-2). For ex-
ample, surface tensions of relatively pristine waters
containing few microorganisms differ líttle from those
of distilled water. Bog lakes, which are heavily stained
with dissolved organic compounds, exhibit depressions
in surface. tensions of 6 to 7 dynes cm-1 (range 0-20).
Where growth of floating algae or of higher aquatic
plants is particularly great, the surface tension is de-
pressed by about 20 dynes cm-l. Later on, we will
demonstrate that concentrations of dissolved organic
compounds are high in more productive waters. More-
over, natural populations of algae and submersed an-
giosperms secrete large quantities of organic com-
pounds during active photosynthesis, as well as during
senescence and lysis. The effects of these organic
compounds on surface tension can vary with the
dominance of photosynthetic organisms. For example,
extracellular organic compounds released from green
algae and cyanobacteria lowered surface tensions to a
greater extent than those from diatoms (Nageli and
Schanz, 1991). Organic pollutants introduced into
fresh water s can also markedly lower surface tensions
(Jarvis, 1967; Jarvis et al., 1967).

TABLE 2-2 Surface Tension of Water with Changes in Temperature and Its Depression in Natural Waters under
Various Conditions

Depression of surface tension range

Temp. (OC) Water tension (dynes cm-!) Condition (dynes cm-!)

Pure water
O 75.6 Oligotrophie lakes 0-2
5 74.9 Eutrophie lakes 0-20
10 74.4 Bog lakes 0-20
15 73.5 Lake water with foam 2-9
20 72.7 Near floating-leaved angiosperms 5-20
25 72.0 Near submersed angiosperms 1-2
30 71.2 During a eyanobaeterial bloom 0-20
35 70.4 Open sea <1
40 69.6 Plymouth Sound, near muddy beaeh 6-20
Harbor, heavy boat traffie 152:20
Sea water
ea. 5 75.0

From data of Adam (1937), Hardman (1941), and Goldaere (1949).

14 2. Wateras a Substance
The air-water interface forms a special habitat for
organisms adapted to living in or on the surface film.
This community is collectively referred to as neuston
and will be discussed in some detail further on (Ch. 8).
The surface tension is sufficient to serve as a supporting
surface for many organisms of considerable size (e.g.,
gyrinid and other beetles) and can destroy others, such
as cladoceran microcrustacea, that happen to become
caught in the interface through wave action and cannot
reenter their normal submersed habitat.
11. SUMMARY
1. Water is a unique substance. Its thermal-density
properties, high specific heat, and liquid-solid
characteristics infIuence extensively the physical,
chemical, and metabolic properties and dynamics
of freshwater ecosystems.
2. The molecular aggregation and bonding char-
acteristics of water result in unique density prop-
erties that permit water molecules to form
quasi-stable polymers.
a. The maximum density of water (1.00000 g ml-l)
occurs at 3.98°C. Molecular expansion and de-
creasing density occur at progressively increasing
rates both above and below 4°C. The density of
ice at O°C (0.9168 g ml-l) is significantly less
than that of liquid water at O°C, and ice conse-
quently fIoats.
b. The density difference between water at a
given temperature and 1°C Iower increases
markedly at temperatures above and below
4°C. The amount of energy required to mix
water of differing densities increases propor-
tionally to the density differences.
3. The specific heat of Iiquid water is very high. As
a result, thermal conditions within standing waters
change slowly, are more stable, and permit a longer
growing season than is commonly found in aerial
habitats. The heat-absorbing and heat-retaining
properties of bodies of water also modify the
climate of adjacent land masses.
4. Water viscosity is far greater than the viscosity of
air and is inversely proportional to temperature.
Aquatic organisms have adapted to the more buoy-
ant aquatic environment and to the resistance water
imposed on locomotion; their distribution is often
infIuenced by thermally induced stratification of
water masses of differing density and viscosity.
5. High surface tension occurs at the air-water
interface. Surface tension decreases with increasing
temperature, salinity, and concentrations of organic
compounds.