Geothermics 44 (2012) 33–42

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Geothermics
journal homepage: www.elsevier.com/locate/geothermics

Inter-laboratory comparison of SiO2 analysis for geothermal water chemistry

Mahendra P. Verma a,∗ , Georgina Izquierdo a , Guima A. Urbino b , Sophie Gangloff c , Roberto García d ,
Alfredo Aparicio e , Thibauld Conte f , Ma. Aurora Armienta g , Mayela Sánchez h , June Rizza P. Gabriel i ,
Irene D. Fajanela j , Roberto Renderos k , Cherry Bernadette A. Acha l , Rasi Prasetio m , Irma Cruz Grajales n ,
Lisette Reyes Delgado o , Kizito Opondo p , Regina Zendejas Esparza q , Luz Angélica Panama r ,
Ruth Tapia Salazar s , Perfecto G. Lim t , Fredolin Javino u
a
Geotermia, Instituto de Investigaciones Eléctricas, Reforma 113, Col. Palmira, Cuernavaca, Mor., CP 62490, Mexico
b
Chemistry and Isotope Laboratory Section (CILS), Geosciences Dept., Energy Development Corporation, Merritt Road, Fort Bonifacio, Taguig City 1634, Philippines
c
Laboratoire d’Hydrologie et de Géochimie de Strasbourg, Université de Strasbourg/EOST, CNRS, 1 rue Blessig, F-67000 Strasbourg Cedex, France
d
Dpto. de Volcanologia, Museo Nacional de Ciencias Naturales -CSIC C/José Gutiérrez Abascal 2, 28006 Madrid, Spain
e
Departamento de Dinámica Terrestre, Instituto de Geociencias, CSIC-UCM, Madrid, Spain
f
BRGM -MMA/ENV, 3 Avenue Claude Guillemin, BP 36009, 45060 Orleans Cedex 2, France
g
Universidad Nacional Autónoma de México, Instituto de Geofísica, Circuito Exterior, C.U., México 04510, D.F., Mexico
h
Dirección de Geotermia, ENEL Central Intersección de Pista Juan Pablo II y Prolongación de Avenida Bolívar, Managua, Nicaragua
i
LRMD Chemistry Laboratory, Energy Development Corporation, Tongonan, Ormoc City, Leyte, Philippines
j
Mindanao Geothermal Production Field, Energy Development Corporation, BRGY Ilomvis, Kidapawan City, Philippines
k
15 Avenida Sur, Colonia Utila, Santa Tecla, La Libertad, El Salvador
l
Energy Development Corporation, Bacman Geothermal Production Field, Palayan Bayan, Manito, Albay, Philippines
m
Center for Application of Isotope and Radiation Technology – BATAN Jl, Lebak Bulus Raya, Jakarta 12070, Indonesia
n
Campamento Los Humeros CFE, Km 20 Carretera Perote-Humeros, Perote, Puebla, Mexico
o
Domicilio Conocido Agua Fría Michoacán, Los Azufres, Mich., Mexico
p
Geochemistry Laboratory, Olkaria Geothermal Project, Moi South Lake Road, P.O. Box 785, Naivasha 20117, Kenya
q
Difaza Laboratorio de Control Industrial S.A. de C.V. - Paseo Cuauhnahuac, Esq. Jacarandas L-206, 1er piso, Col. Satélite, C.P. 62460, Cuernavaca, Morelos, Mexico
r
Materiales y Procesos Químicos, Instituto de Investigaciones Eléctricas, Reforma 113, Col. Palmira, Cuernavaca, Mor., CP 62490, Mexico
s
Gerencia de Proyectos Geotermoelectricos, Residencia Las Tres Vírgenes, A un costado del Parque de Materiales S/N, Zona Antiguo Hospital, Col. La Villita, C.P. 23920, Santa Rosalía,
B.C.S., Mexico
t
Ticala, Valencia, Negros Oriental, Philippines
u
Minerals and Geoscience Department, Locked Bag 2042, 88999 Kota Kinabalu, Sabah, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: The results of an inter-laboratory comparison of silica analysis of seven water samples (coded as
Received 27 July 2011 IIE19–IIE25) are presented. The first six samples (IIE19–IIE24) were prepared by diluting a certain amount
Accepted 18 June 2012 of silicon (Si) standard 1000 ± 0.1% ppm, HYCEL, Mexico, in distilled water, while the seventh sample IIE25
Available online 20 July 2012
is natural geothermal water. The conventional true values for the silica (SiO2 ) concentration of IIE19–IIE24
are 61.1, 213.9, 366.7, 520, 825, and 978 ppm, respectively.
Keywords:
The present analysis database consists of 27 datasets, analyzed by colorimetry (13 sets), atomic
Geothermal water
absorption spectrometry (7 sets) and inductively coupled plasma (7 sets) techniques. The analyses were
Silica
Inter-laboratory comparison
performed with two procedures: (i) individual laboratory procedure (or conventional procedure) and
Atomic absorption spectrometry (AAS) (ii) dilution of samples in the range 50–200 ppm SiO2 . The mean (x̄) and standard deviation (s) calcu-
Colorimetry lation after eliminating extreme values (outliers) with x̄ ± 2s method was used for the statistical data
Inductively coupled plasma (ICP) treatment. Presently, the overall error in the analysis is at least ±10%. A comparison of analytical error
and uncertainty for individual analytical technique suggests that the inductively coupled plasma (ICP)
and colorimetry are relatively better techniques for the analysis of SiO2 in geothermal waters; however,
there are some statistical artifacts on the colorimetric results because their number of measurements
was double that of atomic absorption spectrometry (AAS) and ICP. The analysis quality (i.e., precision and
accuracy) may be improved by using the data control procedure with some high quality standard (e.g.,
NIST standards). One of the factors of systematic error is associated with the preparation of laboratory
standards.
© 2012 Elsevier Ltd. All rights reserved.

∗ Corresponding author. Tel.: +52 777 3623811x7317.

E-mail address: Mahendra@iie.org.mx (M.P. Verma).
0375-6505/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.geothermics.2012.06.003
34 M.P. Verma et al. / Geothermics 44 (2012) 33–42
1. Introduction
Silica geochemistry is vital for understanding geological pro-
cesses in the earth crust like rock weathering, mineral deposition,
mass transport, etc. (Iler, 1979). In the geothermal industry, the
quartz solubility is used in estimating deep reservoir tempera-
ture (White et al., 1956; Bödvarsson and Pálmason, 1961; Morey
et al., 1962; Mahon, 1966; Fournier and Rowe, 1966; Fournier and
Truesdell, 1970; Arnórsson, 1970, 2000; Verma and Santoyo, 1997;
Verma, 2002, 2008), preventing silica scaling during production and
reinjection of geothermal brines (Brown and Bacon, 2000; Sugita
et al., 2000), and enhanced geothermal reservoir modeling (André
et al., 2006). Additionally, to formulate principles and laws on the
basis of comparative evidences obtained from the studies of various
similar geological systems, it is essential to have reproducible and
accurate analytical measurements of all the laboratories around the
world (Verma, in press-a).
Crandall and Blaine (1959) conducted a systematic statistical
evaluation of inter-laboratory cement tests. Presently, there are
many studies worldwide to obtain consistency and accuracy in
geochemical analytical measurements via inter-laboratory com-
parison and calibration for the chemical analysis of rock samples
(De Bièvre, 1997; Kane and Potts, 1997; Thompson et al., 2000;
S.P. Verma et al., 2002), the stable isotope analysis of water
samples (Parr and Clements, 1991; Araguás and Rozanski, 1995;
Lippmann et al., 1999), the chemical analysis of water samples
(Ellis, 1976; Giggenbach et al., 1992; Gerardo-Abaya et al., 1998;
Alvis-Isidro et al., 1999, 2000, 2002; S.P. Verma et al., 2002;
Urbino and Pang, 2004), and the chemical analysis of gas sam-
ples (Corazza, 1986; Mazor et al., 1988; Giggenbach and Matsuo,
1991; Gigganbach et al., 2001). Verma and co-workers (M.P. Verma
et al., 2002; Verma, 2004) conducted initial statistical analyses of
the results of the inter-laboratory comparisons. The higher uncer-
tainty in the analysis of high SiO2 concentration samples was
associated with analytical problems. Similarly, the acid-base titra-
tion procedure for the HCO3 − determination was conceptually
incorrect.
Reed and Mariner (1991) emphasized the quality control of
chemical and isotopic analysis of geothermal waters. The chemical
and isotopic calculations in aquatic systems are complementary
to understand natural processes in geological systems (Parr and
Clements, 1991; Verma, 2004). The International Atomic Energy
Agency (IAEA) has established, in case of stable isotope mass spec-
trometry, the necessity to run some common commercial reference
materials (standards) in all the laboratories, together with the
geothermal water samples, in order to improve the analytical qual-
ity of the participating laboratories (Araguás and Rozanski, 1995;
Lippmann et al., 1999).
This article presents the results of an inter-laboratory compari-
son of SiO2 analysis using commercial standards as water samples.
A statistical analysis of the results is conducted to evaluate the rea-
sons for the observed variations in the analysis and to propose a
revised procedure for the analysis of SiO2 .
2. Previous inter-laboratory SiO2 comparison studies
Table 1 presents a compilation of the characteristics of water
samples distributed during the inter-laboratory comparison of
geothermal water analyses (modified after Verma, 2008b). Ellis
(1976) conducted the first inter-laboratory comparison of geother-
mal water analysis; however, he reported only the statistics of the
datasets without the individual measured value of each chemical
parameter. The deficiency in analytical accuracy is one of the most
important limitations in understanding chemical processes and the
state of water–rock interaction in natural water bodies (Giggenbach
et al., 1992). The IAEA has conducted a series of inter-laboratory
comparisons for geothermal waters within the framework of the
project, “Coordinated Research Program on the Application of Iso-
tope and Geochemical Techniques in Geothermal Exploration” as
follows: (i) 22 laboratories from 19 countries (Giggenbach et al.,
1992), (ii) 15 laboratories from seven countries (Gerardo-Abaya
et al., 1998), (iii) 26 laboratories from 10 countries (Alvis-Isidro
et al., 1999), (iv) 35 laboratories from 16 countries (Alvis-Isidro
et al., 2000), (v) 38 laboratories from 23 countries (Alvis-Isidro et al.,
2002), and (vi) 31 laboratories from 18 countries (Urbino and Pang,
2004). Lim (2005) presented the results of an inter-laboratory com-
parison for the total silica in geothermal brines using the analytical
techniques, colorimetry, and atomic absorption spectrophotome-
try.
Initially, it was accepted that the reason for the dispersion in the
measured values among laboratories was related with the alter-
ation of natural water samples during transportation and storage.
M.P. Verma et al. (2002) conducted an inter-laboratory compari-
son of SiO2 analysis among the Mexican geochemistry laboratories
using commercial standards as water samples to avoid the effect
of sample alteration. However, they observed the same trend of
dispersion in the measured values among the participating lab-
oratories and concluded that sample alteration was not the only
factor for the dispersion in the measured values of the geochemical
parameters.
3. Sample preparation and analysis procedure
Seven samples (coded as IIE19–IIE25) were distributed dur-
ing the present inter-laboratory comparison. The first six samples
(IIE19–IIE24) were prepared by diluting a certain amount of Si stan-
dard 1000 ± 0.1% ppm, HYCEL, Mexico, in distilled water to make a
total volume of 3500 ml (see Appendix A). Each sample was agitated
with a magnetic stirrer for 40–50 min before filling the individ-
ual sample bottle. The sample IIE25 is natural geothermal water.
An amount of 5000 ml of the sample water was stored in the lab-
oratory for 3 months. It was filtered and agitated before filling
the sample bottles. A total of 25 sample sets were prepared. The
sample numbering in each set was assigned randomly in order to
avoid comparison of results among the participating laboratories
during the analysis. At the same time, it provided a framework
for each laboratory to conduct analysis as regular natural water
samples.
The conventional true values for the SiO2 concentration of
IIE19–IIE24 are 61.1, 213.9, 366.7, 520, 825, and 978 ppm, respec-
tively. The overall uncertainty in the SiO2 concentration of the
prepared samples is ±0.2%, which is relatively small and is not
considered in the statistical analysis.
Each laboratory was informed the SiO2 concentration range
(0–1000 ppm) of the sample waters and asked to present the prepa-
ration of standards, calibration curves, and analysis of the samples
with two procedures: (a) regular laboratory procedure (or conven-
tional procedure) and (b) dilution procedure. All the laboratories
prepared the laboratory standards to cover the whole range of con-
centration (i.e., the SiO2 concentrations of all samples were within
the range of the standards concentrations). There were some lab-
oratories which diluted the samples before the analysis; however,
the standards were prepared to cover the SiO2 concentrations of
diluted samples.
Most of the laboratories ran the samples in triplicate (see
Appendix A). The repeated values were very close (i.e., good repro-
ducibility). The reproducibility of each individual laboratory may
be associated with some bias; however, it does not contribute to
understand the differences in values among different laboratories.
The dilution procedure consists of the following steps:
 M.P. Verma et al. / Geothermics 44 (2012) 33–42 35

Table 1
Characteristics of samples distributed during the inter-laboratory comparison programs (modified after Verma, 2008).

Code Labs Characteristics

IAEA01 22 Sample 001 from Giggenbach et al. (1992). A clear colorless boiling (97.5 ◦ C) spring
at Waikite. The sample was collected on 31-12-1985.
IAEA02 22 Sample 002 from Giggenbach et al. (1992). Separated water from the weir box of
well WK66 at Wairakei collected on 30-12-1985.
IAEA03 15 Sample RASINT 1 from Gerardo-Abaya et al. (1998). Cold neutral pH bicarbonate,
low Cl− spring water from China; collected by the East China Geological Institute.
IAEA04 15 Sample RASINT 2 from Gerardo-Abaya et al. (1998). High temperature neutral pH,
Cl− geothermal well water from Palinpinon geothermal field, Philippines collected
by PNOC-EDC.
IAEA05 26 Sample WILC-01 from Alvis-Isidro et al. (1999). High salinity water from a boiling
spring (94 ◦ C) at Suoh, Lampung in South Sumatera, Indonesia; collected by
CAIR-BATAN.
IAEA06 26 Sample WILC-02 from Alvis-Isidro et al. (1999). Water from a low salinity warm
spring in San Kamphaeng, Thailand; collected by the Department of Geological
Sciences, ChiangMai University and the Electricity Generating Authority of
Thailand.
IAEA07 35 Sample IGWC-01 from Alvis-Isidro et al. (2000). Low salinity water from a cold
spring (26 ◦ C) situated in a geothermal area in Southern Luzon, Philippines;
collected by PNOC-EDC.
IAEA08 35 Sample IGWC-02 from Alvis-Isidro et al. (2000). High salinity geothermal water
from a high-temperature production well at Leyte, Philippines; collected by
PNOC-EDC.
IAEA09 38 Sample GWIN-01 from Alvis-Isidro et al. (2002). High salinity water form an
injection pipeline in the PGI-Tiwi geothermal field, Philippines; collected by
PNOC-EDC.
IAEA10 38 Sample GWIN-02 from Alvis-Isidro et al. (2002). Low salinity water from a cold
spring (26 ◦ C) in the province of Laguna, Philippines; collected by PNOC-EDC.
IAEA11 38 Sample GWIN-03 from Alvis-Isidro et al. (2002). Medium salinity water from a
warm spring (60 ◦ C) in Bacon-Manito geothermal field, Philippines; collected by
PNOC-EDC.
IAEA12 31 Sample GW-03-01 from Urbino and Pang (2004). A mixer of 44% GW-03-02 and
56% GW-03-03.
IAEA13 31 Sample GW-03-02 from Urbino and Pang (2004). Medium salinity water from a
geothermal well in the Leyte geothermal field, Philippines; collected by PNOC-EDC.
IIE15–IIE18 4 Samples prepared from commercial standard of SiO2 (M.P. Verma et al., 2002).
IIE19–IIE24 22 Samples prepared from commercial standard of SiO2 (this study).
IIE25 22 A geothermal natural water sample (this study).

a. Tabulation of averaged values of SiO2 concentration of the

samples which were obtained with the individual laboratory
procedure.
b. Dilution of samples within the range 50–200 ppm SiO2 .
c. Recalibration of equipment with standards within 0–250 ppm
SiO2 .
Population mean (µ )

d. Analysis of the diluted samples.

Sample mean(x)
Frequency

e. Recalculation of the SiO2 concentration of original samples.

Systematic error (a)

Err= a+b = x-T

a=µ-T It is worth mentioning here that the individual analytical proce-
True value

σ b=x-µ dure of some laboratories means to highly dilute the samples before
s
the analysis (for more information see Appendix A). For examples,
the dataset 20 was analyzed by diluting first the samples in the
Experimental error (Err)
Random error (b)
range 10–30 ppm Si (see Appendix A). Thus, in the second analyti-
cal procedure, the dilution of samples in the range 50–200 ppm SiO2
was designed to study the systematic error of individual laboratory,
and the comparison of SiO2 concentration among the participat-
ing laboratories when the samples were analyzed with a similar
X
procedure.
Fig. 1. Illustration of the significance of systematic (or bias) and random (or sta- The dilution improves the quality of analysis; but there may
tistical) errors and precision of measurements. The dashed histogram represents a be negative effects on high dilution (M.P. Verma et al., 2002). It
frequency distribution of N measurements with mean x̄ and standard deviation s. If is difficult to define the optimum range. In this work, we consid-
the number of measurements is very large, the frequency distribution results in a
ered 50–200 ppm, but the appropriate dilution range is still being
Gaussian curve with mean  and standard deviation . Let the true value be T. The
bias error (a =  − T) is associated with faulty calibration of equipment and incorrect sought. To highlight this point, there is need to perform new inter-
procedure of measurement. The statistical error (b = x̄ − ) reduces to zero for the laboratory comparison by diluting each sample in a specific and
population distribution. narrow range in all the participating laboratories.
36 M.P. Verma et al. / Geothermics 44 (2012) 33–42

Table 2
Concentration of SiO2 (ppm) for the samples analyzed with individual laboratory procedures and predefined dilution procedure by participating laboratories.

Set no.c Sample

Laboratory procedure Dilution procedure

IIE19 IIE20 IIE21 IIE22 IIE23 IIE24 IIE25 IIE19 IIE20 IIE21 IIE22 IIE23 IIE24 IIE25

1 61 225 387 541 875 966 92 64 226 381 547 853 979 94
2 60 208 303 417b 596 705 74 52 211 319 437 753 823 79
3 64 226 387 546 877 959 96 64 227 390 549 863 973 96
4 67 232 395 568 895 1003 99 71 218 377 564 871 981 103
5 64 225 393 561 876 971 95 67 223 388 558 845 962 98
6 109 233 402 560 888 980 155 66 217 409 530 847 928 104
7 65 225 389 589 830 837 99
8 76 231 426 607 997 1097 114
9 67 233 409 569 907 1006 100
10 65 218 350 522 775 906 96
11 68 236 404 576 912 1035 101
12 47 169 289 425 628 747 69
13 66 258 483 624 838 951 82 65 265 435 603 1062a 930 111
14 122 254 465 797 1065 1118 154 78 230 426 519 863 787 98
15 115 252 465 588 1074 1190 159 95 258 476 581 852 967 116
16 63 233 386 539 864 949 96 64 226 383 544 836 961 98
17 65 233 385 562 946 1031 106 62 203 328 499 872 939 92
18 74 242 369 509 777 701 108 78 252 423 621 1013 950 109
19 60 197 296 708 628 801 88
20 44 205 363 556 871 1079 78 66 189 282 456 688 797 114
21 63 226 382 544 850 962 101 75 231 387 552 876 968 94
22 58 233 396 562 893 1008 72 63 223 373 577 897 1042 76
23 68 242 416 622 966 1059 101 69 243 429 601 952 1056 101
24 81 277 465 638 947 1040 92 72 237 409 610 957 1020 82
25 76 270 447 624 948 1017 76 75 249 415 959 951 80
26 79 277 457 641 947 1033 87 73 250 417 656 879 972 83
27 77 252 437 603 965 1093 99 62 212 358 518 809 880 85
a
Values (marked in bold and underlined) were remove before the statistical analysis.
b
Values (marked in italics and underlined) were remove after the raw data statistics (Verma, in press-a).
c
Sets 1–13 were analyzed by colorimetry, sets 14–20 were analyzed by AAS (atomic absorption spectrometry), and sets 21–27 were analyzed by ICP (inductively coupled
plasma).

4. Statistical data treatment method
The statistical terms involved in the analytical data analysis are
well defined in textbooks (Bevington, 1969; Barnett and Lewis,
1994). Fig. 1 shows a relation between the measured values of a
parameter X and its frequency distribution of measurement. The
dashed histogram represents a frequency distribution of N mea-
surements of X, with mean x̄ and standard deviation s. If the number
of measurements is very large, the frequency distribution results
in a Gaussian curve with mean  and standard deviation , as
shown by solid curve. Additionally, any imperfection of measure-
ment technique can produce some skewness in the distribution
curve, which is not dealt with here.
The types of error and uncertainty in the experimental data are
also explained in Fig. 1. Let a true value of X be T. The experimental
error is the sum of (i) systematic errors or bias and (ii) random
or statistical errors. The bias error (a =  − T) is associated with
faulty calibration of equipment and incorrect procedure of mea-
surement. If the measurement technique is correct, the systematic
error (a) will be zero. The statistical error is b(= x̄ − ). The range
(x̄ − s) to (x̄ + s) is considered as analytical uncertainty for the sam-
ple distribution (N measurements), and is reported here as ±1 s.
The analytical uncertainty is associated with the detection limit
of equipment and statistical fluctuation in the measurements. The
uncertainty is considered as statistical fluctuation, if the value of
detection limit is relatively low and vice versa.
The objective of a statistical data treatment method is to get the
information of population distribution ( and ) from the sample
distribution (x̄ and s). Verma (in press-a) presented the statistical
data treatments for the detection and elimination of extremums
(outliers) using five methods: (i) data visualization (or raw data
statistics), (ii) mean (x̄) and standard deviation (s) calculation after
eliminating outliers with x̄ ± 2s, (iii) median and median absolute
difference (MAD), (iv) Huber method, and (v) single-outlier type
multiple test method involving Dixon, Grubbs, skewness and kur-
tosis tests at 99% confidence level. The results must be reported
in scientific notation with one significant digit of uncertainty. The
statistical data treatment provides a procedure to estimate the pre-
cision of measurement.
The analysis of commercial reference materials (standards) in
all the laboratories together with the water samples is fundamen-
tal to improve the analytical quality (i.e., precision and accuracy of
measurement) of the participating laboratories (Parr and Clements,
1991; Araguás and Rozanski, 1995; Lippmann et al., 1999; Verma,
2004). In this study, the data analysis was performed using the
method, mean (x̄) and standard deviation (s) after eliminating out-
liers with x̄ ± 2s. Thus, the confidence interval is 65.2% instead of
68.3% (Verma, in press-a).
5. Results and discussion
Table 2 presents the results of SiO2 measurements in the water
samples, distributed during the present inter-laboratory compar-
ison. The datasets 1–13, 14–20 and 21–27 were analyzed by
colorimetry (using the Molybdo-silicate method), atomic absorp-
tion spectrometry (AAS), and inductively coupled plasma (ICP),
respectively. Fig. 2 shows the data together with the compiled
data from the literature on the SiO2 inter-laboratory comparisons.
The data correspond to the measured values of the participating
laboratories using their own analytical procedure. The data are clas-
sified according the measurement techniques: colorimetry, atomic
absorption spectrometry (AAS), inductively coupled plasma (ICP),
 M.P. Verma et al. / Geothermics 44 (2012) 33–42 37

2500

IAEA05, 1999

IAEA12, 2004
IAEA08, 2000

IAEA09, 2002

IAEA11, 2002
IAEA07, 2000
IAEA03, 1998

IAEA04, 1998

IAEA10, 2002
IAEA02, 1992
IAEA01, 1992

IAEA06, 1999

IAEA13, 2004

IIE17, 2002
IIE15, 2002

IIE18, 2002
IIE16, 2002
2000

SiO2 (ppm)
1500

1000

500

a
0
0 20 0 20 0 20 0 20 0 20 0 20 0 20 0 20 0 20 0 20 0 20 0 20 0 20 0 20 0 20 0 20 0 20

Lab No.

2500
b
2000
IIE20
IIE19

IIE25
IIE22

IIE23
IIE21

IIE24
SiO2 (ppm)

1500
Colorimetry
AAS
1000 ICP
SP
Not defined
500

0
0 20 0 20 0 20 0 20 0 20 0 20 0 20

Lab No.

Fig. 2. Relations between laboratory number and SiO2 concentration, analyzed as parts of inter-laboratory comparisons. (a) Previous studies. The first 13 samples
(IAEA01–IAEA13) were compiled from the IAEA internal reports (Verma, 2008), and the last four samples (IIE15–IIE19) are from a study conducted among Mexican geo-
chemistry laboratories (M.P. Verma et al., 2002). (b) This study. The results obtained with the analytical procedure of individual laboratory are grouped according to analytical
techniques: colorimetry, atomic absorption spectrometry (AAS), inductively coupled plasma (ICP), UV-spectrophotometry (UV-SP) and undefined method.

UV-spectrophotometry (SP), and undefined method. In the present 213.93 ppm SiO2 (100 ppm Si) was prepared by diluting 0.1 ml of
study (Fig. 2b), there is also high dispersion in the measured val- 10,000 ppm Si standard in 10 ml of distilled water. Any error in
ues for high SiO2 concentration samples as reported in the earlier measuring the standard volume will propagate in the concentra-
studies (Ellis, 1976; Giggenbach et al., 1992). However, there is rel- tion value of laboratory standard. Thus, it is recommended to use
atively less dispersion among the ICP values, even in the earlier in general the 1000 ppm Si commercial standard for the SiO2 anal-
measurements. This suggests that ICP is a better technique for SiO2 ysis of geothermal waters and prepare large volume of laboratory
analysis in geothermal water samples. standard. However, there are some datasets which have both sys-
Fig. 3 shows an XY-plot between the conventional true value tematic and random errors (uncertainties). The reasons are still not
and the measured value of SiO2 . The samples are grouped accord- clear.
ing to the analytical technique and the measurement procedure. For Table 3 shows the results after the statistical data treatment
example, Fig. 3a shows the behavior of values obtained by colorime- of values reported in Table 2. Prior to statistically analyzing the
try using the individual laboratory procedure, while the behavior results, values that were out of trend were removed. Actually, there
of values obtained with the dilution procedure is shown in Fig. 3b. is only one value (1062 ppm). It is marked in bold and underlined
Similarly, Fig. 3c and d correspond to AAS, and Fig. 3e and f are for in Table 2 and shown with a dashed circle in Fig. 3. According to
ICP. the data statistics, the removal of this value will not affect the con-
There are some laboratories which have the same type of fidence limits. These types of values are associated with a variety
systematic error in the measured values for both the analyti- of errors, such as misprints or mistakes made during the handling
cal procedures. For example, the data points corresponding to and analysis of the sample, or passing the information (data) from
set02 are systematically on the lower side of the 45◦ line in person to person.
Fig. 3a and b. If we look at worksheet set02 in the Excel work- The arithmetic mean (x̄) and standard deviation (S.D.) of the
book Interlab2012.xlsx (Appendix A), the standards were prepared remaining values were then computed. The values that fell outside
by dissolving 10,000 ppm Si standard. The laboratory standard the mean ± 2 S.D. were rejected. The values are marked in italics
38 M.P. Verma et al. / Geothermics 44 (2012) 33–42

Fig. 3. Relationship between the “conventional” true value and measured silica concentrations. (a, c, and e) The behavior of measured silica concentration obtained by
colorimetry, AAS and ICP using the individual laboratory procedure, respectively. (b, d, and f) The behavior of respective data obtained by the diluting procedure. The dashed
45◦ line represents the data analytical points which are in agreement with the corresponding true value. The data marked with dashed circles were excluded before conducting
the statistical data treatment analysis.

and underlined in Table 2. Then, the mean and S.D. of the remaining
data were recomputed. For example, the colorimetric dataset for
sample IIE19 has the values 61, 60, 64, 67, 64, 109, 65, 76, 67, 65,
68, 47, and 66 ppm for corresponding laboratories, respectively.
The mean and standard deviation are 68 and 14 ppm, respectively.
Clearly the 109 ppm is out of trend (i.e. mean ± 2 S.D.). According to
the data statistics, the removal of values which are out of mean ± 2
S.D. (i.e., 109 ppm) will not affect significantly the confidence
interval. The same methodology was applied to all the data sets;
but the colorimetric measurements have only outliers. This may be
associated with the fact that the colorimetric dataset has relatively
double the number of points and there is a high spread in the
values of AAS. Any statistical data treatment will be in favor of
colorimetric dataset. Thus, it has some artifacts due to statistical
data treatment; however, the colorimetric mean value for each
sample is relatively close to the corresponding conventional true
value.
Fig. 4 shows histograms to compare the analytical data quality
for the conventional laboratory method and the dilution procedure
implemented in this study. It can be observed that the values
measured with the dilution procedure have significantly low
uncertainty. However, the differences in the uncertainties
 M.P. Verma et al. / Geothermics 44 (2012) 33–42 39

Table 3
Results of statistical data treatment of SiO2 analysis (ppm).

Sample no. IIE19 IIE20 IIE21 IIE22 IIE23 IIE24 IIE25

True value 61.1 213.9 366.7 520 825 978

Colorimetry: lab method

Mean 68 224 386 546 838 935 98
S.D. 14 20 50 62 113 112 21
C.V.a 21 9 13 11 13 12 21
Errorb 11 5 5 5 2 −4
Lower limit 47 169 289 417 596 705 69
Upper limit 109 258 483 624 997 1097 155
No. of data 13 13 13 13 13 13 13
Reporting valuec 7(1)E1 2.2(2)E2 3.9(5)E2 5.5(6)E2 8(1)E2 9(1)E2 1.0(2)E2

Colorimetry: dilution method

Mean 64 227 385 541 839 939 98
S.D. 6 18 35 51 43 56 10
C.V. 10 8 9 9 5 6 10
Error 5 6 5 4 2 −4
Lower limit 52 211 319 437 753 823 79
Upper limit 71 265 435 603 871 981 111
No. of data 7 7 7 7 6 7 7
Reporting value 6.4(6)E1 2.3(2)E2 3.9(4)E2 5.4(5)E2 8.4(4)E2 9.4(6)E2 1.0(1)E2

AAS: lab method

Mean 77 231 390 609 889 981 113
S.D. 29 22 60 105 158 176 32
C.V. 38 9 15 17 18 18 28
Error 27 8 6 17 8 0
Lower limit 44 197 296 509 628 701 78
Upper limit 122 254 465 797 1074 1190 159
No. of data 7 7 7 7 7 7 7
Reporting value 8(3)E1 2.3(2)E2 3.9(6)E2 6(1)E2 9(2)E2 1.0(2)E3 1.1(3)E2

AAS: dilution method

Mean 74 226 386 537 854 900 104
S.D. 12 27 71 59 104 84 10
C.V. 38 9 15 17 18 18 28
Error 21 6 5 3 3 -8
Lower limit 62 189 282 456 688 787 92
Upper limit 95 258 476 621 1013 967 116
No. of data 6 6 6 6 6 6 6
Reporting value 7(1)E1 2.3(3)E2 3.9(7)E2 5.4(6)E2 8 (1)E2 9.0(8)E2 1.0(1)E2

ICP: lab method

Mean 72 254 429 653 931 1030 89
S.D. 9 21 31 139 43 41 12
C.V. 17 12 18 11 12 9 9
Error 17 19 17 25 13 5
Lower limit 58 226 382 544 850 962 72
Upper limit 81 277 465 957 966 1093 101
No. of data 7 7 7 7 7 7 7
Reporting value 7.2(9)E1 2.5(2)E2 4.3(3)E2 6(1)E2 9.3(4)E2 1.03(4)E2 9(1)E1

ICP: dilution method

Mean 70 235 398 586 904 984 86
S.D. 5 14 26 48 56 61 9
C.V. 8 6 7 8 6 6 10
Error 14 10 9 15 10 1
Lower limit 62 212 358 518 809 880 76
Upper limit 75 250 429 656 959 1056 101
No. of data 7 7 7 6 7 7 7
Reporting value 7.0(5)E1 2.4(3)E2 4.0(3)E2 5.9(5)E2 9.0(6)E2 9.8(6)E2 8.6(9)E1
a S.D.
The coefficient of variation (C.V.) is defined as mean × 100.
b
The analytical error is defined as mean−TrueValue
TrueValue
× 100.
c
Values in scientific notation (e.g., 7(1)E1 means that there is one significant digit with exponent 1 and the uncertainty in the last digit “7” is 1. In other words the value
is between 60 and 80 ppm).

are not as pronounced as observed by M.P. Verma et al.
(2002), since the conventional analytical procedure of many
laboratories consists of the dilution of samples prior to analysis.
The binomial distribution curve for each sample is shown in
Fig. 5. The analytical uncertainties for the colorimetry and ICP tech-
niques are approximately the same, while the AAS values have
higher uncertainty. All the measured values are shown on the con-
centration axis for each sample. The data after the statistical data
treatment were used in the derivation of the binomial distribution
curve. The data are shown below each curve. There were only few
outliers since the dispersion among values is relatively large.
Table 3 presents the analysis of uncertainty (C.V.) and error
for each analytical technique. The ranges of uncertainty (in %)
using the analytical procedure of individual laboratory are 9–21,
8–38, and 9–17 for colorimetry, AAS, and ICP, respectively; while
the respective ranges for the dilution method are 5–10, 9–18,
6–8. Similarly, the ranges of analytical error (in %) in the same
order are 4–11, 0–27, and 5–25 for the analytical procedure of
40 M.P. Verma et al. / Geothermics 44 (2012) 33–42
Fig. 4. Comparison of SiO2 analysis data quality for the individual conventional laboratory and dilution methods.
individual laboratory and 4–6, 8–21, and 1–14 for the dilution
method. As mentioned above, the effect of dilution on the data anal-
ysis quality is not possible to study in the present work; however,
there is relatively low uncertainty in the case of dilution proce-
dure for each analytical technique. In other words, there is better
agreement if the samples were analyzed in a similar manner. The
analytical accuracy is also better for the dilution method for each
analytical technique. It suggests that the analysis of SiO2 must be
performed in certain range of dilution. However, the overall ana-
lytical error in the analysis of SiO2 is at least 10%. The suggestions
presented in this study may provide a mechanism to improve in
future the quality of SiO2 analysis in water samples.
The mean value for colorimetry is generally close to the con-
ventional true value. It may be assessed that colorimetry is a better
technique for the analysis of SiO2 in water samples. However, there
are two points to be emphasized. First, the number of values for
colorimetry is almost twice as those for AAS and ICP. Statistically,
the random error and uncertainty reduce with increasing the
number of measurements. Second, there were some laboratories
using colorimetry (see the datasets, set01, and set03 in Appendix
A) which conducted the data control procedure for their calibra-
tion. Presently, the data control procedure consists of two steps:
(i) the calibration of equipment with laboratory standards, and (ii)
measuring the SiO2 concentrations of some standards, prepared
from the NIST commercial standard as samples. If the values are
within ±0.5%, the calibration is appropriate. Otherwise, both the
steps were repeated. There is discussion among the participants to
initiate a common undertaking to create a standard data control
procedure, similar to the SMOW-GISP-SLAP scale used for the
isotopic analysis (oxygen-18 and deuterium) of water sample (Parr
and Clements, 1991; Araguás and Rozanski, 1995; Lippmann et al.,
1999). In other words, there is need to establish some common
standards (e.g., NIST standard) for each chemical parameter in
order to obtain the consistency among the measured values in
different laboratories around the world. Indeed, the mechanism
of quality control for the international standards is of primary
concern.
Verma (in press-b) presented an algorithm for quartz geother-
mometry to propagate the analytical uncertainty in the mea-
surements of the silica concentration and reservoir enthalpy. He
elucidated that there is an uncertainty of ±18 ◦ C in the calcu-
lated geothermal reservoir temperature with quartz solubility
geothermometersin case of Los Azufres geothermal system, if the
uncertainties in the measured values of SiO2 and enthalpy are
10% and 2%, respectively. Thus, the prediction of changes in the
reservoir characteristics during the exploitation of geothermal sys-
tems demands good quality geochemical analysis of geothermal
waters.
 M.P. Verma et al. / Geothermics 44 (2012) 33–42 41

0.10
0.09 IIE19 IIE19 IIE23 IIE23
0.01
0.08
0.07
0.06
0.05 Lab method Dilution method Lab method Dilution method
0.04
0.03
0.02
0.01
0.00 0.00
0 50 100 150 0 50 100 150 500 700 900 1100 1300 500 700 900 1100 1300
0.07
IIE20 IIE20 IIE24 IIE24
0.06 0.01
0.05

Frequency
0.04
0.03
0.02
0.01
Frequency

0.00 0.00
100 150 200 250 300 350 100 150 200 250 300 350 500 700 900 1100 1300 1500 500 700 900 1100 1300 1500
0.02 0.06
IIE21 IIE21 IIE25 IIE25
0.05
0.04
0.01 0.03 True value
Colorimetry
0.02 AAS
0.01 ICP

0.00 0.00
200 300 400 500 600 200 300 400 500 600 0 100 200 0 100 200
IIE22 IIE22 SiO2 (ppm)

0.01
True value
Colorimetry
AAS
ICP

0.00
300 500 700 900 300 500 700 900
SiO2 (ppm)

Fig. 5. Binomial distribution of the measured SiO2 concentration values for each sample. The raw values are shown on the
concentration axis. The values used to draw the binomial distribution are shown below the curve. There were only few extreme values (outliers). The conventional
true value for each sample is shown by the solid vertical line. The analytical error is the difference between the mean (vertical line) for each distribution and corresponding
true value.

6. Conclusions Acknowledgements

From the results of the present inter-laboratory comparison, it Authors appreciate the IIE authorities for the financial support
can be concluded that there is, in general, high analytical uncer- and the authorities of each participating laboratory. Victor Arellano
tainty (error) in the measurement of SiO2 in water samples. The G. encouraged for conducting this project. Many people, especially
overall analytical error (uncertainty) is presently of ±10%. However, A. Aguayo, O. Cruz, and N. Ceniceros helped in the analytical work.
some laboratories have good quality control for each analytical The paper is substantially improved in its content and presentation
technique (e.g., for colorimetry set01 and set03, for AAS set16, and with the constructive comments and suggestions of the anonymous
for ICP set 21). Colorimetry and ICP are relatively better techniques reviewers.
for the analysis of SiO2 . In the present study, the number of values
for colorimetry is almost twice those for AAS and ICP. This makes Appendix A. Supplementary data
it difficult to define the quality of colorimetric measurements with
any certainty. However, analytical error in the colorimetric mea- A.1. Analytical results
surements is relatively small.
Using commercial standards as water samples in this inter- The analytical data of each participating laboratory are pre-
laboratory comparison has highlighted some clues to improve the sented in a worksheet of excel workbook, Interlab2012.xlsx. The
analytical quality. First, there is a need to take special care dur- results of each laboratory are divided in four groups: general infor-
ing the preparation of laboratory standards. Second, the calibration mation, laboratory method, dilution method, and comparison of data.
curve must be verified with the data control procedure (i.e., run- The data of some laboratory are reported as the final results only.
ning some quality standards as water samples). In other words, Supplementary data associated with this article can be
there is need to establish good quality standards for each chemical found, in the online version, at http://dx.doi.org/10.1016/
parameter worldwide. j.geothermics.2012.06.003.
The inter-laboratory comparison program should be continued
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