New Zealand Journal of Agricultural Research

ISSN: 0028-8233 (Print) 1175-8775 (Online) Journal homepage: http://www.tandfonline.com/loi/tnza20

Sources of error in advisory soil tests

N. S. Mountier , J. L. Griggs & G. A. C. Oomen

To cite this article: N. S. Mountier , J. L. Griggs & G. A. C. Oomen (1966) Sources of error
in advisory soil tests, New Zealand Journal of Agricultural Research, 9:2, 328-338, DOI:
10.1080/00288233.1966.10420784

To link to this article: http://dx.doi.org/10.1080/00288233.1966.10420784

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 328

SOURCES OF ERROR IN ADVISORY SOIL TESTS

I. Laboratory sources
By N. S. MOUNTIER,* J. L. GRIGG,+

AND

G. A. c. OOMENt
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(Received 29 November 1965)

ABSTRACT

Soil tests discussed are for pH. calcium, potassium, and phosphate.
The variation between values of a soil sample tested at different
laboratories was found to be much greater than when duplicate tests
were made in the same laboratory on the same day. This was due partly
to a factor that was constant between laboratories and partly to a factor
that fluctuated. The fluctuating factor must have been caused by long-
term variation within a laboratory, and this component of variation must
normally be included when the precision of a soil test value is estimated.
Estimates of the sizes of these components and their relationship to the
soil test value are made.

INTRODUCTION
The N.Z. Department of Agriculture has two soil testing laboratories,
one in Hamilton in the North Island, and the other in the South Island at
Mosgiei. Prior to 1961 the S.L laboratory was at Winchmore. near
Ashburton. At each of these laboratories soil testing is carried out for
farmers, market gardeners, and for the experimental work of the
department. On farms the individual paddock is the unit sampled,
in market gardens it is the area under one crop. In all cases the samples
are taken by an advisory officer of the Department of Agriculture and
forwarded to the appropriate laboratory. The results of the tests are
sent back to the advisory officer for interpretation. The procedure used
by the advisory officer in sampling in the field will be discussed in the
third part of this series.
* Biometrics Section, Department of Agriculture, Box 1500, Wellington. Present
address: cl Lincoln College, Canterbury.
t Taieri Soil Research St-tiou, Taieri Agriculture Centre, Department of
Agriculture, Private Bag, Mosgiel.
t Ruakura Agricultural Research Centre. Department of Agriculture, Private Bag,
Hamilton.
N.Z. Jl agric. Res. 9: 328-38
 N. S. MOUNTlER, J. L GRIGG, AND G. A. C. OOMEN 329

METHODS
Prior to 1959 each laboratory had its own system of checking,
but these systems operated independently. In 1959 a system of inter-
change of samples was commenced: every week each laboratory selected
at random one of the regular samples, dried and ground it, then took
two bags or samples from it, and sent one bag to the other laboratory.
Each laboratory then took duplicate sub-samples with the appropriate
volume measure and analysed for each of the four regular tests.
The methods used for soil testing have been deliberately selected
for speed and simplicity so that they may be carried out by laboratory
technicians trained on the job. Selection of the methods used has been
described by Davies (1952 ) and Hogg (1957). Labour-saving devices
used for handling many samples at a time were described by Hogg and
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Waters (1954).
A brief description of the tests as carried out at Mosgiel is given
below. There may be minor differences of procedure at Hamilton.

1. Preparation of soil samples

The samples as received are dried in a current of air at a tempera-
ture not exceeding 35c, and crushed in a Rukuhia soil grinder (Waters
and Sweetman 1955) to pass a 2 mm round hole sieve.

2. Determination of pH
A 12 ml volume of soil is mixed with 30 ml of distilled water,
allowed to stand overnight in a constant temperature room at 25c,
and the pH measured with a glass electrode. The Hamilton Laboratory
has used an Electronic Instruments Ltd. Model 23A direct reading pH
meter during all four years of this study. At Winchmore in 1959 and
1960 a Cambridge pH meter was used, but on moving to Mosgiel an
instrument of the same model as the one at Hamilton was brought into
use. pH readings are recorded to the nearest 0.1 unit.

3. Determination of calcium and potassium

Prior to 1960 these elements were extracted with Morgan's sodium
acetate-acetic acid buffer (Lunt, Swanson, and Jacobson 1950). From
January 1960 this method was superseded by an extraction with neutral
normal ammonium acetate.
a. Morgan's method. A 4.4 mi volume of soil is shaken with 10 ml
of sodium acetate-acetic acid buffer for one minute. The suspension
is filtered and the calcium and potassium content of the filtrate measured
by a double beam flame photometer using a Beckman atomiser and
burner with an oxy-acetylene flame.
b. Ammonium acetate method. A 4.4 ml volume of soil is shaken
with 20 ml of neutral normal ammonium acetate for two minutes. The
suspension is filtered and flamed in a flame photometer fitted with an
E.E.L atomiser and a Lundegardh-type burner with an air-acetylene
 330 Sources of error in advisory soil tests. I.

flame. In each case the galvanometers of the flame photometers are

calibrated to read directly in "test units" so designed that the range
encountered in the normal run of soils is from 0 to 20 units. The
actual concentrations of these test units in the extracts are:-
Calcium Potassium
Morgan's method: p.p. 20,000 p.p. 200,000
Ammonium acetate method: p.p. 40,000 p.p. 250.000.
These different units were decided on in order to keep the reported
test values approximately the same because of the wider soil : solution
ratio used with ammonium acetate, and the fact that this extracts
relatively more potassium.
Readings are made to the nearest whole unit.
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4. Determination of phosphate
The method of Truog (1930) is used with modifications. A 2.2 ml
measure of soil is shaken for 30 minutes with 400 ml of 0.002 N
sulphuric acid buffered to pH 3.0 with ammonium sulphate. The sus-
pension is filtered and phosphate determined by the molybdenum blue
method of Truog and Meyer (1929). The intensity of the blue colour
is measured in an absorptiometer directly calibrated in test units. One
test unit = one part phosphorus per 50,000,000 of extract. To minimise
changes in the calibration curve all extractions and colorimetry are
carried out at 25c. Readings are taken to the nearest unit.
In practice, samples are tested in batches of 50 for pH, calcium,
and potassium, and 40 for phosphate. Every fifth sample is tested in
duplicate to show up inconsistencies within a batch, such as meter drift.
In addition, a standard check sample is tested at least once in each
batch. Buffer solutions are used to set the pH meter, and standards for
setting the flame photometers and for checking the calibration curves.
Laboratory errors may be introduced in several ways, of which
the most obvious are:-
Errors in the volumetric sub-sampling of soils in the laboratory.
Rounding off readings to the nearest whole number.
Human error.
Changes in the shape and position of the calibration curves, more
particularly in the case of phosphate.
On the other hand, the rate of atomisation in the flame photometer
and changes in flame temperature and photocell response are checked
frequently and therefore are not likely to be of any consequence.

RESULTS AND DISCUSSION

Data collected in the four years 1959-1962 are presented. For each
test, soils were divided into four or five groups according to the mean
test value of the sample, and an analysis of variance as shown on the
next page was carried out on each group:-
 N. S. MOUNTIER, J. L. GRIGG, AND G. A. C. OOMEN 331

Source of variation Degrees of freedom Expected value of mean

square

Soils n-l
Laboratories
Laboratories X soil n-l
Within batch 2n
Total 4n - 1

where n is number of soils in the group.

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This analysis allows us to distinguish the following:-

1. Within-batch variance
aL 2 is the variance between sub-samples of a soil analysed under
virtually indentical laboratory conditions (i.e., analysed in the same
laboratory within minutes of each other).

2. Laboratory by soil interaction

aTL 2 is variance (additional to aI,2) occurring when laboratory
conditions differ slightly (i.e., analysed in different laboratories) but
which is not constant from one soil to another.
In Table I are set out mean values for each laboratory for each
test-group, together with indications of the statistical significance of this
difference (based on a t-test). It can be seen that fairly small but
statistically significant differences exist between laboratories for all tests.
These differences are consistent in sign for each test.
(Since the method of testing Ca and K changed at the beginning
of 1960, data presented in Table 1 and most subsequent tables for these
tests are taken from the three years 1960-62 only. Where 1959 data
for Ca and K have been used they are quoted separately).
Table 2 shows the values of aL 2 and aTL 2 for each test group, and
allows us to see the broad relationship between these components of
variance and the test mean.
The within-batch variance for pH appears independent of the
mean, but there is some indication of a decline in laboratory-by-soil
variance with higher pH values. The other three tests all show an increase
in each variance as the mean value increases. This increase appears
approximately linear for within-batch variance for each of Ca, K, and P,
and also for the laboratory-by-soil component for Ca. In the cases of
the laboratory-by-soil variance for the P and the K test, however, there
is an indication of curvature, and it would seem that here the standard
error (the square root of the variance) is proportional to the mean.
 332 Sources of error in advisory soil tests. f.

TABLE 1. Mean values of each test at each laboratory for different test means

I pH Ca
I

Group I a b c d a b c d e
I I
I 1 I i
N.r. 5.26 5.71 '6.18 6.69 6.7 10.5 14.2 17.9
I 3.4 I
6.83 2.9 , I
1

S.l. ;5.36 5.84 1

6 . 31 1
5.9 9.8 , 13.2 17.4
1 I , i i
Difference 0.10** 0.13** 0.13** 0.14** -0.5* -0.8** -0.7**-1 -0.5
No. of soil I 'I I' I
samples I 52 I 139: 88 28 i 25 ! 87 I 75 29 14
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K P

I I
Group a i b c d e a b c d e
I
I i I
i
N.!. 3.2 5.6 9.7 13.4 18.4 2.7 5.8 8.9 13.7 19.8
S.l. 3.2 6.4 i 10.2 i 14.3 20.0 2.8 6.2 9.4 14.9 20.6
Difference 0.0 0.8** I 0.5* 0.9* i 1.6* 0.1'0.4** 0.5** 1.2**1 0.8
I I
No. of soil I
I j
samples I 29 89 I 58
I
I 42
I
12 81 126 55 19 18

Grouping for pH a < 5.5

b 5.51 to 6.0
c 6.01 to 6.5
d >6.5
Grouping for Ca, a ::; 4
K, P b 4.1 to 8
c 8.1 to 12
d 12.1 to 16
e 16.1 to 25
Note: Ca and K figures from three years 1960-62 only.

If all relationships between variance and mean had been linear, a square
root transformation to make variances independent of the mean might
have had merit, but use of tranformed figures would in any case have
practical difficulties for a group of people accustomed to the present
scale.

Any change through time of laboratory differences or variances

would also be of interest. Table 3 contains the mean values for each
test for each year, and the most notable feature of this table is the change
in the pH difference.
 N. S. MOUNTIER, J. L. GRIGG, AND G. A. C. OOMEN 333

TABLE 2. Variance at different values of the test mean (1959--62)

Group No. of soil 2 Laboratory

samples \ Within batch O'L
by soil O'TL 2
pH
a <5.5 52 0.0016 0.0091
b 5.51-6.0 139 0.0015 0.0060
c 6.01-6.5 88 0.0018 0.0058
d >6.5 28 0.0016 0.0046

Ca (1960-62 only)

a <4 25 0.07 0.22

b 4.1-8 87 0.14 0.51
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c 8.1-12 75 0.24 0.53

d 12.1-16 29 0.42 1.35
e 16.1-25 14 0.39 0.65

Ca (1959 only)

b 4.1-8 30 0.16 0.60

c 8.1-12 23 0.20 0.80

K (1960-62 only)

a <4 29 0.12 0.20

b 4.1-8 89 0.19 0.54
c 8.1-12 58 0.25 1.38
d 12.1-16 42 0.36 2.11
e 16.1-25 12 0.42 3.44

K (1959 only)

b 4.1-8 32 0.08 0.37

c 8.1-12 22 0.27 0.95

a <4 81 0.13 0.22

b 4.1-8 126 0.26 0.36
c 8.1-12 55 0.34 0.62
d 12.1-16 19 0.51 1.14
e 16.1-25 18 0.41 3.20

The North Island pH's were determined under constant temperature

conditions for all four years, but the South Island ones only since 1960.
The marked drop in station difference may be due to this fact, but it
is more likely due to the change in pH meters. There are no obvious
 334 Sources of error in advisory soil tests. I.

TABLE 3. Mean values of each test at each laboratory by years

pH Ca
-~----

1959 1960 1961 1962 1959 1960 1962

_ ... _ _ .. _- 1
1

I
N.l. 5.88 1
5.81 5.83 1
5 .90 8.3 9.1 9.6
I
S.1. 6.06 6.03
5.88 5.98 7.7 7.7 8.3 9.2
1I !
Difference .18** .22**, .05**1 .08** -0.6** -1.4** -0.6** -0.4**
I ' !
I ' I
No. of soil 1 I I
samples 74 63 81 90 I 71 63 77 90
I
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1
!

K P

I I
-- - - - - - - - - -
,
I
1959 I 1960 I 1961 1962 1959 1960 1961 1962
1
I I

N.J. 7.0 7.9 8.1 8.6 6.9 6.5 6.8 6.5

S.l. 1 7.5 7.6 8.8 10.0 7.2 6.7 7.2 7.1
Difference 0.5** -0.3* 0.7** 1.4* 0.3* 0.2 0.4* 0.6**
No. of soil
samples 73 62 77 88 69 61 76 84
_._- - -_._----

trends in the mean levels for the other three tests. Annual figures of
variances are not quoted here, as they show no great fluctuations nor
indications of trend.

For a soil test to be a useful advisory tool, the "critical level" of

the test must be established by field experiments, i.e., the test level below
which a yield response may be expected for a particular crop or pasture,
and above which a response is unlikely. It follows that the soil test
levels for which precision of determination is most important are those
near this critical level. In the units used in this paper the range of
interest lies mainly between 4 and 12 for each of Ca, K, and P tests.

In practice, the North and South Island laboratories service their

own areas, both for the experiments used to calibrate the tests with
respect to yield responses and also for the paddock samples on which
advice is to be given. Hence, any constant over-all difference between
stations as appears in Table 1 is not of great practical importance.

The laboratory-by-soil component of variance has more serious

 N. S. MOUNTIER, J. L. GRIGG, AND G. A. C. OOMEN 335

practical consequences. There are two possible causes for this variance:-
]. It may be due to fluctuations in the test level at either or both
laboratories through time (i.e., an interaction of laboratories and time),
or 2. There could be some tendency for a particular type of soil to
test higher at one laboratory, and another type to test lower (i.e., an
interaction of laboratories and soil type).
Vermeulen (1957) considered this term in his data to be an inter-
action with time, and some such fluctuations might be expected to be
caused by changes in reagents, climatic conditions, and technical staff.
This was investigated further in some testing done in 1963 and 1964 in
which the two laboratories exchanged samples as before, but in addition
each laboratory retested each sample after eight weeks. This allowed
an estimate to be made of the laboratory-by-time interaction where
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time is restricted to an eight-week difference. An analysis of variance

was carried out accord ing to the following pattern:-

Source of variation Degrees of freedom Expected value of mean

square

Soils n -

Laboratories
Soils X laboratories n -

Test V retest within each lab 2

Soils X TVR within lab 2(n - I)

Within batch 4n

where n is the number of soils sampled,

(TL 2 is the within-batch variance as before,
USR 2 is the interaction of soils and time of eight weeks,
and USL 2 is additional variance which will include any true interaction
between soil type and laboratory described in (2) above, but which may
also contain interaction between soil and time interval greater than eight
weeks.
Results of these analyses are set out in Table 4, and it may be seen
that USR 2 is shown to be appreciable in all tests, but that USL 2 is also
of some consequence, especially in the case of the Ca test. It was
possible to examine USR 2 for each laboratory separately, and this made
it clear that the fluctuations that made up this component of variance
occurred at both laboratories.
Sources of error arising from field sampling are substantial, and
these will be discussed in Part III of this series. However, a thorough
knowledge of size of laboratory variation is essential before any true
estimate of precision can be arrived at. It is clear from the present data
 336 Sources of error in advisory soil tests. 1.

TABLE 4. Estimates of variances from retesting soils after eight weeks (1963-64)

Within- Soils by time Other lab

Group batch (8 weeks) !
variance No. of soil
samples
UL 2
0
USR 2 (1SL-
--------- "---- _ _ '0 _ _ _ _ ' _ . _ _ _ _ _ _ _ _ _ _ _ _
----------

pH <5.5 0.0010 0.0036** 0.0021* 25

-5.51-6.0 0.0010 0.0032** 0.0022** 67
6.01-6.5 0.0012 0.0027** 0.0012* 32
>6.5 0.0008 0.0023** 0.0006 14
Ca <4 0.09 0.01 0.06* 8
4.1-8 0.11 0.15** 0.32** 37
8.1-12 0.14 0.28** 1.06** 52
12.1-16 0.34 0.58** 0.93** 29
16.1-25 0.25 0.40** 1.54** 13
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K <4 0.04 0.21** 0.01 7

4.1-8 0.11 0.34** 0.05 49
8.1-12 0.16 0.28** 0.21 ** 47
12.1-16 0.16 0.49* * 0.18 22
16.1-25 0.45 0.31** 0.50* 13
P <4 0.14 0.10** 0.08** 22
-4.1-8 0.20 0.18** 0.12** 63
8.1-12 0.34 0.82** 0.50* 33
12.1-16 0.39 0.98** 0.41 8
16.1-25 1.16 2.70** 0.05 10

* Variance component significant at 5% level.

** Variance component significant at 1% level.

that a realistic estimate of laboratory variance is much greater than the

estimate commonly obtained from duplicate samples carried out at one
time in one laboratory.
In most comparisons of soil test values where tests are not all made
in the same batch it would seem reasonable to use the sum of iTL2 and
iTTL 2 for the laboratory variance. The standard errors obtained from
this sum are given in Table 5, together with the standard errors when
only the "within-batch" component is considered.

CONCLUSIONS
The real laboratory variance of a soil test is much greater than
the estimate obtained from analysing duplicate samples in the same test
batch. A fluctuation of test level through time has been shown to be
substantial.

ACKNOWLEDGMENTS
Thanks are due to Mr E. R. Dearnley for computational assistance
and to the technical assistants at Galloway, Winchmore, and Taieri
Laboratories.
 N. S. MOUNTIER, J. L. GRIGG. AND G. A. C. OOMEN 337

TABLE 5. Standard errors of a determination for different mean test values when:
U) within-batch variation is considered, and (2) long-term variation is also
considered

pH Grouping for pH

Group abc d a ~ 5.5

mean 5.3 5.8 6.2 6.8 b 5.51 6.0
(1) within-batch
only 0.04 0.04 0.04 0.04 c 6.01 6.5
(2) both within-batch
and long-term '0.10 I 0.09 I 0.09 0.08 d >6.5
- - _ . _ , - - - - - - - _...
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Ca 'Grouping for Ca, K, & P

,

-a-~-;--c-I--d--~-'-- a
Group ~ 4
mean 3 6 18 b 4.1 8
(I) within-batch
10 I 14
only 0.26 0.37 0.49 0.65 0.62 c 8.1 12
(2) both within-batch I
and long-term 0.54 0.81 0.88 1.33 1.02 d 12.1 16
e 16.1 - 25

Group a c 1
d e
mean 3 6 I 10 I 14 19
(1) within-batch
only 0.35 0.44 I 0.50 i 0.60 0.65
(2) both within-batch
and long-term 0.57 I 0.85 1.28 1
1.57 1.97
----'-----~.-----c__---------

Group abc d e
mean 3 6 9 14 20
(1) within-batch
only 0.36 0.51 0.58 0.72 1.19
(2) both within-batch
and long-term 0.60 0.79 0.98 1.29 2.65

Note: Ca and K figures from three years 1960-62 only.

REFERENCES
DAVIES, E. B. 1952: Trans. into Soc. Soil Sci. Comm. II and IV: 340-8.
HOGG, D. E. 1957: N.Z. Jl Sci. Technol. A 38: 1015-24.
 338 Sources of error in advisory soil tests. I.

HOGG, D. E.; WATERS, D. F. 1954: Ibid. 35: 414-20.

LUNT, H. A; SWANSON, C. L. W.; JACOBSON, H. G. M. 1950: Conn.
Agric. expo Stn Bull. 541: 1~60.
TRUOG, E. 1930: J. Am. Soc. Agron. 22: 874-82.
TRUOG, E.; MEYER, A H. 1929: Ind. Engng Chern. analyt, Edn 1: 136-9.
VERMEULEN, F. H. B. 1957: Neth. J. agric. Sci. 5: 221-5.
WATERS, D. F.; SWEETMAN, I. C. 1955: Soil Sci. 79: 411-13.
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