EPHM 7070 Research Methodologies in Environmental Monitoring and

Public Health Protection

Environmental
Analysis

Dr Haoxiang Wu
Dept of Biology, HKBU
[email protected]
 LEARNING OUTCOMES
By the end of this lecture, you should be able to:
• Appreciate the diversity of pollution and the importance of
chemical analysis in environmental monitoring
• Explain how pollutants could be transported and
reconcentrated in the environment
• Describe methods for measuring water quality

2
 CONTENT
• Need for chemical analysis
• Steps of environmental analysis
• Transport and reconcentration of organic compounds
• Water analysis
• Measurement of water quality

3
 INTRODUCTION
• The environment is dynamic (never static)
– Interaction between different environmental compartments
themselves and with biota
– Physical, chemical, and biological processes
• Pollution of the environment requires an urgent need for
monitoring and control

4
NECESSITY OF CHEMICAL ANALYSIS
 POLLUTION
• If a pollutant is discharged into the environment, what causes
the effect on individual living organisms:
– The total amount discharged; OR
– Its concentration in the environment?

6
 POLLUTION
• All compounds are toxic at high
enough concentrations. e.g. NaCl
or Cr, Co, Mn for plant growth

• It is necessary to ensure that the

concentration of a particular
ion/compound in water or in the
atmosphere is maintained below
a pre-determined ‘safe’ level

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NECESSITY OF CHEMICAL ANALYSIS:
1. RECOGNITION OF THE PROBLEM

1950 1990

1900 1980 2010

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 NECESSITY OF CHEMICAL ANALYSIS:
1. RECOGNITION OF THE PROBLEM
• Acid rain caused by the localised effects of sulfur oxides
produced from coal combustion (19th century)
• Contribution of other chemical compounds, e.g. nitrogen
oxides, to acid rains (late 1950s)
• Ozone depleting CFCs (late 1980s)
• Concern about the ‘sex-change chemicals’, which could affect
the early stages of fetal development in some species (1990s)

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 NECESSITY OF CHEMICAL ANALYSIS:
2. MONITORING TO DETERMINE THE EXTENT OF THE PROBLEM

• Involve analysis of a compound not naturally found in the

environment
• Or determination of the increase in concentration of a
compound above the ‘natural’ level
• Determination of ‘natural’ level itself involves a substantial
monitoring exercise (locations, seasons etc.)
– Sometimes difficult to determine what an unpolluted environment is

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 NECESSITY OF CHEMICAL ANALYSIS:
3. DETERMINATION OF CONTROL PROCEDURES
• To determine the most appropriate method
• Technological methods
– e.g. lower sulfur oxide emissions from coal-fired gas power stations
• Socially oriented methods
– Promotion of the use of public rather than private transport to
reduce vehicle emissions

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 NECESSITY OF CHEMICAL ANALYSIS:
4. LEGISLATION TO ENSURE THE CONTROL PROCEDURES
ARE IMPLEMENTED
• Legislation is often drafted in terms of analytical concentrations

The European Union

(EU) is defining the
essential quality
standards which
water intended for
human consumption
must meet.

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 NECESSITY OF CHEMICAL ANALYSIS:
5. MONITORING TO ENSURE THE PROBLEM HAS
BEEN CONTROLLED
• Large proportion of current monitoring is to
ensure compliance with legislation
– Examples:
• National programmes to confirm air and water
quality
• Local monitoring of discharges from industries
• Yearly checking of emission from individual
automobiles
• Monitoring also provides scientific evidence
for possible further developments in
legislation
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 ENVIRONMENTAL ANALYSIS
• Environmental analysis involves the following
steps:
1. Recognition of the problem
2. Monitoring to determine the extent of the problem
3. Determination of control procedures
4. Legislation to ensure the control procedures are
implemented
5. Monitoring to ensure the problem has been
controlled

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ENVIRONMENTAL ANALYSIS (con’t)
• Analytical chemistry is an essential component in
the scientific investigation of the environment
– 1) Measuring trace analytes that pose human and/or
ecological health hazards
• Low concentrations (ppb, ppt levels)
– 2) Mixture of pollutants e.g. heavy metals and POPs
– 3) Multiple pathways in the environment
• Mechanism of transport of pollutants in the environment
– Associated with chemical characteristics and
concentration of individual chemical species

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 ENVIRONMENTAL ANALYSIS
• Environmental analysis involve the following
steps:
1. Recognition of the problem
2. Monitoring to determine the extent of the problem
3. Determination of control procedures
4. Legislation to ensure the control procedures are
implemented
5. Monitoring to ensure the problem has been
controlled

Chemical analysis is a necessary component of almost

all of the steps of environmental analysis 16
Exercise
Consider a factory producing a liquid discharge, consisting partly of
side products of the process and partly of contaminants present in
the starting materials.
What analytical monitoring programme would be useful to assess and
control the effluent?
Hint: What are the advantages/disadvantages of the following?
1) Analysis of the discharge before dispersal into the river?
2) Analysis of the river sufficiently downstream from the discharge
point?
3) Analysis of the pollutant in living organisms found in the river?

Downstream Factory
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 TRANSPORT AND
RECONCENTRATION OF ORGANIC
COMPOUNDS
TRANSPORT AND RECONCENTRATION
OF POLLUTANTS

• Some pollutants reconcentrate because:

– The non-degradation of slow degradation of some
pollutants ègradual concentration building up in
the environment
– Contamination of large areas before sufficient
dilution has taken place

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 TRANSPORT AND RECONCENTRATION
OF POLLUTANTS: EXAMPLES
• Toxic metals, e.g. cadmium, may be found in the organs of
shellfish concentrations up to 2 million times greater than in
the surrounding water
• Major constituent of the pesticide DDT is a universal
contaminant due to is widespread use and slow degradation
• Dilution does not take into account localised pollution effects
which may occur around discharge pipes or chimneys before
dispersion occurs, e.g. endocrine disruptors which ‘feminise’
the male fish. This could occur close to sewage outfalls

20
TRANSPORT AND RECONCENTRATION OF POLLUTANTS:
ORGANIC COMPOUNDS
• Compounds in this category are of global
concern and are usually of low volatility and
high relative molecular mass (Mr>200)
• Examples:

p,p’-DDT Dieldrin Malathion

(organochlorine (organochlorine pesticide) (phosphorus-based
pesticide) pesticide)
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 MOLECULAR MASS (MR)
“The mass of a
molecule. It is
calculated as the
sum of the mass
of each
constituent
atom multiplied
by the number
of atoms of that
element in the
molecular
formula”

22
 MOLECULAR MASS (MR)
Example: Water molecule (molecular formula: H 2 O)
• Each water molecule is made up of two hydrogen atoms (H) and one
oxygen atom (O)
• From the periodic table, atomic mass of H=1; and O=16
• Hence, the molecular mass of water = 2(1)+16 = 18

23
 MOLECULAR MASS (MR)
Example: Sulfuric acid (molecular formula: H2SO4)
• Each sulfuric acid is made up of two hydrogen atoms, one
sulphur atom and four oxygen atoms
• From the periodic table, atomic mass of H=1; S=32 and O=16
• Hence, the molecular mass of sulfuric acid = ?= 98

24
 Exercise

MOLECULAR MASS (MR)

• Calculate the molecular mass of the following pollutants:

p,p’-DDT Dieldrin Malathion

(organochlorine (organochlorine pesticide) (phosphorus-based
pesticide) pesticide)

Molecular formula: Molecular formula: Molecular formula:

C 14 H 9 Cl 5 C 12 H 8 Cl 6 O C 10 H 19 O 6 PS 2

Mo le c u lar
mass: 354.25 380.7 330 25
 BIOCONCENTRATION
• Water solubility
– Generally, within related groups of compounds, the
solubility in water decreases with increasing molecular
mass
– As the solubility in water decreases, the solubility in
organic solvent increases
Higher
molecular
mass

26
 BIOCONCENTRATION
• Water solubility(con’t)
– The increase in solubility in organic solvent is equally
true if consider the solubility in fatty tissues in fish and
aquatic mammals
– i.e. the dissolved organic material will readily transfer
into fatty tissue
The lower the solubility of an organic compound in water, the greater is its
ability to accumulate in fatty tissues and the greater is the potential for toxic
effect

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 ACCUMULATION IN SEDIMENTS
• This is also related to the low solubility of high- molecular-mass
organic compounds in water
• The undissolved or precipitated organic material in water will
adhere to any available solid
• The larger the solid surface area, the greater will be its ability to
adsorb the compound
• This is particularly true within estuaries where there are often
discharges from major industries and fine sediment is in abundance
• These organics may then be ingested by organisms which feed by
sediments (e.g. mussels)

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 BIOMAGNIFICATION
• Animals obtain their food by
feeding on other plants or animals
• Food chain can be built up where
one species is dependent for
survival on the consumption of the
previous species
• If a pollutant is present in the first
organism, then as proceed up the
food chain there will be an increase
in concentration in each subsequent
species

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30
WATER ANALYSIS – MAJOR CONSTITUENTS
 DISSOLVED GASES
• Water contacts with the atmosphere

• Respiration
C6H12O6 + 6O2 à 6CO2 + 6H2O + energy
Glucose

• Photosynthesis
6CO2 + 6H2OàC6H12O6 + 6O2
Glucose

32
 DISSOLVED GASES (con’t)
• Apart from respiration and photosynthesis, oxygen levels in
water are depleted by slow oxidation of organic and inorganic
material
• Presence of oxidisable organic material is often the most
serious form of pollution in watercourses
– Example: Ammonia (derived from dead plant materials)
– The concentration of ammonia in water is 0-2 mg/l because ammonia
is rapidly oxidised to nitrate
– Significant toxicity to fish

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WEATHERING OF ROCKS

Downstream 34
 WEATHERING OF ROCKS
• This will produce an increase in inorganic salt content

35
 SEDIMENTATION OF SUSPENDED MATERIALS

• As the river progresses downstream it will generally become less turbulent

and so less capable of supporting suspended material
• In nearly all rivers, the mean velocity decreases downstream

36
 WATER ANALYSIS
• Any environmental water contains a large number of
components
• Usually we will specifically test for several components:
pollutants, oxygen level, toxics etc.

37
Exercise
70

Which results are 60

river water, rain

50

40
water and sea

mg l-1
30

water? 20

10

0
Na K Mg Ca Cl SO4 H CO3 SiO2

25 4.5
4
20
3.5
3
15
2.5
mg l-1

g l-1
10 2
1.5
5 1
0.5
0 0
Na K Mg Ca Cl SO4 H CO3 SiO2 Na K Mg Ca Cl SO4 HCO3 SiO2

38
Exercise
70

UNIT! 60

50

40

mg l-1
30

20

10

0
Na K Mg Ca Cl SO4 H CO3 SiO2

River water
25 4.5
4
20
3.5
3
15
2.5
mg l-1

g l-1
10 2
1.5
5 1
0.5
0 0
Na K Mg Ca Cl SO4 H CO3 SiO2 Na K Mg Ca Cl SO4 HCO3 SiO2

Rain water Sea water 39

MEASUREMENT OF WATER QUALITY
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41
 MEASUREMENT OF WATER QUALITY
• Dissolved oxygen
• Oxygen demand
– Biochemical
– Chemical
• Microbial contamination

42
 DISSOLVED OXYGEN (DO)
• It is the level of free, non-compound oxygen present in water
or other liquids
• An important parameter in assessing water quality
– Influence on the organisms living within a body of water

43
 DISSOLVED OXYGEN
• Dissolved oxygen enters water through the air or as a
plant byproduct (photosynthesis)
• Oxygen can slowly diffuse across the water’s surface
from the surrounding atmosphere, or be mixed in quickly
through aeration (wind, waterfalls, ground water
discharge or other forms of running water
Most photosynthesis
takes place at the
surface (by shallow
water plants an d
algae)

In deeper waters, DO can remain

below 100% due to the respiration of
aquatic organisms an d microbial
44
decomposition
 FACTORS AFFECTING OXYGEN SOLUBILITY

• Actual amount of dissolved oxygen (in mg/L) will vary

depending on temperature, pressure and salinity
– temp↑, DO↓
– DO decreases exponentially as salt levels increase
– Pressure ↑, DO ↑
• Theoretically, colder, deeper fresh waters have the capability to
hold higher concentrations of dissolved oxygen

45
TYPICAL DO LEVELS

46
 TYPICAL DO LEVELS (con’t)
• Saltwater holds less oxygen than freshwater, so oceanic
DO concentrations tend to be lower than those of
freshwater

47
 MEASUREMENT OF WATER QUALITY
Dissolved Oxygen Content (DO)
• Measure of dissolved oxygen in the water
• Effects of oxygen-demanding wastes on rivers depend on volume, flow, and
temperature of river water

Biochemical Oxygen Demand (BOD)

• Quantity of dissolved oxygen (mg/L) required during the stabilisation of
decomposable organic matter by aerobic biochemical action
• Used as a test for organic waste contamination from sewage, paper pulp,
and food waste, etc.

48
 BIOCHEMICAL OXYGEN DEMAND (BOD)
• Measures the amount of oxygen required for the microbial
oxidation of organic compounds in aqueous samples
- Amount of oxygen utilised for the oxidation of organic
materials and oxidisable inorganic ions

• Indicator of water quality

- BOD ↑, organic matter ↑, water quality ↓

49
 SEEDED BOD
• General procedure:
– Different volumes of sample aliquots are placed in 30 ml incubation
bottles and diluted with seeded dilution water
• The “dilution water” provide oxygen for the microbial oxidation
– Bottles are the filled to full capacity without leaving any headspace,
and tightly closed
– BOD bottles are then placed in a thermostatically controlled air
incubator in the dark to prevent any photochemical reaction
– Concentrations of DO before and after incubation is measured

50
 SEEDED BOD

5 days, 20°C,
in the dark Measure DO
+
con cen t ra t ion
(final DO)
Sample A
Seed dilution water
(seed microorganisms)
(oxygen)

Measure DO
concentration (initial DO)

51
 SEEDED BOD
• Oxygen consumed by the microbes is determined from the difference, and the
BOD is calculated as follows:

(A1 -A2 )V2

BOD, mg/L =
V1

Where A1 = initial DO concentration, mg/L in the dilution water

A2= final DO concentration, mg/L in the diluted sample after
5 days
V1= ml sample aliquot diluted
V2= volume of the BOD bottle

52
Exercise
BOD CALCULATION
• A series of dilutions were prepared in 300 mL BOD
bottles using settled raw sewage and unseeded dilution
water. The dilution range, initial DO and final DO are
given in the table below:
B ott le # mL S e e d Initial DO F i n a l DO
1 3 7.95 5.20
2 6 7.95 3.85
3 9 7.90 2.40
4 12 7.85 1.35

• Calculate the average seed BOD 53

 Chemical oxygen demand (COD)
• A measure of the oxygen equivalent of organic matter in the
sample that is susceptible to oxidation by a strong oxidising
agent
– React a sample with excess oxidising agent
– After a fixed period, the concentration of unreacted oxidising agent is
determined
– The quantity of oxidising agent used can be calculated
– Oxygen equivalent can then be determined

54
 CALCULATION OF COD
1. Determine the equivalence between the oxidant used and
oxygen (from the chemical equation)
2. Calculate the relative molecular mass of oxidant
-Check from the periodic table
3. Determine the amount of oxidant used (mol) -
Mass(weight)/molar mass = no. of mol
4. Calculate the corresponding COD in mg/

55
 DETERMINE THE EQUIVALENCE BETWEEN OXIDANT USED
AND OXYGEN
• E.g. Pentane (C5H10 )
2C5H10 + 15O2 à 10CO2 + 10H2O
2 mol pentane reacts with 15 mol oxygen

• E.g. Ethanol (C2H5OH)

C2H5OH + 3O2 à 2CO2 + 3H2O
1 mol ethanol reacts with 3 mol oxygen

56
 Example
• What is the COD of a solution containing 72mg/l of propanol
after reaction? Oxidation of propanol is presented as below:
2C3H7OH + 9O2 à 6CO2 + 8H2O

1. Determine the equivalence between the oxidant used and oxygen

(from the chemical equation)

2 mol of propanol reacts with 9 mol of oxygen

57
 Example
2. Calculate the relative molecular mass of propanol
C3H7OH
12*3 + 1*7 + 16 + 1= 60
Meaning that 1 mole (symbol: mol) of propanol is 60 g.

3. Determine the amount (in mole) of oxidant used

In 1 L of solution, there are 0.072 g / 60 g/mol = 0.0012 mol propanol

4. Calculate the corresponding COD

Since ratio of propanol:oxygen is 2:9, so the oxygen
required=0.0012*4.5= 0.0054 mol oxygen
Relative molecular mass of oxygen (O2) = 16*2 = 32
Therefore, COD = 0.0054 mol * 32 g/mol= 1.7 g/l

58
 BOD COD
Oxidant used Oxidation by K 2 Cr 2 O 7
microorganisms Mn 2 (SO 4) 3

Most suitable use Modeling treatment plant Rapid an d frequent

process an d the effects of monitoring of treatment
organic compounds on the plant efficiency an d water
dissolved oxygen content of quality
receiving waters
Test 5 days 1.5 to 3 days
completion
time
Advantages Most closely models the • Toxic materials do
n atu ral environment not affect oxidant
• Short analysis time

Disadvantages • Toxic materials kill Some organic compounds

microorganisms are not oxidised completely
• Microorganisms do not
oxidise all materials 59
present in waste
 MEMBRANE FILTRATION TEST
• Test water for microbial contamination
• Pass 100 ml of water sample through a membrane
filter
• Pore size: 0.45 µm, Diameter: 47 mm
• Transfer filter paper to a Petri dish
• Incubate for 24-48 hours depending on the broth
• If the indicator organism is present, colonies will
appear on the filter paper and can be counted
• Results are reported as the number of colonies per
100 mL of water sample (CFU/100mL)
– CFU = colony forming units
60
Membrane
Filtration
Test
Typical coliform colony has a pink to dark-red color with a
metallic surface sheen

62
END

63