Chapter 7

Biogeochemical
cycle of chemicals
• Introduction
• Rates of transfer between environmental compartments
• Transfer in aquatic system
• Behavior of Long-Lived Organic Chemicals in the environment
CO & PO FOR CEV420
 Course Outcome (CO)
 Explain the physical and chemistry of the atmosphere, water and solid earth, as well
as the concepts of environmental organic chemistry and biogeochemical cycling of
chemicals (CI, C2, A1).
 Apply the environmental sciences knowledge to solve the chemical processes
problems (C3, C4, A1).
 Evaluate the environmental sciences approach in solving problems related to
environmental issues (C6, A1).

 Programme Outcome (PO)

 PO1:Ability to apply knowledge of mathematics, science, engineering fundamentals

to solve complex engineering problems in chemical and environmental engineering.
 PO2:Ability to identify, formulate, analyze and solve complex chemical and
environmental engineering problems using the principles of mathematics, applied
science and engineering.
Course Learning Outcomes:
 Describe Biogeochemical characteristics and
cycling
 Analyze biogeochemical rates of transfer
between environmental compartments, mediums
and systems.
 Analyze the behavior of long-lived organic
chemicals in the environment
Definition….
 Matter is recycled in ecosystems
 Biogeochemical cycles = chemicals are
passed from one organism to another
(BIO), and also travel through air and soil
(GEO).
Biogeochemical cycle schematic……
 Matter can cycle through the biosphere because
elements are not “used up,” but are only
transformed.
Lifetime of chemicals….
Definition
 To describe the change in the atmospheric
concentration of chemicals as a function of
time and location.

 The lifetime is also often called as

residence time.
 Lifetime of chemicals….
 The concentrations of chemical species in the atmosphere are
controlled by four types of processes:
– Emissions. Chemical species are emitted to the atmosphere by a
variety of sources. Some of these sources, such as fossil fuel
combustion, originate from human activity and are called anthropogenic.
Others, such as photosynthesis of oxygen, originate from natural
functions of biological organisms and are called biogenic. Still others,
such as volcanoes, originate from non-biogenic natural processes.
– Chemistry. Reactions in the atmosphere can lead to the formation and
removal of species.
– Transport. Winds transport atmospheric species away from their point
of origin.
– Deposition. All material in the atmosphere is eventually deposited back
to the Earth's surface. Escape from the atmosphere to outer space is
negligible because of the Earth's gravitational pull. Deposition takes two
forms: " dry deposition" involving direct reaction or absorption at the
Earth's surface, such as the uptake of CO2 by photosynthesis; and " wet
deposition" involving scavenging by precipitation.
One Box Model
 A one-box model for an atmospheric species X is shown in Figure 3-1 .
 It describes the abundance of X inside a box representing a selected
atmospheric domain (which could be for example an urban area, the
United States, or the global atmosphere).
 Transport is treated as a flow of X into the box (Fin) and out of the box
(Fout). If the box is the global atmosphere then Fin = Fout = 0.
 The production and loss rates of X inside the box may include
contributions from emissions (E), chemical production (P), chemical
loss (L), and deposition (D).
 The terms Fin, E, and P are sources of X in the box; the terms Fout, L,
and D are sinks of X in the box. The mass of X in the box is often called
an inventory and the box itself is often called a reservoir.
 The one-box model does not resolve the spatial distribution of the
concentration of X inside the box. It is frequently assumed that the box
is well-mixed in order to facilitate computation of sources and sinks.
 One Box Model
Chemical Chemical
production loss
Inflow Fin Outflow Fout
P L
X
D
E

Emission Deposition

sources  Fin  E  P sinks  Fout  L  D

dm
mass balance:  sources -sinks
dt
mx mx
lifetime:  x  
 Sinks
totallossrate

Note that by dividing both mass and loss rate with “box” volume (m3), it can
be rewritten in terms of concentration.
 Factors Affecting d[X]/dt in a Box
Anthropogenic Biogenic Natural
Emissions

Transport X
Flux out or Flux in

O2 X O3
Chemistry
O XO O2

X X Wet X
Deposition
Dry
Atmospheric Lifetimes
Lifetime = Amount
Removal Rate

X B
X X X
Z
A
Chemical lifetime/s Transport lifetime
Deposition lifetime
Sink-specific lifetimes allow determination of the
importance of a particular process for controlling the
fate of a species
 Rates of Transfer Between Environmental
Components
 Air-Land Exchange

 Land surface is an efficient sink (deposition) for many traces

gases.
 Deposition process is described by the deposition velocity,
vd

 Term flux is referred to a flow of material, in this case

expressed as micrograms of substance depositing per
square meter of ground surface per unit time.
 Rates of Transfer Between Environmental
Components
 Air-Land Exchange (cont.)

 Since the deposition process itself causes a gradient in

atmospheric concentration, so vd is defined in relation to a
reference height, usually in meters.

 Derivation from lifetimes, Ƭ equation, relationship between

deposition velocity vd and reference height:
 Rates of Transfer Between Environmental
Components
 Air-Sea Exchange
 The sea cover some two-thirds of the Earth’s surface and
consequently provide a massive area for matter transfer.
 Some atmospheric matter (particle and gases) will undergo
chemical transformation and subsequently deposit into the
sea (water).
 Total flux (flow of material depositing) for air-borne matter:

 Where Vd (di) is the mean value of deposition velocity of

matter with size fraction di ; while Ci is matter concentration
 Rates of Transfer Between Environmental
Components
 Air-Sea Exchange (cont.)
 The direction of flux is dependent upon the relative
concentration of the matter in air and seawater
 If the concentration in air is Ca, the equilibrium
concentration in seawater, Cw (equ) is given by:

 Where H is the Henry’s Law Constant and expressed as:

Ps = saturation vapor pressure

Saq = equilibrium solubility in water