J. agric. Engng Res.

(1991) 49, 197-208

The Fertilizer Value of Agricultural Manure: Simple Rapid

Methods of Assessment
SERGIO PICCININI; GIUSEPPE BORTONE

Centro Ricerche Produzioni Animali (Research Centre for Animal Production), Via Crispi, 3-42100 Reggio
Emilia, Italy

(Received 2 April 1990; accepted in revised form 25 November 1990)

This paper presents the results of a series of analytical tests performed on pig and dairy cattle
manure in order to establish the extent of the correlation between: dry matter (TS) and
specific gravity (SG); TS and total Kjeldhal nitrogen (TKN) and total phosphorus (Pt); SG
and TKN and Pt. In addition, two N-meters for field use were also used to estimate the
ammonium (NH,-H) content. All the variables (TS, SG, TKN, Pt, NH,-N) show a high index
of correlation for both the pig and dairy cattle slurry and the linear relations applied proved
adequate in all cases. Though the precision of the equations is not very high, the estimate for
TKN and Pt content, obtained from the relationship between the SG and these elements is
nevertheless acceptable for practical farm use of animal manure.

1. Introduction
Agricultural waste is extremely variable in its composition and it is therefore difficult to
estimate its fertilizer value accurately before spreading. Chemical analyses using standard
laboratory methods are accurate but take time are costly and not practical for most
farms.
Fast, simple field tests that can be used by farmers are needed to give adequate
estimates of the fertilzer elements (in particular nitrogen) and this would be a
considerable advantage in deciding the rate of application of manure to meet crop needs.
There would be both economic advantages (savings on fertilizers) as well as environmen-
tal advantages (a reduction in the risk of leaching and run off of the nutrients).
Researchld has shown that there is a statistically significant correlation between the TS
and fertilizer elements in agricultural manure, particular pig and cattle. Research ld has
also shown a significant correlation between TS and SG of manure. Simple density
measurements would help to establish the content of dry matter and from this the content
of fertilizer elements. A correlation between SG and fertilizer elements has also been
found.
This paper presents the results of a series of analytical tests performed on pig and dairy
cattle manure in order to establish, under farming conditions in Italy, the correlation
between TS and SG (for this, both a normal hydrometer and one calibrated in dry matter
were used); TS and TKN and Pt; and SG and TKN and Pt. In addition two N-meters
suitable for field use were also tested in order to measure the NH4-N content of manure.
The aim was to check the precision, accuracy and reliability of such instruments and
compare with standard laboratory analyses.

2. Materials and methods

Analyses were carried out on pig and dairy cattle manure. For pig slurry, 222 samples
were tested with a dry matter content in the range O-4-12%. The samples were taken
from 21 farms including all the different kinds of pig units.
197
198 S. PICCININI; G. BORTONE

Different types of slurry were analysed; raw, after screening, after storage, after
subjecting to aerobic treatment and after anaerobic digestion in mesophilic completely
mixed reactors. For dairy cattle slurry (slurry from cattle where bedding is used to a
limited extent only or not at all), 108 samples were tested with a dry matter content in the
range 2-18%. Both raw slurry and slurry after anaerobic digestion in plug-flow type
mesophilic reactors were used. The samples were taken from houses with cubicles and
with mechanical manure removal. The liquid manure samples were collected from
terminal collection pits and/or directly from the scraper lane. The digested slurry samples
were taken from the end pit of two plug-flow type anaerobic digestors installed on two of
the farms under survey.
The following chemical parameters were determined on the pig and cattle slurry
samples: total solids (TS) total Kjeldhal nitrogen (TKN), ammonium nitrogen (NH,-N),
total phosphorus (Pt), and specific gravity (SG).
The samples were homogenized using special equipment before undergoing analysis.
The analytical laboratory methods were carried out according to methods recommended
by APHA’ and FA07. Specific gravity was determined using a normal hydrometer and a
hydrometer calibrated in % dry matter which is known as a Slurry Meter.ls5 During
analysis particular attention was paid to the previous homogenization and mixing of the
sample, and the choice of a cylinder only slightly higher than the instrument itself for
containing the slurry. Readings were taken within a few seconds of immersion in the
slurry in order to avoid errors due to the sedimentation process which is especially fast in
pig slurry. Ammonium nitrogen was also determined using two simple field
instruments:*”
The Agros nitrogen meter* was developed in 1983 by Agros, a Swedish company. It
consists of a stainless steel container with an airtight lid in which the slurry and the
reagent (calcium hypochlorite) are placed using special measuring cups; the ammonium
reacts with the chlorine to give gaseous molecular nitrogen and a pressure gauge, already
calibrated in kg of N/m3 of slurry, registers the pressure that has developed. The reaction
that takes place is as follows.
3Ca02C12 + 4NH: + 40H-+ CaCl, + 2N2 + lOH*O
The quantity of nitrogen may be deduced from the relationship
PV = nRT,
where P = pressure, V = volume, n = number of moles of Nz, R = gas constant, T=
absolute temperature.
Since R, V and T are constant the pressure is proportional to the molecular nitrogen
formed.
The Quantofix n-volumeterg was developed by the Rimu-Luftungstecmnik Company in
the Federal Republic of Germany. The basic principle is the same as for the previous
instrument. The differences are the construction materials (plastic instead of stainless
steel), the method of measuring the pressure (a column of water), the reagent used,
sodium hypochlorite (NaOCl, 160 g active Cl/l), mixed using a ratio of 5 : 1 with a 30%
NaOH solution.
The reaction equation is as follows:
3NaOCl+ 2NH: + 20H-+ 3NaCI + 5Hz0 + N,
Ammonium nitrogen of a fixed volume of slurry is oxidized by the reagent to gaseous
molecular nitrogen (N2) which displaces an equal volume of water from the base
container in the metric cylinder, whose scale is directly calibrated in kg NH4-N/m3 of
slurry.
ASSESSING AGRICULTURAL MANURE 199

3. Results and discussion

3.1. Correlation between TS and SG

The results from the examinations made of 102 samples of pig slurry and 93 samples of
cattle slurry are shown plotted in Figs 1 and 2. Regression equations have been fitted and
the 95% confidence limits are shown; the significance of these will be further explained.
The two regression equations proved highly significant (p < O-01) and show correlation
coefficients (r) of 0.94 and 0.88 respectively. Both regressions, however, show a
precision no better than 22%. Precision in this case refers to the repeatability of the
measurement calculated on the basis of the ratio between the standard error of the
estimated variable (total solids) and its average value. This means that when the equation
of the straight line regression is used to estimate the total solids content of the slurry, it is
based on only one determination of specific gravity, and the data calculated is liable to a
minimum error of 22% (see in Figs 1 and 2 the two external lines representing the 95%
confidence limits). In order to reduce such an error, it is necessary to carry out further
determinations of specific gravity on the same slurry sample, so that the average value
obtained is liable to less error, as shown in the Figs I and 2 by the two internal lines
representing the 95% confidence limits.

1.00 1.01 1.02 1.03 1.04 1.05 1.06

Specific gravity

Fig. 1. Pig slurry: regression between total soli& (TS%) and specec gravity (SG)
Regression equation:
TS% = -221.6 + 221.0 SG (p < 0.01)
r = O-94
St. err. of the estimation = O-75
SG TS%
Average. 1.018 348
St. Dev. 9.2 x 1O-3 2.22
Min. 1.006 0.36
Max. l-053 12-07
Number of
points 102 102
200 S. PICCININI: G. BORTONE

16 -

. .
0 -
2
VI- 12-
.x
/
I ,’
i -
I,” .
38-

0 ’ ’ I.’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’
1.00 1.02 1.04 1.06 1.08 1.10
Specific gravity

Fig. 2. Cattle slurry: regression between total solids (TS%) and specific grauiv (SC)
Regression equation :
TS% = -215.6 + 216.1 SG (p < 0.01)
r = 0.88
St. err. of the estimation = 2.11
SG TS%
Average. 1.040 9.46
St. Dev. 0.019 4.32
Min 1.009 1.98
Max l-092 18.07
Number of
points 93 93

The hydrometer (Slurry Meter), already calibrated in % total solids, was also used to
experiment on 49 samples of pig slurry and 63 samples of cattle slurry.
The results obtained confirm the good correlation that exists between SG and %TS. In
fact the %TS data registered by the Slurry Meter show good correlation with the %TS
data determined using standard laboratory methods, as can be deduced from the
straight-line regression:
(a) Pig slurry
TS%(lab.) = -0.749 + 0.991 TS% (Slurry Meter) p < 0.01
r = 0.93
(b) Cattle slurry
TS% (lab.) = -0.306 + 1.107 TS% (Slurry Meter) p < 0.01
r = 0.93
The two regression equations show excellent agreement between the two methods of
measuring the TS (standard method and Slurry Meter) showing the high accuracy level of
the calibration of the Slurry Meter.
ASSESSING AGRICULTURAL MANURE 201

It needs to be pointed out, nevertheless, that the analysis of the two regressions has
reconfirmed the low precision level and repeatability of the measurements (>29% for pig
slurries and >21% for cattle slurries) when only one determination is made on a sample.

3.2. Correlation between TS and TKN and Pt

The results for TS versus TKN with regression lines fitted and 95% confidence limits
from the analysis of 218 samples of pig slurry and 76 samples of cattle slurry are shown in
Figs 3 and 4 respectively. The regression is highly significant for pig slurry (p < O-01) with
a correlation coefficient r = 0.90. Though the regression is equally significant for cattle
slurry (p < 0.01) the correlation coefficient is decidedly lower (r = 0456).
Both regressions show a low level of precision no better than 27% for pig slurry and
32% for cattle slurry.
Results for TS versus Pt with regression lines fitted and 95% confidence limits
determined from the analysis of 168 pig slurry samples and 67 cattle slurry samples are
shown in Figs 5 and 6 respectively. The two regression equations emerge as being highly
significant (p <O-01) and their correlation coefficients are O-88 and O-82 respectively.

‘*C

Total solids,glkg

Fig. 3. Pig slurry: regression between total Kjeldhal nitrogen (TKN) and total solids (TS)
Regression equation :
TKN, g/kg = 1.095 + 0.060 TS, g/kg (p < 0.01)
r = O-90
St. err. of the estimation = 0.93

TS, TKN,
g/kg g/kg
Average. 3844 3.408
St. dev. 32.35 2.141
Min 3.57 0.609
Max 12264 10.85
Number of
points 218 218
202 S. PICCININI: G. BORTONE

12 , , , , I, I, I I,, I I,, I I,

.
2 10 -
0-l
z - ,..”
[JI a- l
e - .
. ..
c
c _ .’

..’
..
0 IIll.IIIIL~lIIII’f”
0 40 80 120 160 200
Total solids, g/kg

Fig. 4. Cattle slurry: regression between total Kjeldhal nitrogen (TKN) and total solids (TS)
Regression equation :
TKN, g/kg = 1.554+ 0.0216TS, g/kg (p < 0.01)
r = O-66
St. err. of the estimation= 1.21
TS, TKN
g/kg g/kg
Average. 101.79 3.750
St. dev. 49.01 1.610
Min 19.08 1.46
Max 180.67 10.18
Number of
points 76 76

Both show a low precision level, no better than 40% for pig slurry and 23% for cattle
shIy.
In Fig. 6 a smaller scatter around the straight-line regression for samples with a total
solids content of less than 8% (anaerobically digested cattle slurry) can be seen. One
possible explanation for this is the lower content of cellulose materials (straw) in these
last samples as compared to the raw cattle slurry (the samples with a total solids content
higher than 8%). For management reasons the loading of anaerobic digestors is, in fact,
done using slurry which does not contain coarse fragments.
The correlation between TS and the nutrients was also examined within a group of
slurry samples from pig and dairy cattle, homogeneous both in terms of age and the type
of treatment. Comparison of the various straight-line regressions did not indicate
significant differences (parallel tests).
The direct ratio between SG and TKN and Pt was also looked into on the basis of
previous work2C and for the interest created from a practical point of view.
A significant correlation was found both for the pig and cattle slurry (p ~0.01) even
though the corresponding correlation coefficients were shown to be less than those found
for the regression equations between TS and TKN and Pt. The precision of the estimates
ASSESSING AGRICULTURAL MANURE 203

6 ,,,,,,,,,,,,,,
. 1

Total solids. g/kg

Fig. 5. Pig slurry: regression between total phosphorus (Pt) and total solids (‘IS)
Regression equation :
Pt, g/kg = 0.032 + 0.0312TS, g/kg @ <O-01)
r = 0.88
St. err. of the estimation = O-57
TS, Pt,
g/k dkg
Average. 37.52 1.423
St. dev. 32.21 l-180
Min 3.57 O-106
Max 12264 5.648
Number of
points 168 168

is also no better. The equations of the straight-line regressions calculated are as follows:
(a) Pig slurry
TKN (g/kg) = -67.40 + 69.19 SG p < 0.01
n = 54 r = 0.75 standard error estimate = 25% (1)
Pt (g/kg) = -46*61+ 46.88 SG p co-01
n = 48 r = 0.75 standard error estimate = 46% (2)
(b) Cattle slurry
TKN (g/kg) = -44.61+ 46.22 SG p < 0.01
n = 62 r = 0.56 standard error estimate = 38% (3)
Pt (g/kg) = -14.05 + 14-40 SG p < 0.01
n=54 r = 0.74 standard error estimate = 27% (4)
204 S. PICCININI; G. BORTONE

2.4 , , , , , , , , , , , , , , ,

0 I,.. .,I I I I I I I I I I,, I I I ,-

0 40 80 120 160 200
Total solids,g/kg

Fig. 6. Cattle slurry: regression between total phosphorus (Pt) and total solids (TS)
Regression equation :
Pt, g/kg = 0.3698 + 0.007 TS, g/kg @ < 0.01)
r = 0.82
St. err. of the estimation = O-24
TS, Pt,
g/kg dkg
Average. 99.38 1.050
St. dev. 50.84 0.420
Min 19.80 0.270
Max 180.67 2.040
Number of
points 67 67

3.3. Field application of results

The significant linear regressions found could be used to estimate the Pt and TKN in
pig and cattle slurry. Specific gravity of the slurry is measured using a hydrometer, the
percentage of dry matter is calculated using the respective equation. Then the nitrogen
and phosphorus concentrations are determined using the regression equations between
dry matter and nutrients. This method, however, is inadvisable in as much as it is subject
to a high level of error on account of the combination of poor precision levels or the
repeatability determined in all the linear regressions examined. It is far more advisable to
use the linear regression found between specific gravity and fertilizer elements. This
avoids a series of calculations and thereby reduces the margin of error when estimating
TKN and Pt even if the relative correlation coefficients and the relative precisions both
for pig and cattle slurry are not better than the direct correlations between TS and SG
and between TS and TKN and Pt. Although the margin of error remains rather high [of
Eqns (11, (21, (3) and (4)l I‘t would be more acceptable within the limits of the use of
agricultural manure.
ASSESSING AGRICULTURAL MANURE 205

Laboratory ammonium nitrogen, mg/l

Fig. 7. Pig slurry: comparison of Agros meter and standard laboratory method
Regression equations:
NH,-N(Ag) = 83.94 + 0.922NH,-N (Lab) @ < 0.01)
r = 0.96
St. err. of the estimation = 242.46
NH,-N (Ag), NH,-N (Lab),
mgll w/l
Average. 1959 2033
St. dev. 854 888
Min 200 196
Max 4800 4200
Number of
points 64 64

Hydrometers with a scale already calibrated with the value of fertilizer elements would
give an instant reading without the necessity to consult conversion tables.

3.4. Agros-nitrogen merer and Quantujix N-uolumeter

3.4.1. Agros-nitrogen meter
Pig slurry samples (63) and cattle slurry samples (13) were analysed using this
instrument. Figs 7 and 8 show the results and straight-line regressions with 95%
confidence limits for NH4-N determinations with the Agros meter versus NH.,-N
determined using standard methods for pig slurry and cattle slurry respectively. The
regression equations are highly significant (p < O-01) and show a correlation coefficient of
0.96 and 0.94 respectively. For pig slurry, statistical tests were carried out (Student’s t
test) on the value of the intercept which did not prove to be significantly different from 0,
and on the slope which did not differ significantly from one. This indicates the high
accuracy of the instrument excluding the existence of systematic errors. The precision of
the estimations made with the Agros meter proved high (212%).
206 S. PICCININI; G. BORTONE

0 1000 2000 3000 4000 5000 6000

Laboratory ammonium nitrogen,mgll

Fig. 8. Cattle slurry: comparison of Agros meter and standardlaboratory method

Regression equation :
NH,-N(Ag) = 292.58+ 1.11NH,-N (Lab) (p < 0.01)
r = 0.94
St. err. of the estimation= 462.24
NH,-N (Ag), NH,-N (Lab),
mg/l mg/l
Average. 2469 1963
St. dev. 1269 1074
Min 1300 961
Max 5700 5005
Number of
points 13 13

For cattle liquid manure, statistical tests were carried out (Student’s t test) on the value
of the intercept which did not differ significantly from 0, and on the slope value which did
prove to be significantly different from one (p ~0.01). When used with the cattle liquid
manure, the instrument is therefore considered to be less accurate and affected by a
systematic error of about 20%. As such, the application of a correction factor represented
by the straight-line regression equation is considered appropriate. The level of precision
(320%) proved to be less than for the pig slurry. The lower accuracy and precision found
for the cattle liquid manure are probably attributable to the high straw content which
hinders reliable sampling and analysis.

3.4.2. Comparison between the Agros nitrogen meter and Quantojk N-uolumeter
A comparison was also made between the Agros meter and the Quantofix which has
been available on the market only more recently. A total of 16 pig slurry samples were
used from which the N&-N content was determined using both the two field instruments
and standard laboratory techniques. Table 1 shows the results of the N&-N calculations
carried out on the 16 pig slurry samples using the three methods.
ASSESSING AGRICULTURAL MANURE 207

Table 1
NH,-N values determinated by three methods on 16 pig
slurry samples

N&N (w/l)

Standard Agros Quantotix

method meter N-volumeter
Observations made 16 16 16
Average 1414 1347 1372
Standard deviation 719 715 876
Min. 773 600 400
Max. 3360 3200 4ooa

The equations of the two straight-line regressions of the NH,-N calculated using the
standard laboratory method versus the NH,-N calculated using the two field instruments
were as follows:
NH4-N (standard, mg/l) = 78.47 + 0.992 NH4-N (Agros, mg/l)
n= 16 r = 0.99 p <o-o1
NH4-N (standard, mg/l) = 313.33 + O-802 NH,-N (Quantofix, mg/l)
n= 16 r = 0.98 p < o-01
The Quantofix N-volumeter proved less accurate when compared to the Agros, showing
a systematic error of about 5%. Comparison of precision levels (Fisher test) did not show
any significant differences; both instruments gave a result of ll-12% precision. The two
instruments tested also proved to be simple to use as well as reliable from a maintenance
and hardwearing point of view.
The trend of the NH,-N/TKN ratio in pig slurry was also studied because both the
ammonium nitrogen data and the total nitrogen data are important in the utilization of
agricultural manure. A total of 206 samples were examined and the following results were
found:
average value NH,-N/TKN = 0.65
standard deviation = O-12
It would, therefore, be possible to arrive at the TKN value by dividing the NH4-N
determined using the Agros meter by the coefficient 0.65. This value, however, is subject
to a high level of error attributable to the combination of the errors of the numerator and
the denominator. The most acceptable approximation would be to obtain the TKN data
directly from the TKN straight-line regression equation determined in the laboratory
VU-SW the NHrN determined by the Agros meter.
The equation of this straight-line regression is as follows:
TKN (kg/m3) = 0.347 + l-439NH4-N (Agros, kg/m3) p < o-01
n = 63 r = O-81, standard error estimate = 29%

4. Conclusion
AI1 the variables studied (TS, SG, TKN, NH,-N, Pt) show a high linear correlation-for
both the pig and dairy cattle slurry. Poor precision was found, however, in straight-line
regressions between TS and SG, between TS and fertilizer elements and between SG and
fertilizer elements. The estimate for nitrogen and phosphorus content, obtained from
208 S. PICCININI; G. BORTONE

the existing ratio between these elements and specific gravity was nevertheless acceptable
within the limits of agronomic use of animal manure.
It should be remembered that the SG data will prove representative of the total volume
of slurry contained in the storage tank only if the slurry sample, or samples, are taken
after careful mixing and homogenization of the tank contents.
The two field instruments tested, the Agros nitrogen meter and the Quantofix
N-volumeter were considered useful for determining the ammonium-N content on
account of their good agreement with standard laboratory analyses. A previous mixing of
the slurry in the storage tanks is nevertheless also required for their use.

References
’ Tunney, H. Dry matter, specific gravity, and nutrient relationshipsof cattle and pig slurry. In:
Engineering Problems with Effluents from Livestock. (Hawkins, J. C., ed.) Proceedings.
C.E.C. Seminar, Cambridge,England. Luxembourg, PublicationsC.E.C. 1979
’ Cbeschei, G. M.; Westeman, P. W. Rapid methodsfor determining fertiliser value of livestock
manures. American Society Agricultural Engineers, Paper N”84-4082, presented at ASAE
summermeeting, University of. Tennessee,Knoxville, June 1984
’ Tunney, H. Manure nutrient composition: rapid methodsof assessment.In: Processingand Use
of Organic Sludge and Liquid Agricultural Wastes. (I’Hermite, P., ed.) Proceedingsof 4th.
International SymposiumRome, Italy, 8-11 Oct. 1985
’ Tunney, H. Field testsfor estimatingfertiliser value of agricultural wastes.In: Agricultural Waste
Management and Environmental Protection. (Walte E.; Szabolcs, I., eds). Proceedings4th
International SymposiumCIEC, Braunschweig,F.R.G., 11-14 May 1987
5 Tunney, H.; Bertrand, M. Rapid field testsfor estimatingdry matter and fertiliser value of animal
slurries. In: Agricultural Engineering. (Dodd, V. A.; Grace, P.M., eds) Proceedingsof the 11th
International Congresson Agricultural Engineering, Dublin, 4-8 September 1989
’ American Public Health Association (APHA). Standard methodsfor examination of water and
wastewater1985
’ Food and Agriculture Organisatioo (FAO). Recommendedanalytical methods for first priority
componentsof liquid manure. Intermediate report of Subnetwork 4, Budapest, 1980
’ KjeUerup, V. Agros Nitrogen Meter for estimation of ammonium nitrogen in slurry and liquid
manure. In: Efficient land useof sludgeand manure. (Dam Kofoed, A., ed.) Barking: Elsevier
Applied SciencePublishers,1985
9 Khss, J.; Weber, W. Method for rapid determination of ammonianitrogen in animal slurriesand
sewagesludge.In: Agricultural Waste Management and Environmental Protection. (Welte, E.;
Szabolcs, I., eds) Proceedings4th International Symposium CIEC, Braunschweig, F.R.G.,
11-14 May 1987.