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Strategy for water analysis using ICP-MS

Article  in  Fresenius Journal of Analytical Chemistry · December 2000

DOI: 10.1007/s002160000552 · Source: PubMed

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Fresenius J Anal Chem (2000) 368 : 601–606
O R I G I N A L PA P E R
J. L. Fernández-Turiel · J. F. Llorens · F. López-Vera ·
C. Gómez-Artola · I. Morell · D. Gimeno
Strategy for water analysis using ICP-MS
Received: 18 May 2000 / Revised: 5 July 2000 / Accepted: 7 July 2000
Abstract The developed strategy permits determination
in three steps of sixty-seven elements using inductively
coupled plasma mass spectrometry (ICP-MS). Sodium,
Mg, Si, S, Cl, K, and Ca are determined in a first step;
B, Al, P, Cr, Fe, Mn, Ni, Cu, Zn, As, Se, Ag, Cd, Sb, Ba,
Hg, and Pb are determined in a second step; and Li, Be,
Ti, V, Co, Ga, Ge, Br, Rb, Sr, Y, Zr, Nb, Mo, Sn, Te, I, Cs,
La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu,
Hf, Ta, W, Pt, Au, Tl, Bi, Th, and U are analyzed in a third
step. The figures of merit obtained are adequate to carry
out water quality monitoring and other hydrochemical
studies, such those based in the application of hydro-
chemical fingerprinting to water management.
Introduction
The great importance of water for man makes the accurate
management of this natural resource a priority in order to
preserve its sustainability. Water analysis plays a decisive
role in those regulations that determine the water quality
levels for specific uses (e.g., for drinking water [1–4]),
and those focused on the reduction and removal of poten-
tially toxic substances from the water [5]. On the other
hand, water analysis applicability is also extended to the
J. L. Fernández-Turiel () · J. F. Llorens
Institute of Earth Sciences ‘Jaume Almera’ –
CSIC, C/ Solé i Sabarís s/n, 08028 Barcelona, Spain
F. López-Vera · C. Gómez-Artola
Universidad Autónoma de Madrid, Facultad de Ciencias C-VI,
Ciudad Universitaria de Cantoblanco,
Ctra. de Colmenar, km 15, 28049 Madrid, Spain
I. Morell
Universitat Jaume I,
Esc. Sup. Tecnologia y Ciencias Experimentales,
Campus de Riu Sec, 12080 Castelló, Spain
D. Gimeno
Universitat de Barcelona, Dpt. GPPG,
C/ Marti i Franques s/n, 08028 Barcelona, Spain
© Springer-Verlag 2000
study of water origin and evolution, taking into account
the natural and anthropic influences, e.g., water-water and
water-rock interactions, groundwater exploitation regula-
tion (protection and recharge of aquifers), contamination
processes, etc.
A large variety of solutes is transferred to the water via
complex pathways and processes, such as atmospheric
and terrestrial sources. The result is the occurrence of dif-
ferent components in the water, which define the hydro-
chemical fingerprint. This fingerprint permits identifica-
tion of water, the media and the interactions between
them, including those associated with anthropic activities.
The concept is comparable to individual fingerprint iden-
tification.
Although the concept of the hydrochemical fingerprint
is simple, its practical application has been difficult, since
the determination of hydrochemical parameters has been
seriously limited by the figures of merit of the analytical
instrumentation. In fact, the hydrochemical characteriza-
tion of the water has in practice been based on about ten
parameters (major anions and cations and physico-chemi-
cal parameters). Although these ‘conventional’ param-
eters are sufficient to discriminate between waters of very
different geological media, their application for this pur-
pose is in many cases difficult because the concentration
range of such parameters in water is usually narrow [6].
Occurrence of trace elements in waters is very sensitive to
geological changes and, in many cases, to anthropic influ-
ences [7].
Hence, the advances in analytical techniques facilitate
the application of the hydrochemical fingerprint concept.
Inductively coupled plasma-mass spectrometry (ICP-MS)
is particularly suitable for this purpose due to the possibil-
ity of rapid multi-element analysis in combination with
excellent detection limits [8–14].
The ICP-MS allows one to obtain complete informa-
tion on the trace elements occurring in water, including
those present in sub-µg/L concentrations. The analytical
capability of ICP-MS in this field has led to consideration
of this technique for routine water analysis. Thus, for ex-
ample, the USEPA (United States Environmental Protec-
602
Table 1 Sets of mixed-element standard solutions used in the external calibration (EC) and ICP-MS-tuning for water analysis
Solution Parameters Calibration concentrations
EC-1 Cl, SO4 1–5–10–50 mg/L Cl, 1–10–50–100 mg/L SO4
EC-2 Na 0.05–0.1–0.5–1.0 mg/L
EC-3 Mg, Si, K, Ca 0.05–0.1–0.5–1.0 mg/L
EC-4 Ni, Zn, Hg 1–5–10–25 µg/L Ni, 10–100–500–1000 µg/L Zn,
0.10–0.25–0.50–1.00 µg/L Hg
EC-5 Ti, Mn, Co, Cu, Ga, Ge, As, Se, Y, Zr, Nb, Mo, Ag, Cd, Te, 0.5–1–5–10 µg/L
Cs, Ta, W, Bi, Pb, U
EC-6 Li, Be, V, Cr, Rb, Sn, Sb, Hf, Au 0.5–1–5–10 µg/L
EC-7 La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th 0.5–1–5–10 µg/L
EC-8 B, Al, P, Fe, Sr, Ba 10–25–50–100 µg/L
EC-9 Se 25–50–100 µg/L
EC-10 I 1–5–10–50–100 µg/L
EC-11 Br 10–50–100–500 µg/L
Tune Be, Co, Rh, In, La, Bi, U 10–100 µg/L

tion Agency) Method 200.8 uses ICP-MS to test for many Table 2 ICP-MS operating parameters
trace elements in water [15]. Similar guidelines are imple- Instrument type VG PlasmaQuad PQ2+
mented or are being considered for implementation in RF forward power 1.35 kW
several other countries [16]. Coolant gas flow 14.0 L/min
The aim of this work is to develop a general strategy Auxiliary gas flow 1.0 L/min
for water analysis using ICP-MS. The novelty and rele- Nebulizer gas flow 0.95 L/min
vance to environmental water monitoring of such a strat- Sampling cone Nickel (1.14 mm orifice)
egy is related to the elements analyzed and figures of Skimmer cone Nickel (0.90 mm orifice)
merit obtained, which are adequate for a wide range of ap- Nebulizer type V-groove
plications (e.g., drinking water treatment plant monitor- Solution uptake 1 mL/min controlled by peristaltic pump
ing, surface and groundwater quality monitoring, discrim- Detector type Channeltron multiplier
ination of water origins, water-rock interaction studies,
etc.), and also to its simpleness and rapidity.
ing more than four weeks, with the exceptions of EC-1 and, spe-
cially, EC-4 solutions, which were always prepared just before the
Experimental analysis of the respective analytes.

The recommended sampling protocol for water analysis using ICP-
MS consists of filling a 100 mL bottle of high-density polyethyl-
ene (HDPE) and acidification of the sample (1% v/v HNO3). Pre-
viously, the bottle should be carefully rinsed with the sample
(three times) and then filled to the top. The use of HDPE bottles
minimizes the contamination of the containers and favors the sam-
ple preservation [17]. Filtering is carried out depending on the pur-
pose of the analysis. Thus, for example, filters of 0.45 µm are re-
quired in some legislations, while membrane filters of 0.1 µm are
usually suggested for water solution chemistry [18]. The objec-
tives of other studies do not require this step [12, 13]. In any case,
the sample should be stored cool (4 °C) and dark. This procedure
allows the analytes to be preserved for more than four weeks, and
in many cases for periods of several months. An important excep-
tion is mercury, which should be analyzed as soon as possible. In-
terlaboratory exercises with different techniques carried out with
other analytical groups in Spain have produced similar results
during the first 2–3 days after the sampling for concentrations of
0.10 to 1.0 µg/L of Hg.
Reagents. Nitric acid of analytical grade was purchased from
Merck. All solutions, samples and reference materials, were pre-
pared in 1% v/v HNO3. Purified water of 18.2 MΩ cm–1 type Milli
Q Plus was used for preparation and/or dilution of solutions, if
necessary. Mixed-element reference solutions were prepared from
1000 mg/L single-element standard solutions (Aldrich), from solid
salts (NaCl, KBr and KI from Merck) for Na, Cl, Br and I, and
from sulfuric acid (Merck) for S. The mixed-element standard so-
lutions used are shown in Table 1. These solutions were stable dur-
Instrument. A VG PlasmaQuad PQ2+ (Thermo Group-VG, Man-
chester, UK) ICP-MS was used for all determinations. The water
samples were introduced into the plasma by means of a V-groove
nebulizer and a Scott-Fassel torch. Problems related to a high dis-
solved salt content of the sample (~0.5%) have not been observed
with this nebulizer. Typical instrumental parameters are found in
Table 2. Sample input was controlled with a Gilson Minipuls 3
peristaltic pump and a Gilson Autosampler (Gilson Medical Elec-
tronics, WI, USA).
The isotopes monitored are summarized in Table 3, together
with the acquisition mode and the used residence time. In all cases
three points per spectral peak were measured. These isotopes are
free of polyatomic interferences or the effects of these interfer-
ences are usually negligible in water samples. The exceptions were
V and As. In these cases, the interferences of Cl were corrected us-
ing empirical equations based on experiments carried out using in-
creasing concentrations up to 2000 mg/L of Cl from HCl and
NaCl. The results coincide with those presented in the PQVision
software of the instrument under the label EPA6020 (i.e., 51V =
[51Peak – 3.1081 53Peak + 0.352452 Peak], and 75As = [75Peak
–3.1278 77Peak + 1.0177 78Peak]).
Although, theoretically, the combination of pulse counting and
analogue modes of the multiplier allows simultaneous determina-
tion of elements with concentrations in different orders of magni-
tude, experience has demonstrated that it is better to separate the
analyses of major and trace elements. Thus, three groups of ele-
ments were created: Set 1: major elements (Na, Mg, Si, S, Cl, K,
and Ca); Set 2: trace elements generally included in legislation
[1–4] (B, Al, P, Cr, Fe, Mn, Ni, Cu, Zn, As, Se, Ag, Cd, Sb, Ba,
 603
Table 3 Isotopes used in the Element Mass Residence Table 3 (continued) Element Mass Residence
ICP-MS analysis of water time (ms) time (ms)
(peak jumping acquisition
mode) Set 1 Ho 165 20
Na 23 0.05 Er 166 20
Mg 25 1 Tm 169 20
Si 29 1 Yb 174 20
S 34 10 Lu 175 20
Cl 35 10 Hf 178 20
K 39 1 Ta 181 20
Ca 44 1 W 182 20
In 115 10 Pt 195 20
Set 2 Au 197 20
B 11 10 Tl 203 20
Al 27 5 Bi 209 20
P 31 10 Th 232 20
Cr 52 10 U 238 20
Fe 54 10
Mn 55 10
Ni 60 10 Hg, and Pb); and Set 3: trace elements of interest especially to fin-
Cu 65 10 gerprint the surface and groundwaters (Li, Be, Ti, V, Co, Ga, Ge,
Br, Rb, Sr, Y, Zr, Nb, Mo, Sn, Te, I, Cs, La, Ce, Pr, Nd, Sm, Eu,
Zn 66 10 Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Pt, Au, Tl, Bi, Th, and
As 75 10 U). With respect to Set 1, the sulfur concentration is determined
Se 78 10 using the isotope 34S and is expressed as SO42–. This assumption is
Ag 107 10 generally correct for natural waters, but must carefully be consid-
Cd 111 10 ered in the interpretation of data. In fact, anoxic conditions or ex-
treme pH in water may invalidate this assumption.
Sb 121 10 Consequently, three procedures were created with the respec-
Ba 138 10 tive element menu and sample input method. Timing of 90–10–
In 115 10 90 s of uptake-acquisition-washout for Set 1, and 90–60–90 s for
Hg 202 10 Sets 2 and 3 was determined to be adequate for these procedures.
Pb 208 10 The total actual time required for each sample was 3.45 and
4.45 min for Set 1, and Sets 2 and 3, respectively.
Set 3 The ICP-MS was calibrated for every set using two mixed-ele-
Li 7 20 ment tune solutions (Table 1). A 100 µg/L concentration solution
was used to tune the mass calibration and detector calibration. Fur-
Be 9 20 thermore, the response curve adjustment was checked using a 10
Ti 49 20 µg/L concentration solution.
V 51 20 Indium (10 µg/L) was added to all solutions, including the cal-
Co 59 20 ibration blank, to attempt to correct for time-dependent parameters
Ga 71 20 such as changes in sample matrix, mainly related to water salinity
in the present case. The absolute intensities decreased typically by
Ge 74 20 30–40%, over a typical six-hour ICP-MS analysis. The changes in
Br 81 10 internal reference signal were 1–5% from sample to sample. In-
Rb 85 20 dium was selected due to its low concentration in natural waters
Sr 88 1 (sub-ng/L level).
Y 89 20 The samples were grouped in batches of maximum 30 samples
(due to laboratory capacity, in terms of personnel availability).
Zr 90 20 Conventional external calibration using the software supplied by
Nb 93 20 the instrument manufacturer was used to quantify the analyte con-
Mo 98 20 centrations. A typical batch for Set 1 consisted of: blank, four stan-
In 115 10 dard solutions of EC-1 (Table 1), four standard solutions of EC-2,
Sn 120 20 four standard solutions of EC-3, blank, monitor, samples 1 to 10,
monitor, samples 11 to 20, monitor, samples 21 to 30, and moni-
Te 125 20 tor. The batch for Set 2 was: blank, four standard solutions of EC-
I 127 20 4 (Table 1), seven standard solutions combining EC-5, EC-6, EC-
Cs 133 20 8, and EC-9, blank, monitor, samples 1 to 10, monitor, samples 11
La 139 20 to 20, monitor, samples 21 to 30, and monitor. Finally, a batch for
Ce 140 20 Set 3 is composed of: blank, four standard solutions of EC-10
(Table 1), four standard solutions of EC-11, seven standard solu-
Pr 141 20
tions combining EC-5, EC-6, EC-7, EC-8, blank, monitor, samples
Nd 146 20 1 to 10, monitor, samples 11 to 20, monitor, samples 21 to 30, and
Sm 147 20 monitor. A solution of 1% of HNO3 (v/v) was pumped among the
Eu 151 20 samples. Set 1 samples were diluted 1+99 as general rule, while
Gd 157 20 for Sets 2 and 3 the samples were processed without any treatment.
An in-house standard was analyzed as monitor every ten sam-
Tb 159 20
ples. This standard laboratory tap water was spiked with 0.1 µg/L
Dy 162 20 of Be, Ga, Ge, Y, Zr, Nb, Ag, Cd, Te, La, Ce, Pr, Nd, Sm, Eu, Gd,
604
Table 4 Detection limits and precision for ICP-MS analysis of Table 4 (continued)
water samples (this work), average composition of water in
streams [19], and maximum concentrations levels in waters in dif- Detection RSD % Stream EUc USEPAd WHO
ferent regulations: European Union (EU) [4], Directive 98/83/EC, limit (n = 20)b water
USEPA [25], National Primary and Secondary Drinking Water (3 s)a
Regulations; and World Health Organization (WHO) [3]
Gd 0.012 2.22 (s) 0.0085
Detection RSD % Stream EUc USEPAd WHO Tb 0.002 3.51 (s) 0.0012
limit (n = 20)b water
Dy 0.006 1.38 (s) 0.0072
(3 s)a
Ho 0.002 1.35 (s) 0.0014
Set 1 (Concentrations expressed in mg/L) Er 0.006 3.12 (s) 0.0042
Na 0.007 9.03 6.3 200 (C) 200 Tm 0.003 1.98 (s) 0.00061
Mg 0.0006 3.63 4.1 Yb 0.007 2.41 (s) 0.0036
Si 0.0021 9.82 6.5 Lu 0.002 2.23 (s) 0.00064
SO4 0.496 11.85 3.7 250 (C) 250 (S) 400 Hf 0.02 8.10 (s)
Cl 0.0323 5.59 7.8 250 (C) 250 (S) 250 Ta 0.03 6.02 (s)
K 0.0201 14.2 2.3 W 0.05 2.94 (s) 0.03
Ca 0.0123 3.98 15 Pt 0.03 8.87 (s)
Set 2 (concentrations expressed in µg/L) Au 0.04 5.26 (s) 0.002
B 0.99 1.96 10 1000 (B) Tl 0.01 4.89 (s) 2 (P)
Al 2.78 6.65 50 200 (C) 50–200 (S) 200 Bi 0.07 6.22 (s)
P 2.08 5.74 20 Th 0.005 10.54 < 0.1
Cr 0.16 4.65 1 50 (B) 100 (P) 50 U 0.007 6.35 0.04
Fe 5.85 10.24 40 200 (C) 300 (S) 300 a Based on three times the standard deviation for ten replicate de-
Mn 0.15 6.92 7 50 (C) 50 (S) 100 terminations of the reagent blank
b Relative standard deviation (RSD) based on 20 replicate determi-
Ni 0.2 5.59 0.3 20 (B)
Cu 0.14 4.36 7 2000 (B) 1300 (P) 1000 nations of a tap water sample. (s) 0.1 µg/L of individual elements
spiked in this sample, a spike of 1.0 µg/L was used for Hg
Zn 1.75 9.97 20 5000 (S) 5000 c B and C, Parts B and C of Directive 98/83/EC of European Union
As 0.11 6.88 2 10 (B) 50 (P) 50 [4]
Se 0.32 10.84 0.05 10 (B) 50 (P) 10 d P and S, Primary and Secondary drinking water regulations of

Ag 0.06 12.67 (s) 0.3 100 (S) USEPA [25]

Cd 0.02 8.88 (s) 0.01 5 (B) 5 (P) 5
Sb 0.02 5.97 0.07 5 (B) 6 (P)
Ba 0.07 2.86 20 2000 (P) Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Pt, Au, Tl and Bi, and
Hg 0.01 9.76 (s) 0.07 1 (B) 2 (P) 1 1.0 µg/L of Hg (Table 4), and acidified with HNO3 (1% v/v). Vari-
ations lower than ±10% were required to continue the run. This
Pb 0.03 6.39 1 10 (B) 15 (P) 50 standard was also used for precision measurement. The standard
Set 3 (concentrations expressed in µg/L) reference materials ‘High carbonate content water’ CRM 616 and
Li 0.03 4.96 3 ‘Low carbonate content water’ CRM 617 from European Commis-
sion (Brussels, Belgium), ‘Trace elements in water – 1643c’ from
Be 0.005 9.13 (s) 0.01 4 (P) National Institute of Standards and Technology (Gaithersburg,
Ti 0.24 11.87 3 USA), and the granite AC-E from GIT-IWG (Nancy, France) were
V 0.04 8.78 0.9 used for trueness verification. For the rock standard AC-E, 0.1 g
Co 0.01 2.96 0.1 of the solid sample was digested using a mixture of HF +
Ga 0.01 5.56 (s) 0.09 HClO4+HNO3 (5+2.5+2.5, v/v) and diluted to 100 mL with 1%
(v/v) HNO3. When these reference materials were processed, they
Ge 0.01 3.12 (s) 0.005 were located at the beginning of the group of samples 1 to 10.
Br 2.23 12.09 20 10 (B)
Rb 0.02 5.21 1
Sr 0.05 10.81 70
Table 5 Comparison of reported values of reference materials
Y 0.004 3.12 (s) 0.04 with observed values (concentrations expressed as mg/L)
Zr 0.01 2.66 (s)
Nb 0.18 2.56 (s) BCR CRM 616 This work BCR CRM 617 This work
Mo 0.02 4.64 0.6 Certified (n = 10) Certified (n = 10)
Sn 0.14 7.79 0.03 Na 61.5 ± 0.7 62.1 ± 1.3 14.6 ± 0.3 15.0 ± 0.9
Te 0.2 5.01 (s) Mg 23.9 ± 0.3 23.8 ± 0.4 7.32 ± 0.15 7.35 ± 0.18
I 0.49 11.84 7
Cs 0.01 5.92 0.02 Si
La 0.004 1.60 (s) 0.048 SO4 57.3 ± 1.1 56.1 ± 1.1 26.3 ± 0.5 26.2 ± 0.5
Ce 0.003 2.55 (s) 0.079 Cl 49.8 ± 1.0 50.1 ± 1.2 26.4 ± 0.4 26.2 ± 0.4
Pr 0.002 2.97 (s) 0.0073 K 0.58 ± 0.03 0.60 ± 0.06 9.93 ± 0.26 9.52 ± 0.51
Nd 0.006 2.71 (s) 0.038 Ca 38.5 ± 0.9 38.7 ± 0.9 14.6 ± 0.4 14.7 ± 0.6
Sm 0.011 4.02 (s) 0.0078
Eu 0.004 4.33 (s) 0.0015
 605
Table 6 Comparison of reported values of reference materials Table 6 (continued)
with observed values (concentrations expressed as µg/L)
NIST SRM This work AC-E This work
NIST SRM This work AC-E This work 1643c (n = 10) Recomm- (n = 10)
1643c (n = 10) Recomm- (n = 10) Certified ended
Certified ended
Pt
Set 2 Au
B 119.0 ± 1.4 116.8 ± 2.4 Tl
Al 114.6 ± 5.1 121.2 ± 6.6 Bi
P Th 18.5 18.7 ± 0.4
Cr 19.0 ± 0.6 18.8 ± 0.6 3.4 3.16 ± 0.28 U 4.6 4.66 ± 0.18
Fe 106.9 ± 3.0 98.3 ± 6.1
Mn 35.1 ± 2.2 33.3 ± 2.1
Ni 60.6 ± 7.3 63.2 ± 5.5 1.5 1.62 ± 0.39
Cu 22.3 ± 2.8 23.2 ± 0.9 4 4.16 ± 0.49
Zn 73.9 ± 0.9 79.0 ± 6.1 224 232 ± 21
As 82.1 ± 1.2 77.8 ± 3.1 Results and discussion
Se
Ag 2.21 ± 0.3 2.18 ± 0.3 Two main features confirm the applicability of ICP-MS
Cd 12.2 ± 1.0 11.8 ± 1.0 0.6 0.61 ± 0.04 for water analysis: the multi-elemental detection capabil-
Sb 0.4 0.39 ± 0.06 ity and the sensitivity. The multi-elemental detection ca-
Ba 49.6 ± 3.1 48.6 ± 1.3 55 54.2 ± 1.6 pability has been optimized grouping the analytes in three
Hg sets and adjusting the residence time for each one (Table 3).
Pb 35.3 ± 0.9 34.9 ± 1.1 39 37.8 ± 1.9 After several combinations the best strategy found was
Set 3 the determination in three steps of sixty-seven elements,
Li 16.5 ± 1.0 15.9 ± 0.7 93 94.2 ± 3.0 as described above. This strategy is compatible with the
Be 23.2 ± 2.2 22.4 ± 2.1 12 11.8 ± 0.4 legislation requirements and enables one to obtain a fin-
Ti gerprint of the water, and, in addition, to determine many
V 31.4 ± 2.8 31.8 ± 2.7 3 2.82 ± 0.22 of the parameters generally measured in water (major ele-
Co 23.5 ± 0.8 24.0 ± 0.7 0.2 0.21 ± 0.02 ments).
Ga 39 38.6 ± 2.12 The detection limits are reported in Table 4, and are
Ge three times the standard deviation estimated from ten
Br replicate measurements of the blank (1% v/v HNO3). The
Rb 11.4 ± 0.2 11.5 ± 0.2 152 156 ± 8 detection limits by ICP-MS range between 0.01 and
Sr 263.6 ± 2.6 260.1 ± 4.5 3 2.87 ± 0.33 0.1 µg/L for numerous trace elements. The poorest detec-
Y 184 173 ± 5 tion limits are found for some major elements (e.g., S and
Zr 780 796 ± 19 K), and for some analytes of interest in waters, which are
Nb present as minor elements, such B, Al, Fe, and Br. Fortu-
Mo 104.3 ± 1.9 102.8 ± 4.7 2.5 2.41 ± 0.11 nately, the concentrations generally occurring in natural
Sn 13 13.4 ± 0.9 waters of these elements are also high [19] (Table 4), and
Te thus they can be adequately determined using ICP-MS.
I On the other hand, these detection limits are appropriate
Cs 3 2.83 ± 0.19 for the elements generally indicated in legislation (B, Al,
La 59 58.9 ± 0.9 P, Cr, Fe, Mn, Ni, Cu, Zn, As, Se, Ag, Cd, Sb, Ba, Hg, and
Ce 154 153.8 ± 1.7 Pb). Nevertheless, many potential fingerprint elements in
Pr 22.2 21.8 ± 0.4 the ground and surface water are at or below the detection
Nd 92 91.6 ± 0.3 limits. Although there are exceptions, e.g., REE in surface
Sm 24.2 24.5 ± 0.4 waters of Famatina Range in Argentina [20], the concen-
Eu 2 2.08 ± 0.06 trations of elements such Be, Ga, REE, Pt or Bi are ex-
Gd 26 25.9 ± 0.3 tremely low in natural waters. Some of these elements are
Tb 4.8 4.76 ± 0.06 of particular interest to fingerprint the groundwater
Dy 29 29.5 ± 0.3 sources, such the REE [21]. In these cases, the analytical
Ho 6.5 6.38 ± 0.09 strategy described should only be used to screen the water
Er 17.7 17.9 ± 0.3 composition, and for more detailed studies, if necessary,
Tm 2.6 2.62 ± 0.04 preconcentration procedures will be required [10].
Yb 17.4 17.3 ± 0.3 Precision is also reported in Table 4. This has been es-
Lu 2.45 2.46 ± 0.04 timated taking into account the relative standard deviation
Hf 27.9 28.4 ± 1.4 (RSD) of twenty analyses of an in-house reference water
Ta
sample (laboratory tap water) carried out on different days
W 1.5 1.53 ± 0.04
under routine working conditions over a period of three
606
months. The precision in Set 1 is typically over 10% for
SO42– and K, mainly as a consequence of the low degree
of ionization of sulfur (14%) in a plasma of argon [22],
and the isobaric interference of argon on 39K. In Set 2, a
precision of 10% or more is found for Fe, Zn, Se, Ag, and
Hg. A similar degree of precision is shown by Be, Ti, Br,
Sr, I, and Th in Set 3. On the other hand, the REE are the
group of analytes with lower RSD values.
In relation to the closeness of agreement between the
concentrations found and the accepted reference or true
values, a combination of water and rock reference materi-
als was used due to the lack of a single reference material
for all analytes (Tables 5 and 6). In the case of the granite
AC-E, the uncertainty associated with sample digestion
must be taken into account. Despite this combination of
reference materials, not all the analytes were covered. The
control of the analytes not included in that combination
was performed using an in-house standard, in which the
concentrations of Si, P, Se, Br and I were determined be-
forehand by the method of standard addition, and consid-
ering previously spiked concentrations of Ge, Nb, Te, Ta,
Pt, Au, Tl, Bi, and Hg. In all cases the results were within
± 10% of the known values.
The Set 1 analysis carried out of CRM 616 and CRM
617 produced results that were within ± 5% of the certi-
fied values (Table ). The highest values were shown by
potassium (3.45 and 4.13% for CRM 616 and CRM 617,
respectively). The results of the analysis of Set 2 and Set
3 performed on the reference materials 1643c and AC-E
are presented in Table 6, which were within ±10% of the
known values. Values higher than 5% were shown by Al
(5.76%), Fe (8.04%), Mn (5.13%), Zn (6.90%) and As
(5.24%) in the water standard 1643c, while in the granite
AC-E this situation occurred for Cr (7.06%), Ni (8.08%),
V (6.00%), Y (5.98%) and Cs (5.67%). The granite AC-E
cannot be used to control titanium due to the high content
of this element in the rock. Consequently, titanium was
controlled by the in-house standard (7.23%).
If the concentration of an element was above the high-
est calibration concentration, the sample was diluted and
rerun. These reruns are obviously time-consuming. In or-
der to improve the developed strategy, the availability of
specific conductivity of water samples has been very use-
ful from a practical point of view. Thus, samples with
high values of this parameter (> 2000 µS/cm) can be ade-
quately diluted prior to the analysis.
Conclusions
ICP-MS is an excellent analytical technique for surveying
a large number of elements in water. The strategy devel-
oped, based only on ICP-MS, could in some laboratories
be a feasible alternative to the complementary use of ICP-
MS and ICP-AES, whose advantages and disadvantages
have been described previously [23, 24].
Acknowledgements This work was funded by the Spanish Min-
istry of Science and Culture (R+D National Plan, Project NUPAS,
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Ref. HID-96–1290). The authors would like to thank M.E. Medina
and M. Britos for their technical assistance in the preparation of
the manuscript, and to the reviewers and editor for their valuable
comments.
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