Earth’s Water

Properties of Water

Property Value Comparison with other Environmental

liquids importance
State at room temperature Liquid Rather than a gas like H2S Provides medium for life
and H2Se
Heat capacity 4.18 J/g◦C Very high Moderates climate
Latent heat of fusion 330 J/g Very high Moderating effect;
stabilizes air temperatures
Latent heat of evaporation 2257 J/g Very high Moderating effect;
important in hydrology for
precipitation-evaporation
balances
Surface tension 72.8 dyne/cm at 20◦C Very high Affects adsorption,
wetting, and transport
across membranes
Density 1.0 g/cm3 at 4◦C High; anomalous Causes freezing to occur
maximum at 4◦C from air-water surface;
controls temperature
distribution and water
circulation in lakes and
oceans
Dielectric constant 80.1 at 20◦C Very high Makes water a good
(dimensionless) solvent for ions; shields
electric fields of ions
Dipole moment 1.85 debyes High compared with Cause of above
organic liquids characteristics and
solvent properties of water
Viscosity 1.0 × 10−3 Pa·s at 20◦C 2–8 × higher than organic Slows movement of
liquids solutes
Transparency High Especially in midvisible Allows thick zone for
range photosynthesis and
photochemistry
Thermal conductivity 0.6Wm−1 K−1 High compared with Critical for heat transfer in
organic liquids natural an engineered
systems

The Global Water Cycle

 Salt Water: Earth’s Oceans and Seas

Freshwater, 0.6 Brackish water,

Ice caps and 0.1
glaciers, 2.1

Ocean water,
97.2

Seawater is often referred to as saline water. The salinity of seawater is the mass in grams of dry salts
present in 1 kg of seawater. In the world ocean, salinity averages about 35. To put it another way, seawater contains
about 3.5% dissolved salts by mass. The list of elements present in seawater is very long. Most, however, are
present only in very low concentrations.

Because of high extracting costs, only three substances are obtained from seawater in commercially
important amounts: sodium chloride, bromine (from bromide salts), and magnesium (from its salts).
Seawater temperature varies as a function of depth, as does salinity and density. Sunlight penetrates well
only 200 m into the water; the region between 200 m and 1000 m deep is the “twilight zone,” where visible light is
faint. Below 1000 m, the ocean is pitch-black and cold, about 4 °C. The transport of heat, salt, and other chemicals
throughout the ocean is influenced by these changes in the physical properties of seawater, and in turn the changes
in the way heat and substances are transported affects ocean currents and the global climate.
Absorption of CO2 by the ocean plays a large role in global climate. Because carbon dioxide and water form
carbonic acid, the H2CO3 concentration in the ocean increases as the water absorbs atmospheric CO2. Most of the
carbon in the ocean, however, is in the form of HCO3- and CO32- ions, which form a buffer system that maintains the
ocean’s pH between 8.0 and 8.3.

Freshwater and Groundwater

Freshwater is the term used to denote natural waters that have low concentrations (less than 500 ppm) of
dissolved salts and solids. Freshwater includes the waters of lakes, rivers, ponds, and streams. The total amount of
freshwater on Earth is not a very large fraction of the total water present. Indeed, freshwater is one of our most
precious resources.
As water runs off the land on its way to the oceans, it dissolves a variety of cations (mainly Na+, K+, Mg2+,
Ca , and Fe2+), anions (mainly Cl-, SO42-, and HCO3-), and gases (principally O2, N2, and CO2). As we use water, it
2+

becomes laden with additional dissolved material, including the wastes of human society. As our population and
output
of environmental pollutants increase, ever-increasing amounts of money and resources must be spent to guarantee a
supply of freshwater.
Approximately 20% of the world’s freshwater is under the soil, in the form of groundwater. Groundwater
resides in aquifers, which are layers of porous rock that hold water. The water in aquifers can be very pure, and
accessible for human consumption if near the surface. Dense underground formations that do not allow water to
readily penetrate can hold groundwater for years or even millennia. When their water is removed by drilling and
pumping, such aquifers are slow to recharge via the diffusion of surface water. The nature of the rock that contains
the groundwater has a large influence on the water’s chemical composition. If minerals in the rock are water soluble
to some extent, ions can leach out of the rock and remain dissolved in the groundwater.
Arsenic in the form of HAsO42-, H2AsO4-, and H3AsO3 is found in many groundwater sources across the
world, most infamously in Bangladesh, at concentrations poisonous to humans.

Major and minor ions and their chemical behavior

In spite of the chemical diversity of natural waters, one important feature that freshwaters share is the
identity of the ions that constitute their inorganic solutes. In nearly all cases, just seven ions (four cations and three
anions) and one un-ionized species (silica, which exists as Si(OH)4 at the pH of most natural waters) constitute 95–
99% of the total dissolved inorganic solutes of natural waters. The seven ions are as follows: Ca2+, Mg2+, Na+, K+,
HCO3−, SO42−, and Cl−

The near-ubiquitous status of these species as major ions in water stems from their relative abundance in the
Earth’s crust and the fact that their salts are moderately to very soluble. The proportion of total ionic solutes
represented by a given ion depends on local geochemical conditions, but a few general trends can be stated. First,
although many exceptions occur, the order of the ions in the lists reflects the most common order of abundance in
natural waters. Second, the chemistry of the major cations is relatively simple. None participates in redox reactions,
and as strong base cations (i.e., they form soluble salts, rather than complexes and insoluble minerals with
hydroxide), their acid-base behavior is limited. However, the divalent cations do react with OH− at high pH, which is
important in removing hardness from waters.

Hard versus soft waters

Hardness is defined as the sum of the concentrations of divalent cations in water. In most cases, it is
essentially the sum of Ca2+ and Mg2+, both expressed in mg/L as CaCO3. Various other chemical conditions,
however, are associated with hardness and its converse, softness. Hardness and alkalinity are usually closely
correlated because they are derived in large part from a common source—dissolution of limestone (CaCO3). Hard
waters tend to be high in total dissolved solids (TDS) and have relatively high pH (> 7). Soft waters tend to have low
TDS and lower pH. They also tend to be more corrosive to metals and more susceptible to acidification by
atmospheric acid deposition. We will use the terms hard water and soft water as shorthand way of describing these
broader chemical characteristics.
Waters often are classified according to hardness as follows:

Hardness meq/L mg/L as CaCO3

Soft <1 < 50
Moderately hard 1–3 50–150
Hard 3–6 150–300
Very Hard >6 > 300

Total Hardness is composed of two components, temporary and permanent hardness. The temporary
hardness is due to the presence of carbonates and bi-carbonates of calcium and magnesium. It can be easily
removed by boiling the water or by adding lime to water. The permanent hardness i.e non-carbonate hardness is due
to presence of sulphates, chlorides and nitrates of calcium and magnesium. It requires special methods of water
softening.

Human Activities and Water Quality

All life on Earth depends on the availability of suitable water. Many human activities entail waste disposal
into natural waters without any treatment. These practices result in contaminated water that is detrimental to both
plant and animal aquatic life. Unfortunately people in many parts of the world do not have access to water that has
been treated to remove harmful contaminants, including disease-bearing bacteria.

Effects of some human activities on chemical composition of natural waters

Activity
Municipal water treatment
Home water treatment
Wastewater treatment
Food processing/cooking
Domestic cleaning materials
Effects
Ca2+ and Mg2+ (−); Na+ (possible +); F− (+); Cl− (+); HPO42− (corrosion inhibitor)
(+); suspended solids and natural organic matter (−)
Ca2+ and Mg2+ (−); Na+ (+) by ion-exchange softening
Suspended solids, organic matter and some nutrients (−); Cl− and SO42−
Na+, Cl−, other major ions (+); trace elements (+)
Surfactants (soaps, detergents), HPO42−, NH4+, various organic chemicals (+)
Street deicing
Agriculture
Mining activities
Chemical manufacturing
Construction activities
Na+ and Cl− (+)
N and P forms and K+ from fertilizer (+); suspended solids from soil erosion (+);
organic chemicals (pesticides) (+)
SO42− from pyrite oxidation (+)
Cl−, SO42− (from HCl and H2SO4) (+); Na+ (from NaOH) (+)
Ca2+, HCO3− from concrete (+); Ca2+, SO42− from gypsum (+)

Dissolved Oxygen and Water Quality

The amount of O2 dissolved in water is an important indicator of water quality. Water fully saturated with air
at 1 atm and 20 °C contains about 9 ppm of O2. Oxygen is necessary for fish and most other aquatic life. Cold-water
fish require water containing at least 5 ppm of dissolved oxygen for survival. Aerobic bacteria consume dissolved
oxygen to oxidize organic materials for energy. The organic material the bacteria are able to oxidize is said to be
biodegradable.
Excessive quantities of biodegradable organic materials in water are detrimental because they remove the
oxygen necessary to sustain normal animal life. Typical sources of these biodegradable materials, which are called
oxygen-demanding wastes, include sewage, industrial wastes from food-processing plants and paper mills, and liquid
waste from meatpacking plants.
In the presence of oxygen, the carbon, hydrogen, nitrogen, sulfur, and phosphorus in biodegradable
material end up mainly as CO2, HCO3-, H2O, NO3-, SO42-, and phosphates. The formation of these oxidation products
sometimes reduces the amount of dissolved oxygen to the point where aerobic bacteria can no longer survive.
Anaerobic bacteria then take over the decomposition process, forming CH4, NH3, H2S, PH3, and other products,
several of which contribute to the offensive odors of some polluted waters.
Plant nutrients, particularly nitrogen and phosphorus, contribute to water pollution by stimulating excessive
growth of aquatic plants. The most visible results of excessive plant growth are floating algae and murky water. What
is more significant, however, is that as plant growth becomes excessive, the amount of dead and decaying plant
matter
increases rapidly, a process called eutrophication. The processes by which plants decay consumes O2, and without
sufficient oxygen, the water cannot sustain animal life.
The most significant sources of nitrogen and phosphorus compounds in water are domestic sewage
(phosphate-containing detergents and nitrogen-containing body wastes), runoff from agricultural land (fertilizers
contain both nitrogen and phosphorus), and runoff from livestock areas (animal wastes contain nitrogen).
The oxygen remains in water in dissolved form depending upon the temperature of water. As the
temperature increases, the solubility of D.O in water decreases. A minimum of 4 mg/L D.O is essential for the aquatic
life. The organic matter present in the waste water poses a Biochemical Oxygen Demand. This demand is met with
the Dissolved Oxygen present in the fresh body of water. If the organic load (volume x BOD ) of the waste water is
more than the asset (volume x D.O ) the whole of the oxygen is depleted. This causes the death of fish and other
aquatic animals and plants and they being organic matter further increase the demand of oxygen for the degradation.
So it is necessary to find out the D.O of water to maintain sanitary conditions. It can be achieved by the treatment of
waste water. Treatment means the reduction of BOD below the allowable limits. The limit is 30 mg/L for disposal of
wastewater (sewage) in water.

Water Purification: Desalination

The removal of salts from seawater or brackish water to make the water usable is called desalination.
Water can be separated from dissolved salts by distillation because water is a volatile substance and the salts are
nonvolatile. The principle of distillation is simple enough, but carrying out the process on a large scale presents many
problems. As water is distilled from seawater, for example, the salts become more and more concentrated and
eventually precipitate out. Distillation is also an energy-intensive process.
Seawater can also be desalinated using reverse osmosis. When reverse osmosis occurs, solvent passes
from the more concentrated into the more dilute solution. In a modern reverse-osmosis facility, hollow fibers are used
as the semipermeable membrane. Saline water is introduced under pressure into the fibers, and desalinated water is
recovered.

Water Purification: Municipal Treatment

The water needed for domestic, agricultural, and industrial use is taken either from lakes, rivers, and
underground sources or from reservoirs. Much of the water that finds its way into municipal water systems is “used”
water, meaning it has already passed through one or more sewage systems or industrial plants. Consequently, this
water must be treated before it is distributed to our faucets.

Municipal water treatment usually involves five steps.

 1. After coarse filtration through a screen, the water is allowed to stand in large sedimentation tanks where
sand and other minute particles settle out. To aid in removing very small particles, the water may first be
made slightly basic with CaO.
2. Then Al2(SO4)3 is added and reacts with OH- ions to form a spongy, gelatinous precipitate of Al(OH)3. This
precipitate settles slowly, carrying suspended particles down with it, thereby removing nearly all finely
divided matter and most bacteria.
3. The water is then filtered through a sand bed.
4. Following filtration, the water may be sprayed into the air (aeration) to hasten oxidation of dissolved
inorganic ions of iron and manganese, reduce concentrations of any H2S or NH3 that may be present, and
reduce bacterial concentrations.
5. The final step normally involves treating the water with a chemical agent to ensure the destruction of
bacteria. Ozone is more effective, but chlorine is less expensive. Liquefied Cl2 is dispensed from tanks
through a metering device directly into the water supply. The amount used depends on the presence of
other substances with which the chlorine might react and on the concentrations of bacteria and viruses to be
removed.
The sterilizing action of chlorine is not due to Cl2 itself but to hypochlorous acid, which forms when chlorine
reacts with water:
Cl2 + H2O → HClO + H+ + Cl-
Water disinfection is one of the greatest public health innovations in human history. It has dramatically
decreased the incidences of waterborne bacterial diseases such as cholera and typhus. However, in 1974 scientists
in Europe and the United States discovered that chlorination of water produces a group of by-products called
trihalomethanes (THMs) because all have a single carbon atom and three halogen atoms: CHCl3, CHCl2Br, CHClBr2,
and CHBr3. These and many other chlorine- and bromine-containing organic substances are produced by the
reaction of dissolved chlorine with the organic materials present in nearly all natural waters, as well as with
substances that are by-products of human activity.
Chlorine dissolves in water to form the oxidizing agent HClO. The HClO in turn reacts with organic
substances to form THMs. Bromine enters the reaction sequence through the reaction of HClO with dissolved
bromide ion:
HClO + Br- → HBrO + Cl-
Then both HBrO and HClO can halogenate organic substances to form the THMs.
Some THMs and other halogenated organic substances are suspected carcinogens; others interfere with
the body’s endocrine system. As a result, the World Health Organization and the U.S. Environmental Protection
Agency have placed concentration limits of 80 mg/L (80 ppb) on the total quantity of THMs in drinking water. The
goal is to reduce the levels of THMs and other disinfection by-products in the drinking water supply while preserving
the antibacterial effectiveness of the water treatment. In some cases, lowering the concentration of chlorine may
provide adequate disinfection while reducing the concentrations of THMs formed. Alternative oxidizing agents, such
as ozone or chlorine dioxide, produce less of the halogenated substances but have their own disadvantages.
For example, each is capable of oxidizing dissolved bromide, as shown here for ozone:
O3 + Br- + H2O → HBrO + O2 + OH-
HBrO + 2 O3 → BrO3- + 2O2 + H+
Bromate ion, BrO3-, has been shown to cause cancer in animal tests.
At present, there seem to be no completely satisfactory alternatives to chlorination or ozonation, and we are
faced with a consideration of benefit versus risk. In this case, the risks of cancer from THMs and related substances
in municipal water are very low relative to the risks of cholera, typhus, and gastrointestinal disorders from untreated
water. When the water supply is cleaner to begin with, less disinfectant is needed and thus the risk of THMs is
lowered. Once THMs form, their concentrations in the water supply can be reduced by aeration because the THMs
are more volatile than water. Alternatively, they can be removed by adsorption onto activated charcoal or other
adsorbents.
Concentration units

A variety of units are used to express concentrations of substances dissolved or suspended in natural
waters. An important first step in studying the chemistry of natural waters is to learn about the different concentration
units and how they are related to each other.
In general, concentrations of substances in water can be expressed in two principal ways: mass per unit
volume of solution and mass per unit mass of water. Both mass per unit volume of solution (mass/volume) and
mass per unit mass of solvent (mass/mass) are used widely, often interchangeably, to express concentrations of
dissolved and suspended substances in water. For major ions in freshwater, the most convenient mass/volume unit
is mg/L because major ions generally occur in the range of a few mg/L to a few hundred mg/L.

Common concentration units used in water analysis

Mass/volume Symbol Multiple of Equivalent mass/mass unit∗ Substances for which units are
g used
Gram/liter g/L 1 Part per thousand, ppt (%) Major ions in brackish water and
seawater
Milligram/L mg/L 10−3 Part per million, ppm Major ions in freshwater
Microgram/L μg/L 10−6 Part per billion, ppb Nutrients, minor and trace metals,
many organic contaminants
Nanogram/L ng/L 10−9 Part per trillion Trace organic pollutants and some
trace metals
Picogram/L pg/L 10−12 Not used Ultratrace contaminants, e.g.,
methylmercury
∗ This direct conversion is possible only because the density of water is 1, and so 1 L = 1 kg. This direct relationship
does not hold for other solvents.

Use of chemical units to express solute concentrations is becoming more widespread in aquatic sciences,
especially in limnology and oceanography, but also in environmental engineering.

Unit Symbol Formula Instances for which units

are used
Molarity M 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 Major and minor ions in
𝑀=
𝐿 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 water
Molality m 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 Unit of choice for careful
𝑚=
𝑘𝑔 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 measurements in marine
chemistry and chemical
thermodynamics
Mole 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑖 Often are used in the
𝑋𝑖 =
fraction ∑𝑛𝑖=1 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑖 solubility of organic
substances in water and in
thermodynamic treatment
of solid phases associated
with natural aquatic
systems
Normality N 𝑔 𝑜𝑓 𝑠𝑜𝑙
𝑁=
𝑔 𝑒𝑞. 𝑤𝑡. 𝑜𝑓 𝑠𝑜𝑙 × 𝑣 𝑜𝑓 𝑠𝑜𝑙𝑛
𝑓𝑜𝑟𝑚𝑢𝑙𝑎 𝑤𝑒𝑖𝑔ℎ𝑡
𝑔 𝑒𝑞. 𝑤𝑡. =
𝑟𝑒𝑎𝑐𝑡𝑖𝑣𝑒 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦
𝑚𝑔
mg/L as 𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦 ( 𝑎𝑠 𝐶𝑎𝐶𝑂3 ) Formerly was used in
𝐿
calcium 𝑚𝑒𝑞 50 𝑚𝑔 𝐶𝑎𝐶𝑂3 natural water chemistry to
carbonate = 𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦 (
𝐿
)×(
𝑚𝑒𝑞 𝑜𝑓 𝐶𝑎𝐶𝑂3
) express concentrations of
(CaCO3) 𝑚𝑔
𝑚𝑔
𝑎𝑠 𝐶𝑎 50 𝑚𝑔 𝐶𝑎𝐶𝑂3
alkalinity, hardness, and
𝐶𝑎 2+ ( 𝑎𝑠 𝐶𝑎𝐶𝑂3 ) = 𝐿 ×( ) ions; used widely within
𝐿 20 𝑚𝑔 𝑚𝑒𝑞 𝑜𝑓 𝐶𝑎𝐶𝑂3
𝑚𝑒𝑞 𝑜𝑓 𝐶𝑎 the water treatment
𝑚𝑔
𝑚𝑔
𝑎𝑠 𝑀𝑔 50 𝑚𝑔 𝐶𝑎𝐶𝑂3 industry
2+
𝑀𝑔 ( 𝑎𝑠 𝐶𝑎𝐶𝑂3 ) = 𝐿 ×( )
𝐿 12.15 𝑚𝑔 𝑚𝑒𝑞 𝑜𝑓 𝐶𝑎𝐶𝑂3
𝑚𝑒𝑞 𝑜𝑓 𝐶𝑎