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If the palladium nitrate - magnesium nitrate modifier is applied to the analysis of water, a common set of
conditions for the determination of As, Cu, Mn, Pb, Sb and Se can be used. For Cd and TI lower pyrolysis and
atomisation temperatures are required. Twenty-one possible interferents were investigated at maximum
concentrations between 1 and 500 mg 1-1 and only two were found to have an effect greater than +lo%. The
determination of TI was affected by sodium chloride at concentrations above 100 mg 1-1, hence the addition of
Li is recommended to control this interference. Five mg I-’ of Fe decreased the Se signal by about 15% when
deuterium-arc background correction was used but had no influence in an instrument with Zeeman-effect
background correction. For an instrument with continuum source background correction it was also
necessary to determine Cu using the secondary resonance line at 327.4nm because of spectral interference
due to Pd at the primary resonance line. Precisionwas about 1% in the optimum working range and between 2
and 5% at 0.05 A s. Detection limits (2.33o )were 1.2pg I-’ for As, 0.02 pg 1-1 for Cd, 0.3 pg 1-1 for Cu, 0.45 pg I-’
for Mn and Pb, 1.2 pg 1-1 for Sb, 0.6 pg 1-1 for Se and 0.8 pg 1-1 for TI.
Keywords : Graphite furnace atomic absorption spectrometry; palladium nitrate - magnesium nitrate
modifier; water analysis; background correction; arsenic, cadmium, copper, manganese, lead, antimony,
selenium and thallium determination
Graphite furnace atomic absorption spectrometry (GFAAS) most of the more recent publications apply only to one single
was applied soon after its introduction to analytical chemistry element, discussing ways to eliminate previously observed
to the analysis of natural water because it made possible the interferences. Over the years this has resulted in a confusing
direct determination of numerous trace elements without diversity of individual procedures making use of a variety of
pre-concentration.1-8 Several workers have since reported the modifiers.
routine use of GFAAS for monitoring surface water qual- For the determination of lead, the element about which the
ity.5-8 It was also realised at an early stage that concomitants largest number of publications have appeared, ascorbic acid,10
would cause interferences, hence the analyte addition tech- phosphoric acid” and ammonium phosphate12 have been
nique was recommended for their control.68 This, however, used. The most frequently recommended modifier, however,
made GFAAS time consuming and, hence, less attractive for is lanthanum in nitric acid solution which appears to be
routine purposes. Another drawback of the early graphite remarkably effective in the presence of a variety of concomi-
furnaces was that the sensitivity was not adequate for the tants.13-16 Lanthanum-impregnated tubes have also been
determination of some of the trace elements of interest at investigated as an alternative to the addition of a modifier.17
concentrations <1 pg 1-1. The lanthanum - nitric acid modifier has also been applied
The progress made in instrumentation over the past decade to the determination of cadmium in water16 although ammo-
has, among other things, brought about a substantial improve- nium phosphate mixed with magnesium nitrate is the modifier
ment in signal to noise ratios so that now detection limits more frequently used for this element. 18 Magnesium nitrate is
should be sufficiently low for most applications. Another even the recommended modifier for the determination of man-
greater step forward has been the freedom from interferences ganese9.12 whereas copper is usually determined without the
achieved with the stabilised temperature platform furnace addition of a modifier.12 Nickel is often used as the modifier
(STPF) concept proposed by Slavin et aZ.9 Loss of the analyte for metalloids such as selenium,19,20arsenic21and antimony,12
element during thermal pre-treatment is prevented by an and sulphuric acid is recommended for the determination of
appropriate chemical modifier which permits the use of high thallium.12
pyrolysis temperatures, and the sample is atomised from a This diversity of modifiers and of the associated pyrolysis
L’vov platform using a high heating rate and interrupted purge and atomisation temperatures does not encourage a genera1
gas flow. These conditions allow calibration against matrix- acceptance of GFAAS and the STPF concept for routine
free reference solutions (solutions of the analyte element analysis. In addition, some of the recommended modifiers
containing the same acid and modifier concentration as the have side-effects that make their application less attractive.
samples but no other concomitants) when integrated absor- Lanthanum, for example, has been found to have a substantial
bance (peak area) is used for evaluation of the absorption corrosive effect on graphite tubes and platforms, which may
pulse. seriously limit the useful lifetime of these components.22
This finding has resulted in a great deal of analytical work to Nickel must occasionally be determined at very low concentra-
evaluate the applicability of the STPF concept to a variety of tions, which becomes impossible after this element has been
analytical applications including water analysis. However, used in large excess as a modifier. Finally, phosphates and
~~~
phosphoric acid are often not available in a sufficiently pure
* For Part 1 of this series, see reference 31. form and thus further purification is required before use.
-f On leave from the Department of Chemical Engineering, Indian These limitations have led to an intense search for GFAAS
Institute of Science, Bangalore, India. modifiers that can be applied to a larger number of elements
696 View
JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, AUGUST Article
1988, VOL.Online
3
and which do not have the disadvantages mentioned above. The standard stock solutions of 1000 mg 1-1 were prepared
Stimulated by the work of Shan and Ni,23>24Jin and Ni25 and from Titrisol concentrates (Merck, Darmstadt, FRG). Refer-
Shan and CO-workers26-29we have investigated palladium as a ence solutions were prepared daily by diluting the stock
possible universal modifier for most of the volatile elements. It standard with 0.2% mlV nitric acid and then adding the same
has recently been proposed that a mixture of palladium nitrate amounts of acid and modifier as to the sample solutions.
and magnesium nitrate is applicable for at least nine ele-
ments.30 This modifier also makes the use of sufficiently high
pyrolysis temperatures possible, which are similar for all these Results and Discussion
elements. Additional advantages are that high-purity reagents Graphite Furnace Programme Optimisation
are available and neither palladium nor magnesium is fre-
quently determined using GFAAS. This modifier has also The palladium nitrate - magnesium nitrate modifier allows the
been used successfully for the determination of antimony, use of higher pyrolysis temperatures than previously recom-
mended modifiers for almost all of the elements investigated
arsenic, selenium and thallium in coal fly ash, city waste
in this work. Although it is not usually necessary that the
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Table 4. Calibration data for low and high standards including integrated absorbance and relative standard deviation (RSD) of five replicate
determinations
Table 6 . Interference studies for the determination of trace elements in water. All results are % integrated absorbance with the absorbance of
the matrix-free reference solution being 100%. (The %RSD for five replicate determinations is given in parentheses)
Interferent Analyte element
Compound concentration/
Interferent used mg 1-1 As Cd cu Mn Pb Sb Se T1
C1 . . . . .. .. NaCl 500 102 (3) 101 (2) 102(1) 99 (2) 100 (1) 103 (3) 105 (2) 74 (2)
SO4 . . . . . . .. &SO4 300 101 (2) 102 (2) 99 (1) 91 (2) 96 (1) 90 (2) 95 (2) 103 (2)
SiOz . . . . . . .. Na2Si03 30 104 (2) 104 (1) 99 (2) 101 (1) 100 (2) 102 (1) 99 (1) 100 (3)
C03 . . . . . . .. CaCO, 500 103 (1) 97 (1) 99 (1) 100 (2) 100 (1) 96 (3) 100 (1) 103 (2)
Zn .. .. .. . . ZnClz 15 104 (1) 100 (2) 98 (2) 100 (2) 102 (1) 95 (1) 102 (1) 91 (1)
F , . .. . . .. NaF 10 102 (3) 99 (1) 96 (1) 101 (3) 101 (1) 104 (2) 103 (2) 99 (1)
cu .. .. .. .. cuc1, 5 104 (4) 97 (2) - 104 (3) 100 (1) 99 (2) 104 (1) 97 (1)
Fe .. .. .. .. FeC1, 5 102 (2) 99 (2) 100 (1) 95 (1)
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2;
50 , I , , ,I
5 10 20 50
Fe concentrationirng I-'
.-c>. Fig. 3. Influence of iron on the determination of selenium. A ,
-: I
50
I
study possible, not only with a single modifier but also using
the same graphite furnace programme. Moreover, the use of
this common temperature proqamme does not result in any
degradation in either the sensitivity or any other performance
characteristics compared with conditions optimised for each
individual element. The modifier can also be used for the
1 B A remaining two elements, cadmium and thallium, only it is
: O
...........,.. ........................................... *.,- ...............,.....,.......... .......
I.
27 Shan, X.-Q., Ni, Z.-M., and Zhang, L., At. Spectrosc., 1984,5, 37. Fernandez, F. J., and Giddings, R., At. Spectrosc., 1982,3,61.
1. 38. Fernandez, F. J., and Beaty, M. M . , Spectrochim. Acta, Part B,
28. Shan, X.-Q., Ni, Z.-M., and Zhang, L., Talanta, 1984,31,150. 1984, 39,519.
29. Shan, X.-Q., Ni, Z.-M.., and Yvan, Z.-N., Anal. Chiin. Acta, 39. Bauslaugh, J., Radziuk, B., Saeed, K . , and Thomassen, Y . ,
1985, 171, 269. Anal. Chim. Acta, 1984, 165, 149.
30. Schlemmer, G., and Welz, B., Spectrochim. Acta, Part B, 1986, 40. Saeed, K . , and Thomassen, Y., Anal. Chim. Acta, 1981, 130,
41, 1157. 281.
31. Welz, B., Schlemmer, G., and Mudakavi, J. R., J . Anal. At. 41. The Standing Committee of Analysts, The Department of
Spectrom., 1988, 3, 93. Environment, 2 Marsham Street, London SWlP 3EB, UK,
32. Voth-Beach, L. M . , and Shrader, D. E . , J. Anal. At. personal communication.
Spectrom., 1987, 2 , 45.
33. L’vov, B. V., Spectrochim. Acta, Part B, 1978, 33, 153.
34. Manning, D. C., and Slavin, W., unpublished data.
35. Manning, D. C., At. Absorpt. Newsl., 1978, 17, 107. Paper J7l161
36. Fernandez, F. J., Bohler, W., Beaty, M. M., and Barnett, Received December 14th, 1987
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