TR 581 QC in Prot Med

ISSN 0283-7234
NT TECHN REPORT 581

Approved 2005-04
Authors: Nordic Innovation Centre project number:

Christian Grn, DHI Water & Environment, 04210
Jacqueline Anne Falkenberg, NIRAS A/S, Institution:
Jens Strodl Andersen, JSA-EnviroStat, Nordic Innovation Centre
Marion Brresen & Arne Pettersen,
Norwegian Geotehcnical Institute,
Sren Nilsson and Karsten Hkansson,
Swedish Geotechnical Institute,
Jussi Laiho, Geological Survey of Finland
Title:
Quality Control Manual for Field Measurements
Abstract:
Field measurements are widely used in investigations on contaminated sites as alterna-
tives to and supplementing analysis in chemical laboratories. The requirements for meas-
urement quality and quality control of field measurements are less stringent than those for
laboratory analysis. The present manual provides an introduction to the concepts and cal-
culations of analytical quality control, a set of quality requirements for field measure-
ments for different purpose and intended use of the measurements, a selection of quality
control methods selected to be of practical use and supply the quality information re-
quired in site investigations and a set of examples demonstrating the practical use of the
manual. Statistical factors and control charts are included as appendices.
Technical Group: Expert Group Environment and Natural Resources

ISSN: 0283-7234 Language: Pages: 86
English 3 appendices
Key Words:
Quality control, field measurements, soil,
groundwater
Distributed by: Nordic Innovation Centre Report Internet address:
Holbergs gate 1 www.nordicinnovation.net
N-0166 Oslo
Norway
CONTENTS
1 INTRODUCTION............................................................................................................. 1
2 SCOPE ........................................................................................................................... 2
3 REQUIREMENTS FOR ANALYTICAL QUALITY IN SOIL AND GROUNDWATER

INVESTIGATIONS .......................................................................................................... 3
4 QUALITY CLASSES FOR FIELD MEASUREMENTS .................................................... 5

4.1 Definitions ....................................................................................................................... 5
4.2 Quality requirements ....................................................................................................... 6
5 ANALYTICAL QUALITY CONTROL ............................................................................... 8

5.1 Definitions ....................................................................................................................... 8
5.1.1 False positive, false negative and correct measurements .............................................. 8
5.1.2 Detection limit.................................................................................................................. 9
5.1.3 Precision and uncertainty.............................................................................................. 10
5.1.4 Trueness and bias......................................................................................................... 13
5.1.5 Error and accuracy........................................................................................................ 13
5.1.6 Linearity ........................................................................................................................ 14
5.2 Control types ................................................................................................................. 14
5.2.1 Calibration and check of instrument.............................................................................. 15
5.2.2 Control samples ............................................................................................................ 16
5.2.3 Blank samples............................................................................................................... 16
5.2.4 Duplicates ..................................................................................................................... 17
5.2.5 Spiked samples............................................................................................................. 17
5.2.6 External control ............................................................................................................. 18
5.3 Statistics and calculations ............................................................................................. 18
5.3.1 Linear regression .......................................................................................................... 19
5.3.2 Inverse linear regression............................................................................................... 20
5.3.3 d-statistics ..................................................................................................................... 25
5.3.4 Range errors and correctness....................................................................................... 30
6 QUALITY CONTROL PROCEDURES FOR FIELD MEASUREMENTS....................... 32

6.1 Category 1, quantitative methods ................................................................................. 34
6.1.1 Bench check out............................................................................................................ 35
6.1.2 On site quality control.................................................................................................... 35
6.1.3 Verification .................................................................................................................... 35
6.2 Category II, relative methods ........................................................................................ 36
6.2.1 Bench check out............................................................................................................ 37
6.2.3 Verification .................................................................................................................... 37
6.3 Category III, range methods.......................................................................................... 38
6.3.1 Bench check out............................................................................................................ 39
6.3.3 Verification .................................................................................................................... 39
i
7 EXAMPLES................................................................................................................... 40
7.1 PID measurement of oil in soil ...................................................................................... 41
7.1.1 Site and study description ............................................................................................. 41
7.1.2 Bench check out............................................................................................................ 43
7.1.4 Verification .................................................................................................................... 48
7.1.5 Summary....................................................................................................................... 49
7.2 FFD measurement of TPH in soil.................................................................................. 50
7.2.2 Bench check out............................................................................................................ 52
7.2.4 Verification .................................................................................................................... 56
7.2.5 Summary....................................................................................................................... 57
7.3 PXRF measurement of heavy metals in soil ................................................................. 58
7.3.2 Bench check out............................................................................................................ 60
7.3.4 Verification .................................................................................................................... 66
7.3.5 Summary....................................................................................................................... 67
7.4 Measurement of pH, conductivity and O2 (flow cell) and nitrate in groundwater........... 68
7.4.1 Bench check out............................................................................................................ 71
7.4.2 On-site quality control ................................................................................................... 74
7.4.3 Verification .................................................................................................................... 80
7.4.4 Summary....................................................................................................................... 83
8 REFERENCES.............................................................................................................. 85
APPENDICES
Appendix 1
Students t-factors for a one-sided test 5 % significance level
Appendix 2
Students t-factors for a two-sided test 5 % significance level
Appendix 3
Control charts for differences between duplicate measurements as function of mean duplicate
measurement, 50% and 5% RSD
ii
TERMS AND DEFINITIONS
The manual applies generally accepted terms and definitions from analytical quality
control. Chapter 5 gives an introduction to and definitions of the terms, but a few key
terms are summarized below. Please, note that the vocabulary of precision and trueness
has been selected for use in this manual and not the concepts used in uncertainty estima-
tion of measurements. This has been chosen because the precision/trueness approach is
easier to grasp and use for those not trained as analytical chemists.
Accuracy
The correctness of a single measurement, i.e.: the ratio between a single measurement
and the true value. Includes both systematic and random effects.
Analyte
The property of the sample that is measured.
Bias
The incorrectness of the method, i.e.: the difference between the mean value of infinite
measurements with the method and the true value.
Blank sample
A sample known to be without content of the analyte, that is used for quality control of
measurements.
Certified reference material
Material where the content of the analyte has been certified by analyses by a number of
analytical laboratories, i.e.: where the true value is known.
Control sample
A sample with known content of the analyte, that is used for quality control of meas-
urements.
Detection limit
The concentration below which the measurements can not be trusted, i.e.: where the
risks of false positives and negatives exceed a defined value.
Duplicate sample
One of the two (or more) samples or sub-samples obtained separately at the same time
and place from the same primary sample (* for replicate sample).
Error
The incorrectness of a single measurement, i.e.: the difference between a single meas-
urement and the true value. Includes both systematic and random effects.
iii
External control
Quality control whereby the measurements can be referred to accepted analytical re-
sults.
False positive
A measurement finding an analyte when the analyte is not present.
False negative
A measurement not finding an analyte when the analyte is present.
Interlaboratory comparison
Analysis of samples from the same primary sample at different laboratories in order to
compare the correctness of analytical results from different laboratories.
Precision
The scatter of repeated measurements.
Primary sample
The portion of material selected from a larger quantity of material taken by one sam-
pling procedure and considered the representative of the material.
Spiked sample
A sample added a known amount of the analyte.
True value
The true content of the analyte in a material. The true value is in theory never known
exactly but for practical purposes, the certified values of reference materials and con-
centrations spiked to are often considered true values.
Trueness
The correctness of the method, i.e.: the ratio between the mean value of infinite meas-
urements with the method and the true value.
Uncertainty
An expression of the randomness of a single measurement.
iv
PREFACE
The report:
Quality Control Manual for Field Measurements
was prepared as a practical aid in analytical quality control for field measurements for
those working with field measurements without being trained analytical chemists. Be-
sides being a practical manual for field measurement quality control, the report contains
a number of worked examples demonstrating the methods and calculations of the man-
ual. Finally, spreadsheets have been prepared as calculation aid for the manual proce-
dures and those can be obtained from the authors of the report.
The work was supported by Nordic Innovation Centre under contract 04210 (1642-03).
The project group was:
Christian Grn, DHI Water & Environment,
Jacqueline Anne Falkenberg, NIRAS A/S,
Jens Strodl Andersen, JSA-EnviroStat,
Marion Brresen & Arne Pettersen, Norwegian Geotehcnical Institute,
Sren Nilsson and Karsten Hkansson, Swedish Geotechnical Institute,
Jussi Laiho, Geological Survey of Finland
v
ABSTRACT
Field measurements are widely used in investigations on contaminated sites as alterna-
tives to and supplementing analysis in chemical laboratories. The requirements for
measurement quality and quality control of field measurements are less stringent than
those for laboratory analysis. The present manual provides an introduction to the con-
cepts and calculations of analytical quality control, a set of quality requirements for
field measurements for different purpose and intended use of the measurements, a selec-
tion of quality control methods selected to be of practical use and supply the quality in-
formation required in site investigations and a set of examples demonstrating the practi-
cal use of the manual. Statistical factors and control charts are included as appendices.
vi
1 INTRODUCTION
Field measurements are important tools in environmental monitoring and control with
applications at two different levels:
Compliance testing, e.g.:
Determination of contaminant concentrations with accept or rejection of an item

as uncontaminated relative to maximum contaminant concentrations
Decision support, e.g.:
Provision of increased data basis real time for dynamic planning of an investiga-
tion
The quality requirements for the two levels will be different due to the different conse-
quences of false decisions. It is therefore essential for the use of field analysis to be able
to quantify the quality of the measurements and thus to estimate and evaluate the risk of
errors.
For laboratory analysis, documentation of the analytical quality is done with accepted
methods for quality control, and the resulting uncertainties on measurements are re-
ported with the results.
For field measurements, quality control is far less established but with the increasing
use and acceptance of these methods, quality control procedures giving the required es-
timates of precision and trueness of the applied methods is likely to become mandatory.
For investigations on contaminated sites, the use of field measurements of soil and
groundwater samples is currently increasing at both levels in e.g.: the US. Examples are
the inclusion of field methods as official standard methods of the US Environmental
Protection Agency (EPA), the launching of the triad investigation approach with real
time field measurements as a corner stone and the court acceptance of field measure-
ments reliability.
1
2 SCOPE
This manual provides methods for quality control of field measurements at contami-
nated sites (soil and groundwater) taking into account the different quality requirements
for different purposes. The use of the methods is demonstrated with 4 examples cover-
ing different measurement principles, contaminant types and purposes.
As part of the manual, a set of quality classes and quality requirements for field meas-
urements is developed in order to apply quality requirements compliant with the pur-
pose of the measurement, see chapter 4.
The manual does not cover sampling methods and quality control of sampling (see e.g.:
/1/ and /2/), methods of analysis (see e.g.: national and international standards) and
validation data for field measurements (see e.g.: /3;4/) s these topics are well covered
elsewhere. Also, suggested statistical procedures are given in the manual, but for details
and background of the statistics, the reader is referred to international standards, text-
books and research papers as indicated in the manual text.
The manual is intended for use by the field investigation responsible in planning and
evaluating field measurements, and for those performing field measurements.
The manual is a compilation of methods suggested in the literature for validation of

field analytical methods, for evaluation of sampling quality and for laboratory quality
control. Special reference is made to 3 Nordic manuals for laboratory quality assurance
/5-7/.
2
3 REQUIREMENTS FOR ANALYTICAL QUALITY IN SOIL AND
GROUNDWATER INVESTIGATIONS
In the Nordic countries, requirements for analytical quality have not been put forward
dedicated to field measurements. However, the general requirements for analytical qual-
ity of soil and groundwater analysis in investigations on contaminated sites are summa-
rised for the Nordic countries in table 3.1.
Table 3.1 General requirements for analytical quality of soil and groundwater analysis in in-
vestigations on contaminated sites in the Nordic countries.
Denmark Finland Norway Sweden
Detection limit 1/10 of maxi- Not specified Must be known3 Not specified
mum contami-
nant concentra-
tion1,2
Precision 10-20% relative Not specified Must be known Not specified
standard devia-
tion
Trueness Not specified Not specified Must be known Not specified
In the Drinking Water Directive /8/, a trueness of 75-125%, a precision better than 25%
RSD and an analytical detection limit below 10-25% of the maximum contaminant con-
centration, MCC, are required.
Generally in environmental control, it is recommended or required to use laboratories

accredited according to the international standard for ISO 17025 /9/ and analytical qual-
ity will generally be stated in the accreditations.
The Danish Environmental Protection Agency (DEPA) has defined 3 quality classes for
analysis to be used in environmental monitoring and control (table 3.2, see chapter 5 for
definitions of terms), and most methods for soil and groundwater investigations are re-
quired to meet the class 2 requirements /10/. Required quality classes have not yet been
defined for most organic contaminants, but quality class 3 or a new, less demanding
class 4 is likely to be applied.
Table 3.2 Definitions of Danish quality classes for analysis used in environmental monitoring
and control
Class 1 Class 2 Class 3
Detection limit Depend upon analyte Depend upon analyte Depend upon analyte
Precision <3% relative stan- <5% relative stan- <7% relative stan-
dard deviation dard deviation dard deviation
Trueness 98-102% recovery of 98-102% recovery of 95-105% recovery of
true value true value true value
Accuracy 90-110% recovery of 80-120% recovery of 70-130% recovery of
true value true value true value
1
Legal limit value, regulatory limit, quality criterion
2
/24/
3
For laboratory analyses, accredited analyses are required and according to /9/, analytical performance
parameters must be known and documented
3
It is generally required by DEPA that the analytical detection limit is below 1/10 of the
maximum contaminant concentration controlled and the precision better than 10-20%
relative standard deviation (% RSD) /11/ in investigations of Danish contaminated sites.
The requirement for an analytical detection limit below 1/10 of the maximum contami-
nant concentration is mainly empirical and based upon assumptions on the distribution
of random and systematic errors. An alternative requirement is derived below.
A statistically based calculation of analytical detection limits is frequently used, see sec-
tion 5.1.2, accepting a risk of false negatives of 5% or below (detection limit equal to 4-
5 times the standard deviation of blank determinations or determinations close to blank
samples). In the measuring range close to the detection limit, the RSD is best described
including both the blank standard deviation and a standard deviation contribution pro-
portional to the component concentration /12/. For this approach, the relation between
detection limit, component concentration, precision as % RSD and the width of the 95%
confidence interval of measurements is given in table 2.3 (/12; 13/).
Table 3.3. Relationship between limit of detection, component concentration, precision and
confidence interval of measurements assuming a 10% RSD at high concentrations
(/12; 13/).
Concentration Relative standard deviation 95% confidence interval
for analytical result
(%) (%)
1* detection limit 24 44
Table 3.3 shows that for component concentrations above 3 times the analytical detec-
tion limit, little is gained by improving the detection limit with respect to precision.
Above 3 times the analytical detection limit, the relative standard deviation is better
than 12% and the risk of being more than 25% wrong is below 5%, as long as random
error only is considered. It should be noted that if the proportional % RSD at high con-
centrations is increased to above 12,5%, the confidence interval will increase accord-
ingly to above 25%.
4
4 QUALITY CLASSES FOR FIELD MEASUREMENTS
The requirements for measurement quality must match the intended use of the meas-
urements. Therefore, three separate quality classes are defined for field measurements,
table 4.1. The definitions of the classes combine the type of measurement obtained with
the intended use of the measurements in order to enable establishment of viable and suf-
ficient but not excessive quality requirements.
It should be mentioned here that the uncertainty estimates obtained from quality control
of field measurements to some extent will include variability due to site inhomogenei-
ties in time and space.
4.1 Definitions
Quantitative field measurements are intended to control compliance with regulatory lim-
its, criteria or maximum contaminant concentrations.
Alternatively, field measurements are used only as an aid during investigations, i.e.:
help to find when well purging is sufficient or to select soil samples for analysis. These
methods may be relative, i.e.: designate one sample to have a higher concentration than
another, or range methods, i.e.: show that the concentration in a sample is within a de-
fined range.
Table 4.1 Definition of quality classes for field measurements

Quantitative Relative Range
methods methods methods
Measurement Value Value Interval
type
Application of Compliance testing of Comparison of values Selection of samples
measurement concentration against with concentrations
maximum value above or below target
value
Example Measurement of heavy Measurement of PID5 Measurement of nitrate
metals in soil with XRF4 response during drilling in groundwater during
in order to identify un- in order to identify soil well purging to deter-
contaminated sections samples contaminated mine required pumping
of a site with volatiles for labora- before sampling
tory analysis
The same type of equipment could be used for quantitative and relative measurements,
but the method performance and the quality requirements will differ. Range methods
typically can not be calibrated and do not allow for conventional analytical quality as-
sessment. It should be noted that uses of range methods for relative purposes or even for
compliance testing have been suggested, typically involving large numbers of samples
measured to improve the precision of characterising very heterogenic media.
4
X-ray fluorescence
5
Photo ionization detector
5
Most applications of field measurements in the Nordic countries are at present as rela-
tive or range methods, but the current trend in e.g.: the US is to apply field methods for
compliance testing to an increasing extent.
4.2 Quality requirements

The highest requirements are set for quantitative measurements that must comply with
requirements corresponding to those set for laboratory analysis, but considering also the
sampling precision, see chapter 5. Based upon the laboratory analytical quality require-
ments, a set of requirements for the quality of quantitative field measurements, includ-
ing to some extent the contribution from sampling, is suggested.
It should be noted that it is the total data quality for quantitative field methods that
should be comparable to or better than the quality of accredited laboratory analysis. This
objective can be fulfilled either using methods of an analytical quality comparable or
superior to that of the laboratory methods, or by analysing a larger number of samples
and thus improving the overall precision, see chapter 5.
An analytical detection limit of of the maximum contaminant concentration (concen-

tration to be controlled 4 times the detection limit) is suggested as sufficient. Further-
more, a requirement for 10% RSD from random analytical error and for 5% mean sys-
tematic error (95-105% trueness) is suggested (see chapter 5 for definitions and
explanations of terms). These requirements correspond to accepting a risk of being up to
25% wrong at a 95% confidence level, considering the analytical or measurement error
only.
As the precision estimated for field analysis will include both the analytical precision
and the sampling precision, the 10% RSD requirement must be modified. In this man-
ual, it is suggested to apply a requirement for a 50% RSD on field measurements, in-
cluding both the analytical and the sampling variability. With this RSD requirement,
approximately of all samples will have an accuracy in the range 50-150%.
Lower requirements are set for measurements that are used only as an aid during inves-
tigations, i.e.: the relative and range methods.
For relative methods, it is generally not necessary to set requirements for the trueness
and accuracy of the measurements, but the purpose of the investigation may still require
that the trueness and accuracy are known in order to enable evaluation of the obtained
data quality.
It should be emphasised that for some relative field methods, there is a correlation be-
tween the field result and the result of laboratory analysis for the same sample, but not a
correspondence, see section 5.3.2. For these relative methods, the correlation between
field measurements and laboratory analysis should as a minimum be known, in addition
to the range of accuracies obtained.
For range methods, it should further be noted that a range limit close to the maximum or
target concentration for the parameter in the investigation is likely to give a high fre-
quency of false results. Also, according to the use of range data it may be necessary to
6
apply different requirements for false negatives (we overlook contamination) than for
false positives (we overestimate contamination).
Table 4.2 summarises the suggestions for quality requirements used in this manual, re-
fer to chapter 5 for definitions and explanations of terms. It should be noted, that quality
requirements should always be held against the purpose of the measurements in order to
obtain adequate data quality.
Table 4.2 Suggested quality requirements for field measurements

Quantitative Relative Range
methods methods methods
Detection limit 1/4 of maximum con- All measurements in Maximum concentra-
taminant concentra- decision area above tion above detection
tion detection limit limit
Precision including <50% relative stan- Relative standard Not relevant
sampling dard deviation deviation known
Trueness 95-105% recovery of If required: known Range correctness
true value recovery of true above 90%
value or correlation
factor
Accuracy 50-150% recovery of If required: known Error max 1 range
true value recovery of true
value or correlation
factor
Linearity All measurements in All measurements in All measurements in
decision area within decision area within decision area within
linear range linear range application range
7
5 ANALYTICAL QUALITY CONTROL
The terms and definitions applied in this manual are derived from and to the widest ex-
tent possible compliant with the terms and definitions applied in laboratory quality con-
trol /10;14/. For a more detailed description and explanation of the concepts, methods
and statistics behind laboratory analytical quality control, the reader is referred to a
handbook on the subject prepared for users of analytical data /15/.
5.1 Definitions
The key concepts of analytical quality and their interrelationships are traditionally visu-
alised as in figure 5.1.
Each star symbolises a measurement, and if both precision and trueness is good, the
measurement is close to the true value of the contaminant concentration in the center
spot of the target. The aim of all methods for measurement will of course be as shown
in the lower left corner of figure 5.1.
Trueness
Good Bad
Bad
Precision
Good
Figure 5.1 Visualisation of the concepts of precision and trueness
5.1.1 False positive, false negative and correct measurements

A measurement is false positive, if the presence of a contaminant above a threshold is
shown when the contaminant is not present above that threshold. A measurement is
false negative if the measurement rejects presence above the threshold when the con-
taminant is in reality present above it. Measurements are correct if they are correctly
measured to be above and/or below the stated lower and/or upper thresholds.
8
The frequency of false positives, fp, is calculated as the ratio between the number, np, of false positive
measurements and the total number, nt, of measurements controlled by laboratory measurements and
expressed in percent:
np
f p = 100 %
nt
In the calculation it is assumed that the laboratory measurements give the true values.
The frequencies of false negatives and correct measurements, fn and fc respectively are calculated analo-
gously from the numbers of false negative, nn, and correct, nc, measurements:
nn
f n = 100 %
nt
nc
f c = 100 %
nt
In this manual, the concepts of false positive, false negative and correct measurements
are used for range methods only. For quantitative and relative methods, the concept of
detection limit is used instead.
5.1.2 Detection limit

The detection limit, DL, for a quantitative or a relative method can be calculated from
the precision obtained measuring the concentration in blank samples or in samples with
a low concentration. If calculated as done in this manual, measurements above the DL
have a probability of false positives below 0,5% and the probability of false negatives
below 5%. At the DL, the precision estimated as relative standard deviation is approxi-
mately 20%.
Calculation of the detection limit, DL, can be done from:
1
DL = 2 t 0.95 (df) sb 1 +
n
with:
n= number of blank determinations used in routine measurements for correction of results

sb = standard deviation obtained with m replicate measurements of blank samples or samples with
less than 5 times the concentration resembling the anticipated DL
df = number of degrees of freedom (m-1) for determination of sb
t0.95 = Student t factor from tables with 95% confidence level and the df of the sb determination, see
appendix 1
If no blank correction is used, the DL calculation can be done from:
DL = 2 t 0.95 (df) sb
9
With duplicate blank determinations in each measurement series and 6 replicates deter-
mining the blank standard deviation, sb, the DL is approximately 5 x sb. This calculation
can also be used when blank correction is not applied but will here give a slightly higher
DL than required (x 1,2). Still, for simplicity it is suggested to apply the same calcula-
tion for methods with and without blank corrections.
According to some conventions, the DL is calculated as 3 x sb and according to others

as sb x t0,99, but both methods will give a slightly lower DL and accordingly higher risks
of false results and also a decreased precision close to the DL.
In evaluation and interpretation of data, it can be required to associate a number with a

measurement that is in reality <DL, i.e.: below the detection limit. In this manual,
measurements <DL are set to *DL. Data below the detection limits should not be used
for decisions, as differences among them in reality only reflect the random scatter of
blank samples.
5.1.3 Precision and uncertainty

The scatter of measurements if repeated is described with the precision, see section
5.1. The uncertainty is a measure of the randomness of a single measurement and calcu-
lated as given below.
If a sample with true value is analysed in infinite replicates, the results will group
around the true value in a bell like shape (the normal distribution) with the width de-
termined by the true standard deviation: . Most of the measurements (95%) will be
found within the interval 2, see figure 5.2.
95,44%
-2 +2
Figure 5.2 Normal distribution of measurements
Parameters such as contaminant concentrations are frequently not normally distributed

and the assumptions behind a number of other statistic procedures not valid. In these
cases, either logarithmic transformation (although the concentrations do not follow the
normal distribution, the logarithm to the data might) or robust statistics (statistic ap-
proach where extreme values receive decreased weight in calculations) may be applied.
In order to keep the field measurement quality control simple, these more advanced sta-
10
tistical procedures are not introduced here, and the reader is referred to textbooks on sta-
tistics.
Neither the true value, nor the true standard deviation is known in reality as we are
not capable of performing an infinite number of measurements and as we can not ex-
clude systematic errors in the measurements. Therefore, the terms mean, x , and stan-
dard deviation, s, are used:
The mean, x , is calculated from n replicate measurements, xi, as:
x=
x1 + x 2 + .... + x n
=
x i
n n
The standard deviation, s, is calculated from the n replicate measurements, xi, as:
s=
(x i x)2
n 1
s and x are conveniently calculated using spreadsheets or calculators.
The precision can be given as the relative standard deviation, RSD, in percent:
s 100
RSD = %
x
The precision of a measurement is determined as the standard deviation, s, of replicate

measurements on the same sample.
In evaluating precision of analytical methods, it is important to emphasize that the stan-

dard deviation in a reasonable approximation increases linearly with the concentration:
The standard deviation, s, can as a reasonable approximation be described as a linear function of the
blank standard deviation, s0, and the concentration, c, with k as a constant:
s = s0 + kc
Below the detection limit, the blank standard deviation, s0 will dominate the overall measurement stan-
dard deviation, s, unless the standard deviation contribution proportional to the component concentra-
tion, kc, is very large.
Accordingly, the RSD will decrease with increasing concentration and approach a con-
stant value with a concentration above approximately 100 times the DL, see figure 5.3,
for many geochemical applications /16/. Still, the concentration where RSD has reached
a constant value will depend upon the matrix analysed and the method used. If it is im-
portant to know if this is the case, constant RSD should be checked on a case by case
basis.
11
Relative standard deviation
Standard deviation
Concentration Concentration
Figure 5.3 Relations between standard deviation, relative standard deviation and concentration, modi-
fied after /17/.
The uncertainty, U, of a single measurement can be calculated with a coverage factor of

2 giving the 95% confidence interval and thus the interval around a measurement that
will include the true value with 95% certainty. This uncertainty should include all
steps from sampling to measurement.
The uncertainty, U, can be calculated as:
U = 2 s
and the result, xi, reported as:
X = xi 2 s
giving the range of the true value with 95% confidence.
If the mean, x , of n replicate measurements is reported, the uncertainty, Un, on the mean can be calcu-
lated as:
2 s
Un =
n
and the mean result reported as:
2 s
X =X
n
Two important points should be considered here:
The larger the number of measurements behind the calculation of s, the smaller the
value of s.
The larger the number of measurements behind the calculation of X , the smaller the
value of U.
12
The uncertainty presented here includes only the effect of random scatter and should not
be confused with the term expanded uncertainty that includes also systematic errors,
see section 5.1.4.
5.1.4 Trueness and bias

The correctness of a method is described with the trueness that estimates how close the
mean of an infinite number of measurements will come to the true value, see figure
5.1. The difference between the mean of infinite measurements and the true value is
called bias and is the result of any systematic error of the measurement method. The
trueness and bias of a method can only be calculated from an infinite or in reality a large
number of measurements.
Trueness is calculated from the mean, x , of n measurements, xi, and the accepted true or reference
value, T, for the same material:
x
Trueness = 100 %
T
Similarly, bias can be calculated as:
x T
Bias = 100 %
T
As stated before, the true value is never known exactly. Participation in interlabora-
tory comparisons or replicate analysis of certified reference materials with accepted
true concentrations are the tools used to estimate trueness and bias in laboratory qual-
ity control.
In field measurements, the true value will mostly be the corresponding laboratory
analytical result obtained for a subsample of the sample measured with the field
method, where the laboratory analytical result is obtained with recognised methods with
documented and sufficient quality in an accredited laboratory
5.1.5 Error and accuracy

If a single measurement is made, this will deviate from the true value due to random
scatter (uncertainty) and to any systematic error or bias. This deviation is then a sum of
random and systematic errors, and it is termed error. The accuracy is the correctness of
a single measurement. Error and accuracy are calculated from single measurements:
Accuracy is calculated from one measurement, xi, and the accepted true or reference value, T, for the
same material:
xi
Accuracy = 100 %
T
Similarly, the error can be calculated as:
xi T
Error = 100 %
T
13
5.1.6 Linearity
A measurement method is considered linear if the measurements follow a straight line
when plotted against the concentration. Linearity is mostly established by calibration of
analytical equipment.
A straight line is described by the line equation:
y = ax + b
or for an analytical measurement:
measurement = a concentration + b
The constant a is the slope of the calibration curve and reflects the sensitivity of the method. The con-
stant b is the intercept and reflects the blank contribution in the method.
In reality, measurements will be scattered around the straight line to a degree depending
upon the precision of the method.
5.2 Control Types

The analytical quality control relies upon a limited number of control types or methods,
that combined with appropriate statistical methods provide estimates of the uncertainties
and errors related to a measurement as described in section 5.1. Table 5.1 summarizes
the kind of information available from using each of the control types.
Table 5.1 Analytical quality information obtainable from different control types
Instrument Method Method False posi- Detection
linearity and precision trueness tives and/or limit
response negatives
Calibration
and check
Control
samples
Blank 6
samples
Duplicate ()7
samples
Spiked ()8
samples
Laboratory
comparison
Each control type is described in more details in the subsequent sections. Principles
rather than procedures for preparation of the control samples control samples are given.
For detailed procedures, the reader is referred to analytical quality control literature
such as /18/.
6
Helps preventing only false positives
7
If only samples with concentrations below 5 x the anticipated DL are included
8
Helps preventing only false negatives
14
Only control types suggested for use with field measurements (see chapter 6) are de-
scribed below.
5.2.1 Calibration and check of instrument

Basic calibration of instruments is generally described in manufacturers manuals and
will mostly include setting the blank reading to zero and a max. reading to max. value.
Quantitative and relative methods will in most cases require establishment of a calibra-
tion curve, where the instrument reading is obtained for samples prepared with known
concentrations (standards) from the detection limit to the end of the linear range.
Preparation of aqueous standards is straightforward, where dilutions of a concentrated

stock solution to a range of lower concentrations can easily be done. Reference is made
to textbooks of analytical chemistry or analytical quality control for exact procedures.
Preparation of soil standards is less straight forward, and if a field method uses direct
measurement on soil samples (as is the case with e.g.: XRF), a set of soil samples with
known and accepted concentration can be used. If the analytes (the components ana-
lysed for) are transferred to a solution before measurement (as is the case in e.g.: immu-
noassay for PCB in soil), a standard curve can prepared using the solvent (water, or-
ganic solvent) used in the extraction of the soil samples.
When soil standards of matrix comparable to the soil samples in question are not avail-
able, the field instrument can be calibrated against results obtained with recognised
methods with documented and sufficient quality in an accredited laboratory. True dupli-
cate samples should be analysed using the field method and in the laboratory in order to
make sure that the calibration is based upon analysis of the same sample. Not less
than 5 calibration points should be employed. Evidently, results from the same samples
and analyses can not be used both for calibration and external control, see section 5.2.6.
Check of instrument is done with samples of known concentration, zero and in the up-
per part of the measuring range of the instrument for quantitative and relative measure-
ments. For range methods, manufacturer DL is checked with a control sample (see sec-
tion 5.2.2) prepared with or known to have a concentration 1,25 times the detection
limit (1,25 x DL) which must give a measurement in the first measuring range above
DL. Also, a control sample at concentration 1,25 x lower limit of the upper range is
checked and this must give a measurement in the upper range. If the instrument needs
calibration, the checks are done after calibration to include the calibration in the checks.
Also, the check samples should always be independent of the calibration standards or
stock solutions, preferentially prepared from separate batches of chemicals or bought as
independent control samples, see below. The control samples should be of the same
general matrix as the samples to be measured with the instrument, i.e.: water samples,
soil samples or extracts. Check samples for control of measurements on water samples
and extracts are most conveniently spiked samples, see section 5.2.2, whereas a certified
control sample or a control sample with concentration verified by laboratory analysis,
again see section 5.2.2, is easier to work with for soil samples.
15
5.2.2 Control samples
Control samples are samples with a known concentration. The concentration can be
known because the operator has added the compound in question to a blank sample in a
known and documented amount (spiked control sample, see section 5.2.5). Alterna-
tively, a control sample may be purchased with a certified concentration (certified con-
trol sample) or the control sample may be one with concentration verified by laboratory
analysis (verified control sample). The certified or verified concentration should be con-
trolled by independent laboratories and accepted methods.
Control samples must be stable and homogenous in order to provide a reasonable true
value to compare control measurements with.
It is straightforward to prepare aqueous control samples for nonvolatile compounds as

explained above for calibration standards. For volatile compounds, such as chlorinated
solvents, control samples should be purchased and suppliers procedures followed in
preparation and handling of the control samples. Still, if the field measurements are
done by laboratory technicians in a field laboratory, aqueous control samples can also
be prepared for volatile compounds.
Soil control samples should generally be purchased. Still, if a large quantity of homoge-
nous and stable soil sample is prepared and analysed by field measurement and labora-
tory analysis as suggested in this manual, this may substitute purchased soil control
samples. The homogeneity and stability of custom prepared control sample batches
shall be controlled at regular intervals.
It should be noted that commercial control samples will frequently be of another spe-
cific matrix than the field samples analysed for in the investigation, i.e.: it may be a soil
control sample, but it is not the same soil type as the field soil samples. Differences may
be with respect to ionic strength of water samples, other components present or humid-
ity of soil samples. Furthermore, commercial control samples are often more homoge-
nous than field soil samples. For these reasons, control samples will give a different and
generally better picture of the measurement quality than field control samples.
5.2.3 Blank samples

A blank sample is a sample without a measurable content of the compounds measured
for.
Again, it is for most purposes straightforward to obtain a blank water sample. Blank wa-
ter can be purchased with declared maximum concentrations of most compounds rele-
vant to groundwater investigations. Also, blank water can be produced in most analyti-
cal laboratories and can be obtained from there. It should be emphasized that blank
water is not stable for all compounds, as e.g.: BTEX9 or ammonia can be taken up from
the ambient air.
Blank samples for soil can be obtained for most organic contaminants by heating quartz
sand to above 450C over night, cooling protected against contaminated air and storage
protected against contamination. For many purposes, quartz sand as purchased may be
satisfying, but concentrations below the detection limit of the field measurements
9
BTEX: benzene, toluene, ethylbenzene and xylenes
16
should be checked by laboratory analysis. Blank samples for inorganic contaminants
such as heavy metals are not easily obtained. As a substitute, low level background
samples may be used.
5.2.4 Duplicates
Duplicate samples are two subsamples of one sample taken at one position at one time.
In the American literature, the term used is split samples.
For groundwater, duplicate samples for nonvolatiles should be prepared by taking a

sample in a larger, clean container, mixing it thoroughly and separating it into two sam-
pler containers as those used for all other samples. For volatiles, it may be necessary to
take the two subsamples directly in the sample containers, but care shall be exercized to
take the samples as close in time and space as possible without changing parameters
such as pump yield or position.
For soil, duplicates samples are taken from the same grab, spoon or auger position. For
nonvolatiles, the soil samples is thoroughly mixed in a clean container at the least ten
times larger than the volume of soil sample and then distributed into two sample con-
tainers as those used for other samples. If the field equipment is operated with direct
measurement on the soil surface, a surface is cleared just large enough to enable meas-
urement of two adjacent soil surface positions. If one of the subsamples is to be submit-
ted for laboratory analysis, half of the cleared surface is used for sampling into a sample
container supplied by the laboratory.
It should be mentioned that the replicate readings that many instruments offer are valid
only for estimation of the instrument variability. Separate measurements of true repli-
cate samples as described above are required to obtain the measurement variability.
5.2.5 Spiked samples

Spiked samples are samples from the field that are added a known amount of the com-
pound(s) measured for.
For groundwater, preparation of samples spiked with nonvolatiles is attainable. A

groundwater sample is filled into a sample bottle until a mark indicating the volume of
sample is reached. A known amount of stock solution with known high concentration is
added, the spiked sample is thoroughly mixed and the sample is transferred to a sample
container as those used for the other samples. The volume of stock solution should be
not less than 1 mL and not more than 1% of the volume of the sample under spiking.
Stock solutions should be prepared in the precise volume to be used for spiking by an
analytical laboratory or purchased as such. Still, if the field measurements are done by
laboratory technicians in a field laboratory, spike volumes can be pipetted in the field
from larger volumes of stock solution.
Preparation of a groundwater sample spiked with nitrate can be done as follows:
Fill groundwater sample directly from the sampling tube into a 100 mL clean flask until the 100 mL
mark has been reached.
Add 1 mL stock solution with 1000 mg nitrate/L from a 1 mL vial to the 100 mL flask.
17
Close and shake vigorously.
Use a small amount of the mixed sample to rinse the vial and pour the rinse back into the 100 mL
flask.
Close and shake vigorously.
The sample is now spiked with 10 mg nitrate/L in addition to the original sample concentration and
can be used to control that new measurements reflect this difference.
For soil samples, it is virtually impossible to produce valid spiked samples in the field.
One reason is that mixing of soil after spiking to obtain fairly homogenous distribution
of the added compounds is almost impossible in the field, another reason is than most
soil contaminants becomes bound to the soil matrix over time giving an entirely differ-
ent composition compared to a newly spiked sample. It is not recommended to pre-
pare spiked soils samples in the field for quality control of field measurements.
5.2.6 External control

In laboratory quality assurance, control of trueness and accuracy is by analysing certi-
fied reference materials (samples with a known and accepted concentration after analy-
sis with recognised methods and by several laboratories) and by participation in interla-
boratory comparisons (analysis of the same samples with recognised methods and by
several laboratories).
Certified reference materials (CRMs) may be of use in quality control of field meas-
urements, but due to the matrix and homogeneity aspects described above mostly for in-
strument check rather than for controlling the measurement trueness and accuracy.
Interlaboratory comparisons in the form of joint measuring sessions with field equip-
ment is an option but not generally available.
The primary tool for control of field measurement trueness and accuracy is comparison
of field measurements with measurements performed at an accredited analytical labora-
tory using recognised methods with documented and sufficient analytical quality. Labo-
ratory comparison is made by submitting duplicate samples to laboratory analysis, while
performing field measurements of the other duplicate.
5.3 Statistics and Calculations

The methods applied in this manual for quality control are to the widest extent possible
compliant with methods used in laboratory quality control and assurance /5;7/, with ad-
dition of methods complying with the field operation and the application of field meas-
urements.
The subsequent section gives a description of those statistical procedures and calcula-
tions that are suggested for use in this manual. Other methods may be equally valid.
Also, the formulas for the calculations are given, but in most cases the calculations are
18
most conveniently performed with the help of calculators, spreadsheets or simple statis-
tical software.
It should be mentioned here that control charts are widely used in laboratory quality
control in order to assure continuous surveillance of the analytical performance real
time. This tool is not generally suggested for field measurements in this manual mainly
due to the difference in time between instrument check out, measurement (in the field)
and full quality control data availability (after laboratory analysis).
5.3.1 Linear regression

The calibration curve is validated with linear regression according to the least squares
method. From the regression analysis, the slope 1 (= a in section 5.1.6), the intercept 0
(=b in section 5.1.6) and the coefficient of determination, R2, are obtained as standard.
The coefficient of determination, R2, gives an estimate of the explanatory power of
the linear model. In other words: a R2 of 0,95 indicates that 95% of the variation of the
calibration curve is explained by the linear relationship.
The calibration curve should always be plotted, as deviations from the linearity may be
easier spotted using the eye than from a R2 value far from unity. Furthermore, plotting
the line helps getting the picture of the linear range that allows for correct measure-
ments.
Linear regression and plotting of calibration curve is most conveniently done using a spreadsheet. The
procedures behind the spreadsheet calculations are shown here.
If the analytical measurement is Y and the calibration standard concentrations are x, the linear regression
model can be written as:
Yi = 0 + 1 xi + i
where i is the normally distributed error term, expressing the deviation from the straight line. The re-
gression coefficients can be estimated as:
0 = Y 1 x
where:
1 =
Y (x x)
i i
(x x)i
2
The coefficient of determination is calculated as:
R2 = 1
(Y Y ) i i
2
(Y Y ) i
2
where:
Yi = 0 + 1 xi
19
An example of a plot of analytical measurement against calibration standard concentrations are given
below for photometer absorbance measured after colour reaction to measure nitrate in water.
2,5
y = 0,0041x - 0,0075
2
R2 = 0,999
Measured absorbanse
1,5
0,5
0
0 100 200 300 400 500 600
Concentration (mg nitrat/L)
Evidently, the highest concentration is not within the linear range, but including this measurement in the
linear regression would only diminish the R2 to 0,996 and thus by no means indicate the evident lack of
linearity at high concentration. The method should after this calibration only be used below 220 mg ni-
trate/L which is the highest concentration measured within the linear range.
The information that can be obtained from linear regression is whether there is a corre-
lation between the x- and y-values (coefficient of determination, R2, close to unity).
Furthermore, the slope and the intercept can be used to estimate x values from y values,
i.e.: the concentration in a sample from a measurement. The linear regression does not
give information on the uncertainty associated with this estimate.
Residual plots (plots of the errors not explained by the linear relationship) may help in
interpreting divergences from linearity but for simplicity, these are not considered here.
The reader is referred to textbooks on statistics or statistical software with that option.
5.3.2 Inverse linear regression

In order to obtain an estimate of the trueness of the method, see section 5.1.4, the field
measurements are plotted against the results of laboratory analysis for duplicate sub-
samples. An inverse regression analysis can be used to estimate the true value associ-
ated with a measurement /19;20/. As an additional benefit, the uncertainty associated
with the calculated trueness can be estimated, here as the interval containing the real
trueness with 95% confidence. In some contexts, this interval is termed the Fiducial
limits. The inverse regression analysis is described briefly below but for further aspects
and background, reference is made to textbooks in statistics /19;20/.
20
Inverse regression analysis for estimation of trueness and associated uncertainty
A set of n field measurements (Y) and laboratory analysis (x) are fitted to a straight line with the equa-
tion:
Yi = 0 + 1 x i + i , i=1,2,,n
where ei is expressing the deviation from the fitted straight line. 0 is the intercept and 1 is the slope
of the line, both can easily be found using a simple calculator or a spreadsheet.
A value of the field measurement, Y0 , is selected or measured and a natural estimate of the true value,
x 0 , is found by solving the fitted equation above for x. 0 and 1 are the true values of the intercept
and the slope, respectively, and x and Y are the mean values of the field measurements and laboratory
analysis, respectively:
Y0 0 Y Y
x 0 = =x+ 0

1 1
In the calculations, the 1 value obtained with the simple linear regression on the data is used as a rea-
sonable estimate of 1 . Besides the predicted true value x 0 , it is of equal importance to obtain infor-
mation on how certain the prediction is, i.e.: a confidence interval surrounding x 0 . A 100- % confi-
dence interval for x 0 is given by [x + d1 ; x + d 2 ] , where d1 and d2 are the real roots of the quadratic
equation:
2 s 2

d 2 12

2
( ) (
2d1 Y0 Y + Y0 Y )2 2 s 2 1 + 1n = 0
( xi x )

solved with respect to d, where
s2 =
1
n2
{ (Y Y )
i
2
12 (x i x)2 }
and the confidence level is determined by the statistical factor (appendix 2 gives the factors for 95% con-
fidence intervals):
= t n(1/22)
Quadratic equations on the form:
ad 2 + bd + c = 0
are generally solved using the equation:
b D b+ D
d1 = and d 2 = where D = b 2 4ac
2a 2a
However, if D becomes negative the quadratic equation has no real roots and this inverse regression
method can not be used. This situation only occurs if the data set departs strongly from linearity.
The parameters a, b and c are then here:
21
2 s 2
a = 12 ( ) (
, b = 21 Y0 Y , c = Y0 Y )2 2 s 2 1 + 1n
( xi x ) 2
Said in other words: with a field measurement, selected or real, of Y0, the corresponding expected labora-
tory result x 0 can be estimated with 95% confidence limits. The value Y0 may be selected corresponding
to the maximum contaminant concentration to be controlled or as the median of the field measurements
if an evaluation of the overall measurements is more useful.
The trueness, T, of the field measurements can accordingly be calculated from:
Y0
T= 100 %
x 0
The lower and upper confidence limits of the expected laboratory result, x and x
l u
0 0 can be found as:
x l 0 = x + d1 , x u 0 = x + d 2
The lower and upper confidence limits, Tl and Tu, for the trueness are accordingly:
Y0 Y0
Tl = 100 %, T u = 100 %
x u
0 x l 0
The statistical calculations may appear complicated but are in reality simple as can be seen from the be-
low presented example. The calculations are most conveniently set up in a spreadsheet that will allow
fast and easy performance of the statistics.
The calculations presented here are valid only if one field measurement is done for each sample with a
laboratory result. The calculations can be extended to include also cases with 2 or more field measure-
ments done on each sample with a laboratory result.
Example of inverse regression analysis

Laboratory 0 5,00 10,0 15,0 20,0 30,0 50,0 70,0 90,0 100
data, x
Field data, Y 0,72 4,50 8,95 16,4 20,0 29,3 55,3 72,0 89,0 104
xi x -39 -34 -29 -24 -19 -9 11 31 51 61
( xi x ) 2 1521 1156 841 576 361 81 121 961 2601 3721 11940
Yi Y -39 -36 -31 -24 -20 -11 15 32 49 64
(Yi Y ) 2 1544 1262 965 558 400 115 234 1023 2399 4094 12593
Selected value: Data count value: Table value:

Y0=25,0 n = 10 = 2,31
Simple calculated values (calculator, spreadsheet):
x = 39.0 Y = 40.0 1 = 1.02554
Statistical calculations:
Y Y 25.0 40.0
x 0 = x + 0 = 39.0 + = 24.4

1 1.02553
22
s2 =
1
n2
{ (Y Y )
i
2
12 (x i }
x)2 =
1
10 2
{
12593 1.02553 2 * 11940 = 4.44}
2 s 2 2.312 * 4.44
a = 12 = 1.025532 = 1.05
(x i x)2 11940
( )
b = 21 Y0 Y = 2 * 1.02553(25 40) = 30.8
c = Y0 Y( )2 2 s 2 1 + 1n = 12593 2.312 * 4.441 + 101 = 200

D = b 2 4ac = 30.8 2 4 * 1.05 * 200 = 109
b D - 30.8 - 109 b+ D - 30.8 + 109

d1 = = = 19.6 d1 = = = 9.67
2a 2 * 1.05 2a 2 * 1.05
Calculated field data and method evaluation values:

Selected or measured field concentration, Y0: Corresponding expected laboratory result, x 0 :
25.0 24.4
Lower confidence limit: Upper confidence limit:

x l
0 = x + d 1 = 39.0 19.6 = 19.4 x u 0 = x + d 2 = 39.0 9.67 = 29.3
Trueness: Lower trueness limit:

Y 25,0 Y 25.0
T = 0 100 % = * 100% = 103% T l = u0 100 % = 100 % = 85.3%
x 0 24,4 29.3
x 0
Upper trueness limit: Trueness reported:

Y 25.0 T = 103% (85 129%)
T u = l0 100 % = * 100% = 129%
x 0 19.4
23
Calibration curve and 95% inverse prediction limits
90 100
80
70
Field measurement
60
50
40
30
Y0
20
10
x l 0 x u 0
0
0 10 20 30 40 50 60 70 80 90 100
x0 Laboratory measurement
The method can be employed with down to approximately 5 duplicates analysed as field
measurements and with an accredited analytical laboratory using recognised methods
with documented and sufficient analytical quality.
As added value compared to conventional linear regression, the inverse linear regression
allows not only to calculate the expected x from a y value, e.g.: the expected laboratory
result from a field measurement, but also to estimate the uncertainty associated with the
calculated x taking into account the overall uncertainty of the full set of x,y data behind
the inverse regression.
It should be emphasised that for some field methods, there is a correlation between the
field result and the result of laboratory analysis for the same sample, but not a corre-
spondence. Said in other words, a photo ionization detector (PID) responds to the sum
of organic compounds that can be volatilised from a soil sample, and subsequently ion-
ised and recorded in the instrument. Laboratory analysis for e.g.: total petroleum hydro-
carbons in a soil sample in principle quantifies the sum of volatile and nonvolatile hy-
drocarbons of petroleum origin in the sample. Therefore, it is not to be expected that the
PID response and the laboratory result for petroleum hydrocarbons should be the same
(correspond). In that case, the concept of trueness becomes merely a conversion factor
from field measurements to expected laboratory result, and the trueness limits demon-
strate how much confidence we can have in this conversion. For such methods, the con-
cept of correlation factor should be used in stead of trueness.
24
5.3.3 d-statistics
The basic approach to estimating measurement precision involves repeated measure-
ments on subsamples, preferentially at the least 5-6 samples for each calculation, fol-
lowed by calculation of standard deviation, mean and relative standard deviation. This
approach may be of less use in field measurements due to the large heterogeneity and
concentration variation in the field that will give a requirement for measuring a very
large number of subsamples in order to obtain reliable precision estimates.
A realistic alternative is to assess precision from the relative difference between meas-
urements on duplicates. This approach is available in two versions. The simple d-
statistics can be used when the relative standard deviation is constant over the measur-
ing range. Based upon empirical data, this has been suggested to be the case for most
environmental and geochemical purposes at the least with concentrations above 100 x
DL, see section 5.1.3 and figure 5.3. For measurements where the relative standard de-
viation is not constant, grouped d-statistics can be used.
An indication of constant or non-constant relative standard deviation for the specific

case can be obtained from a plot of differences between duplicates against mean of du-
plicates, the RSD chart, see figure 5.4.
Generally, d-statistics are not applicable with methods that yield both negative and posi-
tive measurement values.
The simple d-statistics require 10 duplicates and enables thus estimation of measure-
ment precision for a single investigation. The higher the number of duplicates used for
the calculations, the better the precision estimate. The simple d-statistics can also me
used including duplicates from several sites to provide method precision estimates.
The grouped d-statistics, as described in references /17; 21;22/, require a larger number
of duplicates (minimum 50 duplicate sets) and are thus generally most fit for estimates
of method precision rather than of single investigation precision. Still, as an additional
advantage, the method DL can be estimated from the obtained blank standard deviation,
s0, see section 5.1.3.
The typical use of grouped d-statistics would be with an aggregated data set from sev-
eral sites in order to achieve method precision and detection limit.
Weighted d-statistics will in many cases probably yield a better statistical model /17/,
but this is not considered to be a realistic option in a simple field measurement quality
control scheme.
It should be noted, that a better estimate of method precision can be obtained with
weighting of the values used in the linear regression /17/, but this is not recommended
here to keep the calculations more simple.
It should also be noted, that other techniques, such as analysis of variances, ANOVA,
are available for estimating precision of duplicates and that those familiar with such sta-
tistical methods may benefit from using those. Robust ANOVA procedures may be
more fit for environmental data that do not follow the normal distribution. ANOVA is
part of the data analysis tools of common spreadsheets, and robust ANOVA procedures
can be found in textbooks or downloaded as add-ins for common spreadsheets.
25
Simple d-statistics for calculating relative standard deviation from duplicates
Measurement of n duplicates, each set of duplicates, i, producing the measurements xi1 and xi2. Normal
distribution of the data and constant relative standard deviation over the measuring interval (concentra-
tions above 100 * DL or demonstrated from RSD chart) is assumed.
The absolute value of the difference D is calculated for each set of duplicates:
Di = xi1 xi 2
The mean, xi , of the 2 measurements in each duplicate is calculated:
xi = ( xi1 + xi 2 ) / 2
The relative difference, di, is calculated from the difference, Di, and the mean for each set of duplicates:
d i = Di / xi
The mean relative differenced is calculated as:
d = di / n
The relative standard deviation, RSD, is calculated using a statistical constant of 1.128 as:
RSD = d * 100 / 1.128%

_
The grand mean of all duplicates, X , is calculated as:
X = xi / n
The standard deviation, s, is calculated as:

s = RSD * X / 100
This calculation of the standard deviation requires that all measurements are within a range where the
standard deviation is close to constant. If this is not true, the standard deviation, s X 0 , at a given concen-
tration, X0, can be estimated from:
s X 0 = RSD * X 0 / 100
If required for statistical evaluations, the degrees of freedom, df, associated with the calculated standard
deviation can be calculated using another statistical factor of 0,88:
df = 0,88 * n
Example with 10 duplicate measurements of total Cr in soil (mg/kg)

x i1 x i2 Di = xi1 xi 2 xi = ( xi1 + xi 2 ) / 2 d i = Di / x i
20 2 18 11 1.64
223 157 66 190 0.35
312 150 162 231 0.70
816 432 384 624 0.62
55 125 70 90 0.78
54 224 170 139 1.22
442 325 117 384 0.31
765 755 10 760 0.01
32 516 484 274 1.77
650 15 635 333 1.91

d = d i / n = 0.93 RSD = d * 100 / 1.128% = 82% s 200 = RSD * X 0 / 100 = 164 df = 9
26
Grouped d-statistics for calculating relative standard deviation from duplicates
Measurement of n duplicates, n>50, each set of duplicates, i, producing the measurements xi1 and xi2.
Normal distribution of the data and constant relative standard deviation over the measuring interval not
necessary.
The absolute value of the difference, Di, is calculated for each set of duplicates:
Di = xi1 xi 2
The mean,xi, of the 2 measurements in each duplicate is calculated:

xi = ( xi1 + xi 2 ) / 2
The duplicates are sorted after increasing means and subdivided into m groups of 11 duplicates.
The median differences, Q0.5j, for each group, j, are found as the difference with an equal number of
smaller and larger differences. Spreadsheets can return this figure easily.

The mean, x j , of the m means of measurements in group j is calculated:

x j = ( x i ) / m

Linear regression is performed with the m sets of x j and Q0.5j as x and y to obtain the regression coef-
ficients a and b according to the equation:

Q0.5 j = a x j + b
As input to the equation:

s = s 0 + kc
The values s0 and k are calculated using the statistical factor 1.048 from:
s 0 = b 1.048 and k = a 1.048
The relative standard deviation, RSD, can be estimated for any concentration, c, from:
s0
RSD = ( + k ) 100%
c
and will with high concentration approach a constant value of:
RSDc = k 100%
The detection limit for a method with blank correction of the result (n blanks in each series) can be de-
rived from, recall section 5.1.2:
1
DL = 4 s0 1 +
n
and for a method without blank correction as:
DL = 4 s0
27
Example with 55 duplicates measurements of Cr in soil
Calculations of differences and mean values as in the previous example. Sorting, grouping and calcula-
tion of median and mean of means gave the results shown below.
Q0.5 j Linear regression
xj
5 0.7 s 0 = b * 1.048 = 0.80 mg Cr / kg k=a*1.048=0.0085
20 0.8 Precision at 100 mg Cr/kg
60 1.6 s=s0+k*c=1.7 mg Cr/kg RSD=(s0/c+k)*100%=9.3%
110 1.4 Detection limit with blank correction (2 blanks)
140 1.7 DL = 4 * s 0 * (1 + ) = 4 mg Cr / kg
2
1.8
Group median of differences
1.6
1.4
y = 0.0081x + 0.76
(mg Cr/kg)
1.2
0.8
0.6
0.4
0.2
0
0 20 40 60 80 100 120 140 160
Group mean of means (mg Cr/kg)
As the simple and grouped d-statistics do not readily provide a real time estimate of
precision for use in the field, a simple control chart can be used to evaluate the precision
as obtained. An example of a control chart is shown in figure 5.4, and two different con-
trol charts are given in appendix 3. The difference between duplicates is plotted in the
chart against the mean of the duplicates. If the difference fall below the lowest diagonal
line, there is a 95% probability that the relative standard deviation, RSD, is below 50%.
If the difference fall above the line, the RSD is with high probability above 50%. In ad-
dition, the diagonal line for 99% probability is inserted.
28
95% limit 99% limit
1000
Difference between duplicate measurements
100
(concentration)
10
1
1 10 100
Mean of duplicate measurements
(concentration)
Figure 5.4 Probability plot of difference between duplicate measurements against mean of the duplicate
measurements for 50% RSD and with the 95 and 99 % probability line inserted, modified
from /22/.
Said in other words, if the RSD of the field measurements is 50%, 5 out of 100 dupli-
cate measurements would fall above the full line and 1 out of 100 above the dotted line.
If a high fraction of duplicate measurements fall above the full line (bullet), the preci-
sion is worse than the minimum 50% RSD that has been set as a requirement for a quan-
titative field method (table 4.2). If all duplicate measurements plot below the full line
(cross), the 50% RSD requirement is likely to be fulfilled. For a more homogenous site
and a higher field measurement precision (e.g.: 5% RSD), the 5% RSD control chart of
appendix 3 can be used.
Calculatation of control charts for duplicate difference against mean of duplicates (modified from /22/)
The absolute difference, d, between duplicate measurements follow the positive half of a normal distri-
bution with a standard deviation sd that is:
sd = s * 2
The standard deviation on measurements, s, can as previously stated be assumed to depend linearly upon
the concentration, c:
s = s0 + k * c
Well above the detection limit, k is simply the ratio between standard deviation and concentration:
s
k c =
c
with:
s
RSDc = *100% = k c *100%
c
29
This means that sd can be calculated from:
RSDc
sd = 2 * *c
100
The concentration c is found as the mean of the two duplicate results.
The percentiles of the distribution of d can be estimated using Students t-factors. The factor giving the
95% percentile is 1.960 and the 99% percentile is 2.575. 95% of all absolute differences between dupli-
cate measurements will fall below the calculated 95% percentile, P95:
RSDc
P95 = 1.960 * 2 * *c
100
P95 and P99 were used to draw the diagonal lines in the control charts, figure 5,4 and appendix 3.
It should be noted that the error of calculating the percentiles exceeds 10% for concentrations below
approximately 5 times the detection limit, if calculated as suggested in section 5.1.2. Therefore, higher
fractions of absolute differences between duplicate analysis must be expected at mean concentrations
below 5 times the detection limit.
The RSD chart can be used to indicate whether the relative standard deviation can be
assumed to be constant over the measuring range. If the differences among duplicates
increase with increasing mean values (seems to follow an upwards trend in the chart,
parallel with the probability limit lines, the RSD is likely to be constant for the meas-
urements plotted. If the differences appear constant (seems to follow a horizontal line
parallel to the abscissa), the RSD is not likely to be constant.
5.3.4 Range errors and correctness

The concepts of precision in terms of relative standard deviation and of trueness in
terms of recovery of true concentration do not apply for range methods, as a discrete
measurement is not obtained and standard deviations and means consequently can not
be calculated.
The probability of measuring an incorrect range will vary from theoretically 50% very
close to a range limit to close to 0% in the middle of the range, see figure 5.4. The form
of the error distribution curve presented in figure 5.4 is arbitrary, but the width will de-
scribe the quality of the range measurement method. A wide distribution curve will give
a high risk of false measurements (low correctness), whereas a narrow curve will give a
low risk and high correctness.
The error distribution function will vary with the range test method and the sample ma-
trix. If the only information aimed at is above or below a target value, a model has
been developed based upon a binomial distribution function of the error of this
above/below target value assignment /23/. Still, to apply this model as a description of
the measurement quality would require measurements of large amounts of samples rep-
resenting each matrix and within the matrix different concentrations, something that is
not feasible as field quality control.
30
In stead, the frequencies of correct measurements, false positives and false negatives are
used to get an objective description of the measurement quality. The range errors and
correctness assessment requires comparative analysis of duplicates using field meas-
urements and analysis with an accredited analytical laboratory using recognised meth-
ods with documented and sufficient analytical quality. Alternatively, a procedure with
spiking of field samples can provide the same type of data real time, but with a less reli-
able description of the error distribution.
False
negative
risk in %
Lower Upper
Range
range range
center
limit limit
Figure 5.4 Distribution curve of range error with distance to range limit
The correctness or trueness of the method can be reported as the frequency of correct
measurements as confirmed by laboratory analysis in percent of all measurements in
each range according to laboratory analysis, see section 5.1.1 for definition of the fre-
quencies. Frequencies of false positives and false negatives are calculated and reported
in analogy for each range. Table 5.2 is an example of a summary of range errors and
correctness.
Table 5.2 Example summary of correctness and range errors of range method
Range Correctness False False Error above Max
negatives positives 1 range error
(mg nitrate/L) (%) (%) (%) (%) (ranges)
<5 100 - 0 0 0
5-25 95 2 3 1 2
25-125 90 5 5 1 2
>125 85 15 - 0 1
The errors can be reported as the frequency of errors above 1 range and the max error
observed.
31
6 QUALITY CONTROL PROCEDURES FOR FIELD
MEASUREMENTS
The quality assurance of field methods is applied at different stages:
Method validation prior to decision of use

Bench check out prior to use
Quality control during use on site
Verification after use
Method validation prior to decision of use is mainly supplied by manufacturers and in
some cases through method studies published by the authorities (e.g.: /4/) or in scien-
tific papers (e.g.: /3/). In selecting the analytical method for field measurements, it is
mandatory that the selection is done by comparing manufacturer validation data with the
requirements of the specific field study as defined by the purpose of this study. The user
should add application specific validation, but the methods for this are outside the scope
of this manual (quality control of field measurements) and the users are referred to
handbooks, standards and manuals on this subject as e.g.: /6/. Still, thorough method
validation is mandatory prior to using any type of field measurements, and the methods
presented here for quality control of field measurements can also be applied in the
method validation stage.
Procedures for quality assurance in the different stages are summarised in table 6.1, re-
ferring to chapter 5 for details of procedures.
Table 6.1 Procedures for quality assurance of field measurements summarised for each
measurement stage
Quantitative methods Relative methods Range methods
Bench Calibration and cali- Calibration and cali- Calibration, if re-
check bration check bration check quired, and range
out check
On site Measurement of Measurement of Range check
quality con- duplicates every 10 duplicates every 10 On demand meas-
trol samples samples urement of spiked
Calibration check Calibration check sample every 10
every 10 samples every 10 samples samples
Duplicate back- Duplicate back-
ground samples at ground samples at
the least once every the least once every
site site
Verification Measurement of On demand mea- On demand mea-
duplicates by field urement of dupli- surement of dupli-
and recognized cates by field and cates by field and
laboratory method recognized labora- recognized labora-
every 10 samples tory method every tory method every
10 samples 10 samples
If the analytical series is below 10, the quality assurance should be performed for each
series.
32
The flow in quality control of field measurements is visualised in figure 6.1.
Bench check out

of instrument
Field check of instrument

and duplicate analysis to
provide precision
Laboratory verification
to provide correctness
Figure 6.1 Flow in field measurement quality control
The procedures that can be applied for quality assurance will differ with the method
types, and for each procedure, a specification after method type is given in tables 6.2-
6.4 in the subsequent sections. In the tables, the procedures are described for each stage
of the quality control process, the statistics to be applied is listed, the information
yielded listed, and the kind of documentation to be supplied given. Refer to the previous
chapters for explanations of the different listed items.
It should be noted that the procedures used for quality assurance of quantitative and
relative measurements are the same, but the necessity of applying the procedures and
the quality requirements differ, compare table 4.2. Also, bench check out will for range
and relative methods mostly rely upon the instrument manufacturers manual, whereas
laboratory procedures should be applied for quantitative methods.
In addition to and in reality between the procedures of bench check out and field check,
it is recommendable to qualitatively check whether the field method is applicable to the
specific matrices of the site investigated. This qualitative check can be made by per-
forming two initial measurements on site: one at a part of the site known (=expected)
to be uncontaminated and one at a part of the site with known high contamination. If
the field measurements do not reflect the expectations with low and high measurements,
respectively, the selection of field measurement principle/equipment (and/or perhaps the
site model) should be reconsidered before any additional fieldwork is done.
In particular for quantitative methods, it is appealing to measure the concentrations in

certified reference materials (CRMs) in the field and calculate field method trueness
based upon these measurements. Still, this approach is misleading, as the CRM matrix
in many cases will differ significantly from the field sample matrix (with respect to e.g.:
soil humidity). Estimates of trueness of field measurements should therefore always be
based upon parallel measurements in the field and at an accredited analytical laboratory
using recognised methods with documented and sufficient analytical quality.
33
6.1 Category 1, Quantitative Methods
Table 6.2 Procedures, statistics and documentation recommended for quantitative methods
Quantitative methods
Procedure Statistics Information Documentation
Bench check out
Calibration and calibra- 1. Calibrate instrument ac- 1. None 1. Instrument stability 1. Record instrument settings
tion check cording to manufacturers 2. Linear regression 2. Linear range in instrument file
manual if required 3. None 3. Check of calibration 2. Record slope, intercept
2. Establish calibration curve 4. None 4. Check of zero and coefficient of determi-
over linear range nation in instrument file,
3. Check calibration with in- report linear range with
dependent control measurements
4. Check zero with blank 3. Record control value with
instrument file
4. Record blank value with
instrument file
On site quality control
Measurement of dupli- 1. Perform measurement on 1. Simple d statistics for the 1. Standard deviation (preci- 1. Report site uncertainty
cates every 10 samples two subsamples site sion) with measurements
Duplicate background 1. Perform measurements of 1. Grouped d statistics for the 1. Detection limit 1. Report method detection
samples at the least two subsamples from un- method for aggregated limit with measurements
once every site contaminated area data set with duplicates
Calibration check every 1. Check calibration with in- 1. None 1. Check of calibration 1. Record control value with
10 samples dependent control 2. None 2. Check of zero sampling file
2. Check zero with blank 2. Record blank value with
sampling file
Verification
Measurement of dupli- 1. Perform field measure- 1.1. None 1.1. Error and accuracy 1.1. Report accuracy range
cates by field and recog- ment of one subsample 1.2. Linear regression 1.2. Correspondence with measurements
nized laboratory method and submit the other sub- 1.3. Inverse linear regression 1.3. Bias and trueness 1.2. None
every 10 samples sample to laboratory 1.3. Report trueness with
analysis measurements
34
6.1.1 Bench check out
For quantitative methods, the bench check out should include both instrument calibra-
tion and a calibration according to normal laboratory methods, see section 5.2.1, the
later in order to allow for reporting of the instrument linear range with the measure-
ments.
6.1.2 On site quality control

For quantitative methods, a field precision should be reported as relative standard devia-
tion (% RSD) based upon simple d-statistics, as the measurements in most cases will be
in a range with constant RSD which is required to apply these statistics. If this is not the
case, grouped d-statistics should be used to estimate method field precision as relative
standard deviation (% RSD). Still, in both cases the d-control chart should be filled in
on site and while measuring in order to ensure a real time check of obtaining the re-
quired precision.
Grouped d-statistics are done using pooled data sets for as many site sites as possible
and give thus a method performance evaluation rather than a site evaluation. Method
DL should be reported with the measurements as obtained employing grouped d-
statistics at intervals.
6.1.3 Verification
For quantitative methods, the total correctness of the measurements is an essential pa-
rameter to document and this should include:
Accuracy (the range of relative recovery in percent obtained with field measure-
ments relative to laboratory analysis, single measurements error), and
Trueness (the mean recovery in percent obtained with field measurements relative to
laboratory analysis, multiple measurements bias, with precision on the mean esti-
mate).
The coefficient of determination obtained from regression analysis of field measure-

ments against laboratory analysis can be reported, but is of less statistical significance
than the accuracy and trueness as described above.
35
6.2 Category II, Relative Methods
Table 6.3 Procedures, statistics and documentation recommended for relative methods
Relative methods
Bench check out
Calibration and calibra- 1. Calibrate instrument ac- 1. None 1. Instrument stability 1. Record instrument settings
tion check cording to manufacturers 2. Linear regression 2. Linear range in instrument file
manual if required 3. None 3. Check of calibration 2. Record slope, intercept
2. Establish calibration curve 4. None 4. Check of zero and coefficient of determi-
over linear range nation in instrument file,
3. Check calibration with in- report linear range with
dependent control measurements
4. Check zero with blank 3. Record control value with
instrument file
4. Record blank value with
instrument file
Measurement of dupli- 1. Perform measurement on 1. Simple d statistics 1. Standard deviation (preci- 1. Report site uncertainty
cates every 10 samples two subsamples sion) with measurements
Duplicate background 1. Perform measurements of 1. Grouped d statistics for the 1. Detection limit 1. Report method detection
samples at the least two subsamples from un- method for aggregated limit with measurements
once every site contaminated area data set with duplicates
Calibration check every 1. Check calibration with in- 1. None 1. Check of calibration 1. Record control value with
10 samples dependent control 2. None 2. Check of zero sampling file
2. Check zero with blank 2. Record blank value with
sampling file
Verification
Measurement of dupli- 1. Perform field measure- 1.1. None 1.1. Error and accuracy 1.1. Report accuracy range
cates by field and recog- ment of one subsample 1.2. Linear regression 1.2. Correspondence with measurements
nized laboratory method and submit the other sub- 1.3. Inverse linear regression 1.3. Bias and trueness 1.2. None
every 10 samples sample to laboratory 1.3. Report trueness with
analysis measurements
36
For most relative methods, the bench check out should include both instrument calibra-
tion and a calibration according to normal laboratory methods, see section 5.2.1, the
later in order to allow for reporting of the instrument linear range with the measure-
ments.
If calibration is not relevant, the linear range should be reported from the instrument de-
tection limit as stated by the manufacturer to the highest check standard employed
yielding linear response.

For relative methods, a method precision should be reported as relative standard devia-
tion (% RSD) based upon grouped d-statistics, as the measurements in most cases will
be in a range with constant RSD which is required to apply these statistics. If this is not
the case, simple d-statistics should be used to estimate field precision as relative stan-
dard deviation (% RSD).
It is mandatory to that the d-control chart be filled in on site and while measuring in or-
der to ensure a real time check of obtaining the required precision.
Grouped d-statistics are done using pooled data sets for as many site studies as possible
and give thus a method performance evaluation rather than a site evaluation. Method
DL should be reported with the measurements as obtained employing grouped d-
statistics at intervals.
6.2.3 Verification
For relative methods, the requirement for verification of field measurements with paral-
lel measurements in the field and at an accredited analytical laboratory using recognised
methods with documented and sufficient analytical quality depends upon the purpose of
the investigation and the requirements set by clients and/or authorities.
It is recommended at the least to include a small number of duplicates for laboratory

verification in order to allow for reporting of general method correctness with the meas-
urements.
The total correctness of the measurements documentation should include:
Accuracy (the range of relative recovery in percent obtained with field measure-
ments relative to laboratory analysis, single measurements error), and
Trueness (the mean recovery in percent obtained with field measurements relative to
laboratory analysis, multiple measurements bias, with precision on the mean esti-
mate).
The coefficient of determination obtained from regression analysis of field measure-

ments against laboratory analysis can be reported, but is of less statistical significance
than the accuracy and trueness as described above.
37
6.3 Category III, Range Methods
Table 6.4 Procedures, statistics and documentation recommended for range methods
Range methods
Bench check out
Calibration and range 1. Calibrate instrument ac- 1. None 1. Instrument stability 1. Record instrument settings
check cording to manufacturers 2. None 2. Check of zero in instrument file
manual if required 3. None 3. Check of DL 2. Record deviations from zero
2. Check zero with blank 4. None 4. Check of range in instrument file
3. Check DL with control at 3. Record false positives (DL
1.25 * DL failure) with instrument file
4. Check range with control 4. Record false negatives
at 1.25*lower limit of upper (range errors) in instrument
range file
Calibration check every 1. Check zero with blank 1. None 1. Check of zero 1. Record deviations from zero
10 samples 2. Check range with control 2. None 2. Check of range in sampling file
at 1.25*lower limit of upper 2. Record false negatives (ran-
range ge errors) in sampling file
Measurement of spiked 1. Perform field measure- 1. Identify range errors 1. Control of max error (false 1. Report number of spikes
sample every 10 sam- ment of one subsample low or negative only) and number of range in-
ples and add a spike of one crease errors with meas-
range to one subsample urements
followed by analysis
Verification
Measurement of dupli- 1. Perform field measure- 1.1. Identify errors > one range 1.1. Control of max error 1.1. Report frequency of error >
cates by field and recog- ment of one subsample 1.2. Calculate correctness 1.2. Trueness in terms of cor- one range with measure-
nized laboratory method and submit the other sub- 1.3. Calculate frequencies of rectness ments
every 10 samples sample to laboratory false positives and nega- 1.3. Trueness in terms of false 1.2. Report correctness with
analysis tives relative to target positive and negative risks measurements
value if relevant 1.3. Report frequency of false
positives and negatives if
relevant
38
Instrument calibration is generally not required for range methods, and calibration curve
measurements is not relevant. Therefore, an increased check out ensuring method per-
formance should be done as given in table 6.4. Following this procedure will prevent
going to the field with an instrument that will by default provide excessive false results.

The calibration check should be repeated in the field in order to ensure continued per-
formance (zero and response) of the measurements.
If a verification of the range measurements against laboratory analysis is not done, the
maximum error (false low or negatives) shall at the least be controlled for the matrix in
question as described in table 6.4. The procedure for spiking water samples presented in
chapter 5 should be followed. Please, note that this approach is not recommended for
soil samples and here, verification against laboratory analysis at method level should at
the least be performed.
6.3.3 Verification
If the range measurements are intended for any legal use, the measurements should be
reported with documentation of error frequency above one measuring range, correctness
and frequencies of false positives and negatives, as described in table 6.4.
39
7 EXAMPLES
The quality requirements for field measurements will depend upon the maximum con-
taminant concentrations and the analytical quality requirements in force. In this project,
total petroleum hydrocarbons (TPH), polycyclic aromatic hydrocarbons (PAH) and
heavy metals in soils have been selected as examples. Furthermore, pH, electrical con-
ductivity, oxygen and nitrate in groundwater have been selected.
The maximum contaminant concentrations (MCC) of the selected contaminants in the

two matrices are shown in table 7.1 as applied in the Nordic countries /24-30/. The val-
ues for drinking water are given as reference for the groundwater study, as no ground-
water MCCs exist in the Nordic countries for the parameters in question.
The specific analytical quality requirements enforced in the Nordic countries for the se-
lected contaminants are summarised in table 7.2. For most parameters, no formal re-
quirements have been set, but the analytical quality may be described in accreditation
documents, see chapter 4.
Table 7.1 Maximum concentrations of the selected contaminants in soil10 or groundwater as

applied in the Nordic countries.
Parameter Denmark Finland Norway Sweden
Soil
Total petro- 100 30011 3013 10015
leum hydro- 60012 10014
carbons
mg/kg dw
C5-C10 hydro- 25 10016 717 10018
carbons
mg/kg dw
Benzene 1.5 0,5 0.005 0.06
mg/kg dw
Total PAH 1.519 2020 221 0.322
mg/kg dw
As 20 10 2 15
Cu 500 100 100 100
Ni 30 60 50 35
Pb 40 60 60 80
Zn 500 150 100 350
mg/kg dw
Drinking water
10
Soil quality criteria for sensitive land use given
11
C11-C23 aliphatic hydrocarbons
12
13
C10-C12 hydrocarbons
14
C12-C35 hydrocarbons
15
16
C6-C10 aromatic hydrocarbons
17
C5-C6 hydrocarbons
18
19
7 PAH
20
16 PAH
21
16 PAH
22
Carcinogenic PAH
40
pH 7.0-8.5 6.5-9.5 6.5-9.5 7.5-9.5
-
Conductivity >30 250 250 250
mS/m
Oxygen not relevant not relevant not relevant not relevant
mg/L
Nitrate 50 50 10 20
mg/L
Table 7.2 Analytical quality requirements for the selected contaminants measured in soil and
groundwater in the Nordic countries.
Soil
Total petro- none none none none
leum hydro-
carbons
mg/kg dw
C5-C10 hydro- none none none none
carbons
mg/kg dw
Benzene none none none none
mg/kg dw
Total PAH none none none none
mg/kg dw
Selected none none none
heavy metals
mg/kg dw
Groundwater
pH Quality class 123 none none none
-
Conductivity Quality class 1 none none none
mS/cm
Oxygen Quality class 2 none none none
mg/L
Nitrate Quality class 1 none none none
mg/L
7.1 PID Measurement of Oil in Soil

Photo Ionisation Detector (PID) determination of oil in soil is an example of a relative
method for field measurements.
7.1.1 Site and study description

The field investigation took place in Malmsltt in the western part of Linkping. The
investigated site is a former depot for jet fuel for the Swedish air force and is located
near the railway. When the depot was in use, the jet fuel came to the depot by railway
and was then pumped in a pipeline about 500 m to the military airport. The site has been
investigated twice before to examine if the site was contaminated with jet fuel. The in-
23
Danish analytical quality classes, see chapter 2 for definitions
41
vestigations showed that an approximate 100 200 m2 large area was contaminated
with jet fuel from about 2 to 4 m below the surface.
The aim of the investigation was to investigate the vertical distribution of the contami-
nation taking soil samples for every 25 cm depth in contaminated spots. The use of the
field PID instrument Photovac 2020 enabled results in high resolution at a relative low
cost and also on site decisions about which samples should be sent to the laboratory.
Soil samples were taken with an auger on a geotechnical bore rig. Replicate samples
were taken from the soil on the screw auger and were separated directly without ho-
mogenisation to reduce the risk of loss of volatile compounds.
Figure 7.1. Site map, Malmsltt, Linkping.

PID measurements were done transferring about 500 g of soil sample directly to a Ril-
san bag, equilibrating at 20C for 20 minutes and measuring the headspace with the
PID.
42
Table 7.3 Methods and objectives for the field investigation in Malmsltt, Linkping.
Parameter Method princi- Target value Data quality Decision
ple and equip- requirement
ment
Sum of VOC24 in Measurement of The target value No specific re- Measurement of
soil soil with PID depends on the quirements for VOC in soil is
(photo ionization chemical sub- this inves- used to decide
detector). stances present tigation. General which samples
at the site. Here requirements for to send to labo-
a >100 ppm PID relative meth- ratory analysis.
measurement is ods: all meas-
used to select urements in de-
samples for cision area
laboratory above DL, RSD
analysis. known, possibly
recovery known,
see table 4.2
It should be noted that there is no general relationship between the soil concentrations
of specific volatile organic contaminants and PID responses. The relationship depends
upon the mixture of contaminants and their individual response factors in PID. Also, the
PID response will reflect the sum of a variety of volatile organic contaminants with dif-
ferent maximum contaminant concentrations, such as the 25 mg/kg dw25 target for C5-
C10 hydrocarbons and 1,5 mg/kg dw for benzene (Danish values). Finally, different soils
with different water content and at different temperatures will produce different re-
sponses for the same content of contaminants due to differences in volatilization from
the soil. Therefore, a target value related to maximum contaminant concentrations can
not be set. A PID measurement of above 100 ppm is usually a good indicator of con-
tamination with petroleum hydrocarbons in this type of soil (sand and silt).

Basic instrument calibration of the PID instrument was done with setting of instrument
zero point to the response of ambient air (no ionizable gasses required in zero air) and a
calibration gas containing 100 ppm isobutylene to set sensitivity. The detection limit
for the instrument was 0,5 ppm as isobutylene in air according to the instrument man-
ual. A calibration curve was made with clean outdoor air (zero), 10 ppm, 100 ppm and
1000 ppm of isobutylene. The calibration curve is shown in figure 7.2.
24
Volatile organic contaminants
25
dw: dry weight
43
PID calibration
1000
Measurement PID (ppm)
800
y = 1.02x - 1.09
600
R2 = 1.000
400
200
0
0 200 400 600 800 1000
Calibration gas (ppm)
Figure 7.2 Calibration curve for PID against calibration gas
The regression analysis gave the following equation:
Measurement PID (ppm) = 1.02 * Conc calibration gas (ppm) - 1.09
The coefficient of determination was 1.000, which demonstrates a perfect linear rela-
tionship between gas concentration and PID response. If the coefficient of determination
had deviated considerably from 1, using a more narrow range of concentrations for the
calibration standards should have been considered. Linearity was demonstrated from 10
to 1000 ppm as isobutylene in the gas phase. A small negative intercept suggests incor-
rect zero setting or non linearity.
Control samples were prepared at SGI by using clean sand, and a mixture of ethanol and
water were used for calibration check. For measurement in the low range, 100 g clean
sand and 5 ml of 1% ethanol was used and for measurement in the high range, 100 g
clean sand and 5 ml of 50% ethanol was used. The samples were prepared at SGIs
laboratory. First, solutions of 1% and 50% ethanol in water were prepared, then the soil
was transferred to Rilsan bags and the ethanol solution was added to the bags. The zero
response was controlled measuring clean sand as a blank. For each type of control sam-
ple, 5 measurements were used to calculate a true value for comparison during field
quality control. The true value was based upon PID measurements as there is no di-
rect relation between analysis of specific components in soils and PID response, table
7.4.
The preparation of spiked soil control samples here is an example of such a procedure
where it succeeds, compare section 6.2.2 for the general caution against preparing
spiked soil control samples.
44
Table 7.4 True value of control samples obtained with PID
Low range control High range control Blanks
(1% ethanol) (50% ethanol)
Mean (ppm) 37.6 537 0.0
Standard deviation (ppm) 0.466 3.36 0
Please, note that one excessive digit is given compared to the normal reporting format in
order to avoid errors due to truncation in subsequent calculations.
The standard deviation for the low range control can be used to estimate an upper limit
for the instrument detection limit, see section 5.1.2, as 5*0.466 ppm = 2.3 ppm.

Totally 50 soil samples from the contaminated area were measured with PID. Every
fifth sample, totally 10 samples, was taken as triplicates where two samples were used
for measurements with PID and one for laboratory analysis. GC-MS with static head-
space (the soil sample is heated, and the soil gas above the sample transferred to the
GC-MS for analysis) was used for the laboratory analysis because the pretreatment
method (head space equilibration) is similar to the method used with PID. The GC-MS
method is considered reliable and is accepted for determining the groups of organic con-
taminants that have threshold values established by the Swedish Environmental Protec-
tion Agency. The data are given in table 7.5.
Table 7.5 Duplicate field measurements and laboratory results from field investigation in
Malmsltt, Linkping.
NT 1 NT 1 NT 2 NT 2 NT 2 NT 3 NT 4 NT 4 NT 5 NT 5
2-2,5m 3,25- 1,75- 2,75- 4,0- 2,25- 2,0- 3,25- 1,5- 3,0-
3,5m 2,0m 3,0m 4,5m 2,5m 2,25m 3,5m 2,0m 3,25m
Field mea-
surements
PID-sample 1 ppm 1717 531 4.2 1179 65.4 710 1651 62.6 1848 948
PID-sample 2 ppm 1735 694 2.8 1040 160 1023 1670 52.7 1913 1190
PID sample ppm 1726 612.5 3.5 1109.5 112.7 866.5 1660.5 57.65 1880.5 1069
average
Laboratory
analysis
Dry weight % 86.1 82.3 87 85.9 83.8 86.1 84.3 79.5 86.3 86.3
Benzene mg/kg dw 0.01 <0.01 <0.01 <0.01 <0.01 0.01 0.05 0.02 <0.01 0.05
Toluene mg/kg dw < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1
Ehtylbenzene mg/kg dw 86 < 0.1 < 0.1 0.58 < 0.1 1.3 30 0.36 0.15 12
Xylenes mg/kg dw 360 0.39 < 0.1 0.94 < 0.1 1.1 180 10 5.2 46
Sum of BTEX mg/kg dw 450 0.4 <0.1 1.5 <0.1 2.4 210 10 5.4 58
Aliphates mg/kg dw 890 5.2 <5 14 <5 <5 470 <5 <5 100
>C5-C8
Aliphates mg/kg dw 3000 16 <5 37 <5 6.7 1100 <5 100 190
>C8-C10
Aliphates mg/kg dw 1200 6.3 <5 35 <5 31 460 <5 42 140
>C10-C12
Aliphates mg/kg dw 540 <5 <5 17 <5 15 210 <5 26 78
>C12-C16
Aromates mg/kg dw 2500 <5 <5 44 <5 27 1300 75 240 500
45
NT 1 NT 1 NT 2 NT 2 NT 2 NT 3 NT 4 NT 4 NT 5 NT 5
2-2,5m 3,25- 1,75- 2,75- 4,0- 2,25- 2,0- 3,25- 1,5- 3,0-
3,5m 2,0m 3,0m 4,5m 2,5m 2,25m 3,5m 2,0m 3,25m
>C8-C10
Sum of vola- mg/kg dw 6840 21.6 <15.1 96.5 <15.1 36.1 3080 85.0 345 848
tile hydrocar-
bons26
It should be noted that several PID results were outside the range of PID response dem-
onstrated to be linear, see figure 7.2: 10-1000 ppm. No PID measurements were below
the upper limit for instrument detection limit, 2.3 ppm.
An RSD chart, section 5.3.3, for 50% relative standard was used to evaluate the preci-
sion for the measurements in field and is shown with plotted data points in figure 7.3.
Evidently, the RSD is below 50% and there was no need for adjustment of subsampling
or measurement strategy in the field. Also, the chart supported that RSD may have been
constant through the measuring range, see section 5.3.3.
50% RSD CHART
95% limit 99% limit
100000
Difference between duplicate analyses
10000
(concentration)
1000
100
10
10 100 1000 10000
Mean of duplicate analyses
Figure 7.3 RSD chart for 50% relative standard deviation with duplicate measurements
Simple d-statistics, section 5.3.3, were performed in order to calculate the standard de-
viation of the measurements including subsampling standard deviation. One of the du-
plicate measurements was excluded because the reading was close to the detection limit
in order to ensure the requirement for constant RSD with simple d-statistics. The calcu-
lations and results from simple the d-statistics are shown in table 7.6.
26
Volatile hydrocarbons are defined as hydrocarbons with equal to or less than 10 carbon atoms
46
Table 7.6 Simple d-statistics calculation.
x i1 xi2 Di = xi1 xi 2 xi = ( xi1 + xi 2 ) / 2 d i = Di / xi
1717 1737 20 1727 0.012
531 694 163 612.5 0.266
1179 1040 139 1109.5 0.125
65.4 160 94.6 112.7 0.839
710 1023 313 866.5 0.361
1651 1670 19 1660.5 0.011
62.6 52.7 9.9 57.65 0.172
1848 1913 65 1880.5 0.035
948 1190 242 1069 0.226

d = d i / n = 0.228 RSD = d * 100 / 1.128% = 20% s 500 = RSD * X 0 / 100 = 101 df = 8
The standard deviation at 500 ppm was found to be 100 ppm and the relative standard
deviation 20 %. The range of measurements is too large to accept a hypothesis of uni-
form standard deviation over the entire range. The relative standard deviation of 20%
gives high credibility to the subsampling and measurement strategy and supports the
conclusions drawn from the RSD chart: RSD well below 50%.
The grouped d-statistics, see section 5.3.3, could not be done for this investigation be-
cause it was going on for only one day and 40 duplicate measurements in the contami-
nated area was not possible to do in only one day. Furthermore, duplicate measurements
from other studies were not available for the grouped d-statistics. Consequently, the
method detection limit could not be evaluated.
During field measurements, the SGI control samples were measured in triplicate for
every 10 samples (totally 6 times) in order to check the calibration. The results from the
measurements of the control samples and blank samples are shown in table 7.7.
Table 7.7 Measurements of control samples and blank samples.

Low range control High range control Blanks
(1% ethanol) (50% ethanol) (clean sand)
Average 40.2 534 0.0
Standard deviation 1.69 4.04 0
There is no significant difference between field calibration control measurements and

the check out calibration control measurements. This indicates that the instrument has
been stable throughout the measuring period.
The standard deviation for the low range control can again be used to estimate an upper
limit for the instrument detection limit, see section 5.1.2, as 5*1.69 ppm = 8.5 ppm. The
slightly higher value during field measurements probably reflects that those measure-
ments were made over a longer time span.
47
7.1.4 Verification
Totally 10 samples were taken as triplicates with one subsample sent to laboratory
analysis using static headspace GC-MS for quantification of the volatile compounds in
the sample which are detected as PID response, see table 7.5 for results.
In the evaluation, regression and inverse regression analyses, the PID measurements are
evaluated against the sum of volatile hydrocarbons: benzene, toluene, ethylbenzene, xy-
lenes, >C5-C8 and >C8-C10 hydrocarbons (VOC), see table 7.5, corresponding to the
definition of volatile hydrocarbons in the method behind the Swedish maximum con-
taminant levels for petroleum hydrocarbons. A plot of PID against laboratory GC-MS
volatiles with regression analysis is shown in figure 7.4. One value was excluded as an
evident outlier (VOC GC-MS 345 mg/kg dw, PID 1880 ppm) because of poor linear re-
lationship between field measurement and laboratory analysis in this point. Laboratory
results below detection limit was set to 0.5 times the sum of the detection limits con-
tributing to the VOC.
The plot demonstrates considerable scatter in the data and a low coefficient of determi-
nation indicating a poor linear relationship between field PID measurements and labora-
tory GC-MS measurements of volatile hydrocarbons, in particular in the lower end of
the measuring range.
Results from the inverse regression analysis, section 5.3.2, are shown in table 7.8. For
the evaluation of correlation between field PID and laboratory GC-MS, a field meas-
urement, Y0, of 968 ppm was selected, as this is the median of the field measurements
and thus a good representative of the set of measurements.
2500
PID measurements (ppm)
2000
1500
1000
y = 0.210x + 545
R2 = 0.555
500
0
0 1000 2000 3000 4000 5000 6000 7000 8000
Volatile hydrocarbon from GC-MS (mg/kg dw)
Figure 7.4 Plot and regression analysis for PID measurements compared to laboratory analy-
sis of sum of volatile hydrocarbons
Table 7.8 Data from inverse regression analysis

Selected field concentration 968 ppm
Corresponding expected laboratory result 2000 mg/kg dw
Lower confidence limit 027 mg/kg dw
Upper confidence limit 7400 mg/kg dw
27
A negative estimate is obtained but set to 0
48
The inverse regression analysis shows a correlation between field PID measurements
and laboratory GC-MS measurements of volatile hydrocarbons (2000 mg/kg dw labora-
tory result corresponding to the 968 ppm PID response, correlation factor 0.48 see sec-
tion 5.3.2) with very broad confidence limits (from 0 to 7400 mg/kg dw laboratory re-
sult). Said in other words: prediction of the laboratory GC-MS volatile hydrocarbon
result from the field PID measurement is associated with a high uncertainty but may on
the average be within a correct order of magnitude.
Accuracy has been calculated according to section 5.1.5 for all duplicates with corre-
sponding field PID measurement and laboratory GC-MS quantification of volatile hy-
drocarbons. The accuracy range for field PID measurements was 25-2800% relative to
laboratory GC-MS results for volatile hydrocarbons. The broad accuracy range corre-
sponds well with the large uncertainty found in the inverse regression analysis.
7.1.5 Summary
The performance data for the field PID measurements are summarised in table 7.9.
Based upon quality control data and statistics, the PID instrument proved stable (field
calibration control) and showed a good precision with 20% relative standard deviation
(duplicate measurements, RSD chart and simple d-statistics). The correlation between
field PID measurements and laboratory GC-MS quantification of volatile hydrocarbons
was associated with large uncertainty (inverse linear regression, 0 to 7400 mg/kg dw
range for 2000 mg/kg dw laboratory result predicted), and the accuracy range was broad
(25-2800% difference within duplicate PID and GC-MS).
Table 7.9 Summary of QC estimates obtained for PID measurements of soil samples from a
fuel contaminated site
Parameter Instrument lin- Field detection Field precision Field accuracy
ear range limit and trueness
Sum of volatile 0-1000 ppm No field detec- RSD=20 % Correlation fac-
hydrocarbons in tion limit for soil tor 0.48
soil by PID measurements Accuracy range:
obtained 25% - 2800%
Upper limit for
instrument de-
tection limit 2-9
ppm
0,5 ppm isobu-
tulene in air ac-
cording to the
instrument
manual
At this point it should be noted, as explained previously, that a direct relationship be-
tween PID responses and GC-MS measurements of specific organic compounds is not
to be expected. If the correlation between PID and GC-MS data had been more constant,
calibration of the PID against GC-MS, section 5.2.1, could have been suggested.
The data do not allow for evaluation of the causes of the differences between PID field
measurements and laboratory GC-MS results, but it should be considered to examine
also the documentation for precision and trueness of the applied laboratory GC-MS
method.
49
With respect to the relative field method quality requirements, see section 4.2, the PID
soil measurements fulfil the requirement of known precision and the precision is better
than the requirement for a quantitative field method. Also, the requirement for known
accuracy range is fulfilled, still with a broad accuracy range obtained. The requirement
for all measurements above the detection limit can not be evaluated as the PID method
detection limit was not evaluated. The requirement for a known correlation factor be-
tween field and laboratory measurements is not fulfilled due to the very large uncer-
tainty associated with the obtained correlation, and the requirement for all measure-
ments within demonstrated linear range is not fulfilled.
7.2 FFD Measurement of TPH in Soil

The use of a fuel fluorescence detector (FFD) for analysing total petroleum hydrocarbon
(TPH) and polycyclic aromatic hydrocarbons (PAH) in soil samples is an example of a
relative method. A FFD hydrocarbon detector from Vertek was used for the field meas-
urements.
FFD is measuring the fluorescence in soil. Aromatic compounds in the soil absorb UV
light from the instrument and re-emit some of the light, i.e.: are fluorescing. The in-
strument detects the emitted, fluorescent light. The instrument has two UV lamps, one
with a wavelength of 360 nm (sensor 1) and one with a wavelength of 450 nm (sensor
2). Sensor 1 is suitable to measure BTEX, naphthalene and other lighter hydrocarbon
compounds from e.g.: petrol, jet fuel and diesel. Sensor 2 is suitable for PAH and other
heavier aromatic compounds found in creosote and coal tar, but also at sites with old
contamination from high boiling petroleum products. The data from sensor 2 are used in
the example.

The field study took place at Waldemar Thranes gate, a construction site in the centre of
Oslo (figure 7.5). The site was filled up with sand, gravel and other materials in the
1920s and today, the site is an ill-defined mixture of different materials and substances.
Previously, a petrol station operated on the site and contamination of petroleum hydro-
carbons up to 1000 mg TPH/kg has been measured. Soil for analysis and measurements
were sampled during excavation of the site.
At each sampling spot, approximately 1.5 kg soil was collected in the field and put into
gastight Rilsan bags. The bags were closed and mixed well before 500 g were trans-
ferred to a clean Rilsan bag for PID analysis (performed in duplicates, data not used
here) and the rest of the soil was used for the FFD measurement (duplicate measure-
ments of the same subsample). After the FFD measurements, the water content of the
soil was determined. All samples were a dark mixture of organic matter, clay, silt and
sand with varying soil moisture.
50
75 m
Figure 7.5. Waldemar Thranes gate, Oslo
It should be noted that there is no general relationship between the soil concentrations
of specific petroleum hydrocarbons or PAH and the FFD responses. The relationship
depends upon the mixture of compounds and their individual response factors in FFD.
Also, the FFD response will reflect the sum of a variety of aromatic organic contami-
nants with different maximum contaminant concentrations, such as the 0.1 mg/kg dw
target for the PAH benzo(a)pyrene and 0.005 mg/kg dw for benzene (Norwegian val-
ues). Here, the target values should be set to the FFD response corresponding to the
Norwegian maximum contaminant concentrations (MCCs) which are 2 mg for
PAH/kg dw and 137 mg C5-C35/kg dw for aliphatic hydrocarbons.
Table 7.10 Methods and objectives for the field investigation at Waldemar Thranes gate, Oslo
Parameter Method princip- Target values Data quality re- Decision
le and equip- quirement
ment
Sum of Measurement of The target value No specific re- Measurement of
PAH and soil with FFD depends on the quirements for FFD in soil is
TPH in soil chemical sub- this investigation. used to decide
stances present General require- which samples to
at the site. ments for relative send to labora-
methods: all tory analysis.
measurements
above DL, RSD
known, possibly
recovery known,
see table 4.2
It should further be noted that the laboratory analysis for total petroleum hydrocarbons,
TPH, used here as primary target parameter will include both the aliphatic and aromatic
hydrocarbons found in petroleum products in the range C6-C35, although aromatic com-
51
pounds will not be fully included due to the extraction solvent (pentane) used. That
means that part of the TPH (aliphatic hydrocarbons) will not contribute to the FFD re-
sponse.
Bench check out of the instrument was done according to the manufacturer manual by
setting the baseline to zero and calibration with calibration cards. The manufacturer
gives an instrument detection limit of <100 ppm TPH in sandy soil, depending of type
of fuel and soil. The manufacturer does not give the linear range.
A calibration curve was made by spiking a dark, slightly humid (5% water content) soil
with 0 to 12000 mg fuel oil/kg (figure 7.6).
The output signal for the FFD is determined by soil colour, and a calibration curve
should be chosen based on the sample colour. This soil gave a linear response between
0 and 12000 mg C5-C35/kg and expressed as FFD, linear sensor 2 response from 0 to 0.7
for this dark, humid soil. Regression analysis gave the following equation (R2 = 0.989):
FFD response = 0.000058 * hydrocarbon concentration 0.028
It should be noted that the calibration curve intercept is negative suggesting an incorrect
zero setting or non-linearity. The target value for the FFD corresponding to 137 mg
C5-C35/kg dw aliphatic hydrocarbons can be estimated to 0.020 for sensor 2 for this
soil from the calibration curve.
FFD calibration
0.8
0.6 y = 0.000058x - 0.028

FFD response
R2 = 0.989
0.4
0.2
0
0 2000 4000 6000 8000 10000 12000
-0.2
Total petroleum hydrocarbons (mg/kg dw)
Figure 7.6. Calibration curve for FFD (sensor 2) against dark, humid soil sample spiked with
fuel oil
Control of the instrument calibration was done by measuring the FFD response of a
standard sample (oil bottle), and the zero was checked with the black calibration card.
The oil bottle is a small, transparent bottle surrounded by a black case and filled with
diesel oil. A blank sample was made by heating quartz sand to 450C over the night (16
hours). A reference soil sample for control of soil TPH response was not available.
52
Table 7.11 describes the readings of the calibration check control samples used during
the FFD analyses.
Table 7.11 True value of control samples obtained with FFD

Black calibration card Blanks Oil bottle
Sensor 2 Sensor 2 Sensor 2
Mean 0.0031 -0.0663 1.33
Standard deviation 0.005 0.008 0.37
The risk of an incorrect zero setting was supported be the negative measurements for the
blank samples. Furthermore, a high RSD of 28% was seen for sensor 2 measuring the
high values for the oil bottle control. An instrument detection limit was not estimated.

The number of measured soil samples altogether was 52, of which 10 were background
samples. 15 contaminated and 3 background samples were sent to an accredited labora-
tory for extraction and analysis for verification of the field measurement. The results are
presented in table 7.12.
Several measurements were outside the range of FFD demonstrated to be linear for sen-
sor 2 (up to 0.7), but all laboratory analysis showed concentrations of TPH in the range
that were tested for linearity during calibration, se figure 7.6 (0 12000 mg C6-C35/kg).
The large number of FFD sensor 2 measurements below the calibration intercept sup-
ports the theory of an incorrect zero setting of the instrument.
Table 7.12 Duplicate field and laboratory results from the field investigation at Waldemar
Thranes gate, Oslo. FFD values are given as fluorescence intensity (VDC)
Sample 12C 12C-4 12D 12D-1 13C 13C-1 13D 13D-3 13D-4
Field measure-
ments
FFD sensor 2 -0.007 0.421 -0.199 -0.184 -0.121 -0.015 0.003 -0.171 -0.147
-0.051 0.347 -0.177 -0.184 -0.114 -0.005 -0.111 -0.188 -0.11
FFD sample -0.061 0.384 -0.188 -0.184 -0.118 -0.010 -0.054 -0.180 -0.129
average S2
Laboratory
analysis
Moisture con- 11.7 17.7 15.6 21.9 4.7 6.9 8.1 17.6 13.8
tent (%)
16 PAH -28 6.3 24 0.06 0 19 - 0.16 0.12
(mg/kg)
benzo(a)pyren - 0.67 2.7 0.007 <0.005 1.4 - 0.017 0.007
(mg/kg)
BTEX <0.1 0.13 - <0.1 <0.1 <0.1 0.22 <0.1 <0.1
(mg/kg)
TPH <5 38 - <5 <5 <5 5.7 <5 <5
C6-C10 (mg/kg)
TPH 16 170 - <10 <10 <10 <10 <10 <10
C10-C12 (mg/kg)
28
-: the sample was not analyzed for this parameter
53
Sample 12C 12C-4 12D 12D-1 13C 13C-1 13D 13D-3 13D-4
TPH 710 2700 - <25 <25 60 31 <25 <25

C12-C35 (mg/kg)
TPH 720 3000 - <40 <40 60 37 <40 <40
(mg/kg)
Sample 13E 14/15D 14/15E 15A 16E 18A 18B 18C 18D
Field measure-
ments
FFD sensor 2 -0.167 1.439 0.539 -0.1 0.251 -0.210 -0.17 -0.203 -0.205
-0.147 1.03 0.274 -0.133 0.003 0.215 0.0032 -0.195 -0.181
FFD sample -0.157 1.235 0.407 -0.117 0.127 0.003 -0.069 -0.199 -0.193
average S2
Laboratory
analysis
Moisture con- 18.9 9.4 18.8 16.1 18.0 18.9 20.2 17.5 12.7
tent (%)
16 PAH 8.2 5.3 20 66 33 - 210 - -
(mg/kg)
benzo(a)pyren 0.83 0.21 0.76 4.9 2.8 - 14 - -
(mg/kg)
BTEX <0.1 16 370 - 0.18 <0.1 - <0.1 0.2
(mg/kg)
TPH <5 120 1200 - 9.6 <5 - <5 <5
C6-C10 (mg/kg)
TPH <10 130 320 - 39 <10 - <10 <10
C10-C12 (mg/kg)
TPH 64 430 390 - 360 92 - 74 96
C12-C35 (mg/kg)
TPH 64 670 1900 - 410 92 - 74 96
(mg/kg)
The field evaluation of the precision was done by plotting the first ten duplicate meas-
urements of FFD sensor 2 in the 50% RSD chart, figure 7.7. All duplicates plotted in the
area indicating less than 50% RSD, and with the lowest differences observed for the
lowest measurements. Still, the applied correction of the negative FFT measurements to
positive values will give an impression of a better precision from the chart than actually
obtained. It should be noted that the procedure used here for duplicate measurements
(same sample measured twice) provides an estimate of the measurement precision only
and does not include subsampling precision.
54
50% RSD CHART
95% limit 99% limit Field measurements
100
10
0,1
0,01
0,001
0,01 0,1 1 10
Figure 7.7. RSD chart for 50% relative standard deviation with duplicate measurements (corrected to
start at positive values)
In order to calculate the standard deviation of the measurements including subsampling,

simple d-statistics were done, see section 5.3.3, as shown in table 7.13. Since most of
the measurements gave negative values on the FFD, only samples with positive readings
were included in simple d-statistics.
Table 7.13 Simple d-statistics calculation for FFD sensor 2, positive readings only
x i1 x i2 Di = x i1 x i 2 x i = ( x i1 + x i 2 ) / 2 d i = Di / x i
1.439 1.03 0.409 1.2345 0.33
0.539 0.274 0.265 0.4065 0.65
0.251 0.003 0.248 0.127 1.95
0.329 0.469 0.14 0.399 0.35
0.421 0.347 0.074 0.384 0.19
5.231 5.026 0.205 5.1285 0.04
0.077 0.051 0.026 0.064 0.41
0.055 0.041 0.014 0.048 0.29
0.095 0.281 0.186 0.188 0.99
0.748 0.933 0.185 0.8405 0.22
0.133 0.03 0.103 0.0815 1.26

d = d i / n = 0.61 RSD = d * 100 / 1.128% = 53.9% s0.4 = RSD * X 0 / 100 = 0.22 df = 10
The standard deviation at a FFD measurement of 0.4 (X0, corresponding to 7400 mg C6-
C35/kg according to the calibration, mid range of positive FFD measurements) was
found to be 0.22 and the relative standard deviation 54%. The range of measurements is
too large to accept a hypothesis of uniform standard deviation for the entire range. The
relative standard deviation of 54% gives credibility to the measurement strategy and
55
supports the conclusions drawn from the RSD chart: RSD just below 50% for measure-
ments in the higher range.
Calculation of the simple d-statistics for all duplicate measurements including negative
values gave an RSD estimate of 485% suggesting very poor precision. This estimate is
the result of the negative values and is an artefact that should not be applied. Correction
of all measurements for the lowest value measured (i.e.: setting the lowest value to zero)
and performing the simple d-statistics gave an estimate of 43% for the RSD. It should
be emphasised that data manipulations like this should be done with the greatest caution
and only if warranted by analytical explanations.
The grouped d-statistics, see section 5.3.3, could not be used here to estimate RSD and
blank standard deviation, s0, as the zero correction would impact the result. A method
detection limit could thus not be estimated.
Calibration check was done after calibration and before use of the instrument in the
field. Calibration check was not done in the field since the maximum number of meas-
urements on a field day was less than ten.
7.2.4 Verification
Totally 18 samples were measured with FFD and subsamples sent to laboratory analy-
sis, see table 7.12. Laboratory analysis of PAH in soil was done by adding aqueous so-
dium pyrophosphate solution to the soil followed by extraction with dichloromethane
and by quantification with GC-MS-SIM. BTEX and TPH (hydrocarbons C6-C35) in soil
were analysed by adding sodium pyrophosphate solution followed by n-pentane extrac-
tion and quantification using GC-FID.
A plot of FFD measurements against laboratory analyses for TPH is shown in figure
7.8. For 11 samples, TPH result was above the analytical detection limit. One value was
excluded as an evident outlier (TPH GC-FID 670 mg/kg dw, FFD 1.235) because of
poor linear relationship between field measurement and laboratory analysis in this point.
The verification showed no correlation between field FFD measurements and neither
PAH or BTEX laboratory results, but some correlation with the TPH results, coefficient
of determination 0.766. The regression coefficients (slope and intercept, see section
5.3.1) obtained were different from those obtained during calibration, figure 7.6, sug-
gesting that the FFD response for this soil and this contaminant composition was differ-
ent than for the dark, humid soil with added diesel used for calibration.
Inverse linear regression analysis, section 5.3.2, was only performed on the results from
the TPH and results are shown in table 7.14. For the evaluation of correlation between
field FFD and laboratory GC-FID, a field measurement, Y0, of -0.03 was selected, as
this is the median of FFD measurements with a corresponding TPH result and thus a
reasonable representative of the set of measurements. One value was still excluded as an
evident outlier (TPH GC-FID 670 mg/kg dw, FFD 1.235) because of poor linear rela-
tionship between field measurement and laboratory analysis in this point.
56
0.6
0.5 y = 0.00019x - 0.097
FFD measurement
0.4 R2 = 0.7567
0.3
0.2
0.1
0
-0.1 0 500 1000 1500 2000 2500 3000 3500
-0.2
-0.3
Total petroleum hydrocarbons from GC-FID (mg/kg dw)
Figure 7.8. Plot and regression for FFD measurements compared to laboratory analysis of to-
tal petroleum hydrocarbons (C6-C35)
The inverse regression analysis shows a correlation between field FFD measurements
and laboratory GC-FID measurements of total petroleum hydrocarbons (360 mg C6-C35
hydrocarbons/kg dw laboratory result corresponding to the -0.03 FFD response) with
very broad confidence limits (from 0 to 2000 mg/kg dw laboratory result). With the
negative measurements, the correlation factor concept should not be applied as defined,
see section 5.3.2.
Selected field measurement -0.03

Corresponding expected laboratory result 360 mg C6-C35/kg dw
Lower confidence limit 0 mg C6-C35/kg dw
Upper confidence limit 2000 mg C6-C35/kg dw
Said in other words: prediction of the laboratory GC-FID result from the field FFD
measurement is associated with a high uncertainty.
Calculation of the accuracy range according to section 5.1.5 for corresponding field
FFD measurement and laboratory GC quantification of C6-C35 in soil is not relevant due
to the negative FFD measurements.
7.2.5 Summary
The performance data for the field FFD measurements are summarised in table 7.15.
57
Table 7.15 Summary of QC estimates obtained for FFD measurements of total hydrocarbons
in soil samples from a fuel contaminated site
Parameter Instrument Field detection Field precision Field accuracy
linear range limit and trueness
Total petro- 0-0.7 on Field detection limit RSD=43-54% Not applicable
leum hy- FFD, for soil measure-
drocarbons 0-12000 mg ments was not ob-
in soil by TPH tained.
FFD C6-C35/kg dw 100 mg TPH/kg dw
was the stated in-
strument detection
limit.
Based upon quality control data and statistics, the FFD measurement showed a precision
of 43-54% relative standard deviation (duplicate measurements, simple d-statistics).
Prediction of laboratory GC-FID quantification of soil total petroleum hydrocarbons
from field FFD measurements was associated with high uncertainty (0-2000 mg C6-
C35/kg range for an estimate of 360 mg C6-C35/kg with a FFD measurement of -0.03).
The interpretation of the FFD measurements was seriously impeded by the negative
measurements, probably caused by incorrect zero setting of the instrument or matrix ef-
fects upon the calibration.
At this point it should be noted, as explained previously, that a direct relationship be-
tween FFD responses and GC measurements of specific organic compounds is not to be
expected. If the correlation between FFD and GC data had been more constant, calibra-
tion of the FFD against GC data from this field site could have been suggested, see sec-
tion 5.2.1.
With respect to the relative field method quality requirements, see section 4.2, the FFD
soil measurements fulfil the requirement of known precision and the precision is in the
same range as the requirement for a quantitative field method (better than 50% RSD).
Still, it should be remembered that the RSD obtained here for FFD does not include
subsampling as assumed in setting the 50% RSD requirement for quantitative methods.
The requirement for known accuracy range is not fulfilled due to the negative measure-
ments. The requirement for all measurements above the detection limit can not be
evaluated as the FFD method detection limit was not evaluated. The requirement for a
known correlation factor between field and laboratory measurements is not fulfilled due
to the very large uncertainty associated with the obtained correlation, and the require-
ment for all measurements within demonstrated linear range is in part fulfilled.
7.3 PXRF Measurement of Heavy Metals in Soil

The use of a portable X-ray fluorescence (PXRF) analyser for analysing heavy metals in
soil samples is an example of a quantitative method.

This field study was done on an abandoned industrial waste site located in Southern
Finland. In previous laboratory investigations (sandy soil samples from the top layer),
the heavy metal contamination was found mostly in a slag deposition area (figure 7.9).
58
Of the heavy metals, the major pollutants exceeding the regulatory threshold values
were lead (<DL3400 mg/kg dw), zinc (<DL7200 mg/kg dw) and copper (<DL46000
mg/kg dw), /31/.
Figure 7.9. Estimate of the spatial distribution of petroleum hydrocarbons and heavy metal
contamination, groundwater flow direction and the positions of the groundwater
monitoring wells at Trollberget, Hanko
The aim of the present investigation was to assess the lead polluted soil mass in order to
enable estimation of costs associated with remediation.
In the study, an Innov-X Systems PXRF instrument was used to investigate vertical dis-
tribution of lead in the 40 m x 30 m slag deposition area.
The following sampling measurement protocol was used:
Remove stones and vegetation from the sampling point

Take a sample for sample preparation (500-1000 g)
Pre-homogenise the sample manually (in plastic bag)
Take >100 g subsample for the PXRF measurements
Sieve the subsample to grain size < 2.0 mm
Dry the subsample (water content must be less than 20 % before measuring)
Place the subsample in a non-contaminated plastic bag (thin polypropylene)
Ensure >10 mm thickness of subsample for measuring
59
Use the same background plate or strong table under all subsamples, in order to
avoid different background effects between the measurements
Flatten the plastic bag containing the subsample evenly on the plate
Measure with >120 seconds count time
Perform three replicate measurements and calculate the measurement result as the
mean value
Soil samples were taken during drilling with a GM50 unit equipped with a 50 mm inter-
nal diameter auger. Two 100 g 500 g samples were chosen from each side of the auger
(duplicates) and placed in non-contaminated plastic bags. The auger was washed with
clean water between each sampling.
Table 7.16 Methods and objectives for the field investigation at Trollberget, Hanko
Parameter Method principle Target value Data quality Decision
and equipment requirement
Lead (Pb) in PXRF measure- 300 mg/kg dw Detection limit If measurement
soil ment of soil sur- lead, MCC for equal to 75 mg is above target
face with Innov-X lead in Finland, Pb/kg dw, a value, the sam-
System instru- highest limit precision of 50% ple is registered
ment RSD, a trueness as contaminated
better than 95- and represented
105% and an soil volume as-
accuracy better signed the
than 70-130% measured con-
is required. centration
Factory calibration of PXRF instruments is based on energy calibration with pure ele-
ments followed by fundamental parameter or empirical calibration with real samples.
When using PXRF as a range or relative method, the Innov-X-Systems analyser can be
operated based on fundamental parameter calibration, which provide a standardless
calibration, with a drift control sample to set up the energies (standardization). Matrix
specific calibration (calibration with real samples) is not necessarily required, but the
results can then only be used as informative (relative method) for preliminary identifica-
tion of hotspots or and contaminants.
Calibration with real samples is required for the use of PXRF as a quantitative method,
as the responses of PXRF instruments depend upon the matrix of the site studied. The
calibration for quantitative PXRF measurements is therefore best done using samples
from the site and analysed with a recognised analytical method with documented and
sufficient quality on an accredited laboratory, see section 5.2.1. In the present study, 14
samples from an initial sampling were sent to ICP-AES29 analyses in the laboratory for
the calibration of the PXRF instrument.
29
Inductively coupled plasma atomic emission spectrometry, a method for quantitative analysis of metals
in soil samples, here after destruction and dissolution with aqua regia, a mixture of hydrochloric and nitric
acid
60
The calibration curve is shown in figure 7.10, and a reasonable linear relationship (R2=
0.988) was found from just above the detection limit to 4500 mg Pb/kg dw. No indica-
tion of non-linearity was seen for the highest concentration measured. The regression
equation was:
PXRF measurement (mg/kg) = 1.06 * laboratory ICP-AES measurement (mg/kg) + 77.3
The linear regression further shows that the difference between field PXRF measure-
ments and laboratory ICP-AES results was generally not large, as the slope of the cali-
bration curve was 1.06 and thus close to unity.
6000
5000
yy==1.06x
1.06x++77.3
77.28
2
R = 0.988
R2 = 0.99
Field PXRF (mg/kg)
4000
3000
2000
1000
0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Laboratory ICP-AES (mg/kg)
Figure 7.10 Calibration curve for PXRF against site samples analysed using ICP-AES
The PXRF instrument calibration was checked with a blank sample and a control sam-
ple containing all the relevant heavy metals before the field investigations. The blank
sample was prepared by washing uncontaminated sand with hydrogenperoxide and 5%
hydrochloric acid. The control sample was prepared by mixing a known amount of a
crystalline lead compound (PbO) into the blank sample. Both samples were milled, ho-
mogenised and analysed in the laboratory using ICP-AES. Table 7.17 describes the
heavy metal concentrations of the control samples used during the PXRF analyses.
Table 7.17 True value of control samples obtained with ICP-AES (2 analyses) and PXRF
measurements (27 measurements)
mg Pb/kg dw Blank Control sample
Theoretical 0 2000
Mean ICP-AES <4,0 2150
Mean PXRF -62 1940
Standard deviation PXRF 8.3 324
An alternative procedure for preparation of control and blank samples would be to pre-
pare large volumes of dried, milled and homogenised soil from one contaminated sam-
ple (concentration near the target value) and one uncontaminated sample in one site
61
study. These samples could then be stored and used as control and blank samples in fu-
ture site studies, if the concentrations in the samples were analysed with a recognised
analytical method with documented and sufficient quality on an accredited laboratory.
The detection limit calculated from 10 blank sample measurements (see 5.1.2) was 40
mg Pb/kg dw. This should be considered an instrument detection limit, as the blank
measurements used here will not reflect sample variation but only the instrument varia-
tion for multiple measurements on the same sample.
The control samples were used to check instrument blank and response during the
fieldwork.

Totally more than 200 soil samples were analysed on site by PXRF, with 30 samples
(15%) from 9 drillings and 3-5 depths sent to the laboratory for verification analyses.
All the 30 samples were also prepared as duplicates and analysed by PXRF in the field.
Several background duplicate samples were also prepared after sampling under labora-
tory conditions to meet requirements for grouped D-statistics.
The results of PXRF (mean value of 3 replicate measurements) and ICP-AES analyses
are presented in table 7.18.
Table 7.18 Duplicate field and laboratory results from the field investigation at Trollberget,
Hanko
Sample Field PXRF measurements, Laboratory ICP-AES analysis,
mg Pb/kg dw mg Pb/kg dw
22 0,5-1,5 -4630 -60 7,56 4,37
22 1,5-2,0 -45 -31 <4 <4
22 2,0-2,5 -45 -58 <4 <4
22 2,5-3,0 - - <4 <4
23 0,2-1,3 319232 2279 1010 1540
24 0-1,0 791 1153 1040 650
24 1,0-2,0 1739 2908 1990 1510
24 2,0-2,9 835 1229 509 740
25 0-1,2 1040 1051 849 956
25 1,2-1,5 -71 -47 13.5 18.5
25 1,5-2,0 -81 -74 <4 <4
25 2,0-2,5 -76 -63 <4 <4
26 0-0,5 1736 2112 2590 2960
26 0,5-1,3 2293 2020 3010 1810
26 1,3-1,5 2328 2348 3250 1760
26 1,5-1,8 5045 5323 8580 14000
26 1,8-2,3 -4 -14 80.2 69.7
26 2,3-2,5 -15 -29 57.1 73.4
27 0-0,8 1509 1268 2090 2060
27 0,8-1,1 79 76 121 171
27 1,1-1,7 1607 931 3060 1180
27 1,7-2,2 -60 -68 19.1 15.2
30
Negative measurements are considered below the instrument detection limit
31
-: no instrument measurement
32
Please, note that more figures than justified by the method precision are given in order to maintain all
information in subsequent calculations
62
Sample Field PXRF measurements, Laboratory ICP-AES analysis,
mg Pb/kg dw mg Pb/kg dw
27 2,2-2,5 -74 -65 10.6 8.35
28 0-0,1 2377 2568 1800 1710
28 1,0-1,5 3058 2537 3300 2870
28 1,5-2,2 2707 2146 3560 1690
28 2,2-2,7 -49 -56 20,4 23.1
28 2,7-3,0 -86 -69 8.05 11.1
29 0-1,2 1555 1484 1960 2720
29 1,2-1,6 1922 2057 1750 2260
It should be noted that a small number of PXRF measurements were outside the range
of PXRF measurements previously demonstrated to be linear: 40-4500 mg Pb/kg dw.
The field evaluation of the precision was done by plotting the duplicate measurements
in the 50% RSD chart, figure 7.11. The chart showed clearly that the measurement pre-
cision was better than 50% RSD. No need for revision of the measurement strategy was
thus indicated during the field work.
50% RSD CHART
95% limit 99% limit
100000
Difference between duplicate analyses
10000
(concentration)
1000
100
10
10 100 1000 10000
Mean of duplicate analyses
Figure 7.11 RSD chart for 50% relative standard deviation with duplicate measurements
In order to calculate the precision of the measurements including subsampling, simple

d-statistics were done, see section 5.3.3, as shown in table 7.19. The standard deviation
at the target value of 300 mg Pb/kg was found to 54 mg Pb/kg and the relative standard
deviation 18 %. The relative standard deviation of 18% gives high credibility to the sub-
sampling and measurement strategy and supports the conclusions drawn from the RSD
chart: RSD well below 50%.
The range of measurements is too large to accept a hypothesis of uniform standard de-
viation of the entire range, but if we consider only the narrow measurement range 1000-
3000 mg/kg, the RSD was 5.4%, and the estimated standard deviation for this range was
107 mg Pb/kg dw. The low RSD and standard deviation indicate good precision in the
high measuring range.
63
Table 7.19 Simple d-statistics calculation
3161 2208 953 2685 0.36
753 1096 343 925 0.37
1602 2859 1257 2231 0.56
795 1168 373 982 0.38
988 999 11 993 0.01
1662 2038 376 1850 0.20
2222 1946 276 2084 0.13
2258 2278 21 2268 0.01
5240 5569 329 5405 0.06
28 38 10 33 0.32
1440 1206 234 1323 0.18
101 99 2 100 0.02
1535 885 651 1210 0.54
2308 2504 197 2406 0.08
3019 2472 547 2746 0.20
2649 2072 576 2360 0.24
1485 1415 69 1450 0.05
1848 1982 135 1915 0.07
749 560 189 655 0.29
2127 3390 1262 2758 0.46
106 97 9 102 0.09
96 83 13 90 0.15
185 183 2 184 0.01
53 46 7 50 0.14
41 49 8 45 0.18
33 43 10 38 0.26
64 58 6 61 0.10
65 54 11 60 0.18
67 56 11 62 0.18
920 1316 396 1118 0.35
2046 3276 1230 2661 0.46
3531 3467 64 3499 0.02

d = d i / n = 0.208 RSD = d *100 / 1.128% = 18% s 300 = RSD * X 0 / 100 = 54 df = 28
Range 1000-3000 mg Pb/kg dw

d = d i / n = 0.05 RSD = d * 100 / 1.128% = 5.35% X = x i / n = 2221

s = RSD * X / 100 = 107 df = 9
The grouped d-statistics, see section 5.3.3, are shown in table 7.20. The relative stan-
dard deviation obtained with grouped d-statistics for 300 mg/kg was 22%, which is
similar to the estimate obtained with simple-d statistics.
The estimated blank standard deviation, s0, is 4,44 mg Pb/kg dw. The negative value is
probably due to too limited number of duplicates, in particular in the low range. A
method detection limit can not be calculated.
64
Table 7.20 Grouped d-statistics calculation
Q 0,5 j Linear regression

xj
10.2 47.7 s 0 = b * 1.047 = 4.44 k = a * 1.047 = 0.236

7,50 198.5 Precision at 300 mg Pb/kg
358.2 1092 s=s0+k*c=66.4 mg Pb/kg RSD=(s0/c+k)*100%=22.1%
326.0 2194 Detection limit with blank correction (2 blanks)
779.6 3160 Can not be calculated due to negative s0
1000.0
800.0
y = 0.225x - 4.24
600.0 R2 = 0.884
Q0,5j
400.0
200.0
0.0
0.0 500.0 1000.0 1500.0 2000.0 2500.0 3000.0 3500.0
xj
The instrument calibration control was done 10 times distributed over the study period,
table 7.21. All blank control measurements were below the instrument detection limit.
The relative standard deviation obtained with the control samples was 22% and thus
close to what was obtained with field measurements on the site. Measurements of the
control sample should be within initial mean PXRF value (1940 mg Pb/kg) 2 times
the standard deviation (+/- 650 mg/kg). This corresponds to a 95% confidence interval
around the established true mean, see section 5.1.3. The obtained mean PXRF meas-
urement was thus not significantly different from the initial true PXRF value found
during the bench check out and calibration control sample preparation, see table 7.17.
Table 7.21 Measurements of control samples and blank samples in the field
mg Pb/kg dw Control sample Blank sample
Average 2.042 <40
Standard deviation 446 -
On two occasions during the field measurements, the control measurements were out-
side the acceptable range. Then, instrument conditions were checked (including possible
contamination and recharge of batteries), followed by restarting and standardization of
the instrument with a drift sample. After this procedure, the control measurements were
back within the acceptable limits and the field measurements were continued.
The calibration check data indicate that the PXRF instrument has been stable through
the measurement period. Also, the versatility of using calibration check measurements
as an early warning of calibration problems was demonstrated.
65
7.3.4 Verification
Totally 30 samples were taken as duplicates and sent to laboratory analysis, see table
7.18 for data. Soil samples were analysed in the laboratory using ICP-AES after an in-
ternational standard method for analysing metals in soils. Destruction and dissolution
was with aqua regia (hydrochloric and nitric acid).
A plot of all PXRF measurements against laboratory analysis is shown in figure 7.12.
For the plot and for regression analysis, the first of the two duplicate measure-
ments/analysis obtained for each sample were used. All PXRF measurements below the
instrument detection limit (40 mg Pb/kg dw) were included as *DL, i.e.: 20 mg Pb/kg
dw.
6000
y = 0.62x + 360
PXRF (mg Pb/kg dw)
R2 = 0.797
4000
2000
0
0 2000 4000 6000 8000 10000
ICP-AES (mg Pb/kg dw)
Figure 7.12 Plot and regression analysis of field PXRF Pb measurements compared to labora-
tory ICP-AES analysis (first set of duplicates)
The plot demonstrates some correspondence between field PXRF measurements and
laboratory ICP-AES analysis with a R2= 0.797. The correspondence is strongly depend-
ent upon the data set with one concentration above the range previously demonstrated to
be linear. It should be recalled that the calibration of the PXRF against ICP-AES results
for samples from the same site showed fine linear relationship, figure 7.10, but with
other regression coefficients (slope and intercept, see section 5.3.1. It should be men-
tioned that using the second set of duplicates would have yielded slightly less linearity
than this first set of duplicates.
Results from inverse regression analysis, section 5.3.2, are shown in table 7.22. For the
evaluation of trueness, a field measurement, Y0, of 1509 mg Pb/kg dw was used as this
is the median of the PXRF measurements (first subsample of duplicates for PXRF) and
thus a good representative of the dataset.
The inverse regression analysis shows good mean correspondence between field PXRF
measurements and laboratory ICP-AES measurements of lead in soil in the median
range of the measurements, but with large uncertainty in predicting the laboratory result
from field measurements. At the target value of 300 mg Pb/kg dw, the correspondence
is poor and the predicted laboratory result would be negative. Said in other words: pre-
66
diction of the laboratory ICP-AES lead concentrations from the field PXRF measure-
ments in the lower range close to the target value would not be possible.
Selected field concentration 1509 mg/kg dw

Corresponding expected laboratory result 1900 mg/kg dw
Lower confidence limit 0 mg/kg dw
Upper confidence limit 4000 mg/kg dw
Trueness 81%
Lower trueness limit 38%
Upper trueness limit -33
Trueness reported 81% (38 - ?%)
Accuracy has been calculated according to section 5.1.5 for the first of all duplicates
with corresponding field PXRF measurement and laboratory ICP-AES quantification of
soil lead. Accuracy range for field PXRF measurements was 18-320% relative to labo-
ratory ICP-AES results. The accuracy range supports the high uncertainty associated
with correlation of field PXRF data with laboratory ICP-AES data. The reason for the
poor accuracy and correspondence between field and laboratory measurements may be a
high variability among the duplicate samples taken, but this is contradicted by the good
precision seen with duplicate PXRF measurements.
It should be noted at this time, that the estimation of the precision for the laboratory
ICP-AES analysis using simple d-statistics with the duplicate results gave a 29% RSD
as compared to the 18% RSD estimated for PRXF. An explanation of the apparently
higher RSD for laboratory results can be that the PXRF in reality performs 3 submeas-
urements for each sample, even though only the means of these submeasurements are
reported as the final PXRF measurements. In theory, this will improve the PXRF preci-
sion by a factor of 3 and indeed, the PXRF RSD is approximately 1 / 3 times the ICP-
AES RSD.
7.3.5 Summary
The performance data for the field PXRF measurements are summarised in table 7.23.
Based upon quality control data and statistics, the PXRF measurement proved stable
(field calibration control), calibration control gave early warning of the need for instru-
ment adjustment, and the method showed a good precision with 18-22% relative stan-
dard deviation (duplicate measurements, RSD chart, simple and grouped d-statistics).
Mean correspondence between field PXRF measurements and laboratory ICP-AES
quantification soil lead was 81% (mean trueness, inverse linear regression) with 38%
lower trueness limit, and the accuracy was 18-320% PXRF measurement relative to
ICP-AES analysis.
33
Upper trueness limit cannot be estimated as the lower confidence limit is negative, here set to 0)
67
Table 7.23 Summary of QC estimates obtained for PXRF measurements of soil samples from
a fuel contaminated site
linear range limit and trueness
Pb in soil 40-4.500 mg Field detection RSD=18-22% from Accuracy range:
by PXRF Pb/kg dw limit for soil simple and 18-320%
measurements grouped d- Trueness (1500 mg
was not deter- statistiscs Pb/kg dw range):
mined. 81% (38-?%)
40 mg Pb/kg dw
was the estima-
ted instrument
detection limit
18 mg Pb/kg dw
was the instru-
ment detection
limit according
to the manufac-
turers manual
With respect to the quantitative field method quality requirements, see section 4.2, the
PXRF soil measurements of lead fulfilled the requirement of precision better than 50%
RSD. The requirements for accuracy (50-150%) and trueness (95-105%) were not ful-
filled. The requirement for a detection limit above 1/4 of the target value (300 mg
Pb/kg), i.e.: 75 mg Pb/kg dw, was fulfilled. The requirement for all measurements
within demonstrated linear range was not fulfilled.
7.4 Measurement of pH, Conductivity and O2 (Flow Cell) and Nitrate

in Groundwater
The field measurement for pH, conductivity, oxygen and temperature are examples of
relative measurements as is the colorimetric test kit (HACH-Lange) for nitrate, while
the method with test sticks for nitrate (HACH) is an example of range method.
The field investigation was conducted on groundwater samples from wells around
Sjls Lake. The groundwater quality in this area is affected by the leaching of pollut-
ants from different source and is therefore monitored regularly to establish trends in wa-
ter quality. The geology of the area comprises moraine clays with inserts of moraine
sand. Under the 15 -30 meter moraine clay layer is a 5 to 55 meter sandy layer, which
decreases in magnitude in the direction towards the lake. The groundwater in the sandy
layer is in contact with the chalk reservoir.
The objective of the field measurements in a flow cell for pH, temperature, conductiv-
ity, oxygen and redox is to ensure the stable quality of water samples, before sampling
for the chemical analysis of pollutants. Furthermore, analysis of the inorganic parame-
ters including nitrate is carried out to evaluate changes in redox conditions. The time se-
ries for field measurements are useful to identify changes in water quality and in rela-
tion to changes in the organics pollutants.
68
The groundwater was sampled with submersible pumps attached to polyethylene tubes.
The field measurements were made in a unit containing 4 electrodes attached to two
WTW multimeters for the measurement of pH, oxygen, redox and conductivity.
Figure 7.13. Site map, Blovstrd, Denmark
The temperature was also recorded simultaneous during the conductivity measurements.
Each electrode was placed individually in a flow cell connected in series, so that the wa-
ter entered at the bottom of each cell and left at the top of each cell. The replicate meas-
urements were taken during pumping after an interval of 1 minute. Water samples were
69
taken to prepare the duplicate/triplicates samples needed for the analysis of nitrate by
nitrate sticks, nitrate colorimetric test kits and for accredited nitrate analysis at a labora-
tory. Other samples were taken for the analysis of contaminants.
The nitrate test sticks (HACH) were dipped in one of the duplicate water samples in the
laboratory. Normally, the test sticks would be dipped in the water stream and measured
on site.
The nitrate test kit (HACH-Lange) are done in cuvettes supplied as individual, dispos-
able units containing an acid solution requiring only addition of 1 mL of the water sam-
ple and the colour reagent. The nitrate ions in acid solution react with 2,6-
dimethylphenol to form 4-nitro-2,6-dimethylphenol. The colour development is meas-
ured with a Lasa 20 photometer using a specific program for nitrate analysis. No cali-
bration is necessary. The measuring range is 1 60 mg NO3/L (0.23- 13.5 mg NO3-
N/L). The readings are in mg NO3-N/L.
The water samples for the nitrate analysis with HACH-Lange test kits were taken in
glass bottles, stored in a cooler box and analysed the same day (after less than 5 hours).
43 replicate samples were taken for accredited laboratory analysis for nitrate and dis-
patched on a daily basis. The field work was carried out over a period of 14 days.
Table 7.24 Methods and objectives for the field investigation in Blovstrd, Denmark.
.Parameter Method princi- Target Data quality re- Decision
ple and equip- value quirement
ment
pH Flow cell array None General require- The measure-
Conductivity with electrodes ments for relative ments must be
Oxygen and multimeter methods: all meas- stabile before
Redox display urements in decision water samples
Temperature area above DL, RSD are taken for
known, possibly re- analysis.
covery known, see
table 4.2.
Colorimetric Colorimetric test None General require- None.
Nitrate with photometer ments for relative Quality meas-
HACH-Lange methods: all measurement used as
LCK 339 urements in decision a reference in
area above DL, RSD the time series
known, possibly re- of the monitoring
covery known, see data.
table 4.2
Test sticks- Colour reaction None General require- None.
HACH on plastic strip. ments for range Quality meas-
Concentration methods: maximum urement used as
determined by concentration above a reference in
comparison with DL, range correct- the time series
colour scale ness above 90%, of the monitoring
error max 1 range, data.
all measurements in
decision area within
application range,
see table 4.2
70
Bench-check of the field equipment was carried out initially before leaving for the field
to make field measurements.
pH- electrode
The pH electrode was calibrated at 25C with two pH-buffers; pH 4 and pH 7. A slope
value can be read from the instrument, which must be must be within -50 and 62
mV/pH and the offset voltage 30 mV. According to the manufacturer, the instrument
resolution is 0.01 and the accuracy is 0.01 1 digit
Table 7.25 Bench check pH electrode.

Date Bench check Slope pH
31-8-04 Calibration -54.8 4 and 7
Oxygen-electrode
The calibration of the oxygen electrode was checked by measurement in an air calibra-
tion beaker with water vapour saturation. The relative slope of the probe must be within
0.6 1.25. According to the manufacturer, the instrument resolution is 0.01 mg/L and
the accuracy is 0.5 % of the measured value.
Table 7.26 Bench check oxygen electrode.

Date Bench check Saturation Slope
31-8-04 Calibration 101.0 % 0.83
Redox
The calibration of the redox electrode was checked by measurement of a redox buffer
(234 mV). According to the manufacturer, the instrument resolution is 1 mV and the ac-
curacy is 1 mV 1digit
Table 7.27 Bench check redox electrode.

Date Bench check mV
31-8-04 Calibration 234
Conductivity
The conductivity electrode was calibrated with a 0.01 mol/L potassium chloride (KCl)
solution and automatic temperature compensation (conductivity 1413 S/cm at 25C).
According to the manufacturer, the instrument resolution is 1S/cm and the accuracy is
1% of the measured value. A calibration curve was prepared with double determina-
tion of 5 different certified KCl solutions as shown in figure 7.14.
The coefficient of determination in figure 7.14 shows an excellent linear agreement with
the standards and demonstrates that a linear response from 250 5000 S/cm can be
expected, which is well within the normal range of values for groundwater in this area
(500 2000 S/cm). Low values below 500 S/cm can be expected to be less accurate.
The equation for the regression analysis also shows very good agreement between the
71
measured values and the nominal values for the conductivity standards (slope close to
unity, intercept close to zero).
5000
Measured cond. S/cm
y = 0.99x + 31
4000 R2 = 1.00
3000
2000
1000
0
0 1000 2000 3000 4000 5000
Calibration standard, conductivity S/cm
Figure 7.14 Calibration curve for Conductivity meter against calibration standards
Test strips for nitrate
The HACH nitrate test strips test for nitrate (and nitrite) measure in the concentration
range 150 mg NO3-N/L. The colour intervals for measurement of nitrate using
HACH nitrate test strips are illustrated in table 7.28.
Table 7.28 Colour range for test sticks for nitrate
mg NO3-N/L, 0 1 2 5 10 20 50
Converted to 0 4.4 8.9 22 44 89 220
mg NO3/L34
Range inter- <1 1 -<2 2 - <5 5 - <10 10 - <20 20 - <50 50
pretation
No calibration is required. The sticks change colour if nitrate is present in the solution,
and the concentration is read from a colour scale. Interpolation between the colour scale
intervals can be attempted, but constitutes a subjective assessment only. It is important
to define how the results are to be interpreted and reported before using a range method.
In table 7.28 the interpretation of the colour scale is shown - the colour development on
a stick is interpreted to be above or below one of the 7 colour scales. It is difficult to
distinguish large differences in concentration at the high end of the concentration range.
Eight calibration solutions were used to control the trueness of the HACH sticks as
shown in table 7.29. The detection limit was controlled by a standard close to the detec-
tion limit (0.3 mg NO3-N/L) and the range was controlled by a standard at about 1.25 x
the lower limit of the upper range (20 mg NO3 -N/L). As can be seen in table 7.29, er-
34
Conversion factor 1 mg NO3-N/L = 4.3 mg NO3/L
72
rors can easily occur close to the individual range limits, even analysing nitrate solu-
tions in clean water.
Table 7.29 Bench control of trueness for HACH test sticks, single measurements
Standard nitrate True range Subjective Test sticks Trueness
solution reading of range results
(mg NO3-N/L) (mg NO3-N/L) result (mg NO3-N /L)
0 <1 0 <1 True
0.3 <1 1 1 - <2 False positive
1.1 1 - <2 2.5 2 - <5 False positive
2.3 2 - <5 4.0 2 - <5 True
4.5 2 - <5 7 5 - <10 False positive
5.7 5 - <10 9 5 - <10 True
10 10 - <20 10 10 - <20 True
15 10 - <20 15 10 - <20 True
25 10 - <20 >20 20 - <50 True
Nitrate test kit (HACH-Lange)
Quality assurance was carried out using the HACH-Lange LCA -703 Addista standard
solution of 26.6 2 mg NO3/L (6 mg NO3-N/L). Additionally, an Addista standard
LCA-704 of 113 2 mg NO3/L (25 mg NO3-N/L) was used to make standard solutions
at the higher end of the measurement scale.
A calibration curve was prepared using the LCA Addista calibration standard, figure
7.15.
50
Measured conc. mg N0 3/L
y = 0.94x + 0.13
40 2
R = 0.999
30
20
10
0
0 10 20 30 40 50
Standard nitrate solution mg N03/L
Figure 7.15 Calibration curve for Nitrate test kit using calibration standards
The coefficient of determination in figure 7.15 shows an excellent linear agreement with
the standards (coefficient of determination, R2, close to 1), and the equation for the re-
gression analysis shows that very good agreement is obtained between the measured
values and the nominal values for the nitrate standards (slope close to unity, intercept
close to zero).
73
7.4.2 On-site quality control
Flow cell electrodes for pH, conductivity, temperature, redox and oxygen
The four electrodes were calibrated or checked each day according to procedures speci-
fied by the manufacturers, and the appropriate control measurements and signals were
noted as described in the bench check, tables 7.30-7.33. Approximately 8 samples were
taken per day which is more or less equivalent to a control measurement every 10 sam-
ples. Duplicates were analysed.
Table 7.30 Daily control before field work: pH -electrode.

Equipment check Slope pH
with pH 4
Mean -57.75 3.99
Standard deviation 1.00 0.01
Number of controls 8 8
Table 7.31 Daily control before field work: oxygen-electrode.

Calibration with Saturation Slope
saturated air va-
pour
Mean 101.92% 0.90
Standard deviation 0.01 0.14
Number of controls 9 9
Table 7.32 Daily control before field work: redox electrode.

Equipment check with Control data
234 mV redox buffer
Mean 232 mV
Standard deviation 3,5
Number of controls 9
Table 7.33 Daily control before field work: conductivity electrode.

Equipment check with Control data
1413 S/cm standard
Mean 1418 S/cm
Standard deviation 4,4
number of controls 9
All calibration checks of electrode demonstrated stable equipment with no significant

deviations from true measurements.
74
Test sticks for nitrate (HACH)
The nitrate sticks can not be calibrated, but to ensure that the colour reaction of the
sticks had not deteriorated, the results for blanks and a standard just above the lower
limit of the upper range were controlled each day (approximately 8 samples were sam-
pled per day which is more or less equivalent to a control measurement every 10 sam-
ples).
Table 7.34 Daily control: nitrate sticks HACH.

Response check Blank 25 mg NO3-N /L
Correctness 100 % 100%
False positives - -
False negatives - -
Number of data 9 9
Furthermore, a number of field samples were tested then spiked and retested with the ni-
trate sticks. The spiking was adjusted to ensure that the resulting concentration should
give a response that was shifted one range of concentration. The purpose was to check
that there was no apparent interference with the colour development due to deterioration
in the quality of the sticks or due to interference from the actual water.
Table 7.35 Spiking of natural samples.

Response with test Spiking Response with test Trueness
stick for sample concentration stick for spiked
without a spike sample
mg NO3-N /L
<1 3 2 - <5 True
<1 3 2 - <5 True
<1 3 2 - <5 True
<1 3 2 - <5 True
<1 3 2 - <5 True
<1 3 2 - <5 True
<1 3 2 - <5 True
<1 3 2 - <5 True
<1 3 2 - <5 True
<1 3 2 - <5 True
<1 7 5 - <10 True
<1 7 5 - <10 True
<1 7 5 - <10 True
<1 7 5 - <10 True
<1 10 10 - <20 True
<1 10 10 - <20 True
<1 10 10 - <20 True
<1 10 10 - <20 True
Nitrate test kit (HACH-Lange)
The Lasa 20 photometer and HACH-Lange testkits are precalibrated. Blanks and stan-
dard solutions can be checked in the field in a similar manner as for the bench control.
In this investigation, samples were collected from a number of wells and analysed at the
home base, and from here, selected samples were send to the accredited laboratory.
75
Blanks and duplicates were analysed during the field work, as well as the spiking stan-
dard solution. The standard contained ortho-phosphate, ammonium, chloride, nitrate,
phosphate, sulphate and organic carbon.
Table 7.36 Results for HACH-Lange test kit for nitrate

Standard solution Number of de- Mean Standard
LCK-339 no. 5676 terminations (mg NO3-N /L) deviation
Spiking solution, true 2 5.74 0.07
value: 5.94-6.08 mg
NO3-N/L
To check the equipment and test kit responses, 5 natural water samples were spiked
with a spiking addition of 3 mg NO3-N/L. According to the HACH-Lange Addista qual-
ity assurance criteria, the results for the spiked samples should be within 3 0.5 mg
NO3-N /L. As seen in table 3.37, all the spiked samples complied with this quality crite-
rion.
Table 7.37 Spiking of natural samples.

Measured sample Measured concentra- Measured spike addi-
concentration, C1 tion after spiking, C2 tion, [C2 (C1/2)]
mg NO3-N /L
133.111 3.00 4.42 2.86
3.15 = 3.08 4.38 = 4.40
133.121 3.00 4.14 2.64
2.99 = 3.00 4.14 = 4.14
134.070 0.10 2.90 2.86
0.17 = 0.14 2.95 = 2.93
133.107 9.37 7.49 2.83
9.31 = 9.34 7.51 = 7.50
133.115 4.71 4.97 2.69
4.65 = 4.68 5.08 = 5.03
Approximately 50 duplicate measurements of water samples were made for each pa-
rameter (pH, oxygen, redox, conductivity, HACH nitrate sticks and HACH-Lange ni-
trate).
Simple d-statistics and grouped d-statistics, section 5.3.3, were performed for measure-
ments where pertinent in order to calculate the measurement precision for the individual
investigation and method respectively.
pH
The evaluation of the precision by plotting the duplicate measurements in the 50% RSD
chart as described in section 5.3.3 was not carried out as the duplicate results are identi-
cal or very close and only a small range of pH values is measured. For the same reason,
the d-statistics and grouped d-statistics are not shown but the standard deviations and
RSD values obtained were close to zero. Calculation of detection limit is not relevant
for pH.
The range of measurements was very small and the difference between the duplicate
measurements was marginal, both indicating that the pH measurements are very stabile.
76
It should be remembered here, that pH is a logarithmic expression of a concentration
(H3O+) and thus rather robust to variation.
Redox
chart as described in section 5.3.3 was not carried out as many of the duplicate results
are identical or very close. Simple d-statistics and grouped d-statistics can not be ap-
plied directly, as parts of the measurements are negative.
The redox measurements showed a much greater range of measurements than the pH
measurements, but the variation for duplicates was still very small. Calculation of detec-
tion limit is not relevant for the redox potential.
Oxygen
chart as described in section 5.3.3 is shown in figure 7.16. As can be seen in the figure
all points lie below the line indicating that there is more than a 95 % probability that the
relative standard deviation, RSD, is below 50%. The chart also suggests that the differ-
ences between duplicate measurements are close to constant over the measuring range
of the study.
50% RSD CHART - Oxygen
95% limit 99% limit
10
0.1
0.01
0.01 0.1 1 10
Figure 7.16 Oxygen: RSD chart for 50% relative standard deviation with duplicate measure-
ments
The results from the simple d-statistics are shown in table 7.42. The calculation of RSD
(4.4%) from the mean relative difference of duplicate measurements in the simple d-
statistics is based upon the assumption that the relative differences are constant over the
measuring range. If in stead, the absolute difference, Di = x i1 x i 2 , is constant, the stan-
dard deviation can be calculated from the mean difference, D = Di / n , as s = D / 1.128 .
77
Using this approach, the standard deviation of the oxygen measurements is calculated to
0.048 mg O2/L and the RSD at 2 mg O2/L is 2.4 %. The two methods give slightly dif-
ferent results as would be expected due to the different requirements for application
(constant or non-constant RSD).
Table 7.38 Oxygen measurements-simple d-statistics calculation (only one data set is shown).
0.61 0.78 0.17 0.70 0.25

d = d i / n = 0.0499 s 2 = RSD * X 0 / 100 = 0.088
RSD = d *100 / 1.128% = 4.4% df = 30
Range 0.32 10.3 mg O2/ l (only measurements above method detection limit included)
The grouped d-statistics are based upon the assumption that there is a linear relationship
between the standard deviation and the measurements obtained, see section 5.3.3. For
the oxygen measurements of this study, the standard deviation appears to be constant
over the measuring range, see figure 7.16, and the grouped d-statistics should thus not
be applied.
The oxygen measurements showed only a small variation between duplicates. The rela-
tive standard deviation obtained with d-statistics was 4.4% compared to 2.4 % based
upon constant differences. Assuming a constant standard deviation of 0.048 mg O2/L,
the resulting method detection limit would be 0.23 mg O2/L. It should be emphasised
here, that the instrument can supply measurements much lower than this detection limit,
but based upon the detection limit found, these will simply reflect random blank meas-
urements and thus be without real meaning.
Conductivity
The conductivity measurements were all clustered in a narrow range around 1000
S/cm with very small variations among duplicate measurements. Therefore there is lit-
tle need to prepare an RSD chart for data with no or marginal variation in the duplicate
measurements.
The results from the simple d-statistics are shown in table 7.43.
Table 7.39 Conductivity-simple d-statistics calculation (only one data set is shown).
808 811 3 809.5 0.0037

d = d i / n = 0.0022 RSD = d *100 / 1.128% = 0.20% s1050 = RSD * X 0 / 100 = 2.1 df = 41
Range 561 -2190 S/cm
With the narrow measuring range, constant standard deviation and differences can be
assumed. The standard deviation and the RSD can thus be calculated from the mean ab-
solute differences between duplicates, D = Di / n , as s = D / 1.128 . Using this approach,
the standard deviation was 2.3 S/cm and the RSD at 1050 S/cm was 0.22 %.
78
As stated above, grouped d-statistics are based upon an assumption of the standard de-
viation varying linearly with the mean. With a very narrow measuring range and an ap-
parently constant standard deviation, grouped d-statistics should not be applied.
The conductivity measurements showed only a small variation between duplicates. The
relative standard deviation obtained with simple d-statistics and based upon constant
differences was 0.20% and 0.22 % respectively. Calculation of detection limit is not
relevant for conductivity measurements.
Nitrate HACH-Lange
chart as described in section 5.3.3 is shown in figure 7.17. As can be seen in the figure,
all points lie below the line indicating that there is more than a 95 % probability that the
relative standard deviation, RSD, is below 50%.
50% RSD CHART - Nitrate
95% limit 99% limit
100
10
0.1
0.01
0.01 0.1 1 10 100
Figure 7.17 Nitrate HACH-lange: RSD chart for 50% relative standard deviation with duplicate
measurements
The results from the simple d-statistics and grouped d-statistics are shown in tables
7.40-7.41.
Table 7.40 Nitrate HACH-Lange-simple d-statistics calculation (only one data set is shown).
14.0 13.3 0.7 13.65 0.051

d = d i / n = 0.093 RSD = d * 100 / 1.128% = 8.2% s = RSD * X 0 / 100 = 0.7 df = 28
9
Range 0.09 -41 mg NO3 /L
79
Table 7.41 Nitrate HACH-Lange-grouped d-statistics calculation
Q 0,5 j Linear regression
xj
0.56 0.09 s 0 = b * 1.047 = 0.079 k=a*1.047= 0.0068

2.69 0.04 Precision at 9 mg NO3 /L
6.02 0.20 s=s0+k*c= 0.14 RSD=(s0/c+k)*100%= 1.6%
10.58 0.09 Detection limit with blank correction (1 blank)
1
DL = 4 * s 0 * (1 + ) = 0.45 mg NO3/L
20.96 0.22 1
0.3
y = 0.0065x + 0.075
2
R = 0.464
0.2
Q0,5j
0.1
0.0
0 5 10 15 20 25
xj
The nitrate measurements showed only a small variation between duplicates. The rela-
tive standard deviation obtained with simple d-statistics was 8.2%. From the grouped d-
statistics, a relative standard deviation of 1.6 % was obtained, and the estimated blank
standard deviation, s0, was 0.08 mg NO3/L. Care should be exercised when interpreting
the grouped d-statistics due to the limited number of duplicates included and the narrow
range of measurements. The resulting method detection limit was 0.5 mg NO3/L. The
detection limit given by the manufacturer is 1 mg NO3/L.
7.4.3 Verification
Verification has been carried out for the nitrate measurements using the HACH-Lange
test kits and the HACH sticks. 30 duplicate samples were analysed as field (HACH-
Lange nitrate and HACH-Nitrate sticks) measurements and by an accredited laboratory
(DS EN ISO-10304-1 filtered samples, detection limit 0.5 mg/L) analysis for content of
nitrate. Of the 30 laboratory samples, double determinations were carried out for 7 of
the samples.
Nitrate sticks
In table 7.42, a summary of correctness and the frequency of false negatives and posi-
tives are shown.
80
Table 7.42 Summary of correctness and range errors of range method
Range number of Correct- False False Error Max
tests ness negatives positives above error
(mg NO3- (%) (%) (%) 1 range (ranges)
N/L) (%)
<1 23 74 22 4 0 0
1 -<2 15 20 33 47 0 1
2 - <5 3 67 0 33 0 1
5 - <10 2 100 0 0 0 0
10 - <20 1 100 0 0 0 0
20 - <50 - - - - - -
50 - - - - - -
All ranges 44 57 23 20 0 1
As noted for the bench calibration test, errors often occurred close to the individual
range limits.
Nitrate HACH-Lange
The results for the laboratory and field measurements are shown in table 7.43 and the
linear regression plot is shown in figure 7.18. Only measurements above the detection
limit are plotted in figure 7.18 and evaluated in the statistical tests.
The plot in figure 7.18 demonstrates a reasonable linear correlation (coefficient of de-
termination, R2, above 0.9) between field nitrate measurements using the HACH-Lange
test kits and laboratory measurements. The regression coefficients, section 5.3.1, ob-
tained here are similar to the coefficients obtained during calibration of the instrument
against standard solutions, figure 7.15.
Results from the inverse regression analysis, section 5.3.2, are shown in table 7.44. For
the evaluation of trueness, a field measurement, Y0, of 9 NO3/L was selected, as this is
the median of the field measurements and thus a good representative of the set of meas-
urements.
The inverse regression analysis shows a reasonable mean correspondence between field
HACH-Lange measurements and laboratory measurements of (83 % trueness), but with
wide confidence limits (from 56 % to 161 % trueness).
Accuracy has been calculated according to section 5.1.5 for all duplicates with both
field and laboratory measurements. Accuracy range for field measurements was 8.4 -
360 % relative to laboratory results. Accuracy was poor close to the field method detec-
tion limit stated as 1 mg NO3/L by the manufacturer. At concentrations greater than 5
mg NO3/L, the range of accuracy for field measurements was 67 189 % relative to
laboratory results and thus more similar to the uncertainty obtained from the inverse re-
gression analysis.
81
Table 7.43 Summary of field and laboratory measurements
Sample HACH-Lange Laboratory
mg NO3 /L
133.016 <1 <1 5.4 <0,5
133.039 13.5 13.6 15 7.2
133.037 0.8 0.9 1.8
133.048 5.7 5.4 6.8
133.106-(N) 16.8 16.7 19
133.107-1 (N) 41.5 41.3 45
133.108 27.7 27.1 36
133.109 5.6 5.6 8
133.111 14.0 13.3 17 19
133.112 <1 <1 <0,5
133.113 7.4 6.1 11
133.114 5.8 6.1 7.9 7.7
133.115 20.6 20.9 24
133.134 8.0 8.3 12
133.121 13.3 13.2 14
133.123 5.8 6.0 7.4 8.1
133.124 () 1.5 1.5 2.3
133.124 (N) 0.7 0.7 1.1
133.127 0.9 0.4 0.5
133.128 0.8 0.9 1.7
133.129 0.5 0.4 5.8
133.132 <1 <1 <0,5
133.137 (N) 3.6 3.6 1
133.139 0.8 0.7 1.3
133.142 () 0.1 <1 <0,5
133.142 (N) <1 <1 <0,5 <0,5
133.143 0.3 0.5 <0,5
133.144 () <1 <1 <0,5
133.144 (N) <1 <1 <0,5
134.067 <1 <1 <0,5
134.069 <1 <1 <0,5
134.070 0.1 0.04 <0,5
132.120 <1 <1 <0,5
132.123 <1 <1 <0,5
132.119 (N) <1 <1 <0,5
132.119 (M) <1 <1 <0,5 <0,5
82
45
Measured concentration, mg/L

40 y = 0.86x - 0.25
2
35 R = 0.944
30
25
20
15
10
5
0
0 10 20 30 40 50
Laboratory result,
Laboratory mg/L
nitrate solution, mg/L
Figure 7.18 Linear regression for field measurements and laboratory results using Nitrate
HACH-Lange test kit
Table 7.44 Data from inverse regression analysis.

Selected field concentration 9 mg NO3 /L
Corresponding expected laboratory result 10.8 mg NO3 /L
Lower confidence limit 5.6 mg NO3 /L
Upper confidence limit 16 mg NO3 /L
Trueness 83 %
Lower trueness limit 56 %
Upper trueness limit 161 %
Trueness reported 83 % (56 -161%)
Said in other words, above approximately 5 mg NO3/L, the laboratory nitrate result can
be predicted from a field nitrate measurement within limits of 50-150% of the labora-
tory result, but on the average giving 80-85% of the laboratory result.
7.4.4 Summary
All field measurements evaluated here were carried out as part of a groundwater well
purging and sampling procedure. The duplicate samples were separated in time and
taken with a 1 minute time interval. Subsampling of the water samples can be carried
out with the introduction of only small variability.
The in line flow measurements of pH, oxygen, redox and conductivity during well purg-
ing are special cases of relative measurements, as the primary function is to demonstrate
stable conditions during purging. Therefore, full sensitivity of the measurements is im-
portant in order to properly reflect stability/instability, but the absolute values of the
measurements can be less importance, although these are of value as indicators for
changes in water quality.
The relative measurements of pH, oxygen, redox and conductivity showed a very good
stability with a low variability. The method detection limit for oxygen was acceptable
83
(0.2 mg O2/L) as shown above. The in line flow measurements satisfied the quality re-
quirements for relative field methods, section 4.2.
Table 7.45 Summary of QC estimates obtained for flow cell measurements of groundwater.
linear range limit (RSD) and trueness
pH (0 14)35 - <<50% -
Oxygen (mg O2/L) (0.01 20) 0.2 2.4 4.4% -
Redox (mV) (-1250 1250) - <<50% -
Conductivity S/cm 250 5000 - 0.20-0.22% -
The nitrate test sticks have shown a correctness of 20-100% varying with the nitrate
concentration. As noted before, errors often occurred close to the individual range lim-
its. No errors were noted at more than one range interval for the actual measurements in
the range 0 10 mg NO3-N/L. Overall, a reasonable performance was obtained for a
range method, but it was difficult to distinguish large differences in concentration at the
high end of the concentration range (10, 20 and 50 mg NO3-N/L) for the HACH test
sticks.
The nitrate sticks satisfy most of the quality requirements for a range field method, sec-
tion 4.2, but the correctness was below the requirement, primarily due to the error men-
tioned for concentrations close to range limits.
The performance data for the HACH-Lange nitrate kit are summarised in table 7.46.
Table 7.46 Summary of QC estimates obtained for HACH-Lange nitrate measurements of

groundwater.
linear range limit (RSD) and trueness
Nitrate 0.5-45 Field detection 8.2 % Accuracy range:
in ground- mg NO3 /L limit for ground- 8.4% - 360%
water water meas- Trueness:
urements was 83 % (56-161%)
0.5 mg NO3/L.
1 mg NO3/L was
the stated in-
strument detec-
tion limit
Based upon quality control data and statistics, the nitrate HACH-Lange test kits proved
stable and showed a good precision with 8.2 % relative standard deviation (duplicate
measurements, RSD chart and simple grouped d-statistics). Mean correspondence be-
tween test kit measurements and laboratory measurements was reasonable (coefficient
of determination 0.944 ) with 83% mean trueness. The accuracy was 8.4% - 360% for
the comparison of the duplicate test kit measurements and laboratory analysis (DS EN
ISO-10304-1 filtered samples, detection limit 0.5 mg/L).
With respect to the relative field method quality requirements, see section 4.2, the
HACH-Lange test kit for nitrate fulfilled the requirements.
35
Not verified
84
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86
APPENDICES
APPENDIX 1
Students t-factors for a one-sided test 5 % significance level

Degrees of freedom, n-1 Students t-factor
(t 0.05 (n-1))
1 6,31
2 2,92
3 2,35
4 2,13
5 2,02
6 1,94
7 1,90
8 1,86
9 1,83
10 1,81
11 1,80
12 1,78
13 1,77
14 1,76
15 1,75
16 1,75
17 1,74
18 1,73
19 1,73
20 1,73
1,65
APPENDIX 2
Students t-factors for a two-sided test 5 % significance level

Degrees of freedom, n-2 Students t-factor
(t 0.025 (n-2))
1 12,7
2 4,30
3 3,18
4 2,78
5 2,57
6 2,45
7 2,37
8 2,31
9 2,26
10 2,23
11 2,20
12 2,181
13 2,16
14 2,15
15 2,13
16 2,12
17 2,11
18 2,10
19 2,09
20 2,09
1,96
APPENDIX 3
Control charts for differences between duplicate measurements

as function of mean duplicate measurements, 50% and 5% RSD
50% RSD CHART
95% limit 99% limit
1000
100
(concentration)
10
1
1 10 100
(concentration)
5% RSD CHART
95% limit 99% limit
100
10
(concentration)
0.1
1 10 100
(concentration)

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TR 581 QC in Prot Med

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ISSN 0283-7234

NT TECHN REPORT 581

Authors: Nordic Innovation Centre project number:

Technical Group: Expert Group Environment and Natural Resources

3 REQUIREMENTS FOR ANALYTICAL QUALITY IN SOIL AND GROUNDWATER

4 QUALITY CLASSES FOR FIELD MEASUREMENTS .................................................... 5

5 ANALYTICAL QUALITY CONTROL ............................................................................... 8

6 QUALITY CONTROL PROCEDURES FOR FIELD MEASUREMENTS....................... 32

The property of the sample that is measured.

Certified reference material

A measurement finding an analyte when the analyte is not present.

A measurement not finding an analyte when the analyte is present.

The scatter of repeated measurements.

A sample added a known amount of the analyte.

An expression of the randomness of a single measurement.

Quality Control Manual for Field Measurements

Christian Grn, DHI Water & Environment,

Jacqueline Anne Falkenberg, NIRAS A/S,

Jens Strodl Andersen, JSA-EnviroStat,

Marion Brresen & Arne Pettersen, Norwegian Geotehcnical Institute,

Sren Nilsson and Karsten Hkansson, Swedish Geotechnical Institute,

Jussi Laiho, Geological Survey of Finland

Compliance testing, e.g.:

Determination of contaminant concentrations with accept or rejection of an item

Decision support, e.g.:

The manual is a compilation of methods suggested in the literature for validation of

Generally in environmental control, it is recommended or required to use laboratories

Table 4.1 Definition of quality classes for field measurements

4.2 Quality requirements

An analytical detection limit of of the maximum contaminant concentration (concen-

Table 4.2 Suggested quality requirements for field measurements

Figure 5.1 Visualisation of the concepts of precision and trueness

5.1.1 False positive, false negative and correct measurements

5.1.2 Detection limit

Calculation of the detection limit, DL, can be done from:

n= number of blank determinations used in routine measurements for correction of results

If no blank correction is used, the DL calculation can be done from:

According to some conventions, the DL is calculated as 3 x sb and according to others

In evaluation and interpretation of data, it can be required to associate a number with a

5.1.3 Precision and uncertainty

Figure 5.2 Normal distribution of measurements

Parameters such as contaminant concentrations are frequently not normally distributed

The mean, x , is calculated from n replicate measurements, xi, as:

s and x are conveniently calculated using spreadsheets or calculators.

The precision of a measurement is determined as the standard deviation, s, of replicate

In evaluating precision of analytical methods, it is important to emphasize that the stan-

The uncertainty, U, of a single measurement can be calculated with a coverage factor of

The uncertainty, U, can be calculated as:

and the result, xi, reported as:

giving the range of the true value with 95% confidence.

and the mean result reported as:

Two important points should be considered here:

5.1.4 Trueness and bias

Similarly, bias can be calculated as:

5.1.5 Error and accuracy

A straight line is described by the line equation:

or for an analytical measurement:

5.2 Control Types

5.2.1 Calibration and check of instrument

Preparation of aqueous standards is straightforward, where dilutions of a concentrated

It is straightforward to prepare aqueous control samples for nonvolatile compounds as

5.2.3 Blank samples

For groundwater, duplicate samples for nonvolatiles should be prepared by taking a

5.2.5 Spiked samples