Inductively Coupled Plasma Emission Spectroscopy

(ICP-AES) - determination of Fe, Co and Ni in the

environmental water samples
Introduction
Inductively coupled plasma atomic emission spectrometry (ICP-AES) is an analytical
technique used for the detection of trace metals. It is a type of emission spectroscopy that
uses inductively coupled plasma to generate excited atoms and ions that emit radiation of a
wavelength particular to that element. The intensity of that radiation emitted indicates the
concentration of that element in the sample being analysed. [1] Inductively coupled plasma
mass spectrometry(ICP-MS) is a type of mass spectrometry which is capable of detecting
metals and several non-metals at concentrations low as part per trillion. This is achieved by
ionizing the sample with inductively coupled plasma and then using a mass spectrometer to
separate and quantify those ions.[1]However, in this experiment, the concentrations of Fe,
Co and Ni in environmental water samples are determined using the ICP-AES analytical
technique.

Experimental procedure
Preparation of standards

From the stock solution containing 10ppm of Ni, Co, and Fe, standards of 0.1ppm, 0.5ppm,
1.0ppm and 2.0ppm were prepared. These standards were run in the ICP-AES and emission
spectra were measured. Thereafter, calibration curves for Ni, Co and Fe were obtained. The
sample concentration was measured.

Results
The concentrations determined in the water samples[2]

Ni= not detected

Co= 0.022ppm

Fe=0.013ppm
 Table 1: The measured emission spectra and the corresponding concentrations of the
Nickel in water sample

concentration(ppm) Intensity(counts/sec)
0.1 3128.83
0.5 12798.7
1 25102.9
2 52191.7

Table 2: The measured emission spectra and corresponding concentrations of Cobalt in water
sample

Concentration(ppm) Intensity(counts/sec)
0.1 12726.8
0.5 63707.6
1 126024
2 259377

Table 2: The measured emission spectra and corresponding concentrations of Iron in water sample

concentration(ppm) intensity(counts/sec)
0.1 7835.35
0.5 42443.2
1 86620.2
2 178123
 Figure 1: the calibration of Nickel

intensity vs. concntration

60000

50000 f(x) = 25890.403960396 x + 4.16893564357451

intensity(counts/sec)

R² = 0.999186972749752
40000

30000

20000

10000

0
0 0.5 1 1.5 2 2.5
concentration(ppm)

Figure 2: the calibration of Nickel

intesity vs. concentration

300000

250000
f(x) = 129828.02970297 x − 1386.37673267323
intensity (counts/sec)

R² = 0.999753896565136
200000

150000

100000

50000

0
0 0.5 1 1.5 2 2.5
cocnentration(ppm)
 Figure 3: the calibration of Iron

intensity vs. concentration

200000
180000
160000 f(x) = 89778.099009901 x − 2044.85160891089
intensity(counts/sec)

140000 R² = 0.999841064600676
120000
100000
80000
60000
40000
20000
0
0 0.5 1 1.5 2 2.5
concentration(ppm)

Answers to questions
a) ICP-MS has a lower detection limit primarily because ‘’there is no fundamental source of
continuum background in ICP/MS (i.e., no source of continuum mass to charge ratio ions)’’.
This is due to the fact that in ICP-MS the quadruple only detects those ions that are analysed
for; no stray (unwanted) ions can pass through to the detector therefore only and only those
ions being analysed for will be detected.
b) The quadruple detection in the ICP-MS is the use of a high frequency mass filter as the mass
spectrometer to separate the ions that are selected for analysis on the basis of their mass to
charge ratios.
c) The faraday cup is an ion collector which detects the ions from the high frequency filter
(quadruple) through direct current whereas a secondary electron multiplier is a vacuum-
tube that multiplies incident charges in the following process: a single electron can, when
bombarded on a secondary emissive material, induce emission of roughly 1-3 electrons. If an
electric potential is applied between this metal plate and induce secondary emission of still
more electrons. If repeated a number of times, a shower of electrons is collected by a metal
anode, all having been triggered by just one. [3]
 Discussion
The concentrations of nickel, cobalt and iron in environmental water samples were
determined using the ICP-AES analytical technique. The calibration curves, in particular,
were used to perform such a determination and the results are found to be 0.022ppm for
Cobalt and 0.013ppm for Iron. However, the concentration of Nickel, as according to the
determinations, was not detected.

Probable errors

The reason why nickel was not detected may be due to spectral overlap, commonly known
as isobaric interferences. Considering the wide linear dynamic range characteristic of ICP-
AES, which allows measurements of trace quantities of one analyte and major quantities of
another simultaneously( without sample dilution, separation, or preconcentration)
substantiates the occurrence of spectral overlap. For instance, in this experiment, Nickel is
analysed together with Iron. And according to John W. Olesik[6] the spectral signal due to
Iron is bound to overlap with that due to Nickel because the most abundant isotope of
Nickel (68.077% natural abundance)[4] has the same mass as the most abundant Iron isotope
(91.754% of 56Fe)[5]. Additionally, the natural abundance of Iron is greater than that of
Nickel, validating the presumption that Iron signal may have overlapped with the Nickel
signal. Nevertheless, the Environmental Protection Agency reports that the concentration of
Nickel in environmental water should be 0.1ppm[7].

It has also been discovered that although Iron was detected, its concentration is very low as
compared to the expected concentration. According to the Environmental Protection
Agency, the concentration of Iron in water is 0.30 ppm but the measured concentration of
iron in sample water was found to me 0.013ppm – a concentration much lower than that
reported in literature. However, the concentration of cobalt determined is 0.022ppm and it
is very more than the concentration as reported by the Environmental Protection Agency
(0.002ppm)[7].

Calibration curves

The R2 value of the intensity versus concentration plots for Nickel, Cobalt and Iron standards,
respectively, are 0.9992, 0.9998 and 0.9998. All these values are close to unity (one). This
thus indicates that the concentrations of the standards used for calibration are linearly
related and fit exceptionally well on a straight line. In so saying, the calibration curves are
deemed worthy to bring about reliable metal concentrations in the samples being analyzed.
 Improvement

Isobaric interferences may be minimized by:

 Using high resolution spectrometers i.e. resolving for iron-nickel isobaric effect, use a
resolution of 29 000 M /∆ M [6]
 Identifying the interfering element
 Measure the intensity of a non-interfering major isotope of the element of interest
 Select only spectral lines with sufficient sensitivity
 Use cleaned glassware

Conclusion

In determination of trace metals using ICP-AES, care should be taken on accuracy in

measurements to minimise the usage of inaccurate dilution factors. It should also be
appreciated that ICP-AES is not as sensitive as ICP-MS. Therefore, careless dilution is bound
to yield very low concentrations if not no detection at all.

Furthermore, prior knowledge on the metals being analysed should be acquired together
with the possible interferences a metal of interest is likely to have, considering the fact that
several metals can be analysed simultaneously. This, as a result, enables the usage of
specified resolutions so as to avoid the noted probable spectral interferences.

References
1) http://pubs.acs.org/doi/pdf/10.1021/ac00001a711 , 06 March 2014
2) Oabile Mothoagae, 668955
3) http://en.wikipedia.org/wiki/Electron_multiplier , 06 March 2014
4) http://en.wikipedia.org/wiki/Isotopes_of_nickel, 06 March 2014
5) http://en.wikipedia.org/wiki/Isotopes_of_iron , 06 March 2014
6) J W Olesik, Elemental Analysis Using An Evaluation And Assessment of Remaining Problems,
pp. 14-16
7) www.epagov//ttnatw01/hlthef/cobalt.html , 07 March 2014