2005-02 IAEA Proficiency Test On The Determination of Total Arsenic Concentration in Water

IAEA / AL / 150
Final Report on the

Proficiency Test on the Determination
of Total Arsenic Concentration in Water
TC Project BGD/08/018
Seibersdorf, February 2005
IAEA / AL / 150
Department of Nuclear Sciences and Applications
Physics, Chemistry and Instrumentation Laboratory
Chemistry Unit
Final Report
Proficiency Test on the Determination of Total Arsenic Concentration in Water

TC Project BGD/08/018
Abdulghani Shakhashiro, Alexander Trinkl, Matthias Rossbach, Thomas Benesch,

Michael Campbell, Umberto Sansone, Karin Will, Renate Schorn, Andras Törvenyi
Seibersdorf, June 2005

CONTENTS
ABSTRACT ............................................................................................................................... 1
1. INTRODUCTION ............................................................................................................ 3
2. PROFICIENCY TEST OBJECTIVES ............................................................................. 3
3. PREPARATION OF PT MATERIALS ........................................................................... 4
4. VERIFICATION OF TARGET VALUES....................................................................... 4

4.1. Graphite Furnace Atomic Absorption Spectrometry determination [6] ............. 4
4.2. Inductively Coupled Plasma Mass Spectrometry ( ICP-MS )
Determination [7] ............................................................................................... 5
5. DESCRIPTION OF THE PT MATERIAL SENT TO THE PARTICIPANTS............... 8
6. PARTICIPATING ANALYTICAL TECHNIQUES ....................................................... 9
7. DATA EVALUATION .................................................................................................... 9

7.1. Data evaluation criteria....................................................................................... 9
7.2. Data evaluation sorted by Sample number ....................................................... 11
7.3. Data evaluation sorted by laboratory code ....................................................... 18
8. CONCLUSIONS AND RECOMMENDATIONS ......................................................... 29
9. REFERENCES ............................................................................................................... 29
APPENDIX I. LIST OF PARTICIPATING INSTITUTES .................................................. 30
APPENDIX II. EXAMPLES OF FORMS AND CORRESPONDENCE............................... 32

ABSTRACT
A proficiency test on the determination of arsenic in drinking water was organised within the
frame of the TC project BGD/8/018 to evaluate the analytical performance of laboratories in
Bangladesh. This report summarises the performance evaluation of the participating
laboratories.
Analytical data evaluation showed that 61% of data obtained a “Passed” final score for both
the accuracy and precision criteria applied to this exercise.
Accuracy criteria Precision criteria Final Score
failed
3%
failed failed
36%
39%
passed passed
passed 61%
64%
97%
1
2
1. INTRODUCTION
The IAEA is actively promoting the establishment of quality systems in Member State
laboratories by providing Technical Support programmes in close cooperation with the
Agency Laboratories in Seibersdorf. For many years, several regional TC projects to
implement “Quality Assurance/Quality Control for Nuclear Analytical Techniques” have
resulted in the establishment of quality systems compliant with ISO/IEC 17025: 1999
standard in several laboratories. This can be considered as an appreciable success, as the base
of much economic, health care or environmental decision relies on analytical data, and as it is
well known, a decision based on incorrect analytical results can be extremely costly and
detrimental. Therefore, it is essential that correct and reliable analytical data are used to make
adequate decisions.
Demonstration of high quality analytical results requires, amongst other measures, regular
participation in proficiency tests. This requirement of the ISO/IEC 17025: 1999 standard
(clause 5.9 b) [1] currently can only be achieved by regular participation in laboratory
analytical performance exercises provided by competent institutions. Generally, participation
is expensive and not always appropriate to the specific needs. Therefore, within the frame of
the IAEA project BGD/8/018 Seibersdorf Agency’s Laboratory was requested to organise a
proficiency test for the laboratories in Bangladesh who are involved in Arsenic analysis.
It is well known that arsenic occurs naturally in variable levels in drinking water. It also can
be introduced into the environment by other means, including mining activities and wood
treatment.
It is now generally agreed that the arsenic contamination of groundwater in Bangladesh is of

geological origin [2]. The arsenic derives from the geological strata underlying Bangladesh
and it is attracting much attention due to its detrimental effect on public health and fears of
future adverse health effects as a result of accumulation of arsenic in the human body. [2]
According to a 1999 study by the USA National Academy of Sciences [3], arsenic in drinking
water causes bladder, lung and skin cancer, and may cause kidney and liver cancer. The study
also found that arsenic harms the central and peripheral nervous systems, as well as heart and
blood vessels, and causes serious skin problems. It also may cause birth defects and
reproductive problems.
The national standard for arsenic in drinking water in Bangladesh is set to 50 µg total As /L,
same as the current USA standard. However, on January 22, 2001 the US Environmental
Protection Agency [4] [5] has adopted a new standard, and public water systems must comply
with the 10 µg total As /L standard beginning January 23, 2006.
2. PROFICIENCY TEST OBJECTIVES
x To evaluate the analytical performance of the participating laboratories from Bangladesh

for the determination of the total arsenic concentration in water.
x To assist in finding the root cause of methodological problems leading to unsatisfactory

analytical performance in certain laboratories.
x To identify the necessity for further actions to improve laboratories performance if

needed.
3
x To provide general recommendations on the overall performance of participating
laboratories
3. PREPARATION OF PT MATERIALS
The proficiency test set consisted of 7 samples: one blank, 2 certified reference materials and
4 spiked drinking water samples.
The water used for this exercise was collected from laboratory tap water (underground origin)
at Seibersdorf. A 25 litre container of hard PE was used to collect the water.
All of the plastic bottles and containers were acid washed prior to use and rinsed three times
with distilled water then air-dried.
The blank and the spiked samples were acidified with nitric acid at 0.5 mol/L . To spike
samples number 02, 04, 05 and 07 aqueous mono elemental Arsenic standard 1000 mg As/L
was used with appropriate dilutions. The uncertainty associated with the dilution was
estimated according to the Guide for Quantifying Measurement Uncertainty issued by
EURACHEM/CITAC (2000). [8]
The sample numbers 02 and 05 were prepared in one batch, i.e., duplicate samples, in order to
verify the repeatability of the method. In similar way, samples number 04 and 07 were
prepared also in one batch to get identical and homogenous duplicate samples.
The bottles were cleaned with acidified water, labelled and then rinsed with small amount of
the sample and filled up to 225-250 ml.
4. VERIFICATION OF TARGET VALUES
The target values are the gravimetrically prepared spike values diluted in a class A volumetric
flask, which were checked by both inductively coupled plasma mass spectrometry (ICP-MS)
and graphite furnace atomic absorption spectrometry. The expanded uncertainty for each
target value was calculated as
U = kuc , k=2
where k is the coverage factor and uc is the combined standard uncertainty calculated
according to the Guide for Quantifying Measurement Uncertainty issued by
EURACHEM/CITAC (2000). [8]. The value of uc is intended to represent, at the level of one
standard deviation, the combined effect of uncertainty components associated with the
material preparation namely: standard solution, weighing and volume uncertainties.
4.1. Graphite Furnace Atomic Absorption Spectrometry determination [6]
A Graphite Furnace AAS using Zeeman background correction, (Perkin-Elmer Analyst 800
AAS Instrument) was used for this analysis. The samples were diluted 1+9 with deionised
water on a gravimetric basis in order to ensure that the As content was within the linear and
working range of the technique. All solutions contained 0.5 % v/v HNO3 (Merck, Suprapur).
4
All volumetric plastic ware had been acid washed prior to use. Optimisation of the system
followed the established method involving maximising the signal response for a single-
element standard by establishing the pyrolysis temperature.
An aqueous single element standard 50 µg As.L-1 was prepared from a single element stock
solution (1000 mg/L, Merck) in 0.5 % nitric acid. The following concentrations of working
standards were prepared by the Autosampler of the AAS Instrument by serial dilution:
0; 10; 20; 30 and 50 µg As.L-1
Three measurements were performed on each calibration solution.
Quantification was achieved against the aqueous calibration.
The following parameters were used:
- The analytical wavelength for As: 193.7 nm.

- Slit width: 0.7.
- Read time 5.0 s.
- Matrix modifier: Pd + Mg(NO3)2
A quality control material (NIST 1643e; Trace elements in water) was analysed in parallel
with the test samples. To check the instrumental drift, an aqueous standard solution was
measured after every 3 samples.
The reported uncertainties are estimated according to the Guide for Quantifying Measurement
Uncertainty issued by EURACHEM/CITAC (2000). [8]
Table. 1 : GF-AAS results

AS concentration U (k-2)
Sample name Chemistry Unit code mgǜL-1 mgǜL-1
PT Sample, #01 CU040400100 0.30 0.60
PT Sample, #02 CU040400200 19.8 1.1
PT Sample, #04 CU040400300 198 5
PT Sample, #05 CU040400400 20.0 1.1
PT Sample, #07 CU040400500 196 5
NIST SRM 1643e QC material 60.4 1.4
Certified conc. NIST 1643e 60.45 ± 0.72 ng/mL
4.2. Inductively Coupled Plasma Mass Spectrometry ( ICP-MS ) Determination [7]
Inductively Coupled Plasma-Source Mass Spectrometry with conventional pneumatic

nebulisation (Perkin-Elmer Sciex Elan 6000 ICP-MS instrument) was used in the analysis of
the PT samples.
In order to incorporate an internal standard conveniently, the samples were diluted 1+9 on a
gravimetric basis prior to analysis.
5
In order to prepare the instrument the sample introduction system was cleaned in situ by
aspirating 1% HNO3. The nickel sample cones were cleaned using Polaris (a proprietary
stainless steel polish), rinsed in deionised water and then placed in an ultrasonic bath for a few
minutes. The ICP torch, bayonet and spray chamber were cleaned by soaking them in nitric
acid (10%) and the peristaltic pump tubing was replaced prior to analysis. Optimisation of the
system followed the established method involving maximising signal response for a multi-
element standard by establishing nebuliser, RF forward power, ion optic and spatial
parameters. A full instrumental optimisation was performed immediately prior to this
experiment.
Calibration of the instrument was achieved by preparing an arsenic stock solution at ~10
µg/mL in 2% v/v HNO3), from a suitable mono elemental standard (Merck Certipur, 1000
µg/mL) on a gravimetric basis. The sub-stock was further diluted (gravimetrically) to produce
working standards at: 0, 5, 10, 20, and 50 µg As.L-1 (in 2% HNO3). All working standards
contained the internal standard (Y) at 25 µg As.L-1. Five measurements were performed on
each sample.
Table No. 2 : ICP-MS results
Chemistry ICP-MS As
Sample name U (k=2)
Unit code Code Concentration
µg.L-1 µg.L-1
PT Sample, #01 CU040400100 As PT 1 0.28 0.015

PT Sample, #02 CU040400200 As PT 2 20.20 0.2
PT Sample, #04 CU040400300 As PT 3 200 1.4
PT Sample, #05 CU040400400 As PT 4 20.3 0.1
PT Sample, #07 CU040400500 As PT 5 200 1.0
6
Sample 01- Blank Analysis
0.43
0.38
As Concentration µg/L
0.33
0.28
0.23
0.18
0.13
ICP-MS GF-AAS
Analytical Technique
Fig. 1
As concentration in Samples 02 and 05
23
As Concentration µg/L
22
21
20
19
18
ICP-MS (02) ICP-MS (05) GF-AAS (02) GF-AAS (05)
Analytical Technique
Fig. 2
As concentration in Samples 04 and 07
210
As Concentration (µg/L)
205
200
195
190
185
ICP-MS (04) ICP-MS (07) GF-AAS (04) GF-AAS (07)
Analytical Technique Fig. 3
7
The results of blank analysis, samples 02 and 05, 04 and 07 are shown in figures 1, 2 and 3
respectively. From these figures it can be concluded that the target values are in agreement
with the measured values by 2 different analytical techniques: GF AAS and ICP-MS.
Table 3 target values and the associated uncertainties:

Target Value
Sample name Description U (k=2)
As µg.L-1
PT Sample, #01 Blank 0.28 0.60

PT Sample, #02 Spiked sample 20.0 0.2
PT Sample, #03 SPS-SW-2 Reference Material 50.0 0.3
PT Sample, #06 SPS-SW-2 Reference Material 50.0 0.3
5. DESCRIPTION OF THE PT MATERIAL SENT TO THE PARTICIPANTS
Each participant received 7 samples and one bottle of 1000 mg/L of As standard solution.
Each sample had its own code, which consisted of four digits, first two digits to code the
sample type, and the third and fourth digits for laboratory coding. The description of these
samples is shown in table 4:
Sample Volume
# code
Description mL
1 01 Blank - tap water used for preparing the spiked PT samples 250
2 02 Low level of As in spiked tap water 250
3 03 Reference material SPS-SW-2 100
4 04 Medium level of As in spiked tap water 250
Duplicate of Low level of As in spiked tap water, prepared
5 05 250
in the same batch as sample 02.
6 06 Reference material SPS-SW-2 100
7 07 Medium level of As in spiked tap water 250
The participants were asked to perform 3 individual analysis of the 7 samples using different
aliquots and to estimate the combined uncertainty of the whole analytical procedure according
to EURACHEM Guide on Quantifying Uncertainty and Method validation in Analytical
Measurements. Analysis results and estimated combined uncertainties had to be reported in
the results and uncertainties reporting form (F-02) ( see Appendix B).
In addition, the participants received a standard solution 1000 As µg.L-1 to verify day-to-day
calibration and to report any discrepancies between laboratory standard and the provided one.
In order to assess the analytical performance of the method, the participating laboratories were
requested to provide information on the method validation parameters and the approach used
in the laboratory for the evaluation of uncertainty components and to compile these
8
information in the Method Validation and Combined Uncertainty Estimation Form (F-03) (
see Appendix B).
Furthermore, the participating laboratories were asked to give a description of the method
used and quality control procedure applied in the laboratory. This information was filled in the
Method and Quality Control Procedure Description Form (F-04) ( see Appendix B).
6. PARTICIPATING ANALYTICAL TECHNIQUES
x Instrumental neutron activation analysis

x Hydride generation atomic absorption spectrometry
x UV-VIS
x Total reflection X-ray fluorescence
x ICP – MS
x ASV - Anodic Stripping Voltammetry
7. DATA EVALUATION
7.1. Data evaluation criteria
The participants’ data were evaluated according to the following three criteria:
A) The relative bias between the Analyst’s value and the IAEA value expressed as a relative
bias in percentage:
ValueLab ValueIAEA
Re lative bias u 100%
ValueIAEA
B) The Z-Score value calculated according to the following equation:
ValueLab ValueIAEA
z Score
V
Where the target values for the standard deviation (V) has been be assigned as the following:
V = 0. 2 * Value IAEA
C) The value of the U-test score to be calculated according to the following equation [9] :
ValueIAEA ValueLab
U test
2 2
UncIAEA UncLab
The calculated U-test value was compared with the critical values listed in the t-statistic tables
to determine if the reported result differs significantly from the expected value at a given level
of probability at 99%:
9
Condition Probability Status
u < 1.64 Greater than 0.1 The reported result does not differ significantly from
the expected value
1.95 > u > Between 0.1 and The reported result probably does not differ
1.64 0.05 significantly from the expected value
2.58 > u > Between 0.05 and It is not clear whether the reported result differs
1.95 0.01 significantly from the expected value
3.29 > u > Between 0.01 and The reported result is probably significantly different
2.58 0.001 from the expected value
The reported result is significantly different from the

u > 3.29 Less than 0.001
expected value
For this proficiency test we have set the limiting value for the u-test parameter to 2.58 to
determine if a result passes the test (U < 2.58).
Acceptance criteria:
The PT results were evaluated against the following acceptance criteria for accuracy and
precision and assigned the status “passed” or “rejected” accordingly. A result must pass both
criteria to be assigned the final status of “passed”.
1) Accuracy: result passes if:
A1
A1 d A2 and X 100 d 30 %
Value IAEA
Where
A1= Value IAEA Value Analyst
2 2
A2= 2.58 u Unc IAEA Unc Analyst
2) Precision: the result passes if:
2 2
§ Unc IAEA · § Unc Analyst ·
P= ¨¨ ¸¸ ¨ ¸ u 100%
Value ¨ Value ¸
© IAEA ¹ © Analyst ¹
is less than, or equal to 20 % the estimated maximum acceptable reproducibility standard

deviation expressed in percentage of the measurement value.
10
7.2. Data evaluation sorted by Sample number
11
Target value: 20.0 µg/L
Data Evaluation for Sample No. 02
Uncertainty (k=2): 0.2 µg/L
Laboratories Results Acceptance criteria Final
Lab. Code Value Unc. Accuracy Precision Score
Bias(%) Z-Score U-Score Laboratory/IAEA
µg/L µg/L % A1 A2 Score P Score
0201 <15 - - - - - - - - - - - rejected
0202 20.15 0.76 3.8% 0.7% 0.04 0.19 1.01 0.15 2.03 passed 3.9% passed passed
0203 29.10 1.50 5.2% 45.5% 2.28 6.01 1.46 9.10 3.90 failed 5.3% passed rejected
0208 6.00 0.36 6.0% -70.0% -3.50 -34.00 0.30 14.00 1.06 failed 6.1% passed rejected
0212 18.30 1.20 6.6% -8.5% -0.43 -1.40 0.92 1.70 3.14 passed 6.6% passed passed
Table legend:
Sample 02 Results
35 A1: Value IAEA Value Laboratory
30 2 2
A2: 2.58 u UncIAEA UncLaboratory
25
20 2 2
P: § UncIAEA · § UncLab ·
¨ ¸ ¨ ¸
15 ¨ Value ¸ ¨ Value ¸ X100%
© IAEA ¹ © Lab. ¹
10
5
0201 0202 0203 0204 0207 0208 0209 0210 0211 0212
Laboratory Code
12
Target value: 50 µg/L
Table legend:
Sample 03 Results
80.00 Value
A1: Value IAEA Laboratory
70.00
2 2
60.00
50.00 2 2
¨ ¸ ¨ ¸
40.00 ¨ Value ¸ ¨ Value ¸ X100%
30.00
20.00
0301 0302 0303 0304 0307 0308 0309 0310 0311 0312
Laboratory Code
13
Table legend:
Sample 04 Results
260.00 A1: Value IAEA Value Laboratory
240.00 2 2
220.00
200.00 2 2
180.00 ¨ ¸ ¨ ¸
¨ Value ¸ ¨ Value ¸ X100%
160.00
140.00
01 402 403 404 407 408 409 410 411 412

04 0 0 0 0 0 0 0 0 0
Laboratory Code
14
0501 <15 - - - - - - - - - - - rejected
0511 17.33 4.00 23.1% -13.4% -0.67 -0.67 0.87 2.67 10.33 passed 23.1% failed rejected
Table legend:
Sample 05 Results
30.000 2 2
25.000
20.000
2 2
15.000 P: § UncIAEA · § UncLab ·
¨ ¸ ¨ ¸
10.000 © IAEA ¹ © Lab. ¹
5.000
01 502 503 504 507 508 509 510 511 512

05 0 0 0 0 0 0 0 0 0
Laboratory Code
15
0601 52.82 11.84 22.4% 5.6% 0.28 0.24 1.06 2.82 30.56 passed 22.4% failed rejected
Table legend:
Sample 06 Results
80.00 Value
A1: Value IAEA Laboratory
70.00
2 2
60.00
50.00 2 2
¨ ¸ ¨ ¸
40.00 ¨ Value ¸ ¨ Value ¸ X100%
30.00
20.00
0601 0602 0603 0604 0607 0608 0609 0610 0611 0612
Laboratory Code
16
Table legend:
Sample 07 Results
240.00 2 2
220.00
2 2
200.00 P: § UncIAEA · § UncLab ·
¸
¨ ¸ ¨
180.00
160.00
140.00
0701 0702 0703 0704 0707 0708 0709 0710 0711 0712
Laboratory Code
17
7.3. Data evaluation sorted by laboratory code
18
Analytical Performance Evaluation of Laboratory 01
IAEA Laboratory Acceptance criteria

Sample Code Value Unc. Value Unc. R. bias Z-score U-Test Laboratory/IAEA Accuracy Precision Final score
µg/L µg/L µg/L µg/L % % A1 A2 Score P Score
0101 0.3 0.6 <15 - - - - - - - - - - - passed
0201 20.0 0.2 <15 - - - - - - - - - - - rejected
0301 50.0 0.3 77.00 12.07 15.7% 54% 2.70 2.24 1.54 27.00 31.15 passed 15.7% passed passed
0401 202.3 2.7 196.00 22.49 11.5% -3% -0.16 -0.28 0.97 6.30 58.44 passed 11.6% passed passed
0501 20.0 0.2 <15 - - - - - - - - - - - rejected
0601 50.0 0.3 52.82 11.84 22.4% 6% 0.28 0.24 1.06 2.820 30.56 passed 22.4% failed rejected
Reported Method Validation Parameters

MDL rL RL RC
15 µg/L 1.45% 1.94% NR
Recommendations:
1- Sample 201 reported <15 µg/L, while it contains 20 µg/L, this means that MDL should be revised, or sample intake to be increased if the techniques allows.
2- Reported rL indicates only 1.45% of variations, while duplicate samples of the PT gave more than 15% variations, method reproducibility needs to be improved,
may be the way of adding the internal standard should be reviewed.
3- If the laboratory is interested in improving and/or maintaining the performance of the analytical technique, the Chemistry Unit at Agency's Laboratories
is ready to assist the laboratory. For further information please contact the Chemistry Unit at u.sansone@iaea.org
MDL Method Minimum Detection Limit

rL Repeatability limit
RL Reproducibility limit
RC Recovery coefficient
NR Not reported 19
IAEA Laboratory [u < 2.58] Acceptance criteria

Sample Code Value Unc. Value Unc. R. bias Z-score u-statistic Laboratory/IAEA Accuracy Precision Final score
µg/L µg/L µg/L µg/L % %
0102 0.3 0.6 BDL 0.70 - - - - - - - - - - passed

MDL rL RL RC
1.9 µg/L 0.36µg/L NR 99.50%
at 25.9 µg/L
Recommendations:
1- According to the available data the analytical results of the laboratory are meeting both accuracy and precision criteria.
2- The laboratory reported result for sample 0102 should not expressed as BDL, the laboratory should instead report the result as < 1.9, which is the MDL.
3- In order to monitor the statistical control and the performance of the method, the laboratory should use control charts by plotting the control samples results
and checking for trends and any possible out of control situations to apply preventive and may be corrective actions when needed.
NR Not reported
BDL Below detection limit 20

0103 0.3 0.6 0.64 0.05 - - - - - - - - - - passed
0203 20.0 0.2 29.10 1.50 5.2% 46% 2.28 6.01 1.46 9.10 3.90 failed 5.3% passed rejected

MDL rL RL RC
1.9 µg/L 0.36µg/L NR 99.50%
at 25.9 µg/L
Recommendations:
1- From the PT result it appears that the technique precision is satisfactory, but there is a systematic positive bias,which is more visible at lower concentrations.
2- From the reported Quality control data, it is already stated that a positive bias of up-to 15% is observed, but no corrective action was taken.
3- The root cause of the bias should be invistigated and appropriate corrective actions should be taken.
5- Method validation procedure should be applied.
NR Not reported 21

0104 0.3 0.6 BDL - - - - - - - - - - - passed
0704 202.3 2.7 201.70 2.50 1.2% 0% -0.01 -0.16 1.00 0.600 9.49 passed 1.8% passed passed

MDL rL RL RC
NR NR NR NR
Recommendations:
1- According to the available data the analytical results of the laboratory are meeting both accuracy and precision criteria.
2- The laboratory reported result for sample 0104 should not expressed as BDL, the laboratory should instead report the result of the MDL
which could be estimated from method validation procedure.
3- Although the method is performing well, the laboratory should estimate the quality parameters of the method when it is under statistical control
and then to monitor these parameters by means of control charts to maintain good performance level.
RC Recovery coefficient 22
NR Not reported
BDL Below detection limit

0107 0.3 0.6 <3 - - - - - - - - - - - passed

MDL rL RL RC
N.R N.R N.R N.R
Recommendations:
1- The low and medium concentration samples were successfully analysed, but at higher level of As the laboratory overestimated the values. The sample dilution may be the cause.
2- The laboratory reported a result for sample 0107 <3, while the laboratory did not perform any method validation.
3- The laboratory should estimate the quality parameters of the method when it is under statistical control
and then to monitor these parameters by means of control charts to maintain the good performance.
RL Reproducibility limit 23
NR Not reported

0108 0.3 0.6 6.00 0.81 - - - - - - - - - - rejected
0208 20.0 0.2 6.00 0.36 6.0% -70% -3.50 -34.00 0.30 14.00 1.06 failed 6.1% passed rejected

MDL rL RL RC
30 µg/L 2% 20% N.R
Recommendations:
1- The technique is not functioning at all, it can not diffrentiate between the blank and the highest concentration. Complete revision of the mthod is neded.
2- Quality control samples should be able to detect such shortcomings, but it seems that it failed, threfore revision of QC mechanism is also recommended.

NR Not reported

0109 0.3 0.6 <1 - - - - - - - - - - - passed

MDL rL RL RC
<1 µg/L NR NR NR
Recommendations:
1- Repeatability has to be improved, samples 0309 and 0609 are duplicate, but the technique gives a difference of 16% between these duplicates.
The root cause must be invistigated and corrected.

NR Not reported

0110 0.3 0.6 0 0.00 - - - - - - - - - - passed

MDL rL RL RC
NR NR NR NR
Recommendations:
1- According to the available data the method performs properly, but for unknown reason a bias of 20% occurred in samples 0310, 0610.
The root cause should be invistigated and corrected.
2- Zero value for detection limit is not acceptable, when the laboratory can not detect the analyte as in sample 0110, the MDL estimated by method validation should be reported.

NR Not reported
26

0111 0.3 0.6 0 2.66 - - - - - - - - - - passed
0211 20.0 0.2 25.33 4.00 15.8% 27% 1.33 1.33 1.27 5.33 10.33 passed 16% passed passed
0311 50.0 0.3 57.33 7.30 12.7% 15% 0.73 1.00 1.15 7.33 18.85 passed 13% passed passed
0411 202.3 2.7 134.00 12.33 9.2% -34% -1.68 -5.41 0.66 68.30 32.57 failed 9% passed rejected
0511 20.0 0.2 17.33 4.00 23.1% -13% -0.67 -0.67 0.87 2.67 10.33 passed 23% failed rejected

MDL rL RL RC
5µg/L 20 µg/L NR NR
Recommendations:
1- Repeatability has to be improved, samples 0311 and 0611 are duplicate, but the technique gives a difference of 50% between these duplicates.
2- Zero value for detection limit is not acceptable, when the laboratory can not detect the analyte as in sample 0111 the MDL estimated from method validation should be reported.
3- The linear range of the method must be checked, since the methods gives systematic low values for samples 0411, 0711
NR Not reported

0112 0.3 0.6 0.30 0.10 - - - - - - - - - - passed

MDL rL RL RC
NR NR NR NR
Recommendations:
1- The method repeatability is satisfactory, but the results are systematically biased at around 3-9 % below the target value.
2- The MDL of the method was not reported as a result of method validation data, but the method proves to be able to detect accurately below 1 µg/L.
3- The laboratory should estimate the quality parameters of the method when it is under statistical control
and then to monitor these parameters by means of control charts to maintain and demonstrate the performance level.
is ready to assist the laboratory. For further information please contact the Chemistry Unit at u.sansone@iaea.org.
NR Not reported
28
8. CONCLUSIONS AND RECOMMENDATIONS
x This exercise shows the importance of participation in proficiency tests to assure the
quality of the analytical data, especially when the analyte is of a great effect on the health
such as arsenic.
x The PT samples were sent to 14 laboratories, 10 of them reported the results. 65 % of the
reported results passed the accuracy criteria and 100% passed the precision criteria, while
65% of the results obtained a “Passed” grade as a final score.
x It is recommended for all laboratories to apply the Eurachem guide on method validation
to estimate the method performance characteristics and to use control charts to monitor the
stability of their methods.
x Only one case showed that the method used needs a complete revision, while in others
cases some corrective actions might improve the performance.
x The analytical performance of each laboratory was studied and appropriate

recommendations were suggested.
x The results of this report will be discussed in a forthcoming meeting, where also a
workshop on method validation and uncertainty estimation can be organised.
9. REFERENCES
[1] ISO/IEC 17025:1999, General Requirements for the Competence of Testing and
Calibration Laboratories, ISO, Geneva.
[2] Contamination of water supplies by arsenic in Bangladesh, Press Release WHO/55 8
September 2000.
[3] Arsenic in Drinking Water, Committee on Toxicology, Board on Environmental Studies
and Toxicology, National Research Council, National Academy Press, Washington,
DC, 1999.
[4] US Environmental Protection Agency, 40 CFR Parts 9, 141, and 142
[5] US Environmental Protection Agency, Implementation Guidance for the Arsenic Rule -
Drinking Water Regulations for Arsenic and Clarifications to Compliance and New
Source Contaminants Monitoring - (EPA-816-K-02-018)
[6] TOERVENYI, A., IAEA Chemistry Unit, PCI Seibersdorf Laboratories, Analysis report
No. CU 2004-018, Determination of the arsenic concentration in water samples for an
AQCS PT exercise, 2004-11-25.
[7] CAMPBELL, M., IAEA Chemistry Unit, PCI Seibersdorf Laboratories, Analysis report
No. CU 2004-15, Determination of the arsenic concentration in water samples for an
AQCS PT exercise, 2004-10-22.
[8] Quantifying uncertainties in analytical measurements, Eurachem/Citac Guide, 2000.
[9] BROOKES, C.J., BETTELEY, I.G. and LOXTON, S.M.; Fundamentals of
Mathematics and Statistics, Wiley 1979
29
APPENDIX I. LIST OF PARTICIPATING INSTITUTES
Dr. Sayed Mohammad Hossain

Reactor and Neutron Physics Division,
Institute of Nuclear Science & Technology, Tel: 880-2-7701829 (Off.)
Atomic Energy Research Establishment, Fax: 880-2-8613051
Ganakbari, Savar E-mail: inst@bangla.net
Bangladesh
Prof. Dr. A. M. Shafiqul Alam

Tel: 880-2-9661920-59 Ext. 4864 (Off.),
Department Chemistry,
880-2-8629985 (Res.)
University of Dhaka,
Fax: 880-2-8615583,
Dhaka 1000.
E-mail: amsalam@bangla.net
Bangladesh
Nuclear Chemistry Division,

Institute of Nuclear Science & Technology, Tel: 880-2-7702009 (Off.)
Atomic Energy Research Establishment, Fax: 880-2-8613051
Ganakbari, Savar E-mail: inst@bangla.net
Bangladesh
Mr. Ahmed Ataul Muneem

Geological Survey of Bangladesh,
153, Pioneer Road,
Segunbagicha,
Dhaka 1000
Bangladesh
Prof. Sk. Sekender Ali

Department of Civil Engineering,
Tel: 880-2-9665639, 880-2-9665650-80
Bangladesh University of Engineering
Ext. 7284
& Technology,
Fax: 880-2-8613026
Dhaka 1000
Bangladesh
SMA Rashid
Executive Director
NGO FORUM for Drinking Water Supply Tel: 880-2-8154273, 880-2-8154274,
& Sanitation Fax: 880-2-8117924,
4/6, Block – E , Lalmatia E-mail: ngof@bangla.net
Dhaka – 1207
Bangladesh
Dr. Quazi Quamruzzaman, G. Mohiuddin

Dhaka Community Hospital,
Tel: 9351190-1
190/1, Bara Mogbazar,
Fax: 8313385
Wirless Rail Gate,
E-mail: dch@bangla.net
Dhaka 1217
Bangladesh
30
Dr. A. K.M. Munir
Sono Diagnostic Centre Ltd.
Tel: 071-61335
Dept. of Environment Initiative,
Fax: 071-61235
College More, Courtpara,
E-mail: akmmunir2003@yahoo.com
Kushtia,
Bangladesh
Mr. Siddique Amin Talukder

Department of Public Health Engineering,
Zonal Laboratory,
Rajshahi
Dr. Muhammad Alauddin

Exonics Technology Centre (ETC)
Tel: 0173002632, 0171197979,
House # 10, Road # 06,
0172084444
Sector 1, Uttara,
E-mail: malauddin@aol.com
Dhaka
Bangladesh
Chemistry Division,
Atomic Energy Centre,
4 Kazi Nazrul Islam Avenue,
P.O. Box 164, Ramna,
Dhaka 1000
Bangladesh
Dr. Akram Hossain

Bangladesh Council of Scientific & Industrial
Research (BCSIR),
Analytical Research Division,
Dr. Qudrati-e-Khuda Road, Dhanmondi,
Dhaka 1205
Bangladesh
Prof. Dr.S. M. Imamul Huq Tel: 880-2-9661900-59 Ext. 6130 (W), 880-
Department of Soil, Water & Environment 2-8625680, 880-2-8612453 (H)
University of Dhaka, Fax: 880-2-8615583,
Dhaka 1000 E-mail: imamh@udhaka.net,
Bangladesh imamh@bttb.net.bd
Professor Dr. Ali Hossain

School of Environmental Science & Management,
Independent University, Bangladesh
House # 3, Road # 10, Baridhara,
Dhaka 1212
Bangladesh
31
APPENDIX II. EXAMPLES OF FORMS AND CORRESPONDENCE
Att. «NAME» Atoms For Peace

Wagramer Strasse 5, P.O. Box 100, A-1400 Wien, Austria
«ADDRESS» Phone: (+43 1) 2600 x Fax: (+43 1) 26007
E-mail: Official.Mail@iaea.org x Internet: http://www.iaea.org
In reply please refer to: Analytical Quality Control Services
Dial directly to extension: (+431) 2600 28226
E-mail: AQCS@iaea.org x Internet: http://www.iaea.org/programmes/aqcs
Seibersdorf, Date
Subject:
Samples of the Proficiency Test for the Determination of Total Arsenic Concentration in
Water
Dear Participant,
Please find enclosed a set of samples together with the relevant documentation pertaining to
the IAEA AQCS Proficiency Test for the Determination of Total Arsenic in Water. This
Proficiency Test was initiated by the Technical Officer of the project BGD/8/018 Mr.
Matthias ROSSBACH.
Please read the documentation carefully before commencing the analyses and return the
sample receipt form to us at your earliest convenience.
In the package you should find 8 PE containers as the following:
7 samples including one Blank,
(Expected total arsenic concentration is between 10 and 300 µg/L).
100 mL standard solution 1000 (mg As/L)
You are kindly asked to perform 3 individual analysis of the 7 samples using different
aliquots and to estimate the combined uncertainty of the whole analytical procedure. Analysis
results and estimated combined uncertainties must be reported in the attached results and
uncertainties reporting form (F-02).
32
(Oct. 04)
The enclosed standard solution 1000 (mg As/L) should be used to verify day-to-day
calibration and to report any discrepancies between laboratory standard and the provided one.
In order to assess the analytical performance of the method, we would like to have
information on the method validation parameters and the approach used in your laboratory for
the evaluation of uncertainty components. Kindly refer to Method Validation and Combined
Uncertainty Estimation Form (F-03) to fill the requested information.
In addition, it is important to have a short description of your method and quality control
procedure applied in your laboratory. This information can be filled in the Method and
Quality Control Procedure Description Form (F-04).
In the Reporting Form (F-01), the name of the person performing the analyses should be
clearly indicated to distinguish the analyst from those in a supervisory role. You are requested
to send the results before 15th of December 2004 to the attention of Mr. A. Shakhashiro e-
mail: a.shakhashiro@iaea.org, who is the responsible for this exercise.
The participants data shall be evaluated according to the following three criteria:
A) The relative bias between the Analyst’s value and the IAEA value expressed as a relative
bias in percentage:
Value Analyst Value IAEA

Re lative bias u 100%
Value IAEA
B) The Z-Score value calculated according to the following equation:
Value Analyst ValueIAEA

z Score
V
Where the target values for the standard deviation (V) shall be assigned on the basis of the
reproducibility standard deviation (the standard deviation of the consensus mean after outlier
rejection which expresses inter-laboratory precision)
C) The value of the U-test score to be calculated according to the following equation1:
ValueIAEA Value Analyst

U test
2 2
UncIAEA Unc Analyst
The calculated U-test value shall be compared with the critical values listed in the t-statistic
tables to determine if the reported result differs significantly from the expected value at a
given level of probability:
1
Brookes, C.J., Betteley, I.G. and Loxton, S.M.; Fundamentals of Mathematics and Statistics, Wiley 1979
33
For this proficiency test we have set the limiting value for the u-test parameter to 2.58 to
determine if a result passes the test (U < 2.58).
Acceptance criteria:
Your results will be evaluated against the following acceptance criteria for accuracy and
precision and assigned the status “passed” or “rejected” accordingly. A result must pass both
criteria to be assigned the final status of “passed”.
1- Accuracy: result passes if
2 2
Value IAEA Value Analyst d 2.58 u Unc IAEA Unc Analyst and < 30
2. Precision (dependent on the concentration level): the result passes if:
2 2
§ Unc IAEA · § Unc Analyst ·
¨¨ ¸¸ ¨ ¸ u 100%
Value ¨ Value ¸
© IAEA ¹ © Analyst ¹
is less than, or equal to the reproducibility standard deviation as estimated for Z-Scores.
You are requested to report your results to us as a hard copy and return them to us by post. It
is imperative that we receive the Reporting Forms duly completed as this will constitute your
official results for this exercise and will be used as the definitive source of information for
your laboratory. However, you should also submit your results to us electronically using the
data reporting program provided in the package. In the event of results being sent near to the
closing date for this exercise (15 December 2004) we will accept electronic input or fax
submissions as constituting results submitted within the reporting period provided that the
Reporting Forms are received by post within 2 weeks of the closing date.
It is planned to discuss the final results of this exercise in one of the forthcoming meetings.
Sincerely yours,
Umberto Sansone
Head, Chemistry Unit
Agency’s Laboratories Seibersdorf
34
To:
Analytical Quality Control Services,
International Atomic Energy Agency,
Agency’s Laboratories, A 2444 Seibersdorf, AUSTRIA.
Our Fax no.: + 43 1 2600 28222
Our E-mail: AQCS@iaea.org
Acknowledgment of Receipt of Materials
BGD/8/018 PROFICIENCY TEST

ON THE DETERMINATION OF TOTAL ARSENIC CONCENTRATION IN WATER
Please sign and return this page to confirm the receipt of this package, noting any missing
or damaged items at the bottom of this page.
Address:
This package contains the following samples:
0101 PT Sample, 250 ml

1000 mg/L Arsenic standard solution (100mL),
I acknowledge the receipt of the samples described above.
------------------------------------
Signature and date
The following items were missing/broken:
35
Proficiency Test on the Determination of Total Arsenic in Water (AS/BGD/2004)
Code No.:
Please include name and address of responsible analyst (if other than given or wrong).
Responsible Analyst: For IAEA use only!
Name and Title: ………………………. Customer Number «CUNO»

Laboratory / Division: ……………………….
Organisation / Institute: ……………………….
Street / Number: ……………………….
City / Postal Code: ……………………….
Country: ……………………….
Tel.: ……………………….
«COMMNUM» Fax: ……………………….
E-mail: ……………………….
Signature: ……………………….
Date: ……………………….
Collaborators: ………………………. Customer Number
Please send back to: ………………………. Customer Number
A. Shakhashiro ………………………. Customer Number
Analytical Quality Control Services Customer Number
Chemistry Unit, Agency's Laboratories Seibersdorf
A-2444 Seibersdorf - Austria
Tel: + 43 1 2600 28226
Fax: + 43 1 2600 28222
Email: a.shakhashiro@iaea.org
36
Proficiency Test on the Determination of Total Arsenic in Water (AS/BGD/2004)
Individual Determinations Your estimates

total Date of
Unit Average Unc.* Sample measurement
Value Unc.1 Unc. Unc. at
Sample number Value 2 Value 3
(µg/L) 1 * 2* 3* Value 1V Volume (yyyy-mm-dd)
level (ml)
«samplecode»,
«description»,
«size»
«samplecode»,
«description»,
«size»
«samplecode»,
«description»,
«size»
«samplecode»,
«description»,
«size»
«samplecode»,
«description»,
«size»
«samplecode»,
«description»,
«size»
«samplecode»,
«description»,
«size»
«samplecode»,
«description»,
«size»
* Standard uncertainty of individual determination expressed in (µg/L) (see uncertainty quantification sheet)
** Detection limit should be reported in the same units as results (µg/L)
If not enough space please copy this page.
37
Proficiency Test on the Determination of Total Arsenic in Water
(AS/BGD/2004)
Measurement Results – Method Validation and Uncertainty Estimation
Please provide us with the following information related to method validation:

1- Did you perform method validation?
2- If yes, kindly submit the obtained validation parameters such as: Minimum detection
limit , Repeatability limit, Reproducibility limit, Recovery coefficient
3- Please describe your approach for evaluation of uncertainty components and give the
formula used for calculation of the expanded uncertainty.
4- You are kindly asked to list the sources of uncertainties included in the estimation of the
combined uncertainty.
Remark:
In practice, there are many possible sources of uncertainty in a measurement, both, of random
nature or manifested as bias, including:
1) reproducibility of measurement;
2) bias or drift of measurement;
3) uncertainty in calibration process; of blank; in instrument readings (e.g. peak integration)
4) uncertainties of calibration sources; in sample preparation (mass, dilution, etc.).
These sources of uncertainty are not necessarily independent and some my be combined in 1).
Of course, these possible sources of uncertainty are not an exhaustive list. Individual standard
uncertainties may be estimated from repeated observations (any valid statistical method for
treating data) or by using all relevant information which may include previous measurement
data, experience with or general knowledge of the behaviour and properties of relevant materials
and instruments, manufacturers specifications, data provided in calibration and other certificates,
and uncertainties assigned to reference data taken from handbooks.
EURACHEM Guide on Quantifying Uncertainty and Method validation in Analytical
Measurements should be used as a general guidance. Copies can be downloaded from
http://www.eurachem.ul.pt/guidesanddocuments.htm
If you have further questions regarding uncertainty evaluation do not hesitate to contact AQCS.
If not enough space please add separate sheets to this page.

38
Proficiency Test on the Determination of Total Arsenic in Water
(AS/BGD/2004)
_________________________________________________________________________________________________________________
1. DESCRIPTION OF SAMPLE PREPARATION METHOD

_________________________________________________________________________________________________________________
_________________________________________________________________________________________________________________
2. DESCRIPTION OF MEASUREMENT METHOD

_________________________________________________________________________________________________________________
_________________________________________________________________________________________________________________
3. DESCRIPTION OF QUALITY CONTROL PROCEDURE

_________________________________________________________________________________________________________________
Use of blanks, CRM, Control samples, duplicate, replicate, spike sample and control charts.
Kindly report quality control data.
39

2005-02 IAEA Proficiency Test On The Determination of Total Arsenic Concentration in Water

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IAEA / AL / 150

Final Report on the

Department of Nuclear Sciences and Applications

Physics, Chemistry and Instrumentation Laboratory

Proficiency Test on the Determination of Total Arsenic Concentration in Water

Abdulghani Shakhashiro, Alexander Trinkl, Matthias Rossbach, Thomas Benesch,

Seibersdorf, June 2005

2. PROFICIENCY TEST OBJECTIVES ............................................................................. 3

3. PREPARATION OF PT MATERIALS ........................................................................... 4

4. VERIFICATION OF TARGET VALUES....................................................................... 4

5. DESCRIPTION OF THE PT MATERIAL SENT TO THE PARTICIPANTS............... 8

6. PARTICIPATING ANALYTICAL TECHNIQUES ....................................................... 9

7. DATA EVALUATION .................................................................................................... 9

8. CONCLUSIONS AND RECOMMENDATIONS ......................................................... 29

APPENDIX I. LIST OF PARTICIPATING INSTITUTES .................................................. 30

APPENDIX II. EXAMPLES OF FORMS AND CORRESPONDENCE............................... 32

Accuracy criteria Precision criteria Final Score

It is now generally agreed that the arsenic contamination of groundwater in Bangladesh is of

2. PROFICIENCY TEST OBJECTIVES

x To evaluate the analytical performance of the participating laboratories from Bangladesh

x To assist in finding the root cause of methodological problems leading to unsatisfactory

x To identify the necessity for further actions to improve laboratories performance if

4. VERIFICATION OF TARGET VALUES

4.1. Graphite Furnace Atomic Absorption Spectrometry determination [6]

0; 10; 20; 30 and 50 µg As.L-1

Three measurements were performed on each calibration solution.

Quantification was achieved against the aqueous calibration.

The following parameters were used:

- The analytical wavelength for As: 193.7 nm.

Table. 1 : GF-AAS results

Certified conc. NIST 1643e 60.45 ± 0.72 ng/mL

4.2. Inductively Coupled Plasma Mass Spectrometry ( ICP-MS ) Determination [7]

Inductively Coupled Plasma-Source Mass Spectrometry with conventional pneumatic

Table No. 2 : ICP-MS results

PT Sample, #01 CU040400100 As PT 1 0.28 0.015

As concentration in Samples 02 and 05

As concentration in Samples 04 and 07

Table 3 target values and the associated uncertainties:

PT Sample, #01 Blank 0.28 0.60

5. DESCRIPTION OF THE PT MATERIAL SENT TO THE PARTICIPANTS

6. PARTICIPATING ANALYTICAL TECHNIQUES

x Instrumental neutron activation analysis

7.1. Data evaluation criteria

The reported result is significantly different from the

1) Accuracy: result passes if:

A1= Value IAEA  Value Analyst

2) Precision: the result passes if:

is less than, or equal to 20 % the estimated maximum acceptable reproducibility standard

01 402 403 404 407 408 409 410 411 412

01 502 503 504 507 508 509 510 511 512

IAEA Laboratory Acceptance criteria

Reported Method Validation Parameters

MDL Method Minimum Detection Limit

IAEA Laboratory [u < 2.58] Acceptance criteria

Reported Method Validation Parameters

IAEA Laboratory [u < 2.58] Acceptance criteria

Reported Method Validation Parameters

IAEA Laboratory [u < 2.58] Acceptance criteria

Reported Method Validation Parameters

IAEA Laboratory [u < 2.58] Acceptance criteria

Reported Method Validation Parameters

IAEA Laboratory [u < 2.58] Acceptance criteria

Reported Method Validation Parameters

A1= Value IAEA Value Analyst

Value Analyst Value IAEA

Value Analyst ValueIAEA

ValueIAEA Value Analyst