SKALAR METHODS

ANALYSIS: AMMONIA
RANGE: 1 - 800 µg N/liter
SAMPLE: SEA WATER
SAN++
Catnr. 155-006Xw/r issue 032613/MH/99279552

PRINCIPLE

The automated procedure for the determination of Ammonia is based on the modified Berthelot reaction;
ammonia is chlorinated to monochloramine which reacts with salicylate to 5-aminosalicylate. After
oxidation and oxidative coupling a green coloured complex is formed. The absorption of the formed
complex is measured at 660 nm.

LABORATORY FACILITIES

1. Maximum power consumption depending on the analyser configuration, 2000 VA. Check voltage at the
back of the instrument before installation.
2. Facilities for chemical wastes. Check environmental regulations for proper disposal of waste.

PROCEDURE SAMPLE PREPARATION

Water no. 1.1.3

Field of application

Sample preparation for the determination of total alkalinity, aluminium, amino acids, ammonia, anionic
surfactants (MBAS), bromide, calcium, C.O.D., chromium, conductivity, D.O.C., ethanol, hardness,
magnesium, manganese, methanol, nitrate + nitrite, nitrite, nonionics, ortho-phosphate, potassium
permanganate, potassium, total-N (UV digestion), protein, silicate, sodium, volatile acids and urea in water.

Principle

The sample is not preserved and analysed as soon as possible, at least within 24 hours after collection.
Store the sample at 4°C till analysis.

Note : The sample preparation in this method is only meant to be an example procedure. It requires
validation on its correct procedure for all types of samples to be analyzed, which is the responsibility of the
user.

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REAGENTS

A. Buffer solution (1 liter)

Required chemicals: Potassium sodium
tartrate........................... 33 g.
C4H4O6KNa.4H2O
tri-Sodium citrate........... 24 g.
C6H5O7Na3.2H2O
Distilled water
H2O
Brij 35 (30%)................... 3 ml.
Preparation: Dissolve the potassium sodium tartrate in
± 800 ml distilled water. Add the tri-
sodium citrate and dissolve. Fill up to 1
liter with distilled water, add the Brij 35
and mix.
Note: Check the pH and adjust if necessary with
hydrochloric acid to 5.2 ± 0.1. Solution is
stable for 1 week. Store at 4°C when the
solution is not used.

B. Sodium salicylate solution (1 liter)

Required chemicals: Sodium hydroxide .......... 25 g. Preparation: Dissolve the sodium hydroxide in ± 50 ml
NaOH distilled water. Add ± 800 ml distilled
Sodium salicylate ........... 80 g. water. Add the sodium salicylate. Fill up to
C7H5NaO3 1 liter with distilled water and mix.
Distilled water
H2O Note: Store in a dark coloured bottle. Solution is
stable for 1 week. Store at 4°C when the
solution is not used.

C. Sodium nitroprusside solution (1 liter)

Required chemicals: Sodium nitroprusside .... 1.0 g. Preparation: Dissolve the sodium nitroprusside in
Na2[Fe(CN)5NO].2H2O ± 800 ml distilled water. Fill up to 1 liter
Distilled water with distilled water and mix.
H2O
Note: Store in a dark coloured bottle. Solution is
stable for 1 week. Store at 4°C when the
solution is not used.

D. Dichloroisocyanuric acid sodium salt (1 liter)

Required chemicals: Dichloroisocyanuric acid Preparation: Dissolve the dichloroisocyanuric acid

sodium salt.................... 2.0 g. sodium salt in ± 800 ml distilled water. Fill
C3N3O3Cl2Na.2H2O up to 1 liter with distilled water and mix.
Distilled water
H2O Note: Solution is stable for 1 week. Store at 4°C
when the solution is not used.

E. Distilled water

Required chemicals: Distilled water Note: Refresh weekly.

H2O

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F. Rinsing liquid sampler

Required chemicals: Distilled water Note: For sea water samples, adjust the salinity
H2O of the rinsing water sampler to the same
level as the salinity of the sea water
samples when matrix peaks reach the
same level as the detection limit. Use ultra
pure sodium chloride or “zero” seawater
for adjustment.
Refresh weekly.

STANDARDS

Stock solution 100 mg N/liter (1 liter)

Required chemicals: Ammonium Preparation: Dissolve the ammonium chloride in ± 800

chloride .................. 381.9 mg. ml distilled water. Fill up to 1 liter with
NH4Cl distilled water and mix.
Distilled water
H2O Note: Solution is stable for 1 month. Store at
4°C when the solution is not used.

Stock solution 10 mg N/liter

Dilute 10 ml stock solution 100 mg N/liter to 100 ml with distilled water.

Working standards

800 µg N/liter: Dilute 8.0 ml stock solution 10 mg N/liter to 100 ml with rinsing liquid sampler.
640 µg N/liter: Dilute 6.4 ml stock solution 10 mg N/liter to 100 ml with rinsing liquid sampler.
480 µg N/liter: Dilute 4.8 ml stock solution 10 mg N/liter to 100 ml with rinsing liquid sampler.
320 µg N/liter: Dilute 3.2 ml stock solution 10 mg N/liter to 100 ml with rinsing liquid sampler.
160 µg N/liter: Dilute 1.6 ml stock solution 10 mg N/liter to 100 ml with rinsing liquid sampler.

Note:
1. Prepare the working standards fresh daily.
2. The water used for the reagents and standards must be degassed properly before making up the
reagents and standards. Especially water produced by reverse osmosis or ion exchange equipment
contains a lot of gasses, which must be removed by degassing (degassing procedure see operational
remarks and trouble shooting).

CATALOGUE NUMBERS REQUIRED CHEMICALS

Product Supplier and catnr. Danger classification

Potassium sodium tartrate tetrahydrate Merck 108087

tri-Sodium citrate dihydrate Merck 106448
Brij 35 (30%) Skalar SC 13900
Sodium hydroxide Merck 106498 corrosive
Sodium salicylate Merck 106601 harmful, irritant
Sodium nitroprusside dihydrate Merck 106541 toxic
Dichloroisocyanuric acid sodium salt dihydrate Merck 110887 harmful, oxidising

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Sodium chloride Merck 106404
Ammonium chloride Merck 101145 harmful, irritant
Sodium hypochlorite solution (13% active chlorine) Acros 21925 corrosive

RECOMMENDED OPERATIONAL SETTINGS

1. System sample time: 60 sec., wash time: 60 sec., air time: 0 sec.
2. Module sample time: 60 sec., wash time: 60 sec., air time: 0 sec.
3. Calibration type: 1st order ISO 8466-1.

OPERATIONAL REMARKS AND TROUBLE SHOOTING

1. The stabilising time of the system is approximately 20 minutes.

2. The sensitivity of the highest standard 800 µg N/liter is ± 0.400 AU.
3. Persons using this Skalar method should be familiar with normal laboratory practice. This Skalar
method does not purport to address all of the safety problems, if any, associated with its use. It is the
responsibility of the user to establish appropriate safety and health practices and to ensure compliance
with any national regulatory conditions.
4. The connection between the sampler and the sample pump tube is made of 5175 tube.
5. If a digital matrix photometer 28505901, is in use, a correction interference filter of 520 nm ± 10 nm is
advised.
6. Avoid any turbidity in the reagents, filter if necessary.
7. After 6 months the amount of Brij 35 can be reduced to 1 ml/liter.
8. If reaction coils with water heating are used, the water bath has to be cooled with tap water when the
environment temperature is above 25°C.
9. The reagent bottles must be rinsed thoroughly with distilled water before refilling with fresh reagents.
This is done to remove precipitation of micro organism and other interferences.
10. If solvents or high concentrated acids (> 2M) must be controlled by a rinsing valve, use the solvent/acid
resistant type.
11. Degassing procedures;
a) Good: degas the water with a helium gas flow of approximately 20 liter/hour with aid of a sparger.
Degas 5 liter water for 15 minutes. This procedure removes all dissolved air or, degas the water by
boiling the water for 10 minutes. Cool down to room temperature before usage.
b) Medium: degas the water with a nitrogen gas flow of approximately 20 liter/hour with aid of sparger.
Degas 5 liter water for 15 minutes. This procedure will remove most of the dissolved gasses.
c) Bad: degas the water by ultrasonic waves. This procedure will remove a small part of the dissolved
gasses.

GENERAL REMARKS

1. In most analyses, the first peak coming from the baseline is lower than it should be. The first peak
coming from the baseline is rejected and will not be included in the calculation of the CV-value.
2. If the sample take up volume is less than 1.00 ml/min, a bypass is required to increase the sample
stream to approximately 1.00 ml/min. For 5210 debubbler, when the sample is 1.00 ml/min and higher
use 0.23 ml/min debubble tube.

MAINTENANCE

1. Daily; when daily analysis is finished rinse all reagent lines with distilled water for 30 minutes.

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2. Weekly; to decontaminate the system, rinse with 1% hypochlorite solution for 30 minutes and with
distilled water for 15 minutes.
3. Monthly; replace all pump tubing (or shift pump tube one colour bridge on pump).

MODULE CONSUMABLES

silicone tube catnr. 3150 acid flex sleeves catnr. 5415

polyethylene tube catnr. 3142 pump tube 1.60 ml/min. catnr. 3034
polyethylene tube catnr. 5141 pump tube 0.32 ml/min. catnr. 3027
polyethylene tube catnr. 5142 pump tube 0.80 ml/min. catnr. 3030
sleeves catnr. 5400 pump tube 0.16 ml/min. catnr. 3025
sleeves catnr. 5401 pump tube 0.60 ml/min. catnr. 3029
sleeves catnr. 5406

MODULE COMPONENTS (for cartridge with electrical heating)

manifold holder catnr. 25200105 connector catnr. 9220 4x

module catnr. 5107 reactor catnr. 25500951
end block catnr. 5109 clamps small catnr. 5111 3x
inlet connector catnr. 9245 sinkers catnr. 5380
inlet connector catnr. 5246 4x flow cell 50 mm catnr. 6425
glass coil catnr. 5325 filter 660 nm catnr. 6565
glass coil catnr. 5326 3x air wash bottle catnr. SA 5781

REFERENCES

Chemical method (no. 155)

1. Krom, M.,"Spectrophotometric determination of ammonia; a study of modified Berthelot reaction using

salicylate and dichloroisocyanurate", The Analyst, April 1980, Vol. 105, page 305-316.
2. Searle, P.L.,"The Berthelot or indophenol reaction and its use in the analysis chemistry of nitrogen", The
Analyst, Vol. 109, May 1984, page 549-565.
3. ISO 3696:1987, Water for analytical laboratory use. Specification and test methods.
4. ASTM, D1193, Standard Specification for Reagent Water.

Sample preparation (water no. 1.1.3)

1. Environmental Protection Agency, methods for chemical analysis of water and wastes, 1983.
2. Standard Methods for the determination of water and waste water, 17th edition, 1989.
3. ASTM, 1990.
4. International Organisation for Standardization, ISO-5667-3.

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 FLOW DIAGRAM
waste
ml/min
Flow cell 50 mm
Distilled water 0.60 5246 9220 5326 Filter 660 nm

25500951/5300

40°C
Sodium dichloroisocyanuric
acid sodium salt 0.32 5246 9220
Sodium nitroprusside solution 0.16 5246
Sodium salicylate solution 0.32 5246
Air *
Buffer solution 0.80 9245 5325 5326 5326
9220 9220
Sample 0.32

1.60
waste
Sampler

* via air wash bottle (filled with 2.5M sulfuric acid solution)

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