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Assessment of Environmental Acidity - Fieldwork

Assessment of environmental acidity: A cross-curriculum field excursion incorporating


year 11-12 Chemistry and Earth and Environmental Science concepts

Environmental issues caused by increasing inputs of acidity are of global significance and
include impacts from acid rain, mine drainage and ocean acidification. These issues are
addressed in passing in both the Earth and Environmental Science and the Chemistry school
curricula, but generally in an abstract and theoretical manner without a “hands on” practical
component.
In order to address this deficiency, the Department of Environment Regulation (DER) has
worked closely with the John XXXIII College to develop a ½ day excursion at Spoonbill
Reserve in the City of Stirling to assess the extent to which soil and water has been affected
by the disturbance of acid sulfate soils. During the excursion, students explore concepts
associated with oxidation-reduction and acid-base chemical reactions, and become aware of
the difference between pH and total acidity in water bodies. Undertaking field
measurements is an important component of the field trip, and students are required to
undertake titrations using total acidity test-kits to determine how much calcium carbonate
would be required to completely neutralise the acidity of lakes affected by the discharge of
acidic groundwater.
The explanatory notes and exercises for the excursion in Appendix A were developed on the
basis of investigations undertaken at Spoonbill Reserve by DER and Curtin University, and on
the basis of educational material previously developed for the site by the SPICE secondary
teachers’ enrichment program
(http://spice.duit.uwa.edu.au/samples/ast0869/Solving%20acid%20soil%20problems.pdf).
The excursion was first carried out by Year 12 Chemistry students from John XXIII College in
July 2013 and was generally well received by the students. The equipment used on the
excursion included:
Hanna HI 3830 acidity test kits (enough for groups of 2-3 to use); pH meters (test-strips
could also be used); small plastic tubes for soil sample collection (volume of about 20 mL is
adequate); and plastic teaspoons and garden trowels to collect soil samples.
The acidity test kits are the most expensive equipment used, and the cost of about $80 for
each kit may be too expensive for many schools. However, it is possible to make test kits
that will do the same job for a fraction of this cost using materials obtained from
supermarkets and pharmacies. Appendix B explains how such kits can be made.

ESWA acknowledges the compilation of this material by Steve Appleyard (DER) and Angela Schoen (John XXIII College)
Assessment of Environmental Acidity - Fieldwork

Appendix A – Field Notes and Exercises

Assessment of Acid Drainage in the Spoonbill Reserve Lakes

ESWA acknowledges the compilation of this material by Steve Appleyard (DER) and Angela Schoen (John XXIII College)
Assessment of Environmental Acidity - Fieldwork

Acid drainage in Spoonbill Reserve

1. Source of acidity in Spoonbill Reserve

The lakes in Spoonbill Reserve are constructed wetlands that were excavated in the 1980s.
Testing carried out in 2003 by the Department of Environment and Conservation indicated
that the lakes were highly acidic having a pH of about 2.5. The level of acidity in the lakes
was considered to pose a threat to the health of wildlife that utilised the lake and to public
amenity. Subsequent testing indicated that most of the acidity in the lakes was derived
from the disposal of peaty soil containing pyrite (an iron sulfide mineral) in the reserve
immediately to the north of the lakes. The pyrite in this soil material is very fine grained and
can only be seen with an electron microscope.
Acid and dissolved metals from these soils are percolating to the water table, and then
these contaminants are carried in a south-westerly direction by groundwater into and
through the lakes. Research by Curtin University suggested that acidity equivalent to
between 4.5 and 15 kg of CaCO3 is discharged daily by groundwater flow into the lakes.

Question 1: How main moles of hydrogen ions are discharged daily by groundwater flow
into the Spoonbill Reserve lakes if the main product of the acid-neutralisation reaction is
dissolved bicarbonate ions (HCO3-)?

Soils that naturally contain iron sulfide minerals (predominantly the mineral pyrite, FeS2) are
known as acid sulfate soils. These soils are harmless when kept under waterlogged
conditions, but exposure to air by excavation of drainage will cause sulfide minerals to
oxidise through reactions such as:

Reaction 1.
The sulfuric acid released by this reaction can make soils too acidic to sustain plant growth,
and can leach metals and arsenic from soil minerals into groundwater, often making
groundwater unsuitable for use.

Question 2: Reaction 1 is an example of an oxidation-reduction reaction. Which chemical


substance is oxidised and which is reduced in this reaction? What is the oxidation state of
iron in the ochre produced by this reaction?
This reaction rarely goes to completion and a variety of unstable iron hydroxy-sulfate
minerals such as schwertmannite are initially formed under acidic conditions (pH <4.0).
These intermediate reaction products slowly decompose, releasing further acidity that may
maintain acidic drainage for many decades or centuries after the initial pyrite oxidation
event has taken place.

ESWA acknowledges the compilation of this material by Steve Appleyard (DER) and Angela Schoen (John XXIII College)
Assessment of Environmental Acidity - Fieldwork

Figure 2 Accumulation of the mineral schwertmannite (approximate formula


Fe16O16(OH, SO4)12-13.10-12H2O) on soil where pyrite is oxidising. This mineral, which is
named after the German soil scientist Udo Schwertmann, commonly occurs at mine sites in
soils where the pH is less than 4.0. As the mineral slowly decomposes to form other iron
oxides, it buffers the acidity of drainage at a pH of about 3.5-4.0.

2. Testing of acid sulfate soils

Although the presence of pyrite and the amount of acidity in soils can only be accurately
determined by undertaking chemical analysis in a laboratory, there are some simple field
tests that can be carried out to indicate that acid sulfate soils are likely to be present at a
site. These tests can be carried out to determine whether soil s contain unoxidised pyrite
(i.e. they are “potential” acid sulfate or “sulfidic” soils) or whether they contain substantial
amounts of acidity released from the oxidation of pyrite (i.e. they are “actual” acid sulfate
or “sulfuric” soils).
The testing is carried out by measuring and comparing the pH of a sample of soil mixed with
both deionised water and 30% hydrogen peroxide (approximately a 1:5 solid to liquid paste
in both cases). The sample that is mixed with concentrated hydrogen peroxide is left to
react with the soil material to force sulfide minerals in the soil to oxidise.
The vigour of the (highly exothermic) reaction of the hydrogen peroxide reaction with soil
and the magnitude of the pH decline after reaction give an indication of whether pyrite is
likely to be in the soil. A measurement of soil pH with deionised water (known as a pHf
measurement) of less than 4.0 generally indicates that the soil is an actual acid sulfate soil.
A measurement of soil pH with hydrogen peroxide (known as a pHfox measurement) that
produces a vigorous reaction and a final pH value of less than 3.0 typically indicates that
potential acid sulfate soils are present. Other interpretations are possible for pH
measurements in these media that fall outside of this range (refer to the DEC acid sulfate
soil investigation guidelines for more information about this).

ESWA acknowledges the compilation of this material by Steve Appleyard (DER) and Angela Schoen (John XXIII College)
Assessment of Environmental Acidity - Fieldwork

Activity 1. Measuring pHf values of soils next to the Spoonbill Reserve lakes
DEC staff will demonstrate the use of concentrated hydrogen peroxide to make pH fox
measurements of soil samples, but you will be required to make pHf measurements on soil
samples at two locations: one in a bare, sandy area next to the northern lake, and one in an
area covered by wood-mulch next to the southern lake. At each site use the trowel and
plastic teaspoons provided to collect a small soil sample (teaspoon sized) from near the soil
surface, from a depth of about 5 cm, and from a depth of about 25 cm below the ground
surface. At each depth interval, note the colour of the soil, whether iron oxides are present,
and whether water flows into the hole. Make pHf measurements at each depth interval by
placing 1 teaspoon of soil into a small plastic container, adding about 5 teaspoons of
deionised water and stirring with a teaspoon. Measure the pH of the resultant slurry with a
pH test strip. Please ensure that you backfill the holes at each sampling site.

Question 3: How do pHf measurements vary with depth at each sampling site and with
sampling location? Why do you think that there may be differences in pHf values at sites
with bare soil and where the soil is covered with wood mulch?

3. Measuring the acidity of lakes and groundwater and remediation options

Although we are used to making pH measurements to indicate whether a water sample is


acidic or not, in practice only a very small proportion of the acidity of natural waters is
instantly available for reaction in the form of hydrogen ions. In most surface water bodies
and groundwater affected by mine drainage or disturbed acid sulfate soils, the majority of
the acidity in the water is “stored” in the form of dissolved iron and aluminium ions which
hydrolyse on exposure to oxygen to release additional hydrogen ions. An example of such a
hydrolysis reaction is shown below:

Reaction 2
As a consequence of this, pH measurements cannot generally be used to assess the how
much acid neutralising material might be required to fully remediate a water body affected
by acidity.
The total acidity of a water sample is measured by titrating it with a solution of sodium
hydroxide of known concentration using phenolphthalein as an acid-base indicator. This can
be carried out in the field using a test kit that has been designed for this purpose and the
total acidity is determined in units of the equivalent mass of calcium carbonate that would
be required to fully neutralise the acidity.

Question 4: Why do you think powdered calcium carbonate would be preferred for
neutralising acidity in a natural water body rather than a strong base such as sodium
hydroxide? Give the neutralisation reactions for sulfuric acid with calcium carbonate and
sodium hydroxide.

ESWA acknowledges the compilation of this material by Steve Appleyard (DER) and Angela Schoen (John XXIII College)
Assessment of Environmental Acidity - Fieldwork

Activity 2: Measuring the acidity of water in the Spoonbill Reserve lakes and in
groundwater
Using the acidity test kit provided, measure the acidity of water at one site in each of the
two lakes and from the monitoring bore at the site. Also measure the pH of water at the
three sites using pH test strips, and the iron concentration at each sampling location using
the test kit provided. Using the total acidity value you measured in the northern lake in the
reserve, determine the mass of calcium carbonate you would require to neutralise the
acidity of the lake water if the volume of water in the lake is assumed to be 5 million litres.
Repeat the exercise using the acidity result obtained from the groundwater monitoring bore
which is likely to be indicative of water quality in the lake in early summer.

Question 5: Why is the acidity of the lake likely to differ between summer and winter
months?

Periodically adding a large mass of calcium carbonate or other neutralising agent to the
lakes in Spoonbill Reserve is unlikely to be an acceptable remediation option because of the
large cost of carrying out such a treatment program, and because the ongoing discharge of
acidity by groundwater flow is likely to re-acidify the lakes within a few months of adding
the neutralisation agent.

Figure 3. Variation of pH in the northern lake in 2003 after the addition of 5 tonnes of
calcium hydroxide

This effect was observed in the summer of 2003 when 5 tonnes of calcium hydroxide was
added to the northern lake. Although the pH of the water in the lake initially became very
alkaline, water in the lake was progressively re-acidified over a period of about a month
(Figure 3).
Question 6: On the basis of the plot of pH versus time shown in Figure 3, do you think that
environmental regulators would consider calcium hydroxide to be a suitable neutralising
agent for acidic lakes? Why does the rate of pH-decline in the lake suddenly change after
about 16 days? (Hint: you have probably already seen a graph that looks like this when
studying acid-base reactions)

ESWA acknowledges the compilation of this material by Steve Appleyard (DER) and Angela Schoen (John XXIII College)
Assessment of Environmental Acidity - Fieldwork
A more sustainable method of removing acidity from water bodies like the Spoonbill
Reserve wetlands is to utilise naturally occurring microbes that live in anoxic environments
and “breathe” sulfate as a means of metabolising organic carbon through chemical
reactions such as:

Reaction 3
This chemical process consumes acidity, and the hydrogen sulfide produced reacts with
dissolved iron to form new, black-coloured iron sulfide minerals with an approximate
chemical formula of FeS in sediments where sulfate reduction is taking place.
Sulfate reduction has been used to treat soil and water acidity in two ways in the southern
lake in Spoonbill Reserve:
1. By adding wood mulch to soils to provide a food source and anoxic conditions to
encourage sulfate reduction to take place in the soil profile
2. By the use of bioreactor, large tanks containing potatoes as a readily bioavailable
food source into which lime-treated water is pumped to allow sulfate-reduction to
take place and metals to be removed from solution. Anoxic water from the process
is pumped into the upper part of the southern lake to become oxygenated and to
allow iron oxides and hydroxides (ochre) to precipitate and be filtered out by reeds
planted in this part of the wetland (Figure 2).

Figure 4. Acid drainage treatment system in the southern lake at Spoonbill Reserve (graphics
from the SPICE educational resource, ”Solving acid soils” (see web site
http://spice.duit.uwa.edu.au/samples/ast0869/Solving%20acid%20soil%20problems.pdf)

ESWA acknowledges the compilation of this material by Steve Appleyard (DER) and Angela Schoen (John XXIII College)
Assessment of Environmental Acidity - Fieldwork

Appendix B – Making total acidity test kits

The total acidity of a water sample is determined by titrating a known volume of a water
sample with a standard sodium hydroxide solution using phenolphthalein as an acid-base
indicator. The titrations carried out in the field are not carried out using a burette as they
would be in a laboratory, but rather using a small syringe or an eyedropper to dispense a
known volume of sodium hydroxide solution.
Components of the test kit
The components of a test kit include:
A 50-100 mL plastic bottle containing the standard sodium hydroxide solution;
A small syringe or an eyedropper which is graduated in fractions of a mL;
A medicine glass or a small plastic container which has a mark indicating a volume of
5 mL;
A small bottle (5-10mL) with a drop dispenser (or use another eyedropper)
containing phenolphthalein or turmeric-based indicator (see below for details of
how to make this).

Making the standard sodium hydroxide solution

The sodium hydroxide solution can be made using sodium hydroxide pellets and distilled
water that can be obtained cheaply from a supermarket or hardware store (i.e. reagent
grade materials are not needed). Weigh 8 grams of pellets of sodium hydroxide solution
and add to 1 litre of deionised water. This solution is further diluted by a factor of 10 with
deionised water to make the standard solution (i.e. a concentration of 0.02 M NaOH). This
solution can be made using kitchen scales and plastic measuring jugs so it is not necessary to
have access to laboratory equipment.

Making an acid-base indicator with turmeric

If phenolphthalein is not available, an alcoholic extract of powdered turmeric (the spice


available in supermarkets) will provide an acid-base indicator which has a similar pKa to
phenolphthalein. This is made by placing a teaspoon of powdered turmeric in a small, dark-
coloured glass or plastic container (turmeric extracts are light-sensitive) and covering the
powder with methylated spirits. The active ingredient in the extract is the dye curcumin
which changes colour from yellow to bright red at a pH of about 8.5. This solution is used in
the same way at phenolphthalein, and only 1-2 drops should be added to the water sample
before carrying out a titration.

ESWA acknowledges the compilation of this material by Steve Appleyard (DER) and Angela Schoen (John XXIII College)
Assessment of Environmental Acidity - Fieldwork

Using the acidity test kit

A 5 mL aliquot of water is added to the medicine glass and 1-2 drops of the indicator
solution is added to the sample. The standard sodium hydroxide solution is added drop-
wise with the eyedropper or small syringe while swirling the water sample until the colour
of the solution permanently changes colour from yellow to red. The volume of sodium
hydroxide added to the water sample is then read off, and the acidity (in units of mg/L of
the equivalent mass of calcium carbonate required to neutralise the acidity, or mg/L as
CaCO3) is determined by multiplying the volume in mL by 500.

The total acidity of groundwater in areas affected by disturbed acid sulfate soils in the
Stirling area varies between about 100 to 1000 mg/L as CaCO3, whereas unaffected
groundwater usually has TA values less than 50 mg/L as CaCO3.

ESWA acknowledges the compilation of this material by Steve Appleyard (DER) and Angela Schoen (John XXIII College)

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