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(Anon.)

6.1 Introduction

6.2 Definitions

6.3 Basic Statistics

6.4 Statistical tests

6.1 Introduction

In the preceding chapters basic elements for the proper execution of analytical work such as

personnel, laboratory facilities, equipment, and reagents were discussed. Before embarking

upon the actual analytical work, however, one more tool for the quality assurance of the work

must be dealt with: the statistical operations necessary to control and verify the analytical

procedures (Chapter 7) as well as the resulting data (Chapter 8).

It was stated before that making mistakes in analytical work is unavoidable. This is the reason

why a complex system of precautions to prevent errors and traps to detect them has to be set

up. An important aspect of the quality control is the detection of both random and systematic

errors. This can be done by critically looking at the performance of the analysis as a whole and

also of the instruments and operators involved in the JOB . For the detection itself as well as

for the quantification of the errors, statistical treatment of data is indispensable.

A multitude of different statistical tools is available, some of them simple, some complicated,

and often very specific for certain purposes. In analytical work, the most important common

operation is the comparison of data, or sets of data, to quantify accuracy (bias) and precision.

Fortunately, with a few simple convenient statistical tools most of the information needed in

regular laboratory work can be obtained: the "t-test, the "F-test", and regression analysis.

Therefore, examples of these will be given in the ensuing pages.

Clearly, statistics are a tool, not an aim. Simple inspection of data, without statistical treatment,

by an experienced and dedicated analyst may be just as useful as statistical figures on the desk

of the disinterested. The value of statistics lies with organizing and simplifying data, to permit

some objective estimate showing that an analysis is under control or that a change has

occurred. Equally important is that the results of these statistical procedures are recorded and

can be retrieved.

6.2 Definitions

6.2.1 Error

6.2.2 Accuracy

6.2.3 Precision

6.2.4 Bias

Discussing Quality Control implies the use of several terms and concepts with a specific (and

sometimes confusing) meaning. Therefore, some of the most important concepts will be defined

first.

6.2.1 Error

Error is the collective noun for any departure of the result from the "true" value*. Analytical

errors can be:

1. Random or unpredictable deviations between replicates, quantified with the "standard

deviation".

2. Systematic or predictable regular deviation from the "true" value, quantified as "mean

difference" (i.e. the difference between the true value and the mean of replicate determinations).

3. Constant, unrelated to the concentration of the substance analyzed (the analyte).

4. Proportional, i.e. related to the concentration of the analyte.

* The "true" value of an attribute is by nature indeterminate and often has only a very relative

meaning. Particularly in soil science for several attributes there is no such thing as the true

value as any value obtained is method-dependent (e.g. cation exchange capacity). Obviously,

this does not mean that no adequate analysis serving a purpose is possible. It does, however,

emphasize the need for the establishment of standard reference methods and the importance of

external QC (see Chapter 9).

6.2.2 Accuracy

The "trueness" or the closeness of the analytical result to the "true" value. It is constituted by a

combination of random and systematic errors (precision and bias) and cannot be quantified

directly. The test result may be a mean of several values. An accurate determination produces a

"true" quantitative value, i.e. it is precise and free of bias.

6.2.3 Precision

The closeness with which results of replicate analyses of a sample agree. It is a measure of

dispersion or scattering around the mean value and usually expressed in terms of standard

deviation, standard error or a range (difference between the highest and the lowest result).

6.2.4 Bias

The consistent deviation of analytical results from the "true" value caused by systematic errors

in a procedure. Bias is the opposite but most used measure for "trueness" which is the

agreement of the mean of analytical results with the true value, i.e. excluding the contribution of

randomness represented in precision. There are several components contributing to bias:

1. Method bias

The difference between the (mean) test result obtained from a number of laboratories using the

same method and an accepted reference value. The method bias may depend on the analyte

level.

2. Laboratory bias

The difference between the (mean) test result from a particular laboratory and the accepted

reference value.

3. Sample bias

The difference between the mean of replicate test results of a sample and the ("true") value of

the target population from which the sample was taken. In practice, for a laboratory this refers

mainly to sample preparation, subsampling and weighing techniques. Whether a sample is

representative for the population in the field is an extremely important aspect but usually falls

outside the responsibility of the laboratory (in some cases laboratories have their own field

sampling personnel).

The relationship between these concepts can be expressed in the following equation:

Figure

Fig. 6-1. Accuracy and precision in laboratory measurements. (Note that the

qualifications apply to the mean of results: in c the mean is accurate but some individual

results are inaccurate)

6.3.1 Mean

6.3.2 Standard deviation

6.3.3 Relative standard deviation. Coefficient of variation

6.3.4 Confidence limits of a measurement

6.3.5 Propagation of errors

In the discussions of Chapters 7 and 8 basic statistical treatment of data will be considered.

Therefore, some understanding of these statistics is essential and they will briefly be discussed

here.

The basic assumption to be made is that a set of data, obtained by repeated analysis of the

same analyte in the same sample under the same conditions, has

a normal orGaussian distribution. (When the distribution is skewed statistical treatment is more

complicated). The primary parameters used are the mean (or average) and thestandard

deviation (see Fig. 6-2) and the main tools the F-test, the t-test, and regression and correlation

analysis.

Fig. 6-2. A Gaussian or normal distribution. The figure shows that (approx.) 68% of the

data fall in the range x s, 95% in the range x 2s, and 99.7% in the range x 3s.

6.3.1 Mean

The average of a set of n data xi:

(6.1)

This is the most commonly used measure of the spread or dispersion of data around the mean.

The standard deviation is defined as the square root of the variance (V).The variance is defined

as the sum of the squared deviations from the mean, divided by n-1. Operationally, there are

several ways of calculation:

(6.1)

or

(6.3)

or

(6.4)

The calculation of the mean and the standard deviation can easily be done on a calculator but

most conveniently on a PC with computer programs such as dBASE, Lotus 123, Quattro-Pro,

Excel, and others, which have simple ready-to-use functions. (Warning: some programs

use n rather than n- 1!).

Although the standard deviation of analytical data may not vary much over limited ranges of

such data, it usually depends on the magnitude of such data: the larger the figures, the

larger s. Therefore, for comparison of variations (e.g. precision) it is often more convenient to

use the relative standard deviation (RSD) than the standard deviation itself. The RSD is

expressed as a fraction, but more usually as a percentage and is then called coefficient of

variation (CV). Often, however, these terms are confused.

(6.5; 6.6)

Note. When needed (e.g. for the F-test, see Eq. 6.11) the variance can, of course, be calculated

by squaring the standard deviation:

V = s2

(6.7)

The more an analysis or measurement is replicated, the closer the mean x of the results will

approach the "true" value , of the analyte content (assuming absence of bias).

A single analysis of a test sample can be regarded as literally sampling the imaginary set of a

multitude of results obtained for that test sample. The uncertainty of such subsampling is

expressed by

(6.8)

where

x = mean of subsamples

t = a statistical value which depends on the number of data and the required confidence (usually

95%).

s = standard deviation of mean of subsamples

n = number of subsamples

(The term

The critical values for t are tabulated in Appendix 1 (they are, therefore, here referred to

as ttab ). To find the applicable value, the number of degrees of freedom has to be established

by: df = n -1 (see also Section 6.4.2).

Example

For the determination of the clay content in the particle-size analysis, a semi-automatic pipette

installation is used with a 20 mL pipette. This volume is approximate and the operation involves

the opening and closing of taps. Therefore, the pipette has to be calibrated, i.e. both the

accuracy (trueness) and precision have to be established.

A tenfold measurement of the volume yielded the following set of data (in mL):

19.941

19.812

19.829

19.828

19.742

19.797

19.937

19.847

19.885

19.804

The mean is 19.842 mL and the standard deviation 0.0627 mL. According to Appendix 1 for n =

10 is ttab = 2.26 (df = 9) and using Eq. (6.8) this calibration yields:

pipette volume = 19.842 2.26 (0.0627/

) = 19.84 0.04 mL

(Note that the pipette has a systematic deviation from 20 mL as this is outside the found

confidence interval. See also bias).

In routine analytical work, results are usually single values obtained in batches of several test

samples. No laboratory will analyze a test sample 50 times to be confident that the result is

reliable. Therefore, the statistical parameters have to be obtained in another way. Most usually

this is done by method validation (see Chapter 7) and/or by keeping control charts, which is

basically the collection of analytical results from one or more control samples in each batch (see

Chapter 8). Equation (6.8) is then reduced to

(6.9)

where

= "true" value

x = single measurement

s = standard deviation of set of previous measurements.

In Appendix 1 can be seen that if the set of replicated measurements is large (say > 30), t is

close to 2. Therefore, the (95%) confidence of the result x of a single test sample (n = 1 in Eq.

6.8) is approximated by the commonly used and well known expression

(6.10)

where S is the previously determined standard deviation of the large set of replicates (see also

Fig. 6-2).

Note: This "method-s" or s of a control sample is not a constant and may vary for different test

materials, analyte levels, and with analytical conditions.

Running duplicates will, according to Equation (6.8), increase the confidence of the (mean)

result by a factor

where

x = mean of duplicates

s = known standard deviation of large set

Similarly, triplicate analysis will increase the confidence by a factor

further discussed in Section 8.3.3.

Thus, in summary, Equation (6.8) can be applied in various ways to determine the size of errors

(confidence) in analytical work or measurements: single determinations in routine work,

determinations for which no previous data exist, certain calibrations, etc.

6.3.5.2 Propagation of systematic errors

The final result of an analysis is often calculated from several measurements performed during

the procedure (weighing, calibration, dilution, titration, instrument readings, moisture correction,

etc.). As was indicated in Section 6.2, the total error in an analytical result is an adding-up of the

sub-errors made in the various steps. For daily practice, the bias and precision of the whole

method are usually the most relevant parameters (obtained from validation, Chapter 7; or from

control charts, Chapter 8). However, sometimes it is useful to get an insight in the contributions

of the subprocedures (and then these have to be determined separately). For instance if one

wants to change (part of) the method.

Because the "adding-up" of errors is usually not a simple summation, this will be discussed. The

main distinction to be made is between random errors (precision) and systematic errors (bias).

6.3.5.1. Propagation of random errors

In estimating the total random error from factors in a final calculation, the treatment of

summation or subtraction of factors is different from that of multiplication or division.

I. Summation calculations

If the final result x is obtained from the sum (or difference) of (sub)measurements a, b, c, etc.:

x = a + b + c +...

then the total precision is expressed by the standard deviation obtained by taking the square

root of the sum of individual variances (squares of standard deviation):

dilution), then this is included to calculate the effect of the variance concerned, e.g. (2b)2

Example

The Effective Cation Exchange Capacity of soils (ECEC) is obtained by summation of the

exchangeable cations:

ECEC = Exch. (Ca + Mg + Na + K + H + Al)

Standard deviations experimentally obtained for exchangeable Ca, Mg, Na, K and (H + Al) on a

certain sample, e.g. a control sample, are: 0.30, 0.25, 0.15, 0.15, and 0.60 cmolc/kg

respectively. The total precision is:

It can be seen that the total standard deviation is larger than the highest individual standard

deviation, but (much) less than their sum. It is also clear that if one wants to reduce the total

standard deviation, qualitatively the best result can be expected from reducing the largest

individual contribution, in this case the exchangeable acidity.

2. Multiplication calculations

If the final result x is obtained from multiplication (or subtraction) of (sub)measurements

according to

then the total error is expressed by the standard deviation obtained by taking the square root of

the sum of the individual relative standard deviations (RSD or CV, as a fraction or as

percentage, see Eqs. 6.6 and 6.7):

calculate the effect of the RSD concerned, e.g. (2RSDb)2.

Example

The calculation of Kjeldahl-nitrogen may be as follows:

where

a = ml HCl required for titration sample

b = ml HCl required for titration blank

s = air-dry sample weight in gram

M = molarity of HCl

1.4 = 1410-3100% (14 = atomic weight of N)

mcf = moisture correction factor

Note that in addition to multiplications, this calculation contains a subtraction also (often,

calculations contain both summations and multiplications.)

Firstly, the standard deviation of the titration (a -b) is determined as indicated in Section 7

above. This is then transformed to RSD using Equations (6.5) or (6.6). Then theRSD of the

other individual parameters have to be determined experimentally. The found RSDs are, for

instance:

distillation: 0.8%,

titration: 0.5%,

molarity: 0.2%,

sample weight: 0.2%,

mcf: 0.2%.

The total calculated precision is:

Here again, the highest RSD (of distillation) dominates the total precision. In practice, the

precision of the Kjeldahl method is usually considerably worse ( 2.5%) probably mainly as a

result of the heterogeneity of the sample. The present example does not take that into account.

It would imply that 2.5% - 1.0% = 1.5% or 3/5 of the total random error is due to sample

heterogeneity (or other overlooked cause). This implies that painstaking efforts to improve

subprocedures such as the titration or the preparation of standard solutions may not be very

rewarding. It would, however, pay to improve the homogeneity of the sample, e.g. by careful

grinding and mixing in the preparatory stage.

Note. Sample heterogeneity is also represented in the moisture correction factor. However, the

influence of this factor on the final result is usually very small.

6.3.5.2 Propagation of systematic errors

Systematic errors of (sub)measurements contribute directly to the total bias of the result since

the individual parameters in the calculation of the final result each carry their own bias. For

instance, the systematic error in a balance will cause a systematic error in the sample weight

(as well as in the moisture determination). Note that some systematic errors may cancel out,

e.g. weighings by difference may not be affected by a biased balance.

The only way to detect or avoid systematic errors is by comparison (calibration) with

independent standards and outside reference or control samples.

6.4.2 F-test for precision

6.4.3 t-Tests for bias

6.4.4 Linear correlation and regression

6.4.5 Analysis of variance (ANOVA)

comparison of data. Some examples of comparisons in practice are:

- performance of two instruments,

- performance of two methods,

- performance of a procedure in different periods,

- performance of two analysts or laboratories,

- results obtained for a reference or control sample with the "true", "target" or "assigned" value

of this sample.

Some of the most common and convenient statistical tools to quantify such comparisons are

the F-test, the t-tests, and regression analysis.

Because the F-test and the t-tests are the most basic tests they will be discussed first. These

tests examine if two sets of normally distributed data are similar or dissimilar (belong or not

belong to the same "population") by comparing their standard

deviations and means respectively. This is illustrated in Fig. 6-3.

Fig. 6-3. Three possible cases when comparing two sets of data (n1 = n2). A. Different

mean (bias), same precision; B. Same mean (no bias), different precision; C. Both mean

and precision are different. (The fourth case, identical sets, has not been drawn).

These tests for comparison, for instance between methods A and B, are based on the

assumption that there is no significant difference (the "null hypothesis"). In other words, when

the difference is so small that a tabulated critical value of F or t is not exceeded, we can be

confident (usually at 95% level) that A and B are not different. Two fundamentally different

questions can be asked concerning both the comparison of the standard

deviations s1 and s2 with the F-test, and of the meansx1, and x2, with the t-test:

1. are A and B different? (two-sided test)

2. is A higher (or lower) than B? (one-sided test).

This distinction has an important practical implication as statistically the probabilities for the two

situations are different: the chance that A and B are only different ("it can go two ways") is twice

as large as the chance that A is higher (or lower) than B ("it can go only one way"). The most

common case is the two-sided (also called two-tailed)test: there are no particular reasons to

expect that the means or the standard deviations of two data sets are different. An example is

the routine comparison of a control chart with the previous one (see 8.3). However, when it is

expected or suspected that the mean and/or the standard deviation will go only one way, e.g.

after a change in an analytical procedure, the one-sided (or one-tailed) test is appropriate. In

this case the probability that it goes the other way than expected is assumed to be zero and,

therefore, the probability that it goes the expected way is doubled. Or, more correctly, the

uncertainty in the two-way test of 5% (or the probability of 5% that the critical value is exceeded)

is divided over the two tails of the Gaussian curve (see Fig. 6-2), i.e. 2.5% at the end of each tail

beyond 2s. If we perform the one-sided test with 5% uncertainty, we actually increase this 2.5%

to 5% at the end of one tail. (Note that for the whole gaussian curve, which is symmetrical, this

is then equivalent to an uncertainty of 10% in two ways!)

This difference in probability in the tests is expressed in the use of two tables of critical values

for both F and t. In fact, the one-sided table at 95% confidence level is equivalent to the twosided table at 90% confidence level.

It is emphasized that the one-sided test is only appropriate when a difference in one direction is

expected or aimed at. Of course it is tempting to perform this test after the results show a clear

(unexpected) effect. In fact, however, then a two times higher probability level was used in

retrospect. This is underscored by the observation that in this way even contradictory

conclusions may arise: if in an experiment calculated values of F and t are found within the

range between the two-sided and one-sided values of Ftab, and ttab, the two-sided test indicates

no significant difference, whereas the one-sided test says that the result of A is significantly

higher (or lower) than that of B. What actually happens is that in the first case the 2.5%

boundary in the tail was just not exceeded, and then, subsequently, this 2.5% boundary is

relaxed to 5% which is then obviously more easily exceeded. This illustrates that statistical tests

differ in strictness and that for proper interpretation of results in reports, the statistical

techniques used, including the confidence limits or probability, should always be specified.

Because the result of the F-test may be needed to choose between the Student's t-test and the

Cochran variant (see next section), the F-test is discussed first.

The F-test (or Fisher's test) is a comparison of the spread of two sets of data to test if the sets

belong to the same population, in other words if the precisions are similar or dissimilar.

The test makes use of the ratio of the two variances:

(6.11)

where the larger s2 must be the numerator by convention. If the performances are not very

different, then the estimates s1, and s2, do not differ much and their ratio (and that of their

squares) should not deviate much from unity. In practice, the calculated F is compared with the

applicable F value in the F-table (also called the critical value, see Appendix 2). To read the

table it is necessary to know the applicable number of degrees of freedom for s1, and s2. These

are calculated by:

df1 = n1-1

df2 = n2-1

If Fcal Ftab one can conclude with 95% confidence that there is no significant difference in

precision (the "null hypothesis" that s1, = s, is accepted). Thus, there is still a 5% chance that

we draw the wrong conclusion. In certain cases more confidence may be needed, then a 99%

confidence table can be used, which can be found in statistical textbooks.

Example I (two-sided test)

Table 6-1 gives the data sets obtained by two analysts for the cation exchange capacity (CEC)

of a control sample. Using Equation (6.11) the calculated F value is 1.62. As we had no

particular reason to expect that the analysts would perform differently, we use the F-table for

the two-sided test and find Ftab = 4.03 (Appendix 2, df1, = df2= 9). This exceeds the calculated

value and the null hypothesis (no difference) is accepted. It can be concluded with 95%

confidence that there is no significant difference in precision between the work of Analyst 1 and

2.

Table 6-1. CEC values (in cmolc/kg) of a control sample determined by two analysts.

10.2

9.7

10.7

9.0

10.5

10.2

9.9

10.3

9.0

10.8

11.2

11.1

11.5

9.4

10.9

9.2

8.9

9.8

10.6

10.2

x:

10.34

9.97

s:

0.819

0.644

n:

10

10

Fcal = 1.62

tcal = 1.12

Ftab = 4.03

ttab = 2.10

The determination of the calcium carbonate content with the Scheibler standard method is

compared with the simple and more rapid "acid-neutralization" method using one and the same

sample. The results are given in Table 6-2. Because of the nature of the rapid method we

suspect it to produce a lower precision then obtained with the Scheibler method and we can,

therefore, perform the one sided F-test. The applicable Ftab = 3.07 (App. 2, df1, = 12, df2 = 9)

which is lower than Fcal (=18.3) and the null hypothesis (no difference) is rejected. It can be

concluded (with 95% confidence) that for this one sample the precision of the rapid titration

method is significantly worse than that of the Scheibler method.

Table 6-2. Contents of CaCO3 (in mass/mass %) in a soil sample determined with the Scheibler

method (A) and the rapid titration method (B).

2.5

1.7

2.4

1.9

2.5

2.3

2.6

2.3

2.5

2.8

2.5

2.5

2.4

1.6

2.6

1.9

2.7

2.6

2.4

1.7

2.4

2.2

2.6

x:

2.51

2.13

s:

0.099

0.424

n:

10

13

Fcal = 18.3

tcal = 3.12

Ftab = 3.07

ttab* = 2.18

6.4.3.2 Cochran's t-test

6.4.3.3 t-Test for large data sets (n 30)

6.4.3.4 Paired t-test

Depending on the nature of two sets of data (n, s, sampling nature), the means of the sets can

be compared for bias by several variants of the t-test. The following most common types will be

discussed:

1. Student's t-test for comparison of two independent sets of data with very similar standard

deviations;

2. the Cochran variant of the t-test when the standard deviations of the independent

sets differ significantly;

3. the paired t-test for comparison of strongly dependent sets of data.

Basically, for the t-tests Equation (6.8) is used but written in a different way:

(6.12)

where

x = mean of test results of a sample

= "true" or reference value

s = standard deviation of test results

n = number of test results of the sample.

To compare the mean of a data set with a reference value normally the "two-sided t-table of

critical values" is used (Appendix 1). The applicable number of degrees of freedom here is:

df = n-1

If a value for t calculated with Equation (6.12) does not exceed the critical value in the table, the

data are taken to belong to the same population: there is no difference and the "null hypothesis"

is accepted (with the applicable probability, usually 95%).

As with the F-test, when it is expected or suspected that the obtained results are higher or lower

than that of the reference value, the one-sided t-test can be performed: iftcal > ttab, then the

results are significantly higher (or lower) than the reference value.

More commonly, however, the "true" value of proper reference samples is accompanied by the

associated standard deviation and number of replicates used to determine these parameters.

We can then apply the more general case of comparing the means of two data sets: the "true"

value in Equation (6.12) is then replaced by the mean of a second data set. As is shown in Fig.

6-3, to test if two data sets belong to the same population it is tested if the two Gauss curves do

sufficiently overlap. In other words, if the difference between the means x1-x2 is small. This is

discussed next.

Similarity or non-similarity of standard deviations

When using the t-test for two small sets of data (n1 and/or n2<30), a choice of the type of test

must be made depending on the similarity (or non-similarity) of the standard deviations of the

two sets. If the standard deviations are sufficiently similar they can be "pooled" and

the Student t-test can be used. When the standard deviations are not sufficiently similar an

alternative procedure for the t-test must be followed in which the standard deviations are not

pooled. A convenient alternative is the Cochran variant of the t-test. The criterion for the choice

is the passing or non-passing of the F-test (see 6.4.2), that is, if the variances do or do not

significantly differ. Therefore, for small data sets, the F-test should precede the t-test.

For dealing with large data sets (n1, n2, 30) the "normal" t-test is used (see Section 6.4.3.3 and

App. 3).

6.4.3.1. Student's t-test

(To be applied to small data sets (n1, n2 < 30) where s1, and s2 are similar according to F-test.

When comparing two sets of data, Equation (6.12) is rewritten as:

(6.13)

where

x1 = mean of data set 1

x2 = mean of data set 2

sp = "pooled" standard deviation of the sets

n1 = number of data in set 1

n2 = number of data in set 2.

The pooled standard deviation sp is calculated by:

6.14

where

s1 = standard deviation of data set 1

s2 = standard deviation of data set 2

n1 = number of data in set 1

n2 = number of data in set 2.

To perform the t-test, the critical ttab has to be found in the table (Appendix 1); the applicable

number of degrees of freedom df is here calculated by:

df = n1 + n2 -2

Example

The two data sets of Table 6-1 can be used: With Equations (6.13) and (6.14) tcal, is calculated

as 1.12 which is lower than the critical value ttab of 2.10 (App. 1, df = 18, two-sided), hence the

null hypothesis (no difference) is accepted and the two data sets are assumed to belong to the

same population: there is no significant difference between the mean results of the two analysts

(with 95% confidence).

Note. Another illustrative way to perform this test for bias is to calculate if the difference

between the means falls within or outside the range where this difference is still not significantly

large. In other words, if this difference is less than the least significant difference (lsd). This can

be derived from Equation (6.13):

6.15

In the present example of Table 6-1, the calculation yields lsd = 0.69. The measured difference

between the means is 10.34 -9.97 = 0.37 which is smaller than the lsdindicating that there is no

significant difference between the performance of the analysts.

In addition, in this approach the 95% confidence limits of the difference between the means can

be calculated (cf. Equation 6.8):

confidence limits = 0.37 0.69 = -0.32 and 1.06

Note that the value 0 for the difference is situated within this confidence interval which agrees

with the null hypothesis of x1 = x2 (no difference) having been accepted.

6.4.3.2 Cochran's t-test

To be applied to small data sets (n1, n2, < 30) where s1 and s2, are dissimilar according to Ftest.

Calculate t with:

6.16

6.17

where

t1 = ttab at n1-1 degrees of freedom

t2 = ttab at n2-1 degrees of freedom

Now the t-test can be performed as usual: if tcal< ttab* then the null hypothesis that the means do

not significantly differ is accepted.

Example

The two data sets of Table 6-2 can be used.

According to the F-test, the standard deviations differ significantly so that the Cochran variant

must be used. Furthermore, in contrast to our expectation that the precision of the rapid test

would be inferior, we have no idea about the bias and therefore the two-sided test is

appropriate. The calculations yield tcal = 3.12 and ttab*= 2.18 meaning that tcal exceeds ttab* which

implies that the null hypothesis (no difference) is rejected and that the mean of the rapid

analysis deviates significantly from that of the standard analysis (with 95% confidence, and for

this sample only). Further investigation of the rapid method would have to include the use of

more different samples and then comparison with the one-sided t-test would be justified (see

6.4.3.4, Example 1).

6.4.3.3 t-Test for large data sets (n 30)

In the example above (6.4.3.2) the conclusion happens to have been the same if the

Student's t-test with pooled standard deviations had been used. This is caused by the fact that

the difference in result of the Student and Cochran variants of the t-test is largest when small

sets of data are compared, and decreases with increasing number of data. Namely, with

increasing number of data a better estimate of the real distribution of the population is obtained

(the flatter t-distribution converges then to the standardized normal distribution). When n 30 for

both sets, e.g. when comparing Control Charts (see 8.3), for all practical purposes the

difference between the Student and Cochran variant is negligible. The procedure is then

reduced to the "normal" t-test by simply calculating tcal with Eq. (6.16) and comparing this with

ttab at df = n1 + n2-2. (Note in App. 1 that the two-sided ttab is now close to 2).

The proper choice of the t-test as discussed above is summarized in a flow diagram in Appendix

3.

6.4.3.4 Paired t-test

When two data sets are not independent, the paired t-test can be a better tool for comparison

than the "normal" t-test described in the previous sections. This is for instance the case when

two methods are compared by the same analyst using the same sample(s). It could, in fact, also

be applied to the example of Table 6-1 if the two analysts used the same analytical method at

(about) the same time.

As stated previously, comparison of two methods using different levels of analyte gives more

validation information about the methods than using only one level. Comparison of results at

each level could be done by the F and t-tests as described above. The paired t-test, however,

allows for different levels provided the concentration range is not too wide. As a rule of fist, the

range of results should be within the same magnitude. If the analysis covers a longer range, i.e.

several powers of ten, regression analysis must be considered (see Section 6.4.4). In

intermediate cases, either technique may be chosen.

The null hypothesis is that there is no difference between the data sets, so the test is to see if

the mean of the differences between the data deviates significantly from zero or not (two-sided

test). If it is expected that one set is systematically higher (or lower) than the other set, then the

one-sided test is appropriate.

Example 1

The "promising" rapid single-extraction method for the determination of the cation exchange

capacity of soils using the silver thiourea complex (AgTU, buffered at pH 7) was compared with

the traditional ammonium acetate method (NH4OAc, pH 7). Although for certain soil types the

difference in results appeared insignificant, for other types differences seemed larger. Such a

suspect group were soils with ferralic (oxic) properties (i.e. highly weathered sesquioxide-rich

soils). In Table 6-3 the results often soils with these properties are grouped to test if the CEC

methods give different results. The difference d within each pair and the parameters needed for

the paired t-test are given also.

Table 6-3. CEC values (in cmolc/kg) obtained by the NH4OAc and AgTU methods (both at pH 7)

for ten soils with ferralic properties.

Sample

NH4OAc

AgTU

7.1

6.5

-0.6

4.6

5.6

+1.0

10.6

14.5

+3.9

2.3

5.6

+3.3

25.2

23.8

-1.4

4.4

10.4

+6.0

7.8

8.4

+0.6

2.7

5.5

+2.8

14.3

19.2

+4.9

10

13.6

15.0

d = +2.19

tcal = 2.89

sd = 2.395

ttab = 2.26

+1.4

Using Equation (6.12) and noting that d = 0 (hypothesis value of the differences, i.e. no

difference), the t-value can be calculated as:

where

= mean of differences within each pair of data

sd = standard deviation of the mean of differences

n = number of pairs of data

The calculated t value (=2.89) exceeds the critical value of 1.83 (App. 1, df = n -1 = 9, onesided), hence the null hypothesis that the methods do not differ is rejected and it is concluded

that the silver thiourea method gives significantly higher results as compared with the

ammonium acetate method when applied to such highly weathered soils.

Note. Since such data sets do not have a normal distribution, the "normal" t-test which

compares means of sets cannot be used here (the means do not constitute a fair representation

of the sets). For the same reason no information about the precision of the two methods can be

obtained, nor can the F-test be applied. For information about precision, replicate

determinations are needed.

Example 2

Table 6-4 shows the data of total-P in four plant tissue samples obtained by a laboratory L and

the median values obtained by 123 laboratories in a proficiency (round-robin) test.

Table 6-4. Total-P contents (in mmol/kg) of plant tissue as determined by 123

laboratories (Median) and Laboratory L.

Sample

Median

Lab L

93.0

85.2

-7.8

201

224

23

78.9

84.5

5.6

175

185

10

d = 7.70

tcal =1.21

sd = 12.702

ttab = 3.18

Using Eq. (6.12) and noting that d=0 (hypothesis value of the differences, i.e. no difference),

the t value can be calculated as:

The calculated t-value is below the critical value of 3.18 (Appendix 1, df = n - 1 = 3, two-sided),

hence the null hypothesis that the laboratory does not significantly differ from the group of

laboratories is accepted, and the results of Laboratory L seem to agree with those of "the rest of

the world" (this is a so-called third-line control).

6.4.4.2 Comparing two sets of data using many samples at different analyte levels

These also belong to the most common useful statistical tools to compare effects and

performances X and Y. Although the technique is in principle the same for both, there is a

fundamental difference in concept: correlation analysis is applied to independent factors:

if X increases, what will Y do (increase, decrease, or perhaps not change at all)? In regression

analysis a unilateral response is assumed: changes in X result in changes in Y, but changes

in Y do not result in changes in X.

For example, in analytical work, correlation analysis can be used for comparing methods or

laboratories, whereas regression analysis can be used to construct calibration graphs. In

practice, however, comparison of laboratories or methods is usually also done by regression

analysis. The calculations can be performed on a (programmed) calculator or more conveniently

on a PC using a home-made program. Even more convenient are the regression programs

included in statistical packages such asStatistix, Mathcad, Eureka, Genstat, Statcal, SPSS, and

others. Also, most spreadsheet programs such as Lotus 123, Excel, and Quattro-Pro have

functions for this.

Laboratories or methods are in fact independent factors. However, for regression analysis one

factor has to be the independent or "constant" factor (e.g. the reference method, or the factor

with the smallest standard deviation). This factor is by convention designated X, whereas the

other factor is then the dependent factor Y (thus, we speak of "regression of Y on X").

As was discussed in Section 6.4.3, such comparisons can often been done with the

Student/Cochran or paired t-tests. However, correlation analysis is indicated:

1. When the concentration range is so wide that the errors, both random and systematic, are not

independent (which is the assumption for the t-tests). This is often the case where concentration

ranges of several magnitudes are involved.

2. When pairing is inappropriate for other reasons, notably a long time span between the two

analyses (sample aging, change in laboratory conditions, etc.).

The principle is to establish a statistical linear relationship between two sets of corresponding

data by fitting the data to a straight line by means of the "least squares" technique. Such data

are, for example, analytical results of two methods applied to the same samples (correlation), or

the response of an instrument to a series of standard solutions (regression).

Note: Naturally, non-linear higher-order relationships are also possible, but since these are less

common in analytical work and more complex to handle mathematically, they will not be

discussed here. Nevertheless, to avoid misinterpretation, always inspect the kind of relationship

by plotting the data, either on paper or on the computer monitor.

The resulting line takes the general form:

y = bx + a

(6.18)

where

a = intercept of the line with the y-axis

b = slope (tangent)

In laboratory work ideally, when there is perfect positive correlation without bias, the intercept a

= 0 and the slope = 1. This is the so-called "1:1 line" passing through the origin (dashed line in

Fig. 6-5).

between X and Y; when b 1 then there is a proportional response or difference

between X andY.

The correlation between X and Y is expressed by the correlation coefficient r which can be

calculated with the following equation:

6.19

where

xi = data X

x = mean of data X

yi = data Y

y = mean of data Y

It can be shown that r can vary from 1 to -1:

r = 1 perfect positive linear correlation

r = 0 no linear correlation (maybe other correlation)

r = -1 perfect negative linear correlation

Often, the correlation coefficient r is expressed as r2: the coefficient of

determination or coefficient of variance. The advantage of r2 is that, when multiplied by 100, it

indicates the percentage of variation in Y associated with variation in X. Thus, for example,

when r = 0.71 about 50% (r2 = 0.504) of the variation in Y is due to the variation in X.

The line parameters b and a are calculated with the following equations:

6.20

and

a = y - bx

6.21

It is worth to note that r is independent of the choice which factor is the independent factory and

which is the dependent Y. However, the regression parameters a and do depend on this choice

as the regression lines will be different (except when there is ideal 1:1 correlation).

As an example, we take a standard series of P (0-1.0 mg/L) for the spectrophotometric

determination of phosphate in a Bray-I extract ("available P"), reading in absorbance units. The

data and calculated terms needed to determine the parameters of the calibration graph are

given in Table 6-5. The line itself is plotted in Fig. 6-4.

Table 6-5 is presented here to give an insight in the steps and terms involved. The calculation of

the correlation coefficient r with Equation (6.19) yields a value of 0.997 (r2= 0.995). Such high

values are common for calibration graphs. When the value is not close to 1 (say, below 0.98)

this must be taken as a warning and it might then be advisable to repeat or review the

procedure. Errors may have been made (e.g. in pipetting) or the used range of the graph may

not be linear. On the other hand, a high rmay be misleading as it does not necessarily indicate

linearity. Therefore, to verify this, the calibration graph should always be plotted, either on paper

or on computer monitor.

Using Equations (6.20 and (6.21) we obtain:

and

a = 0.350 - 0.313 = 0.037

Thus, the equation of the calibration line is:

y = 0.626x + 0.037

(6.22)

xi

yi

x1-x

(xi-x)2

yi-y

(yi-y)2

(x1-x)(yi-y)

0.0

0.05

-0.5

0.25

-0.30

0.090

0.150

0.2

0.14

-0.3

0.09

-0.21

0.044

0.063

0.4

0.29

-0.1

0.01

-0.06

0.004

0.006

0.6

0.43

0.1

0.01

0.08

0.006

0.008

0.8

0.52

0.3

0.09

0.17

0.029

0.051

1.0

0.67

0.5

0.25

0.32

0.102

0.160

3.0

2.10

0.70

0.2754

0.438

x=0.5

y = 0.35

Fig. 6-4. Calibration graph plotted from data of Table 6-5. The dashed lines delineate the

95% confidence area of the graph. Note that the confidence is highest at the centroid of

the graph.

During calculation, the maximum number of decimals is used, rounding off to the last significant

figure is done at the end (see instruction for rounding off in Section 8.2).

Once the calibration graph is established, its use is simple: for each y value measured the

corresponding concentration x can be determined either by direct reading or by calculation

using Equation (6.22). The use of calibration graphs is further discussed in Section 7.2.2.

Note. A treatise of the error or uncertainty in the regression line is given.

6.4.4.2 Comparing two sets of data using many samples at different analyte levels

Although regression analysis assumes that one factor (on the x-axis) is constant, when certain

conditions are met the technique can also successfully be applied to comparing two variables

such as laboratories or methods. These conditions are:

- The most precise data set is plotted on the x-axis

- At least 6, but preferably more than 10 different samples are analyzed

- The samples should rather uniformly cover the analyte level range of interest.

To decide which laboratory or method is the most precise, multi-replicate results have to be

used to calculate standard deviations (see 6.4.2). If these are not available then the standard

deviations of the present sets could be compared (note that we are now not dealing with

normally distributed sets of replicate results). Another convenient way is to run the regression

analysis on the computer, reverse the variables and run the analysis again. Observe which

variable has the lowest standard deviation (or standard error of the intercept a, both given by

the computer) and then use the results of the regression analysis where this variable was

plotted on the x-axis.

If the analyte level range is incomplete, one might have to resort to spiking or standard

additions, with the inherent drawback that the original analyte-sample combination may not

adequately be reflected.

Example

In the framework of a performance verification programme, a large number of soil samples were

analyzed by two laboratories X and Y (a form of "third-line control", see Chapter 9) and the data

compared by regression. (In this particular case, the paired t-test might have been considered

also). The regression line of a common attribute, the pH, is shown here as an illustration. Figure

6-5 shows the so-called "scatter plot" of 124 soil pH-H2O determinations by the two laboratories.

The correlation coefficient r is 0.97 which is very satisfactory. The slope (= 1.03) indicates that

the regression line is only slightly steeper than the 1:1 ideal regression line. Very disturbing,

however, is the intercept a of -1.18. This implies that laboratory Y measures the pH more than a

whole unit lower than laboratory X at the low end of the pH range (the intercept -1.18 is at pHx =

0) which difference decreases to about 0.8 unit at the high end.

Fig. 6-5. Scatter plot of pH data of two laboratories. Drawn line: regression line; dashed

line: 1:1 ideal regression line.

For intercept a: a = 0 (null hypothesis: no bias; ideal intercept is then zero), standard error

=0.14 (calculated by the computer), and using Equation (6.12) we obtain:

Here, ttab = 1.98 (App. 1, two-sided, df = n - 2 = 122 (n-2 because an extra degree of freedom is

lost as the data are used for both a and b) hence, the laboratories have a significant mutual

bias.

For slope: b = 1 (ideal slope: null hypothesis is no difference), standard error = 0.02 (given by

computer), and again using Equation (6.12) we obtain:

Again, ttab = 1.98 (App. 1; two-sided, df = 122), hence, the difference between the laboratories is

not significantly proportional (or: the laboratories do not have a significant difference in

sensitivity). These results suggest that in spite of the good correlation, the two laboratories

would have to look into the cause of the bias.

Note. In the present example, the scattering of the points around the regression line does not

seem to change much over the whole range. This indicates that the precision of

laboratory Y does not change very much over the range with respect to laboratory X. This is not

always the case. In such cases, weighted regression (not discussed here) is more appropriate

than the unweighted regression as used here.

Validation of a method (see Section 7.5) may reveal that precision can change significantly with

the level of analyte (and with other factors such as sample matrix).

When results of laboratories or methods are compared where more than one factor can be of

influence and must be distinguished from random effects, then ANOVA is a powerful statistical

tool to be used. Examples of such factors are: different analysts, samples with different pretreatments, different analyte levels, different methods within one of the laboratories). Most

statistical packages for the PC can perform this analysis.

As a treatise of ANOVA is beyond the scope of the present Guidelines, for further discussion the

reader is referred to statistical textbooks, some of which are given in the list of Literature.

Error or uncertainty in the regression line

The "fitting" of the calibration graph is necessary because the response points yi, composing the

line do not fall exactly on the line. Hence, random errors are implied. This is expressed by an

uncertainty about the slope and intercept b and a defining the line. A quantification can be found

in the standard deviation of these parameters. Most computer programmes for regression will

automatically produce figures for these. To illustrate the procedure, the example of the

calibration graph in Section 6.4.3.1 is elaborated here.

A practical quantification of the uncertainty is obtained by calculating the standard deviation of

the points on the line; the "residual standard deviation" or "standard error of the yestimate", which we assumed to be constant (but which is only approximately so, see Fig. 6-4):

(6.23)

where

= "fitted" y-value for each xi, (read from graph or calculated with Eq. 6.22). Thus,

the (vertical) deviation of the found y-values from the line.

is

Note: Only the y-deviations of the points from the line are considered. It is assumed that

deviations in the x-direction are negligible. This is, of course, only the case if the standards are

very accurately prepared.

Now the standard deviations for the intercept a and slope b can be calculated with:

6.24

and

6.25

To make this procedure clear, the parameters involved are listed in Table 6-6.

The uncertainty about the regression line is expressed by the confidence limits of a

and b according to Eq. (6.9): a t.sa and b t.sb

Table 6-6. Parameters for calculating errors due to calibration graph (use also figures of Table

6-5).

xi

yi

0.05

0.037

0.013

0.0002

0.2

0.14

0.162

-0.022

0.0005

0.4

0.29

0.287

0.003

0.0000

0.6

0.43

0.413

0.017

0.0003

0.8

0.52

0.538

-0.018

0.0003

1.0

0.67

0.663

0.007

0.0001

0.001364

The applicable ttab is 2.78 (App. 1, two-sided, df = n -1 = 4) hence, using Eq. (6.9):

a = 0.037 2.78 0.0132 = 0.037 0.037

and

b = 0.626 2.78 0.0219 = 0.626 0.061

Note that if sa is large enough, a negative value for a is possible, i.e. a negative reading for the

blank or zero-standard. (For a discussion about the error in x resulting from a reading in y, which

is particularly relevant for reading a calibration graph, see Section 7.2.3)

The uncertainty about the line is somewhat decreased by using more calibration points

(assuming sy has not increased): one more point reduces ttab from 2.78 to 2.57 (see Appendix 1).

hypothetical research study.

Remember that there are different ways of approaching a

research question and how we put together our research

question will determine the type of methodology, data

collection method, statistics, analysis and presentation

that we will use to approach our research problem.

Is the proportion of males who are nurses the same

as the proportion of females?

Is there a relationship between gender and becoming

a nurse?

In the example in the box above, you can see that there

are three different ways of approaching the research

problem, which is concerned with the relationship between

males and females in nursing.

gender and smoking, there are 2

categorical variables (gender & smoker), with two or more

categories in each, for example:

Gender (male/female)

Smoker (yes/no)

You are looking for whether or not there is any significance

in the results

Reflection

Before we proceed, you may want to briefly refresh your

knowledge and understanding of some basics, namely:

hypothesis

variables

accompanying book, and/or click on the hyperlink below:

statistics are fun

Now to return to statistical analysis

Alpha level (p level)

In statistical analysis we are looking to see if there is any

significance in the results. The acceptance or rejection of

a hypothesis is based upon a level of significance the

alpha () level

This is usually set at the 5% (0.05) level, followed in

popularity by the 1% (0.01) level

We usually designate these as p, i.e. p =0.05 or p = 0.01

So, what do we mean by levels of significance that the 'p'

value can give us?

Statistical tests

There are many tests that we can use to analyse our data,

and which particular one we use to analyse our data

depends upon what we are looking for, and what data we

collected (and how we collected it).

Below are just a few of the more common ones that you

may come across in research papers.

Mann-Whitney U-test

This test is used to test for differences between 2

independent groups on a continuous measure, e.g. do

males and females differ in terms of their levels of selfesteem.

This test requires two variables (e.g. male/female gender)

and one continuous variable (e.g. self-esteem).

It actually compares medians.

It converts the scores on the continuous variable

to ranks, across the two groups.

It then evaluates whether the medians for the two groups

differ significantly.

This test is used to demonstrate the relationship between

two ranked variables

judges on two objects, or the scores of a group of subjects

on two measures.

This is a coefficient correlation based on ranks.

It shows the association between two variables (X and Y),

which are not normally distributed.

Dont worry about the details just remember that it is an

acceptable method for parametric data when there are

less than 30 but more than 9 paired variables.

Kruskal-Wallis test

This test is used to compare the means among more than

two samples, when either the data are ordinal or the

distribution is not normal.

If there are only two groups then it is the equivalent of the

Mann-Whitney U-test, so you may as well use that test.

This test would normally be used when you wanted to

determine the significance of difference among three or

more groups.

information on statistical tests, read chapter 9 of the

accompanying book.

t-test

The t-test assesses whether the means of two groups

are statisticallydifferent from each other. This analysis is appropriate

whenever you want to compare the means of two groups.

Pearson Correlation

We use the Pearson's correlation in order to find a correlation

between at least two continuous variables. The value for such a

correlation lies between 0.00 (no correlation) and 1.00 (perfect

correlation).

ANOVA is one of a number of tests (ANCOVA - analysis of

covariance - and MANOVA - multivariate analysis of variance) that

are used to describe/compare the relationship among a number of

groups.

Chi-square test

There are two different types of chi-square tests - but both involve

categorical data (Pallant 2001).

expected in theory against what is actually observed.

two variables or the chi-square test for independence.

This is the most common nonparametric test for the two-sampled

repeated measures design of research study, and is also known as

the Wilcoxon matched-pairs test.

This has just been a very brief look at some of the more

common statistical tests for the analysis of data obtained

from quantitative research - more details are given in

chapter 9 of the accompanying book. There are, of course,

many others, and any good statistics book will have details

of them.

Selecting your statistical test

When it comes to the selection of the appropriate test for

your research in order to determine the p-value, you need

to base the selection of four major factors, namely:

(one, two, or more).

groups/samples or from related groups? Remember

that independent groups are two or more separated

groups of participants, whilst related groups are often

e.g. pre- and post-testing, or even a different

environment.

the data).

but if ever you are involved in quantitative research and

have to do statistical analysis, don't worry because help is

at hand.

There is a computer package for statistical analysis known

as SPSS

SPSS stands for:

Statistical Package for Social Sciences

SPSS is one of a number of computer packages that can

do just about any calculation that you want, using any

statistical test.

Before we finish this section, we just need to remind you

to be careful when you are looking at research that uses

statistics.

Limitations of research study/data/statistical tests

their study and discuss anything that did not make it

perfect, for example:

size of sample

tests used

initial question

statistics as part of your research, or when reading

research papers, so remember two things:

1. Keep things simple

2. Statistics by themselves are meaningless, it is the

analysis and

discussion of statistics which makes them meaningful

and brings

them to life.

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