APPLICATION KJELDATHERM + VAPODEST PAGE 1 OF 4

TOTAL NITROGEN IN SOIL

1. Principle
The nitrogen content of the sample is digested in acid solution. The reduction of the nitrate nitrogen is
achieved with Devarda's alloy. The digested sample is made alkaline with caustic soda. The thus freed
ammonia is separated by distillation, received in boric acid and determined volumetrically.

2. Method and Application area

Based on
 German Standard Methods for the examination of water, waste water and sludge; general measures of
effects and substances (group H), determination of bound nitrogen, method after reduction with Devarda's
alloy and catalytic mineralization (H28), DIN 38409, Part 28, April 1992
 Chemical Laboratory Research, Determination of the Total Nitrogen content in Soil:
DIN 19684, partl 4, Feb. 1977

Type of Sample Amount of Sample

Soil 2 - 10 g, depending on the humus content
Sludge 1 - 2 g wet from the original sample
Compost 1-5g

3. Chemicals
Quality: p.a.
Water: demineralised or distilled
3.1. Sulphuric acid H2SO4 98% at least
3.2. Catalyst tablets Kjeltabs CX, cat. no. 12-0328
3.3. Caustic soda NaOH 32%
3.4. Boric acid H3BO3 2%
3.5. Indicator solution M5 (Merck) or similar
3.6. Sulphuric acid H2SO4 c = 0.05 mol/l, alternatively HCl c = 0.1 mol/l,
for low contents sulphuric acid H2SO4 c = 0.005 mol/l
3.7. Devarda's alloy

4. Instruments
4.1. Analytical balance (0.001 g)
4.2. Kjeldahl digestion block KJELDATHERM, TURBOTHERM or flask heater for Kjeldahl flasks with wide
neck opening
4.3. TURBOSOG scrubber, cat. no. 12-0057
4.4. VAPODEST distillation system
4.5. Burette, 50 ml nominal capacity, with a scale on 0.05 ml or titrator (not necessary with VAP 50s) or
pH-meter with combined electrode

5. Analysis
5.1. Sample Preparation and Digestion Chemicals
The prepared samples are weighed in weighing paper and put into the digestion flask. Then the chemicals
are added. Any sample residue at the glass wall is washed down into the flask using sulphuric acid (3.1).
Be careful with soil samples rich in carbonate, as they tend to foam, especially directly after adding the acid
and at the beginning of the digestion. Samples with a high organic content should be watched extra carefully.
A pre-reaction in a fume hood at moderate warming might be helpful.

Chemicals per sample:

Sulphuric acid (3.1.) 20 ml
Devarda's alloy (3.7.) 0.2 g
Kjeltabs (3.2.) 2

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TOTAL NITROGEN IN SOIL

5.2. Digestion with KJELDATHERM

When working with a KJELDATHERM system with 250 ml digestion tubes, the following digestion parameters
are recommended in connection with a VARIOSTAT controlling unit:

Time [min] Temperature [°C] Comments

30 120 Dehydration of the sample and pre-reaction
30 170 Carbonization of the sample and solid black foam
45 280 Further reaction
90 400 White fume forms, solution turns translucent*

When working with unproblematic samples, the sample with the digestion mixture can be put directly into the
preheated block:

Time [min] Temperature [°C] Comments

45 400 The digestion tubes are placed into the pre-heated
block; period until the sample turns translucent*
45 400

* Due to undiluted content of the soil, like e.g. silicates or oxides, the solution may become turbid.

5.3. Digestion with TURBOTHERM

When working with a TURBOTHERM system with 12 x 250 ml digestion tubes, the following parameters are
recommended:

Time [min] Power [%] Comments

20 100 Heating time until the digestion solution boils
70 70 - 80 After 20 - 30 minutes the digestion solution
should be translucent

Recommendation to heat excessively foaming samples (230 V):

Heating step Power % Time min

1 100 5
2 0 5
3 100 5
4 0 5
5 100 5
6 0 5
7 65 120

This program can only be used as a guideline. The problem of excessive foaming at the beginning of the
digestion can be solved with heat intervals. It is important that no black particles remain at the glass’ walls.
The reflux line of the sulphuric acid should not reach the exhaust manifold. When running the first digestion,
it is advisable to watch the samples in order to be able to react if heavy foaming should occur. In this case,
the insert rack must be taken out of the digestor.
However, it is important to continue the digestion process for at least 90 minutes after the digestion solution
has turned translucent and to keep the sulphuric acid boiling. The cooling period after taking out the insert
rack should be at least 30 minutes; make sure that the scrubber continues working during that time.
This program is adequate for 230 V; since the power depends very much on the voltage, a change of the
program might be advisable.

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TOTAL NITROGEN IN SOIL

5.4. Digestion with Flask Heater

For working with flask heaters with 500 or 750 ml Kjeldahl flasks with enlarged neck the following settings are
recommended:

Time [min] Power setting Comments

20 3 Heating time until the digestion solution boils and
white fume forms
70 1.5 After 20 - 30 minutes the digestion solution should
be translucent, sample residues should be washed
back into the flask with sulphuric acid

5.5. Suction of the Digestion Gases with TURBOSOG

During the entire digestion time the TURBOSOG scrubber should work. About 1200 ml of a 15 % caustic-
soda solution are recommended for the washing bottle. This amount is sufficient to neutralize digestion gases
of about 60 digestions. The cooling period after lifting the insert rack or after turning off the heating should be
about 30 minutes, during this time the scrubber should continue working.

5.6. Distillation with VAPODEST

After the digested sample has cooled down, water steam distillation is performed according to the following
program:

Program parameters VAP 10/s VAP 20s VAP 30s VAP 45s VAP 50s
1) 1)
H2O Addition ~90 ml ~90 ml ~90 ml ~90 ml ~90 ml
NaOH Addition ~80 ml ~80 ml ~80 ml ~80 ml ~80 ml
Reaction Time - 0s 0s 0s 0s
Distillation Time 240 s 240 s 240 s 240 s 240 s
Steam Power 100 % 100 % 100 % 100 % 100 %
1) 1) 1)
H3BO3 Addition 70 - 80 ml 70 - 80 ml 70 - 80 ml 70 - 80 ml 70 - 80 ml
Suction Sample manual manual 30 s 30 s 30 s
Suction Receiver manual manual manual 30 s 30 s
2)
Titration manual manual manual automatic automatic
Calculation manual manual manual manual automatic
1)
All activities or additions that have to be done manually are written in italic print.
2)
external titrator

5.7. Titration (automatic with VAP 50s)

About 3 - 4 drops of the mixed indicator M5 (3.5.) are added to the distillate which is then titrated with
standard solution (3.6.) until the colour changes from green to grey/violet.
Should the end-point determination be done with a pH meter or a titrator, no mixed indicator is necessary.

5.8. Blank Value

In order to determine the blank value, the analysis (digestion and distillation) is run without sample, only with
the recommended chemicals. The consumption of standard solution is to be taken into account when the
calculation is done.

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TOTAL NITROGEN IN SOIL

6. Calculation

1.4007  c  (V - Vb)
%N=
E

+
c - H ion oncentration of the titration solution [mol/l]:
sulphuric acid 0.05 mol/l: c(H+) = 0.1 mol/l
hydrochloric acid 0.1 mol/l: c(H+) = 0.1 mol/l
V - consumption of titration solution - sample [ml]
Vb - consumption of standard acid solution - blank sample [ml]
E - initial sample weight [g]

7. Comments
Using the Kjeldahl method and the water steam distillation, the concentration of ammonium, nitrate and of the
organically bound nitrogen can be determined.
The sum of these three nitrogen compounds corresponds to the total N-content of a sample:

Total N = ammonium content + nitrate/nitrite content + organically bound nitrogen

The respective compounds can be determined after the following procedure:

First, the sample is homogenized and split into three equal parts.
The ammonium content is determined by water steam distillation from a buffer solution (also see application:
C.2.2. Ammonium in Aqueous Samples).

Then, the nitrate/nitrite content is determined.

The nitrate-nitrogen of the sample is reduced using Devarda's alloy and is distilled as ammonia (also see
application: C3. Nitrate in Aquaeus Samples and Eluates).
The ammonium content is detected at the same time and must be deducted from the result.

After that, the total N is determined with Devarda's alloy, following the procedure described above.

The portion of organically bound nitrogen can be determined by deducting the respective nitrogen portions.

Determination of the organic nitrogen content in soil:

The procedure can be compared to the one used for the total-N determination, with the exception of
Devarda's alloy which is not used in this case. All other things are identical: the relevant data for the sample,
program parameters and the instruments.
Since the ammonium is detected with this method at the same time, its content must be known to be
deducted from the result.

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