CH2ENC: Environmental

Chemistry I

Aquatic Chemistry &

Water Quality (Tutorial)

• Dr Sarah Alexander
• [email protected]
 Question 1

Metals are transported in aquatic systems, explain the following

terms:

i) Deposition of Solids
ii) Uptake by Organisms
i) Deposition of sediments

• This occurs with an increase in pH, under sufficient alkaline conditions all
transition metals will precipitate. There will be some variation in the pH needed.
Deposition of high concentration metals may result in traces of other metal ions
being deposited, this is known as co precipitation.

• Other mechanisms of interaction are: adsorption, ion exchange and complex

formation within the sediment.
ii) Uptake by Organisms

• This is done via the food chain (DDT example). Filter feeders take in metals
from the sediment. Many of these metals remain in the organism as a simple
ion, however metals like cadmium and mercury can be converted into covalent
organometals, which can accumulate in fatty tissues.

• The distribution of the metal within the organism is dependent on the individual
metal and the detailed chemistry.
 Question 2

When testing water quality, specific parameters are checked, define what
is meant by the following terms:

i) Turbidity
ii) Threshold Odour Number
iii) Total Organic Carbon
iv) Total Dissolved Solids
v) Total Suspended Solids
i) Turbidity

• Turbidity measures the relative clarity of a fluid.

• It is the cloudiness/haziness in a fluid due to the presence of a large number of

individual particles. These particles are not visible to the naked eye, only when there is
a large number present. It is determined by the amount of light that is scattered off the
surface of these particles - this light has been obstructed by the particles, causing the
cloudiness to appear.

• The particles are normally fine suspended solids: sediment from beds (clay, silt etc.),
fine organic and inorganic matter, algae and other microscopic organisms.
ii) Threshold Odour Number

• Odour is measured using the threshold odour number (TON)

• This is the dilution ratio at which odour is just detectable.

𝐹𝑖𝑛𝑎𝑙 𝑆𝑎𝑚𝑝𝑙𝑒 𝑉𝑜𝑙𝑢𝑚𝑒 (𝑉𝑓)

𝑇𝑂𝑁 =
𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑆𝑎𝑚𝑝𝑙𝑒 𝑉𝑜𝑙𝑢𝑚𝑒 (𝑉𝑖)

• If the odour is no longer present, the ratio is wrong (diluted too much)
• If the odour is still very strong, the ratio is wrong (not diluted enough)
iii) Total Organic Carbon (TOC)

• The oxidation of organic matter to carbon dioxide, after acidification to remove

carbonates. CO2 can be measured by absorption or conductivity in solution.
iv) Total Dissolved Solids (TDS)

• Solids that are dissolved in water. TDS include inorganic salts (Ca, Mg, K, Na,
bicarbonates, chlorides, and sulphates) and some small amounts of organic
matter that are dissolved in water.

v) Total Suspended Solids (TSS)

• Solids that can be removed by filtration

Question 3

Photosynthesis converts CO2 and H2O (with light energy) to energy and O2. How
to this process occur in light limited environments?

• Temperature dependent reactions, which are catalysed by enzymes. These

occur regardless of light availability. As the enzymes approach their
optimum temperatures the overall rate of photosynthesis increases.
 Question 4

a) What do the following terms mean?

i) Biological Oxygen Demand

ii) Chemical Oxygen Demand

b) How do the two methods compare?

i) Biological Oxygen Demand (BOD)

• The method of replicating the oxidation conditions found in the environment. The dissolved
oxygen level of a fully aerated water sample is tested (using Winkler or an electrode). The
sample is then tested again after it has been stored in the dark under standard conditions to
promote microbiological activity (20°C pH 6.5 - 8.5 in an incubator). For an expected high
oxygen demand the sample should be diluted, where the diluent can contain magnesium,
calcium, iron (III) or phosphate.

• No dilution results in:

• BOD = initial oxygen concentration - final oxygen concentration (mg l-1).

ii) Chemical Oxygen Demand (COD)

• A family of techniques which involve reacting a sample with excess of oxidising

agent.

• After a fixed period of time, the concentration of unreacted oxidising agent is

determined by titration. The quantity of oxidising agent is then calculated and
the oxygen equivalent determined.

• Methods include: Two hour dichromate value and Permanganate tests.

b) How do the two methods compare?

• BOD replicates natural process

• BOD can take a significant amount of time to be completed
• BOD difficult to reproduce
• COD more time efficient
• COD can be reproduced
• COD can be used for heavily polluted water
• COD not as connected with the natural process
 Question 5

Explain the “Winkler” method for the determination of dissolved oxygen in aqueous
samples, including all relevant equations.
The Winkler Method

• The Winkler method is “fixed” after sampling by reaction with Mn2+

(added as manganese(II) sulphate), together with alkaline
iodide/azide mixture:

Mn2+ + 2OH- + 0.5 O2 ------> MnO2(s) + H2O

• The iodine is necessary for the analytical procedure in the lab.

• The sample needs to fill the entire bottle to ensure additional oxygen
is not introduced.

• At the lab, the sample is acidified with sulphuric or phosphoric acid.

MnO2 + 2I- + 4H+ -----> Mn2+ + I2 +2H2O

• The iodine is then titrated with sodium thiosulphate using a starch

indicator
 I2 + 2S2O32- ----> S4O62- + 2I-

• So, the overall reaction is:

2S3O32- + 2H+ + 0.5O2 ----> S4O62- + 3H2O

• So in the sample: 4 mol thiosulphate in the final titration is

equivalent to 1 mol of oxygen
Question 6

What processes cause Acid Rain?

Question 6

• An increase in the production of SO2 and NO2 in the last century from fossil
fuel burning (heat and power)

• Gases are dispersed into the atmosphere via tall chimneys as flue gas

• The gases react with atmospheric water and O2 to form H2SO4 and HNO3
Question 7

List the different techniques and preservatives used when sampling, and describe
what each would be used for.
Preservation/ Effect on Sample Type of samples the method is used
Technique Used for
Nitric acid Keeps metals in solution Metal-containing samples

Sulphuric acid Bactericide Biodegradable samples containing

carbon, oil, grease

Samples containing amines/ammonia

Formation of sulphates with volatile
bases
Sodium hydroxide Formation of sodium salts from volatile Samples containing volatile organic acids
acids or cyanides

Chemical Reaction Fix a particular constituent Samples to be analysed for Winkler

method (dissolved oxygen)
Question 8

How to a change in pH affect freshwater life? Give examples of how different

species of aquatic life are affected.
 pH Level Effect

Below pH 6.5. Salmon population decrease

Below pH 6.0 Perch population decrease
Below pH 5.5 Eel population decrease
Below pH 5.0 Little life possible

• Life is eradicated in a pH change of just over 1 pH unit.

Question 9

Describe the impact of suspended solids

Question 9

• In water these suspended solids can:

• block light to aquatic plants (reducing food supplies)
• smother aquatic organisms (affects gill function)
• carry contaminants and pathogens (including lead, mercury, and
bacteria).
• increase water temperature by solar radiation and heat transfer

• Human usage: the greater their presence - the higher the level of
water treatment required prior to consumption
Question 10

A 100 cm3 of a hard water sample required 18.2 cm3 of a 0.01 M

EDTA solution for complete complexing of the metal ions.

Calculate the total hardness of the water in ppm of calcium carbonate.

Since the EDTA chemical reaction is:

H2Y2- + M2+ → MY2- + 2H+

The ratio of EDTA ion : metal ion = 1:1

The hard water sample required 18.2 cm3 of a 0.01 M EDTA
solution.

No. of moles of EDTA = (18.2 x 0.01)/1000 = 1.82 x 10-4 mol

As ratio of EDTA ion to metal ion is 1:1

Number of moles of metal ions (Ca2+ ions) = 1.82 x 10-4 mol in

200ml sample.
Therefore the 1000 ml sample contains:

(1.82 x 10-4 x 1000/100) = 0.00182 moles/litre of Ca2+ ions

Molar Mass of CaCO3 is 100 g/mol

= 0.00182 mol/l x 100 g/mol

= 0.182 g/l CaCO3
= 0.182 x 1000 mg/l CaCO3
= 182 ppm CaCO3
 2018 Exam Paper Question

(b) A 150 cm3 sample of river water was analysed for dissolved oxygen using the
Winkler method. The iodine liberated required 36.0 cm3 of a 0.005 M sodium
thiosulphate solution for complete reaction. Calculate the dissolved oxygen
content of the water in ppm (parts per million), include all relevant equations
in your answer.
(8 marks)
 2018 Exam Paper Question

(b) Overall reaction is

2S2O32- + 2H+ + 0.5O2 ----> S4O62- + 3H2O
So form the sample: 4 mol thiosulphate in the final titration is equivalent to 1 mol of oxygen

Number of moles of thiosulphate = (36 x 0.005)/1000= 1.8 x 10-4 mol

Concentration of dissolved oxygen = 1.8 x 10-4/4 = 0.000045 mol

= 0.000045 x 32 g/l = 0.00144

= 0.00144/(150/1000) = 0.0096 g/l = 9.6 mg/l

= 9.6 ppm
 2018 Exam Paper Question

(c) Potassium hydrogen phthalate is commonly used for the determination of

Chemical Oxygen Demand (COD) in aqueous samples.

Calculate the Chemical Oxygen Demand (COD) in ppm (parts per million)
for a sample containing 0.440 g L‒1 of potassium hydrogen phthalate
(KC8H5O5), include all balanced equations used.

(7 marks)
 2018 Exam Paper Question

(c) KC8H5O5 + 7.5 O2 ----→ 8CO2 +2H2O + K+ + OH-

1 mol potassium hydrogen phthalate = 7.5 mol of oxygen.
Number of moles of KC8H5O5 = 0.440/204 mol/L

Number of moles of O2 = 7.5 x 0.44/204 = 0.016176 mols

Number of grams of oxygen = 0.016176 x 32 x 1000 = 517.6 mg/L
i.e. COD = 517.6 ppm
(7 marks)