Analytica Chimica Acta 357 (1997) 151±156

Standard additions in ¯ow injection analysis

with atomic absorption spectrometry
B. Haghighi, N. Maleki, A. Safavi*
Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71454, Iran

Received 28 August 1997; received in revised form 1 September 1997; accepted 17 September 1997

Abstract

A standard additions method in ¯ow injection atomic absorption analysis has been described. The proposed method was
applied to the determination of calcium in synthetic samples with and without chemical interference and the results were
compared with those obtained by the conventional standard additions method in atomic absorption spectrometry. The
in¯uence of parameters of the ¯ow injection system was studied. The results showed that the proposed method was
independent of such parameters. The relative standard deviations within and between analyses were found to be 1.61 and
1.81%, respectively, at the 1.5 mg mlÿ1 Ca level. The method was used for the determination of calcium in tap water. # 1997
Elsevier Science B.V.

Keywords: Flow injection analysis; Atomic absorption spectrometry; Standard additions

1. Introduction a manual standard addition procedure is cumbersome

The standard additions method (SAM) [1] is
exceedingly important particularly in the areas of
instrumental methods such as spectrophotometry,
atomic absorption spectrometry (AAS), and electro-
chemistry where the inherent utility of the instrument
may be reduced by a poor set up of the chemical
system (sample matrix effects). A SAM requires
successive additions of known amounts of the analyte
to the sample. If a linear response of the detection
system is assumed, a linear regression calculation
permits the original concentration to be evaluated
regardless of the matrix effect, while also providing
information on the magnitude of this effect. However,
*Corresponding author. Fax: +98 (071) 20027.
and is also wasteful.
The term `Flow Injection Analysis' (FIA) [2] is
generally understood to encompass analytical techni-
ques in which a discrete sample volume is injected into
a continuously ¯owing carrier stream after which the
sample undergoes controlled mixing with a reagent
(reagents) and usually the reaction product is mea-
sured by a ¯ow-through detector. The increasing
interest in FIA is due to its characteristics of simpli-
city, versatility, cost, precision, and high sampling
rate. This high sample throughput makes FIA parti-
cularly suitable for long runs of samples, e.g., in
hydrological, biomedical, agronomic and geological
work.
The feasibility of using standard additions in FIA
has been demonstrated by several workers, who have

0003-2670/97/$17.00 # 1997 Elsevier Science B.V. All rights reserved.

PII S0003-2670(97)00552-7
152 B. Haghighi et al. / Analytica Chimica Acta 357 (1997) 151±156
pointed out that most of the drawbacks of the manual
method are minimized in an FI system, which always
yield highly precise measurements after rapid proces-
sing of small sample volumes. Different ¯ow injection
methods [3] have been proposed for calibration by a
SAM;
1.1. Merging zone
The simplest form of a merging zone SAM mani-
fold was used by Zagatto et al. [4]. The method was
applied for the determination of Cu, Ni and Zn by the
so-called `generalized SAM', which compensates for
both matrix and spectral interferences, in conjunction
with inductively coupled plasma atomic emission
spectrometry (ICP-AES). In order to vary the concen-
tration of standard, a zone sampling manifold was
combined with the merging zone principle by Gine et
al. [5]. The manifold was again used for the imple-
mentation of the generalized SAM, this time for the
determination of 19 elements in rock samples by ICP-
AES [6].
1.2. Reagent injection FIA
The simplest version of this method (a single line
manifold) was ®rst described by Tyson [7] and has
been used for the determination of Ca in iron ore [8],
Cr in steel [6], Mg in aluminate [9], Ca in cement [10],
Si in phosphoric acid [11], and Ba and Cr in river
sediment and coal ¯y ash [12]. In this technique, the
sample is used as the carrier stream and standards are
injected. A merging stream version of the method has
been described by Araujo et al. [13] for the determi-
nation of Na, K and Ca by ¯ame AES.
1.3. Zone penetration method
Fang et al. [14] used the manifold which produced
an analyte solution zone sandwiched between water
(in front) and standard (at the rear). Based on the
overlapping zone, it is possible to calculate the con-
centration of the standard at a point of known disper-
sion coef®cient of the sample. The concentration of
sample can be calculated from the concentration of
standard.
The main purpose of this paper is to introduce a
method for standard additions in ¯ow injection
atomic absorption analysis. The idea of the proposed
method is based on the `compensation method'
[15], in which the pumping rate is less than the
nebulization rate. The standard solutions are injected
via a rotary valve into the carrier stream of water, and
the sample solution is sucked by the compensation
branch. The ¯ow rate of the compensation branch is
just suf®cient to compensate the ¯ow rate of carrier
stream and so the nebulization rate is steadily kept
constant.
2. Experimental
2.1. Apparatus
A Unicam SP9 atomic absorption spectrometer and
a Perkin±Elmer R100 recorder were employed. The
atomic absorption spectrometer was operated as
recommended by the manufacturer for maximum
sensitivity with an acetylene/nitrous oxide ¯ame. A
Desaga PLG±Peristaltic pump with Desaga silicone
tubing E, Rheodyne PTFE rotary valve type 50 and
Supelco PTFE tubing (0.5 mm i.d.) with couplings
were used in the FI system.
2.2. Reagents
The stock standard solution of calcium (1000 mg
mlÿ1) was prepared by dissolving 0.5892 g of
Ca(NO3)2
4H2O (Fluka, purum p.a.) in 100 ml of
triply distilled water. The working standard calcium
solutions were prepared by appropriate dilution of the
stock solution with the pure water. The stock solution
of sodium (50 mg mlÿ1) as the chemical interference
was prepared by dissolving 18.4849 g of NaNO3
(Merck, zur analyse) in 100 ml of triply distilled
water.
The sample solutions without interference were
prepared by taking known volumes of standard cal-
cium solutions and diluting to the appropriate volume
with water. The sample solutions with chemical inter-
ference were prepared by mixing known volumes of
standard calcium and sodium solutions. The concen-
tration of sodium in sample solutions with chemical
interference was kept constant at 2000 mg mlÿ1. Tri-
ply distilled water was used in all experiments as the
carrier stream.
 B. Haghighi et al. / Analytica Chimica Acta 357 (1997) 151±156 153

Fig. 1. Manifold of the standard additions method in flow injection atomic absorption spectrometry. P, pump; I, injection valve; C1 and C2,
mixing coils; T, three-way connector; AAS, atomic absorption spectrometer; Vs, flow rate of carrier solution; Vx, flow rate of compensation
branch; Vn, nebulization rate.

2.3. Manifold procedure and mathematical concepts
The manifold based on the compensation method
was used and is shown in Fig. 1. The calibration
procedure is performed in three stages. At ®rst, water
is used as carrier and compensation eluent. The ¯ow
rate of carrier stream is adjusted to Vs, which is less
than the aspiration rate of the nebulizer (Vn). Sample
solution with concentration Cx is injected via the
rotary valve. The response is shown as X in Fig. 2.
In the second stage, sample solution is used as eluent
from the compensation branch, the ¯ow rate of which
is Vx. The steady state response to this is shown as Y in
Fig. 2. The total ¯ow rate into the nebulizer Vn (ˆ Vs
‡ Vx) is steadily kept constant, and thus as Vs is
increased, Vx is decreased and vice versa. In the last
stage, while water is used as carrier and sample as
compensation eluent, a standard solution with con-

Fig. 2. Typical recorder trace of the proposed standard additions method. For details see text.
154 B. Haghighi et al. / Analytica Chimica Acta 357 (1997) 151±156

centration Cs is injected via the rotary valve. The
transient response to this is shown as S in Fig. 2.
From a mathematical point of view, in an instrument
such as an atomic absorption spectrometer [1], the
response signal (R) is linearly related to the concen-
tration of species of interest:
R ˆ kC
in which k is the constant of proportionality. So, in the
similar manner,
kCx Vs kCx Vx
Xˆ ; Yˆ
DVn Vn
;in which D is the diffusion coef®cient of the species
through the ®rst and second mixing coils. The plot of
signal (S) vs. Cs yields the calibration equation with a
slope of kVs/DVn and intercept of kCxVx/Vn, i.e.
Cs Vs Cx Vx
S ˆ k… ‡ †:
DVn Vn
Therefore, X ˆ SlopeCx and Cx ˆ Slopeÿ1X.
3. Results and discussion
The concentrations of calcium of a series of work-
ing solutions were determined by the proposed
method and the results were compared with the results
of a conventional SAM (an ordinary standard addition
procedure without using a ¯ow system) by AAS. In
these studies, the in¯uence of parameters of the FI
system such as the ¯ow rate of the carrier stream,
length of the mixing coils and sample volume on the
Table 1
Influence of flow rates of carrier solution on the results for determination of calcium with and without chemical interference by the proposed
method and comparison with the results of a conventional standard additions method (CSAM) by atomic absorption analysis. Conditions; C1,
50 cm; C2, 30 cm; sample volume, 200 ml; Vn, ca. 6.4 ml minÿ1
results were investigated. Details of these studies are
presented in the following section.
3.1. Effect of flow rate of carrier solution
As was noted before, Vx is a function of Vs, while Vn
is constant. Three levels of Vs were chosen, in which
VsˆVx (approximately), Vs>Vx and Vs<Vx. The in¯u-
ence of Vs on the results was investigated. The results,
which are summarized in Table 1, show that at any Vs,
while Vs<Vn, the proposed method is in good agree-
ment with the conventional SAM, and the proposed
method is independent of Vs or Vx.
3.2. Effect of lengths of mixing coils C1 and C2
Mixing coil C1 is used to damp the shock caused by
the injection valve and mixing coil C2 is used to
improve the mixing of standard and sample solutions.
In addition to this effect, the dispersion coef®cient is
affected by the change of the lengths of C1 and C2. The
effect of the lengths of C1 and C2 on the results were
studied and summarized in Table 2. The results of the
proposed method are in good agreement with the
results of a conventional SAM and independent of
the lengths of C1 and C2.
3.3. Effect of sample volume
The in¯uence of sample volume on the results of the
proposed method was investigated and is summarized
in Table 3. The results of the proposed method are

Flow rates (mg mlÿ1 Ca)

Without chemical interference With chemical interference

CSAM Proposed method CSAM Proposed method
VsˆVx 2.08 a 1.98 (0.9994) 3.30 d 3.18 (0.9996)
Vs>Vx 2.17 b 2.18 (0.9993) 3.38 d 3.16 (0.9995)
Vs<Vx 2.38 c 2.31 (0.9999) 3.34 d 3.20 (0.9985)
Numbers in the parentheses are correlation coefficients for the linear regressions. The number of points in each regression is 6. The
concentrations present were:
a
2.00.
b
2.20.
c
2.40.
d
3.20 mg mlÿ1.
 B. Haghighi et al. / Analytica Chimica Acta 357 (1997) 151±156 155

Table 2
Influence of lengths of mixing coils C1 and C2 on the results of
determination of calcium with and without chemical interference
by the proposed method. Conditions; C2, 30 cm (for studying the
effect of C1); C1, 25 cm (for studying the effect of C2); sample
volume, 200 ml; Vs, 3.2 ml minÿ1
Table 3
Influence of sample volume on the results of determination of
calcium with and without chemical interference by the proposed
method. Conditions; C1, 25 cm; C2, 15 cm; Vs, 3.2 ml minÿ1
Sample volume (ml) mg mlÿ1 Ca

Length of C1 (cm) mg mlÿ1 Ca Without chemical With chemical

interference a interference b
Without chemical With chemical 50 2.74 (0.9996) 3.39 (0.9998)
interference a interference b 100 2.71 (0.9993) 3.60 (0.9979)
25 2.01 (0.9994) 3.16 (0.9992) 200 2.72 (0.9998) 3.49 (0.9985)
50 2.01 (0.9996) 3.19 (0.9991) 400 2.72 (0.9994) 3.39 (0.9991)
100 2.04 (0.9998) 3.09 (0.9993)
The concentrations of Ca by the CSAM with AAS were found to be
200 2.04 (0.9996) 3.20 (0.9995) a
, 2.70; b, 3.50 mg mlÿ1. The concentrations present were a, 2.80; b,
3.40 mg mlÿ1. Numbers in parentheses are the correlation coeffi-
cients of the regressions. The number of points in each regression is
Length of C2 (cm) mg mlÿ1 Ca 6.
Without chemical With chemical
interference c interference d
15 2.09 (0.9998) 2.89 (0.9999) deviations of six groups of four injections of
30 2.13 (0.9993) 3.04 (0.9993) 2 mg mlÿ1 of calcium was found to be 1.81%.
60 2.21 (0.9991) 3.02 (0.9997)
80 2.19 (0.9980) 2.90 (0.9999) 3.5. Application
The concentrations of Ca by the CSAM with AAS were found to be
a
, 2.08; b, 3.21; c, 2.17; d, 2.97 mg mlÿ1. The concentrations present The proposed method was applied to the determi-
were a, 2.00; b, 3.20; c, 2.20; d, 3.00 mg mlÿ1. Numbers in nation of calcium in two samples of tap water. Table 4
parentheses are the correlation coefficients of the regressions. The
number of points in each regression is 6.
shows the results of analyses which are compared with
the results of conventional SAM by AAS.

independent of the sample volume and in good agree-

ment with the results of a conventional SAM. 4. Conclusion

3.4. Precision The proposed standard additions method for atomic

The relative standard deviations of twelve injec-
tions of 1.5 mg mlÿ1 calcium with and without
2000 mg mlÿ1 sodium as the chemical interferent,
while the concentration of calcium in the sample
reservoir was 2.5 mg mlÿ1 were found to be 2.15
and 1.61%, respectively. The average relative standard
absorption spectrometry based on ¯ow injection com-
pensation method is simple, reliable, accurate and
precise. The method is applicable under any condi-
tions with respect to carrier ¯ow rate, path length and
sample volume. The use of water as the carrier stream
minimizes the carry over of the sample which is
sucked from the compensation branch, which is

Table 4
Results of water samples analyses by the proposed method and the conventional standard additions method (CSAM) by atomic absorption
analysis. Conditions; C1, 25 cm; C2, 15 cm; sample volume, 50 ml; Vs, 3.2 ml minÿ1

Sample no. mg mlÿ1 Ca by RSD mg mlÿ1 Ca by RSD

CSAM (nˆ6, %) Proposed method (nˆ6, %)
1 0.9197 (0.9995) 0.75 0.9220 (0.9996) 0.82
2 0.9134 (0.9996) 0.93 0.9152 (0.9998) 0.90
Numbers in the parentheses are the correlation coefficients of the regressions. The number of points in each regression is 6.
156 B. Haghighi et al. / Analytica Chimica Acta 357 (1997) 151±156

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