CHAPTER 2
Ecosystem and
Biogeochemical
Processes
Environmental Studies
There are 3 schools of thought
● Environmental Science (Geography)
● Environmental Engineering (Civil)
● Environmental Engineering
(Chemical)
2
Ecosystems and
Nutrient Cycles
Definitions
• Ecology – the study of the
interrelation-ships between plants and
animals that live in a particular
physical environment
• Ecosystems – communities of
organisms that interact with one
another and their physical
environment
• Habitats – places where a populations
of organisms live
• We normally separate non-human
(natural) aspects of ecosystems
from human (anthropogenic)
influences
• Many ways to describe perturbations
– chemical
Human physical
− biological −
Influences on – land use − pollution
− global
Ecosystems • Response may be complex due to
the interrelationships
• Primary interest is on health, but
how to define
Role of Energy
• Primary source of energy that drives
ecosystems is the sun
• Process starts with primary producers
that convert inorganic carbon into
organic compounds that store energy
• Photosynthesis
6CO2 + 6H2O + energy → C6H12O6 +
6O2
Role of Energy
• Stored energy can then be recovered in the “reverse”
reaction, respiration
C6H12O6 + 6O2 → 6CO2 + 6H2O + energy
• Release energy is available to drive other reactions, e.g.
cell metabolism and growth
• On simplest level, ecosystems involve
– energy transfer processes
– carbon cycling (inorganic →organic→inorganic)
– oxygen cycling (O2, carbonates, organics)
Food Webs
Bioaccumulation
• Many organic compounds are highly
hydrophobic (water hating)
• Hydrophobic compounds partition to other
phases, such as the plankton, in aquatic
systems
• The partition coefficient is the equilibrium
constant for reaction
chemicalwater == chemicalother phase
Cother phase
K
Cwater
Biomagnification
• When partitioning concentrates a chemical in
one phase that is the food for a higher phase,
the chemical can further concentrate as we
move up the food chain
Biomagnification
• While partitioning is primarily
a chemical process,
biomagnification is a
complex biological process
• Biomagnification factors are
empirical
Example
• Hexachlorobenzene (HCB) has a water to plankton
partition coefficient of 200,000; a plankton to smelt
magnification factor of 7.5; and a smelt to lake trout
magification factor of 3.5. If the concentration of HCB in
the water is 1.0 ppt will either fish exceed the fish
consumption standards:
5 ppm for general consumption
1 ppm for pregnant and nursing women
Solution
Cplankton
K p/w
Cwater
L ng ng mg
Cplankton 2 x 105 1 2 x 105 0.2
kg L kg kg
mg mg
Csmelt 7.5Cplankton 7.5 0.2 1.5
kg kg
mg mg
Ctrout 3.5Csmelt 3.5 1.5 5.25
kg kg
Interpretation
• The lake trout exceed the general consumption standard
and both species exceed the standard for pregnant and
nursing women
• Both could easily argued on the basis of uncertainty
Carbon Cycle
Carbon Cycle
Inputs of “new” CO2 Plants are responsible Carbon is lost to deep
comes naturally from for most of the CO 2 ocean zone via the
minerals and that is converted to solubility and
anthropogenically organic carbon biological pumps
from the combustion
of fossil fuels
Carbon cycles within
the biosphere by
photosynthesis and
respiration
Nitrogen
Cycle
Nitrogen Cycle
• Atmosphere provides an abundant
reservoir of N2
• N2 is converted to biologically available
forms naturally by nitrogen-fixing
organisms and anthropogenically by
combustion
• Nitrogen cycles between NO3-, NO2-,NH3,
and organic N by different organism
• N2 is returned to atmosphere by
denitrification under anaerobic conditions
Phosphorus Cycle
Phosphorus Cycle
Inputs from Biological Losses through
mineral cycling between Some chemical precipitation and
weathering and phosphates and cycling burial in
fertilizer use organic P sediments
Sulfur Cycle
Sulfur Cycle
• Natural inputs from minerals
• Anthropogenic inputs from fossil fuel combustion, mining,
and metal processing
• Biological cycling elemental S, sulfides, sulfates, organic
S
• Chemical cycling via precipitation and volatilization
• Losses through precipitation
Human Influences on Ecosystems
We normally separate Many ways to describe Response may be Primary interest is on
non-human (natural) perturbations complex due to the health, but how to
aspects of ecosystems interrelationships define
from human
(anthropogenic)
influences
chemical − biological
− physical
land use − pollution
− global
Role of Energy
Primary source of energy that drives ecosystems is the sun
Process starts with primary producers that convert inorganic carbon
into organic compounds that store energy
Photosynthesis
6CO2 + 6H2O + energy → C6H12O6 + 6O2
Role of Energy
Stored energy can then be Release energy is available to On simplest level, ecosystems
recovered in the “reverse” drive other reactions, e.g. cell involve
reaction, respiration metabolism and growth
C6H12O6 + 6O2 → 6CO2 + 6H2O + energy energy transfer processes
carbon cycling (inorganic
→organic→inorganic)
oxygen cycling (O2, carbonates, organics)
Brief Introduction to
Bacteria A study of
Microbiology
Fungi microorganism
⊷ Bacteria
⊷ Fungi
⊷ Protozoa
⊷ Algae
Algae ⊷ Virus (Non
Protozoa living)
5
Resources for
Life:
⊷ Major Elements
(macronutrients): Carbon,
Growth Limiting Resource Nitrogen, Phosphorous in varying
proportions (e.g. C:N:P ratio of
(Liebig’s Law of the Minimum): eukaryote algae ≈ [Link];
Nutrient in least supply relative bacteria ≈ [Link]; fungi ≈
to bacterial needs will cap [Link]).
growth yield. ⊷ Trace Elements (micronutrients):
H, S, Mn, Zn, Co, Cu, Mo, Fe, Mg,
Ca, K, Na, & Ni.
⊷ Growth Factors: essential
amino acids, vitamins, and
nucleoside bases are needed
for growth but cannot be made
Microorganisms Tolerance to Environmental
Factors •
Temperature
• Solute Concentration / Water Activity
(Osmotolerant, Halophiles- requires >0.2M
NaCl) )
• pH (acidity versus alkalinity)
• Oxygen Concentration
• Barometric Pressure (Barophiles)
• Electromagnetic Radiation
Classification of Microbes base on Optimum
Temperatures of Growth
Classification of Microbes base on Optimum pH for
Growth
Environmental
Chemistry
1
Environmental
Chemisty
Environmental chemistry is
the study of chemical
processes that occur in
water, air, terrestrial and
living environments, and
the effects of human
activity on them
1
The Scope
Environmental
of Chemistry
♣ Water Chemistry and Pollution
Stoichiometry, chemical equilibria, solubility
of matter, redox
♣ Toxic and Organic Compound
Heavy metals and hydrocarbon appear
building block for toxic
as
♣ chemicals Change
Climate
The cause and effect of climate
change
1
Chemical View of
Environmental Quality
Environmental Chemistry
• to move beyond simple descriptions of the
environment, we need to quantify
environmental quality
• many approaches -- species, land-use,
visual indicators, surveys
• most common is to use a chemical
concentrations and chemical change as the
base
Stoichiometry
• previously described units of measurement
for chemical concentrations
• a balanced chemical equations describes:
– qualitative information on what reacts with
what and what is formed
– quantitative information on how much reacts
and how much is formed
• stoichiometry is the formation of balanced
equations
Example
CH4 + 2 O2 CO2 + 2 H2O
molecules 1 2 1 2
Is this what we want to know?
Molecules and Mass
• Atomic weight
– mass of atom in atomic mass units (amu).
– 12.00 amu weight of carbon atom with 6 protons and 6
neutrons
– carbon listed in tables as having an atomic weight of 12.01 --
small % of atoms have 7 and 8 neutrons (isotopes)
Molecules and Mass
• Atomic number
– the number of protons in the nucleus of an element
– defines the element
– all isotopes of an element have the same atomic number
• Molecular weight
– sum of the atomic weights for molecules
Example
• Calcium chloride, CaCl2
40.08 atomic weight Ca
35.45 atomic weight Cl
35.45 atomic weight Cl
110.98 molecular weight CaCl2
Mole (mol)
• A mole is a fixed number of molecules
found in a mass of an element or molecule
equal to its atomic or molecular weight
• g-mole = 6.022 x 1023 molecules
• lb-mole = 2.7 x 1026 molecules
• # moles = mass/molecular weight
• for CE 280 use g-mole -- units are g/mol
• e.g. 12.01 g C = 1 mole
Example
A sugar packet contains about 3 grams of sugar. How many
moles is this?
Sucrose = C12H22O11
MW = 12(12) + 22(1) + 11(16) = 342 g/mol
# mole = 3 g/(342 g/mol) = 0.009 mol
Balancing Equations
• must have an equal number of each element on each side of
the equation
Example: combustion of propane
C3H8 + O2 = CO2 +
H2O
C3H8 + 5 O2 = 3 CO2 + 4
H2O
C 3 3
H 8 8
O 10 6 4
Example: combustion of propane
• How many g of O2 are required to burn
100 g propane?
MW propane = 3(12.01)+ 8(1.008) = 44.09
g/mol
moles propane = 100 g/(44.09 g/mol) = 2.27 mol
moles oxygen required = 2.27 x 5 = 11.34 mol
MW oxygen = 2(16.00) = 32.00 g/mol
mass oxygen = moles x MW
= (11.34 mol)(32.00 g/mol) = 363 g O
Example: combustion of propane
• At STP, what volume of air at STP is required to burn 100 g
propane?
(11.34 mol)(22.4 L/mol) = 254 L O2
since air is 21% oxygen by volume:
(254 L O2)/(0.21 L O2/L air) = 1210 L air
Oxygen Demand
• theoretical oxygen demand - O2 required to completely
oxidize a chemical substance to CO2 and H2O. Based on
stoichiometry.
• biochemical oxygen demand (BOD) - O2 consumed by a
substance in a standard test using microorganisms for
oxidation
• chemical oxygen demand (COD) - …. standard test using
strong chemical oxidants
Example
• Determine the theoretical oxygen demand
for a solution containing 200 mg/L acetic
acid (vinegar)?
CH3COOH + 2O2 == 2CO2 +
2H2O
C 2 2
H 4 4
O 2 4 4 2
Example (cont.)
MW acetic acid = 2(12.01) + 4(1.008) + 2(16.00)
= 60.05 g/mol
200 mg/L mol
3.33 x 10-3 acetic acid
(1000 mg/g)(60.05 g/mol) L
mol
we need (3.33 x 10-3 )(2) 6.66 x 10-3 O2
L
mol g mg mg
(6.66 x 10-3 )(32 )(1000 ) 213 O2
L mol g L
Enthalpy
• for gases, the “heat content” depends not only on the
internal energy (U) but on the pressure (P) and volume (V)
• define thermodynamic term enthalpy
H = U + PV
• depends on T
• units of kJ or BTU common
Enthalpy
• values can be looked up in table of thermodynamic data
H 0298 standard enthalpy
enthalpy at 298 K and 1 atm
Enthalpy
• change in enthalpy in a reaction is termed the heat of
reaction
Hproducts - Hreactants = H
• if there is no pressure change, then this is the heat absorbed
H positive heat absorbed endothermic
H negative heat released exothermic
Heat of combustion
C3H8(g) + 5 O2(g) = 3 CO2 (g) + 4 H2O (l)
from tables H (kJ/mol):
(-104.7) 5(0) 3(-393.5) 4(-285.8)
H = [3(-393.5) + 4(-285.8)] - [(-104.7) + 5(0)]
= -2219 kJ/mol of propane heat released
Heat of combustion
• gross heat of combustion or higher heating value (HHV)
assumes liquid water is product
• net heat of combustion or lower heating value (LHV)
assumes gaseous water is product
• high efficiency (>90%) furnaces recover this heat by
condensing water vapor
In-class calculation
• Previous example was gross heat of combustion
• Calculate the net heat of combustion for propane.
H C3H8(g) = -104.7 kJ/mol
O2(g) = 0
CO2 (g) = -393.5
H2O (g) = -241.8
Solution - net heat of combustion of propane
C3H8(g) + 5 O2(g) = 3 CO2 (g) + 4 H2O (g)
from tables, H (kJ/mol):
(-104.7) 5(0) 3(-393.5) 4(-241.8)
H = [3(-393.5) + 4(-241.8)] - [(-104.7) + 5(0)]
= -2043 kJ/mol of propane heat released
