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NATIONAL STATE
OFFICE FOR
SURFACE AND WASTEWATERS STAS 8601-70
Constructions, hydraulic
STANDARDIZATION Determination of Sulphates works, communication ways
and installations
Approval date: Replaces: Date standard comes into
31.05.1970 force: 01.07.1971

1. GENERAL PROVISIONS

1.1. The standard hereunder refers to determination methods for sulphate (SO )
content in surface and wastewaters.
1.2. Determination methods:
- The gravimetric method, applicable to waters with a sulphate ion content (SO )
between 40-500 mg/dm ; the error margin of this method is maximum 2%.
- The complexometric method, applicable to waters with a sulphate ion content (SO )
between 25-500 mg/dm ; the error margin of this method is maximum 5%.
1.3. The methods may also be employed for waters with a higher ion sulphate content
provided the water samples are diluted accordingly. They can also be used for waters
with a lower content than the one specified in item 1.2, by collecting a higher volume of
water samples, which is then concentrated by evaporation.
1.4. In case of any litigation, the gravimetric methods will be used.

2. COLLECTION AND PREPARATION OF WATER SAMPLES.

Water samples shall be collected in glass or plastic recipients, in compliance with

current prescriptions concerning collection of surface water and wastewater sample
collection.
The sulphate content must be determined immediately after the water samples are
collected. If this is not possible, the samples shall be stored at low temperature. However
before storage the sample pH must be verified; if the pH is alkaline, hydrochloric acid
shall be added into the sample (1+1 ratio), until the pH drops below 8. Calculation must
take into account the volume of hydrochloric acid added into the sample.
Before determination, the water samples shall be filtered through fine porosity
filter paper or they shall be centrifuged.
If the insoluble sulphate content of the water sample must be determined, then the
suspension sulphates must be made soluble via alkaline decomposition/ break-up. Thus
the filter paper, together with the suspensions from the filtered sample, shall be
introduced into a pot/ crucible, where it shall be dried and calcinated. 0.5 g sodium
carbonate and potassium carbonate (1+1 ratio) shall then be added, and calcination shall
continue for another 15 minutes. After cooling, the waste in the pot shall be dissolved
into distilled water and shall be brought to a measured volume; after that the sulphates in
the suspensions shall be determined with one of the methods indicated in chapter 3 or
chapter 4.
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3. THE GRAVIMETRIC METHOD

3.1. Method principle

Sulphate ions (SO ) in a hydrochloric acid are precipitated as barium sulphate, via
addition of barium chloride; then the sulphate content is measured via the gravimetric
method.
3.2. Equipment
- Ion exchanger column: transparent glass or plastic tube 30 mm in diameter and 250 mm
high, whose upper part is enlarged in the shape of a funnel with a 50 mm diameter; the
inferior part of the tube is equipped with a faucet; right above the faucet there is a glass
filter plate, which may be replaced with a mineral cotton tampon.
3.3. Reagents.
The reagents used must be of a chemically pure quality (c.p.) or ‘for analysis’ quality
(p.a.). Reagent solutions shall be prepared using water distilled in a 100% glass recipient.
- Ion exchanger resin: strong acid H cationite, type polystyrene-divinyl-benzene
with sulphonic groups, in the shape of grains 0.5-1 mm in diameter
- Hydrochloric acid (d= 1.19), 5% vol and 1+9 vol.
- Ammonia tampon solution: 67 g ammonium chloride is dissolved in 100 cm of
distilled water; 570 cm ammonium solution 25% is added and diluted at 1,000
cm , with distilled water.
- Eriochrome black T: 1 g of T eriochrome black is mixed in a jar with 100 g
sodium chloride, until a fine homogenous powder is obtained, which is then
stored in a hermetically sealed brown glass bottle.
- The disodic salt of the ethylene-diammonium- tetraacetic acid (EDTA), 0.01 n
solution: 1.8613 g EDTA shall be weighed with a 0.0002 g margin (EDTA
previously dried in a drying cabinet at 80±3°C, and then cooled into the
dehydrator) and then introduced into a 1,000 cm calibrated flask, with a small
quantity of distilled water; the obtained solution is brought to the required mark
using distilled water and is then homogenized by stirring.
- Nitric acid (d= 1.41)
- Barium chloride, 12% solution; the solution shall be filtered before use
- Silver nitrate, 10% solution
- Methyl orange, 0.1% solution
3.4. Removal of interfering substances
Local total cation concentrations higher than 250 mg/dm , or a total of heavy
metal ions higher than 10 mg/dm , interfere with the determination process.
Silica interferes with the determination process if its concentration exceeds 25
mg/dm .

3.4.1. Cation removal

The water sample under analysis shall be passed through an ion exchanger
column for removal of cations as well as of heavy metal ions. This process requires that
at least 500 cm of the water sample under analysis -neutralized at pH 7- be passed
through the ion exchanger column (prepared as in 3.4.1.1), with an approximate speed of
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60 drops per minute. The first 150 dm of effluent are removed, while the rest shall be
used for sulphate determination.

3.4.1.1. Preparation of the ion exchanger column

The ion exchanger is mixed with a double volume of distilled water and left in the
distilled water for 2 hours, so that the grains can dilate. After that the ion exchanger is
filtered through mineral cotton introduced in the neck of a funnel and then washed
several times with distilled water. The washed ion exchanger is then stirred with distilled
water and introduced into the column, and then it is washed with distilled water until no
air bubble is left inside the column.
The ion exchanger layer shall be 150…170 mm in height; it must always be
covered in liquid. A mineral cotton stopper shall be introduced above the ion exchanger.
Before use, the ion exchanger in the column must be regenerated via eluation with
circa 500 cm of hydrochloric acid 5% for a 100 cm volume of ion exchanger; then
the ion exchanger is washed with distilled water until chloride ions are removed from the
washing waters. Removal of chloride ions is verified by mixing circa 20 cm washing
water with 1 cm silver nitrate solution and 2 drops of nitric acid; no opalescence effect
must occur after 10 minutes.
The exchange capacity of the ion exchanger column must not be lower than 99%;
capacity is verify by testing the hardness of the water sample to be analysed, which was
passed through the column. Thus, after removal of he first 150 cm of effluent, 10 cm
shall be taken of the remaining effluent and then mixed with 0.2 cm tampon
ammonium solution and T eriochrome black, on the tip of a spatula. If one drop of EDTA
0.01 n causes disappearance of the red coloration and generates a net blue coloration. In
the contrary case the ion exchanger must be regenerated again, as indicated above.

3.4.2. Removal of silica

A measured volume of the water sample under analysis shall be vaporized in a
platinum capsule, by heating a water bath. The residue obtained is wetted with a small
quantity of hydrochloric acid (d= 1.19), and full vaporization is then continued.
2 cm of distilled water and 1 cm of hydrochloric acid (d= 1.19) shall be added
and then fully vaporized. After that, 2 cm of hydrochloric acid (d = 1.19) are introduced
into the capsule, diluted with hot distilled water and then filtered through filter paper. The
filter paper containing the silica made insoluble is washed several times with distilled
water. The filtrate and the washing water are combined again; they are completed until
the initial volume of the working water sample is obtained, and then it is used to
determine the sulphates, as indicated in item 3.5.

3.5. Working method

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A quantity of 20-250 cm , corresponding to 10-125 mg of (SO ), is taken

from the water sample under analysis, extracted as per chapter 2 pr treated as indicated in
item 3.4. In case the volume of the water sample is lower than 250 cm , distilled water
shall be added in order to reach the respective volume; if water sample volume exceeds
250 cm , then the sample shall be concentrated by vaporization.
Two drops of methyl orange solutions are added and drops of hydrochloric acid
until the solution is coloured in red, the a 1-2 cm excess of hydrochloric acid is added.
The solution is heated to the boiling point; while thoroughly stirring the solution,
warm barium chloride solution is added in drops, until complete precipitation is obtained,
and then an excess of 1-2 cm is added. After that the solution is kept on the water bath
for at least 2 hours; a few drops of barium chloride solution shall then be added to verify
if precipitation was completed. After 12 hours, the solution is quantitatively filtered,
through fine porosity filter paper; the precipitate on the filter paper shall be washed with
distilled water, until the chloride ions are removed from the washing waters (verifications
with silver nitrate as in item 3.4.1.1.).
The filter paper with the barium sulphate sediment/precipitate/ deposit shall be
introduced in a porcelain jar, previously brought to constant weight, and then dried in the
oven. After that the jar is carefully calcinated, at first with weak flame and then at 800°C,
for an hour. The filter paper must not be set aflame. The jar with barium sulphate is
cooled into the dehydrator and then weight with a 0.0002 g error margin. Calcination,
cooling and weighing procedures are repeated until constant mass is reached.

3.6. Calculation

Sulphates [mg/dm ]
Where:
0.411 5 Sulphate ion (SO ) quantity, in mg, for 1 mg of barium sulphate.
m The mass of calcinated sulphate precipitate
V Volume of water sample taken for the determination, (cm )

4. THE COMPLEXOMETRIC METHOD

4.1. Method principle

Sulphate ions (SO ) shall be precipitated as barium sulphate, with volumetric
barium chloride solution. Barium ion excess shall be subjected to titration with EDTA
solution, in the presence if magnesium ions, using T eriochrome as an indicator.
4.2. Equipment
Ion exchanger column/ tower (as per item 3.2.)

4.3. Reagents
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The reagents used must be of a chemically pure quality (c.p.) or ‘for analysis’ quality
(p.a.). Reagent solutions shall be prepared using water distilled in a 100% glass recipient.

- Active coal powder, with no calcium, magnesium or phosphate content

- Hydrochloric acid (d= 1.19), 10% and 5% vol
- Ethylic alcohol 96% vol
- Ammonia 25%
- Ion exchanger resin (as per item 3.3)
- Magnesium chloride solution, circa 0.1 n: 10.2 magnesium chloride (
) is dissolved into distilled water and then completed with
distilled water until reaching volume of 1,000 cm , in a calibrated flask
- Calcium chloride, 0.02 n solution: 1.0009 g calcium carbonate (previously dried
in the oven at 105 ±3°C and then cooled into the dehydrator) shall be weighed
with a 0.0002 g error margin; then it shall be introduced into a 1,000 cm
calibrated flask with a small quantity of distilled water; hydrochloric acid 10%
shall be added in drops, until the carbonate is fully dissolved and the carbon
dioxide is released, avoiding excess of hydrochloric acid; after that the solution is
brought to the required mark with distilled water and stirred in order to acquire
homogeneity.
- Sodium hydroxide, circa 2 n solution: 8 g of sodium hydroxide are weighed, then
dissolved into distilled water and diluted at 100 cm , with distilled water.
- Indicator- Purpuric acid ammonium salt: 1 g of purpuric acid ammonium salt is
mixed with 100 g sodium chloride [dried in the oven/ drying chamber at
105±3°C] and it is finely grinded; it is kept in a sealed brown bottle.
- The disodic salt of the ethylene-diammonium- tetra-acetic acid (EDTA), 0.02 n
solution: 3.7226 g EDTA shall be weighed with a 0.0002 g margin (EDTA
previously dried or 2 hours in a oven at 80±3°C, and then cooled into the
dehydrator) and then introduced into a 1,000 cm calibrated flask, with a small
quantity of distilled water; the obtained solution is brought to the required mark
using distilled water and is then homogenized by stirring.
The factor of the solution is verified as follows: 23 cm of 0.02 n calcium
chloride solution are introduced into an Erlenmeyer container; 6 cm of sodium
hydroxide solution (circa 2 n) are added, and then 0.1-0.2 g indicator purpuric
acid ammonium salt; then the calcium chloride solution is subjected to titration
with EDTA solution circa 0.02 n, until the pink solution acquires a pink-purple
colour.

V Volume of EDTA solution 0.02 n, used in titration, in cm

- Tampon ammonium solution (prepared as in item 3.3)
- Eriochrome black T (prepared as indicated in item 3.3)
- Barium chloride solution, 0.02 n: 2.4428 g barium chloride ( ) shall
be weighed with a 0.0002 g error margin and then introduced into a 1,000 cm
calibrated flask, with a small quantity of distilled water; the obtained solution is
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brought to the required mark using distilled water and is then homogenized by
stirring
The solution factor shall be determined as follows: 23 cm of 0.02 n barium
chloride solution are introduced into an Erlenmeyer container; 0.2 cm of
magnesium chloride (0.1 n), 6 cm of tampon ammonium solution and
eriochrome T (a tip of a spatula) are brought to boiling point and added; then the
solution is subjected to titration with EDTA solution circa 0.02 n, until the red
solution acquires a net blue colour.

V- Volume of EDTA solution 0.02 n, used in titration, in cm

- Factor of t EDTA solution 0.02 n used in titration

4.4. Removal of interfering substances

The determination interferes with: water coloration; chromates and
bi-chromates larger than 10 mg( and 10 mg , phosphates in a
concentration higher than 10 mg , as well as cations: magnesium, calcium,
copper, aluminium, if they exceed 10 mg/ , zinc, lead, trivalent iron when their
concentration exceeds 100 mg/ .

When the cations and the anions indicated above are simultaneously present into
the water sample, they interfere with the determination if their concentration exceeds 10
mg/ .

4.4.1. Removal of the water sample coloration

A certain volume of the water sample is stirred with active coal for 10-15 minutes
and then filtered through filter paper.

4.4.2. Removal of chromates and bi-chromates

An exact volume measured from the water sample is heated to boiling point, and
then brought to pH= 4 with hydrochloric acid (d = 1.19); boiling is continued and ethylic
alcohol is added until the solution changes colour from yellow to green. This way the
ions ( ) and ( ) are reduced to .
The solution is neutralized with ammonium solution (verification with universal
indicator paper) and then vaporized in order to decrease volume. After cooling, the
solution is completed with distilled water in order to reach the initial water sample
volume, and after that it is passed through the ion exchanger column (as in item 3.4.1) for
removal of the cation.

4.4.3. Phosphate removal

The phosphates present into the sample cause important positive errors. In order
to eliminate this interference, the sample shall first be diluted accordingly, so that
phosphate concentration is brought below 10 mg/ .
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4.4.4. Cation removal

A minimum volume of 500 of water sample to be analysed, neutralized at pH= 7,
shall be passed through an ion exchanger column. (as in item 3.4.1.)

4.4. Working method

A volume of 10-100 of the water sample to be analysed (extracted as per

chapter 2 or treated as per chapter item 4.4), corresponding to a 2.5-50 mg ( )
content, shall be introduced into a 500 Erlenmeyer container.
If the sample volume is lower than 100 , then distilled water shall be added;
if the sample volume exceeds 100 , the sample shall be concentrated by evaporation.
The water sample shall be heated up to boiling point; 25 barium chloride
solution shall be added (measured accurately) and the sample is boiled for 1 minute.
After cooling 0.2 magnesium chloride solution, 6 of tampon ammonium
solution and T eriochrome black (a tip of a spatula) shall be added. The resulting solution
is subjected to titration with EDTA solution 0.02 n, until the solution changes colour
from red to net blue.

4.6. Calculation

Sulphates [mg/ ]

0.096 64 - Sulphate quantity in mg, corresponding to 1 of EDTA

solution, 0.02 n
- Volume of 0.02 n barium chloride solution introduced into the water
sample, in
- Factor of 0.02 n barium chloride solution introduced into the water sample
- Volume of 0.02 n EDTA solution used for water sample titration, in
- Factor of 0.02 n EDTA solution used for water sample titration
V- Volume of water sample considered for determination, in