THE HYDROLOGIC CYCLE

Defined as the pathways for how water moves and is distributed above, on, and below the surface of the Earth.
It’s a continuous circulation of water in the Earth-atmosphere system. it plays an important role in moving
chemical elements through the ecosphere. Refer Figure 1
Hydrologic cycle is governed by geographical location, time of the year, and year, Changes in landuse and
climate. The quantity and quality of water also vary as it moves through the hydrologic cycle. Water resources
engineering includes the management of hydrological cycle to transport water for supply and wastewater for
collection, prevent flooding, and provide water transportation networks.

Key processes involved in the water cycle:

 evaporation
 transpiration
 Condensation
 Precipitation
 Interception
 Runoff
 Infiltration
 Combination of evaporation and transpiration is called evapotranspiration

Evaporation, one of the major processes in the cycle, is the transfer of water from the surface of the Earth
surface (ocean, land surface, water bodies) to the atmosphere. By evaporation, water in the liquid state is
transferred to the gaseous, or vapour, state. This transfer occurs when some molecules in a water mass have
attained sufficient kinetic energy to eject themselves from the water surface. The main factors affecting
evaporation are temperature, humidity, wind speed, and solar radiation.

Transpiration is the evaporation of water through the pores in the leaves of plants.

For practical purposes, transpiration and the evaporation are lumped together and called evapotranspiration

The transition process from the vapour state to the liquid state is called condensation. Condensation may take
place as soon as the air contains more water vapour than it can receive from a free water surface through
evaporation at the prevailing temperature.

By condensation, water vapour in the atmosphere is released to form precipitation. Precipitation is fall of all
forms of water particles from the atmosphere to the earth surface. It can be rain, snow, hail or sleet.

Precipitation that falls to the Earth is distributed in four main ways:

1. some is returned to the atmosphere by evaporation,

2. some may be intercepted by vegetation and then evaporated from the surface of leaves,
3. some percolates into the soil by infiltration,
4. and the remainder flows directly as surface runoff into the sea.

Some of the infiltrated precipitation may later percolate into streams as groundwater runoff. Direct
measurement of runoff is made by stream gauges and plotted against time on hydrographs.

Most groundwater is derived from precipitation that has percolated through the soil.
 BIOGEOCHEMICAL CYCLES

The Biogeochemical cycle refers to the continuous movement / circulation of chemical elements in the Earth’s
Systems (reservoirs). Five chemicals are of particular importance in environmental engineering: C, O, N, P,
and S.
Note that humans use and cycle a much greater number of chemical elements in industrial applications than
are found in living organisms. This can affect the environment through the mining of exotic elements,
concentrating these once-dispersed chemicals, and exposing humans and natural systems to elevated
concentrations, often damaging healthy function.

OXYGEN AND CARBON CYCLES

The oxygen cycle and carbon cycle are closely linked through the processes of photosynthesis (Equation 5.19)
and respiration. Photosynthesis is the primary source term in the oxygen cycle and the origin of the organic
carbon converted to carbon dioxide in the carbon cycle. Respiration is the major sink term in the oxygen cycle
and is responsible for the conversion of organic carbon to carbon dioxide in the carbon cycle. Photosynthesis is
carried out by plants and some bacteria, and respiration is carried out by all organisms, including those that
photosynthesize. The interplay of photosynthesis and respiration plays a key role in regulating ecosystem
energy balances and in maintaining the oxygen levels required by life in aquatic environments.

Figure 5.27 depicts how the natural carbon cycle has been altered by humans. Note in the top figure how the
natural carbon cycle has maintained a constant reservoir of carbon in the air with balanced transfer between
the air, oceans, and land. However, anthropogenic activities such as burning of fossil fuels are displacing
carbon that was once stored in the land to the atmosphere. The natural carbon cycle has not been able to
assimilate this released carbon into existing ocean and land reservoirs. This has resulted in large increases in
global CO2 concentrations (see Figure 4.14). In fact, Figure 4.14 showed that in the past 50 years, atmospheric
global CO2 concentrations have risen from under 320 ppm to close to 400 ppm.

Table 5.13 describes the particular economic activities that contribute to the majority of global greenhouse
emissions.
Most global GHG emissions are carbon dioxide from burning of fossil fuels (approximately 57 percent of the
total). These emissions are associated with economic activities such as supplying energy, industrial activities
associated with chemical, mineral, and metallurgical processes, and transportation. GHG emissions associated
with deforestation and decay of biomass are also quite large, accounting for another 17 percent of the total
emissions. Methane emissions account for 14 percent of total GHG emissions and nitrogen oxide emissions
account for 8 percent of the total are two other major contributors.
Figure 5.28 shows that China and the United States are now the top two producers of CO2 emissions
associated with the consumption of energy. This figure shows other large global emitters of greenhouse gases,
including the European Union, India, Russian Federation, Japan, and Canada. The United States’ contribution
in 2010 for total greenhouse gas emissions was 6,821.8 Tg CO2e (remember that 1 Tg equals 1 million metric
tons) of which 5,706.4 Tg CO2e were carbon dioxide emissions.
NITROGEN CYCLE

The biogeochemical transformations embodied in the nitrogen cycle (Figure 5.29) are important in both natural
and engineered systems. As a result of their association with bacteria and plants, many features of the nitrogen
cycle are linked with the oxygen and carbon cycles. Plants take up and utilize nitrogen in the form of ammonia
or nitrate, chemicals typically in short supply in agricultural soils, thus leading to requirements for fertilization.
Certain bacteria and some plant species (such as legumes and clover) can also utilize atmospheric nitrogen
(N2), converting it to ammonia through a process termed nitrogen fixation.
Nitrogen fixation is a process by which nitrogen in the air is converted into ammonia (NH3) or related
nitrogenous compounds.[1] Atmospheric nitrogen is molecular dinitrogen, a relatively nonreactive molecule that
is metabolically useless to all but a few microorganisms. Biological nitrogen fixation converts N 2 into ammonia,
which is metabolized by most organisms.

Plants incorporate ammonia and nitrate into a variety of organic compounds, such as proteins and nucleic
acids, critical to metabolic function. Consumers (both herbivores and carnivores) transfer those nitrogen-rich
compounds further up the food chain. The nitrogen species present in organisms are released to the
environment through excretion and mortality, whether in nature or in the form of human waste emissions.
The forms of nitrogen depicted in Figure 5.29 are referred as reactive nitrogen. Other reactive nitrogen species
include other chemical oxidized inorganic forms such as peroxyactyl nitrate (PAN) and organic compounds
such as urea, amines, amino acids, and proteins.
Reactive nitrogen consists of all the biologically active, chemically reactive, and radiatively active nitrogen
compounds that are found in the Earth’s atmosphere and biosphere. Figure 5.30 shows the breakdown of the
sources of reactive nitrogen in the United States.
Note the dominant roles played by anthropological activities of agriculture, industry, and combustion of fossil
fuels. The production of anthropogenic reactive nitrogen through fertilizer production (referred to as Haber
Bosch N fertilizer in Figure 5.30) and planting agricultural fields with nitrogen fixing legumes (referred to as
cultivation BNF in Figure 5.30) have brought many economic and social benefits to humans, especially through
increases in food production that sustain billions of people worldwide. Unfortunately, almost all reactive
nitrogen that has been created by humans is ultimately released to the environment.
This major disturbance in the natural nitrogen cycle has brought many adverse public health and environmental
effects. Table 5.14 summarizes many of these impacts, including reactive nitrogen’s role in production of
photochemical smog, decreased atmospheric visibility, acidification of terrestrial and aquatic ecosystems,
eutrophication of inland and coastal waters, negative impacts on our drinking water, and contributing to
greenhouse gas emissions (EPA, 2011).
Note the dominant roles played by anthropological activities of agriculture, industry, and combustion of fossil
fuels. The production of anthropogenic reactive nitrogen through fertilizer production (referred to as Haber
Bosch N fertilizer in Figure 5.30) and planting agricultural fields with nitrogen fixing legumes (referred to as
cultivation BNF in Figure 5.30) have brought many economic and social benefits to humans, especially through
increases in food production that sustain billions of people worldwide. Unfortunately, almost all reactive
nitrogen that has been created by humans is ultimately released to the environment.
PHOSPHORUS CYCLE
Phosphorus-bearing minerals are poorly soluble, so most surface waters naturally contain very little of this
important plant nutrient. In addition, readily available sources of this mined material are expected to run out
during this century. When phosphorus is mined and incorporated into cleaning agents and fertilizers,
biogeochemical cycling (the routing of the element through the environment) is vastly accelerated. Subsequent
discharges to lakes, estuaries, and rivers, where phosphorus is the limiting nutrient, can stimulate nuisance
algal growth and eutrophication (discussed further in Chapter 7), making lakes unpleasant and unavailable for
a variety of uses. Approximately half of the phosphorus excreted by humans is found in urine. The remainder is
found in the feces. In contrast, approximately 75 percent of N excreted by humans is in urine. The global
demand of P demand is approximately 14 million metric tons. However, currently only 1.5 million metric tons
are recovered annually from human waste (through water reuse, biosolids). Thus, integrating the phosphorus
cycle with wastewater treatment and resource recovery process streams is very important.
SULFUR CYCLE
Like the oxygen and nitrogen cycles, the sulfur cycle (Figure 5.32) is to a large extent microbially mediated and
thus linked to the carbon cycle. Sulfur reaches lakes and rivers as organic S, incorporated into materials such
as proteins, and as inorganic S, primarily in the form of sulfate (SO42_).
Hydrogen sulfide (H2S) is malodorous and toxic to aquatic life at very low concentrations. Pyrite (FeS2) is often
found in and around geologic formations that are mined commercially, as in the case of coal or metals such as
silver and zinc. Exposure of pyrite to the atmosphere initiates a three-step oxidation process catalyzed by
bacteria including Thiobacillus thiooxidans, Thiobacillus ferrooxidans, and Ferrobacillus ferrooxidans:

This process yields acid mine drainage rich in sulfate, acidity, and ferric hydroxides (a yellowish-orange
precipitate or floc termed“yellow boy”).
While the sulfate is rather innocuous, acidity lowers the pH of the surface waters (often to levels severely
impairing water quality), and the floc covers stream beds, eliminating macroinvertebrate habitat. In addition, the
low pH of the water dissolves rocks and minerals, releasing hardness and total dissolved solids.
REACTION KENITICS

The kinetic approach to environmental chemistry addresses the rate of reactions. Concepts include the rate
law, zero-order and first-order reactions, half-life, and factors that affect the rate ofreaction.

THE RATE LAW

The rate law expresses the dependence of the reaction rate on measurable, environmental parameters. Of
particular interest is the dependence of the rate on the concentrations of the reactants. Other parameters that
may influence the reaction rate include temperature and the presence of catalysts (including microorganisms).
The rate of an irreversible reaction and the exact form of the rate law depend on the mechanism of the
reaction. Consider the hydrolysis of dichloromethane (DCM). In this reaction, one molecule of DCM reacts with
a hydroxide ion (OH_) to produce chloromethanol (CM) and chloride ion:

For the reaction depicted here to occur, one molecule of DCM must collide and react with one molecule of
OH_. The rate of an irreversible binary reaction is proportional to the concentration of each chemical species.
For the hydrolysis of DCM, it can be written as

where R is the rate of reaction, k is the rate constant for this particular reaction, [DCM] is the concentration of
DCM, [OH_] is the concentration of hydroxide ion, [CM] is the concentration of CM, [Cl_] is the concentration of
chloride ion, and t is time. The negative signs in Equation 3.35 indicate that the products’ concentrations are
decreasing over time.
The bold portion on the left side of Equation 3.35 is referred to as the reaction’s rate law, which expresses the
dependence of the reaction rate on the concentrations of the reactants. The rate law in this case would be
called first order with respect to DCM and first order with respect to OH_. The term first order indicates that
each species is raised to the first power. The rate law is second order overall because it involves the product of
two species, each raised to the first power.
Because the reaction was depicted as irreversible, it was assumed that the concentration of products did not
influence the rate of the forward reaction.

ZERO-ORDER AND FIRST-ORDER REACTIONS

Many environmental situations can be described by zero-order or first order kinetics. Figure 3.12 compares the
major differences between these two types of kinetics. In this section, we discuss these kinetic expressions in
depth by first constructing a generic chemical reaction whereby a chemical, C, is converted to some unknown
products:

The rate law that describes the decrease in concentration of chemical C with time can be written as
Here, [C] is the concentration of C, t is time, k is a rate constant that has units dependent on the order of the
reaction, and the reaction order, n, typically is an integer (0, 1, 2).

ZERO-ORDER REACTION If n is 0, Equation 3.39 becomes

This is the rate law describing a zero-order reaction. Here, the rate of disappearance of C with time is zero-
order with respect to C, and the overall order of the reaction is zero-order.
Equation 3.40 can be rearranged and integrated for the following conditions; at time 0, the concentration of C
equals C0, and at some future time t, the concentration equals C:

Integration of Equation 3.41 yields

A reaction is zero-order if concentration data plotted versus time result in a straight line (illustrated in Figure
3.12). The slope of the resulting line is the zero-order rate constant k, which has units of concentration/time (for
example, moles/liter-day).

FIRST-ORDER REACTION If n ¼ 1, Equation 3.39 becomes

This is the rate law for a first-order reaction. Here, the rate of disappearance of C with time is first-order with
respect to [C], and the overall order of the reaction is first-order.
Equation 3.43 can be rearranged and integrated for the same two conditions used in Equation 3.40 to obtain
an expression that describes the concentration of C with time:

Here, k is the first-order reaction rate constant and has units of time_1 (for example, h _1, day_1).
A reaction is first-order when the natural logarithm of concentration data plotted versus time results in a straight
line. The slope of this straight line is the first-order rate constant, k, as illustrated in Figure 3.12.
There are some important things to note about first- and zero-order chemical reactions. First, when comparing
the concentration over time in the two reactions (as shown in the figure), the rate of the first-order reaction
(slope of concentration data versus time) decreases over time, while in the zero-order reaction, the slope
remains constant over time.
This suggests that the rate of a zero-order reaction is independent of chemical concentration (see Equation
3.42), while the rate of a first order reaction is dependent on the concentration of the chemical (see
Equation 3.44). Thus, a chemical whose disappearance follows concentration- dependent kinetics, like first-
order, will disappear more slowly as its concentration decreases.

PSEUDO FIRST-ORDER REACTIONS

There are many circumstances in which the concentration of one participant in a reaction remains constant
during the reaction. For example, if the concentration of one reactant initially is much higher than the
concentration of another, it is impossible for the reaction to cause a significant change in the concentration of
the substance with the high initial concentration. Alternatively, if the concentration of one substance is buffered
at a constant value (for example, pH in a lake does not change because it is buffered by the dissolution and
precipitation of alkalinity-containing solid CaCO3), then the concentration of the buffered species will not
change, even if the substance participates in a reaction. A pseudo first-order reaction is used in these
situations. It can be modeled as if it were a first-order reaction.
Consider the following irreversible elementary reaction:

The rate law for this reaction is

If the concentration of A does not change significantly during thereaction for one of the reasons previously
discussed (that is, ½A0_ ½B0_ or ½A_ ffi ½A0_), the concentration of A may be assumed to remain
constant and can be incorporated into the rate constant, k. The rate law then becomes

where k

0 is the pseudo first-order rate constant and equals k½A0_a. This manipulation greatly simplifies the rate law
for the disappearance of substance B:

If b is equal to 1, then the solution of Equation 3.48 is identical to that for Equation 3.44. In this case, the
pseudo first-order expression can be written as follows: