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JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, AUGUST 1988, VOL. 3 695

Palladium Nitrate = Magnesium Nitrate Modifier for Graphite Furnace


Atomic Absorption Spectrometry
Part 2.* Determination of Arsenic, Cadmium, Copper, Manganese,
Lead, Antimony, Selenium and Thallium in Water
Bernhard Welz, Gerhard Schlemmer and Jayateerth R. Mudakavit
Department of Applied Research, Bodenseewerk Perkin-Elmer and Co GmbH, 0-7770Uberlingen,
Federal Republic of Germany
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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
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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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incineration ash and urban particulate matter.31 Work on this


highest possible pyrolysis temperature be applied for the
modifier has also been published by Voth-Beach and
analysis of water samples, a better thermal stability of the
Shrader .32
analyte element offers more flexibility in selecting the
The aim of this work was to investigate the use of the
temperature programme. The eight elements can be divided
palladium nitrate - magnesium nitrate modifier for the deter-
into two groups within which the same graphite furnace
mination of As, Cd, Cu, Mn, Pb, Sb, Se and T1 in natural
parameters were used. The two most volatile elements,
water samples under routine conditions. These had to be such
cadmium and thallium, were best determined using a pyrolysis
that as many parameters as possible were common for the
temperature of 800 "C, an atomisation temperature of 1650 "C
elements under investigation, and that calibration against
and the temperature programme given in Table 2. For the
matrix-free reference solutions was possible. The latter other elements a pyrolysis temperature of at least 1000 "C was
condition pre-supposes a high degree of freedom from
applicable and atomisation at 2200 "C is recommended (Table
interferences. Therefore, the influence of a wide variety of 1). These "compromise" conditions did not have a negative
concomitants on the analyte elements was investigated under effect on sensitivity or on over-all analytical performance and
the proposed conditions for routine analysis. This also are regarded as greatly facilitating routine analysis. However,
included the examination of spectral interferences when
continuum-source background correction was used.
Table 1. Graphite furnace temperature programme for the deter-
mination of As, Cu, Mn, Pb, Sb and Se in water using the palladium
nitrate - magnesium nitrate modifier
Experimental
Instrumentation Step

A Perkin-Elmer Model 1100 atomic absorption spectrometer Parameter 1 2 3 4 5 6


with deuterium-arc background correction, equipped with an TemperaturePC . . .. 90 120 1000 2200 2650 20
HGA-500 graphite furnace and an AS-40 furnace autosampler Ramptimels .. .. 1 10 10 0 1 1
was used for most of this work. For part of the investigation a Holdtimek . . . . .. 10 20 20 6 5 5
Perkin-Elmer Zeeman/3030 atomic absorption spectrometer Read . , , . . . .. - - - ON - -
with an HGA-600 graphite furnace and AS-60 furnace Internal Ar
autosampler was used. Signals were evaluated exclusively flow/mlmin-l . . .. 300 300 300 0 300 300
from integrated absorbance values computed by the AA
Table 2. Graphite furnace temperature programme for the determina-
instrument. Pyrolytic graphite coated tubes (Perkin-Elmer tion of Cd and T1 in water using the palladium nitrate - magnesium
Part No. B010-9322) with pyrolytic graphite platforms (Per- nitrate modifier
kin-Elmer Part No. B010-9324) were used for all experiments.
The recommended graphite furnace temperature programmes Step
are given in Tables 1 and 2; other instrumental parameters are
listed in Table 3. Parameter 1 2 3 4 5 6
Temperature/"C . . .. 90 120 800 1650 2650 20
Ramp time/s .. .. 1 10 10 0 1 1
Holdtime/s . . . . . . l o 20 20 6 5 5
Reagents Read . . . . . . .. - - - ON - -
All reagents used were of the highest purity available and of at Internal Ar
flow/mlmin-' . . . . 300 300 300 0 300 300
least analytical-reagent grade. Nitric acid was further purified
by distillation in a quartz sub-boiling still (Kuerner Analysen- Table 3. Instrumental parameters for the determination of trace
technik, Rosenheim, FRG). Palladium nitrate solution was elements in water
prepared by dissolving 300 mg of palladium metal powder
(Ventron Alfa Products, Karlsruhe, FRG) in 1 ml of Wavelength/ Slit/ Light Power/ Current/
concentrated nitric acid and diluting to 100 ml with de-ionised Element nm nm source* W mA
water. If dissolution was incomplete 10 p1 of concentrated As . . . . 193.7 0.7 EDL
hydrochloric acid were added to the cold nitric acid and heated Cd . . . . 228.8 0.7 EDL
gently until the solution cleared. The solution was then heated c u . . .. 327.41- 0.7 HCL
to gentle boiling in order to volatilise the excess of chloride. A Mn .. 279.4 0.2 HCL
200-mg amount of magnesium nitrate was dissolved in Pb . . . . 283.3 0.7 HCL
de-ionised water and diluted to 100 ml. The palladium nitrate - Sb . . . . 217.6 0.2 EDL
Se . . . . 196.0 2.0 EDL
magnesium nitrate modifier was prepared by mixing equal T1 . . . . 276.8 0.7 EDL
volumes of a solution containing 3000 mg 1-1 of Pd and 2000
mg 1-1 of Mg(NO&. A 10-11 aliquot of this solution was * EDL = Electrodeless discharge lamp; HCL = hollow-cathode
added to the measurement solution (irrespective of the sample lamp.
volume used) for each determination, corresponding to 15 yg
t A spectral interference was observed at the 324.8-nm primary
resonance line (see text).
of Pd [32.5 pg Pd(N03)*] and 10 pg of Mg(N03)2.
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JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, AUGUST 1988, VOL. 3 697

Table 4. Calibration data for low and high standards including integrated absorbance and relative standard deviation (RSD) of five replicate
determinations

Sample Analyte Integrated Anal yte Integrated


Element volume/pl concentrationiyg 1- 1 absorbance/A s RSD, "/a concentrationipg 1-1 absorbance/A s RSD, %
As .. .. .. 20 10 0.062 4.5 50 0.321 1.1
Cd .. .. .. 10 0.5 0.052 1.6 5.0 0.496 0.8
cu .. .. .. 20 10 0.076 1.9 60 0.444 0.5
Mn ,. .. .. 10 5 0.079 1.7 30 0.457 0.9
Pb .. .. .. 20 10 0.051 2.6 70 0.335 1.2
Sb . . . . .. 20 10 0.047 6.7 90 0.372 1.2
Se ._ .. .. 20 10 0.041 1.7 70 0.301 0.6
Tl.. .. .. .. 20 10 0.076 5.2 70 0.530 1.3
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Table 5. Linear regression analysis (integrated absorbance/A s versus


the use of the same temperature programme for all eight analyte concentrationipg I - 1 ) and characteristic mass (mo)for trace
elements, i.e., pyrolysis at 800 "C and atomisation at 2200 "C elements in water using the palladium nitrate - magnesium nitrate
would haved resulted in a substantial loss of sensitivity (up to modifier
50%) for cadmium and thallium due to increased diffusional
losses at the high atomisation temperature. Such a further Element Linear regression equation mdpg
simplification was therefore not considered in this work. In AS .. .. .. .. y = 6.4700~- 0.0015 r = 0.9987 14
addition, as will be shown later, at the higher atomisation Cd .. .. .. .. y = 98.600~+ 0.0054 r = 0.9999 0.45
temperature, palladium caused a spectral interference in the Cu .. .. .. .. y = 7.3343~+ 0.0038 r = 0.9990 12
determination of thallium when continuum source back- Mn .. .. .. ,. y = 15.1143~+0.0053 r=0.9999 2.9
ground correction was used. Pb .. ., .. .. y = 4.7500~+ 0.0077 r = 0.9992 18
Sb .. ., .. .. y = 4.1701~ + 0.0003 r = 0.9984 21
Se .. .. .. .. y = 4.3571~-0.0006 r=0.9998 20
Calibration and Linear Regression Analysis T1 .. .. .. .. y = 7.5357~+ 0.0087 r = 0.9962 12

The calibration data including the average blank-corrected


integrated absorbance and the relative standard deviation
(RSD) for five replicate determinations of a low and a high Substantially higher concentrations may be tolerated,
standard are given in Table 4, Table 5 gives, in addition, the however, without causing an interference in the determination
linear regression equations and the characteristic mass for all of most analyte elements.
eight elements. The data indicate that the analytical curves The six analyte - interferent combinations for which a
show little or no deviation from linearity up to integrated deviation greater than 2 5 % in the integrated absorbance
absorbance values of 0.3-0.5 A s, depending on the element. signal was found, were investigated in more detail. This
The precision of a replicate determination ( n = 5 ) in the included variation of the interferent concentration and deter-
optimum working range is typically around 1% for all mination with an instrument using Zeeman-effect background
elements investigated in this work, and increases to values correction in order to obtain information on the nature of the
between ca. 2 and 5% at 0.05 A s. The characteristic mass observed interference, i. e . , spectral or non-spectral origin.
values found in this work agree in general with published
data12 except for lead, for which we consistently found a
higher characteristic mass with the palladium modifier. The
Non-spectral Interferences
integrated absorbance of the reagent blank, i.e., predomi- The influence of sodium chloride on the determination of
nantly the modifier, was typically within the noise level except thallium was found to be independent of the type of
for cadmium and manganese. For these elements blank signals background correction system used. However, it was found to
of 0.010 and 0.016 A s were obtained corresponding to about depend, clearly, on the pyrolysis temperature as is depicted in
0.1 vg 1-1 of Cd and 1 pg 1-1 of Mn, respectively. For antimony Fig. 1. This suggests that the interference is due to pre-
and thallium the modifier solution caused a slight base-line atomisation losses of thallium as the volatile chloride, a
distortion when using continuum source background correc- mechanism which has been proposed previously.~3J4It is
tion, resulting in small negative integrated absorbances of interesting to note that the interference is most pronounced
-0.012 and -0.009 A s, respectively. when a pyrolysis temperature of 750 "C is used and decreases
when lower or higher temperatures are used. This phenom-
enon was not investigated further in this work. L'vov33
Interference Studies
proposed that this effect be reduced by binding free chlorine
The effect of 21 potentially interfering ions and compounds on into a molecule which is more stable than the monochloride of
the signals of the eight analyte elements was investigated. The the analyte. Lithium chloride is amongst the molecules that
relative integrated absorbances obtained in comparison with have the highest dissociation energies. Fig. 1 shows that the
the interferent-free solution and the relative standard devia- addition of 100 pg of lithium as the nitrate reduced the
tion calculated for five replicate determinations are given in chloride interference on thallium to values of about 10740, in
Table 6. An effect exceeding & l o % , which must be con- the presence of 300-600 mg 1-1 of sodium chloride. The
sidered an interference, was found €or only two analyte - addition of larger amounts of lithium had no further releasing
concomitant combinations. These were the combinations effect on this interference. The addition of 100 pg of lithium is
sodium chloride - thallium and iron - selenium. In addition therefore recommended when high sodium chloride concen-
there was a minor influence exceeding +5% from potassium trations are expected to be in a sample. The moderate
sulphate on manganese and antimony, calcium phosphate on decrease in the thallium signal in the presence of zinc chloride
arsenic and zinc chloride on thallium. A difference of t5% or was also found to be due to the chloride and not to the zinc. As
less in the integrated absorbance of the analyte in the presence expected, this interference could be controlled by the addition
and absence of a concomitant was not considered an interfer- of lithium in a manner similar to that described for sodium
ence because it will not be of significance in practical trace chloride. Although lithium clearly reduces the chloride
element determinations. Concomitant concentrations higher interference on thallium it apparently cannot remove it
than those given in Table 6 were not investigated in this work. completely. For the present application lithium appears to be
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JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, AUGUST Article
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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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96 (3) 99 (1) 84 (2) 98 (1)


MO . . . . . . .. (NH4)2M004 5 103 (1) 103 (1) 103 (3) 102 (2) 101 (1) 97 (6) 102 (2) 103 (1)
Pb .. ., .. .. Pb(N03)I 5 104 (3) 98 (1) 100 (1) 101 (2) - 96 (1) 101 (2) 97 (2)
PO4 . . . . . . .. CaHP04 5 95 ( 5 ) 100 (1) 97 (1) 97 (1) 97 (2) 100 (1) 99 (6) 100 (4)
Sugar . . . . . . .. - 5 99 (3) 101 (1) 99 (1) 95 (2) 102 (1) 105 (2) 102 (1) 99 (1)
A1 .. .. .. .. AlC13 2 97 (1) 99 (3) 99 (1) 98 (1) 100 (1) 104 (3) 103 (1) 96 (1)
Ba .. .. .. .. Ba(NO& 2 97 (2) 98 (1) 100 (1) 99 (3) 102 (I) 95 (2) 100 (1) 101 (1)
Na2EDTA . . . . .. - 2 99 ( 3 ) 101 (1) 100 (2) 96 (1) 100 (1) 104 (2) 100 (1) 101 (1)
Ni .. .. .. .. NiClz 2 96 (1) 97 (1) 100 (2) 101 (2) 95 (1) 104 (2) 99 (1) 100 (1)
Mn .. .. .. .. MnCl, 2 104 (2) 98 (2) 99 (1) -
98 (2) 100 (2) 98 (1) 99 (1)
Cr ., .. . . .. K2Cr207 1 98 (2) 100 (1) 101 (2) 96 (3) 97 (1) 103(1) 97 (1) 105 (1)
Sn . . .. . . .. SnC1, 1 103 (2) 97 (1) 101 (1) 96 (1) 97 (1) 104 (1) 101 (1) 104 (2)
TritonX-100 .. .. - 0.5 99 (2) 98 (1) 99 (1) 96 (3) 98 (1) 99 (2) 99 (3) 99 (1)
B .. .. ,. .. H3B03 1 99 (2) 99 (1) 101 (1) 101 (1) 99 (1) 99 (1) 98 (3) 100 (1)

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

100 200 500


I
Continuum source background correction and B , Zeeman-effect
Cc NaCl concentration/mg I-' background correction

Fig. 1. Influence of sodium chloride on the determination of Spectral Interferences


thallium under various experimental conditions. A , Pyrolysis temper-
ature 900 "C; B, pyrolysis temperature 750 "C; C, pyrolysis temper- Spectral interferences in the determination of selenium, using
ature 500 "C; and D, 100 pg of lithium added, pyrolysis temperature continuum source background correction have been reported
800 "C and attributed to iron35-39 and phosphate.37>39,40 The results in
Table 6 show that there is an interference in the presence of
iron, but not in the presence of phosphate. This discrepancy
may be due to differences in the experimental conditions.39
Both interferences were therefore investigated in more detail
B
with increasing concentrations of iron and phosphate, respec-
tively.
Fig. 3 shows the influence of increasing iron concentration
on the integrated absorbance signal of selenium using a
I I t 1 spectrometer with continuum source background correction.
50 100 200 500 The influence exceeds the 5 % limit, which may be considered
S o p concentration/mg I-' as the onset of an interference, at an iron concentration
Fig. 2. Influence of potassium sulphate on the determination of A, greater than 1 mg 1-1, yet there is no influence from iron
manganese and B, antimony concentrations of up to 50 mg 1-1 on selenium when
Zeeman-effect background correction is used, which is in
agreement with prior reports.3638 Another solution to this
sufficient as a releasing agent for thallium. However, the problem, suggested in the literature,35 is to determine
chloride interference in the determination of this element selenium at the 204.0-nm line. This approach was not
would require special attention and more work when higher considered in this work as the sensitivity is about a factor of
chloride concentrations are to be expected in samples such as five inferior at this line.
sea water. The signal obtained in the presence of 5 mg 1-1 of phosphate
The influence of an increasing concentration of potassium was within k 5% of that obtained for the pure analyte solution
sulphate on the determination of manganese and antimony is for all elements investigated. This may, at least in part, be due
shown in Fig. 2. For both elements the integrated absorbance to the modifier used in this work. Bauslaugh et al. 39 found that
is decreased by ca. 10% in the presence of 100 mg 1-1 of phosphorus atom formation is enhanced by platinum, thereby
interferent. However, this influence remains essentially con- decreasing the spectral interferences which arise from mole-
stant at least up to an interferent concentration of 500 mg 1-1. cules present in the gas phase. A similar effect can be expected
The addition of 100 mg 1-1 of potassium sulphate to both for palladium .40
sample and standards should minimise the interference. From the data in Table 6 it appears that arsenic is affected
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JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, AUGUST 1988. VOL. 3

most by the presence of phosphate. This element was BGC 0.05


therefore investigated in more detail. The time-resolved BG 0.05 ( a ) 1
background and background-corrected signals for two calcium I A I
phosphates under different experimental conditions are
shown in Fig. 4. In the absence of a modifier, C a H P 0 4gives a
sharp background signal early in the atomisation stage which 0
results in a significant over-correction (negative base-line
deflection). In the presence of palladium, the background
signal appears much later and slower and causes no significant 8 BG 0.05 ( b )
c
m
base-line distortion. However, the same amount of n
L
Ca3(P04)2,based on phosphate, results in a similarly shaped 2
background absorbance which is almost one order of magni- n
a
tude higher. Consequently the base-line noise is somewhat
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higher, but there is again no apparent base-line distortion.


Phosphate at a concentration of 5 mg 1-1, when added as
Ca3(P0&, decreased the arsenic signal to about 75% of that
obtained in the absence of phosphate. This is due, most
probably to a non-spectral interference because there is no
visible base-line distortion (Fig. 4) and the interference is also
observed 'in an instrument with Zeeman-effect background
correction. When C a H P 0 4 is used as the interferent, the
phosphate concentration can be an order of magnitude higher 0 8
Time/s
( L e a ,50 mg 1-1) to cause the same 25% decrease in the arsenic
signal, most probably because of the higher volatility of Fig. 4. Time-resolved blank signals for 10 mg 1-1 of phosphate
recorded at the 193.7-nm arsenic wavelength. A, Background
CaHP04 which allows a more efficient removal during absorption and B, background corrected (continuum source) signal: ( a )
pyrolysis. CaHPO,, no modifier; ( b CaHPO, with Pd(N03)2 - Mg(N,O&
Copper was determined interference-free in this study. modifier; and (c) Ca3(P0,)), with Pd(NO& - Mg(NO& modifier.
However, it was necessary to use the less sensitive resonance (BG = background absorbance and BGC = background corrected
absorbance)
line at 327.4 nm because of a spectral interference which was
observed at the 324.75-nm primary resonance line. This effect 0.05I I
is shown in Fig. 5. The base-line distortion is caused by the
palladium lines at 324.27 and 325.16 nm which fall within the
spectral band width of 0.7 nm used for copper determination.
These palladium lines absorb the radiation of the deuterium-
arc source lamp. This interference could be reduced but
cannot be removed completely if a spectral band width of 0.2
nm is used. At the same time, however, the noise level
increased substantially, which made this solution less attrac-
tive. This interference is not observed when Zeeman-effect
background correction is used as can be seen in Fig. 5. This
0.05
1 (6)
type of correction is therefore recommended whenever the
highest sensitivity and best detection limit are required.
Another spectral interference of the same type has been n
observed for thallium. The 276.31-nm palladium line falls a
within the 0.7-nm spectral band width used for the determina-
tion of thallium at the 276.79-nm primary resonance line. The
effect is only minor when the recommended atomisation 0.1 r 1
temperature for thallium of 1650 "C is used, as palladium
would not be volatilised to a significant extent at this
temperature. With increasing atomisation temperature,
however , base-line distortion becomes more pronounced as
seen in Fig. 6. Again, this interference is not seen when an
instrument with Zeeman-effect background correction is
used. 0 6
Time/s
Limit of Detection Fig. 5. Influence of 15 pg of palladium on A, base line and B,
In this work calculation of the detection limit follows the background absorbance at different copper wavelengths: ( a ) 324.75-
recommendations of the Standing Committee of Analysts, nm line, continuum source background correction (integrated absor-
bance -0.031); (b) 327.40-nm line, continuum source background
The Department of Environment, London, UK;41 in which correction (integrated absorbance 0.001); and ( c ) 324.75-nm line,
two limits are given. The qualitative detection limit (criterion Zeeman-effect background correction (integrated absorbance 0.004)
of detection) is defined as 2.33 times the within-batch standard
deviation of single blank determinations, corresponding to a
95% confidence level. The quantitative limit of detection is and of a low analyte concentration close to the actual
defined as twice this value, i.e., 4.66 times the within-batch detection limit. The detection limit calculated for the blank
standard deviation. Table 7 summarises both these detection and the low analyte concentration were in agreement, within
limits both in terms of absolute analyte mass and of experimental error, for all the eight elements.
concentration related to the sample volumes used in this work.
An improvement in the latter detection limit is possible by Analysis of NBS Trace Elements in Water
using larger sample volumes.
All detection limits listed in Table 7 are based on ten In order to test the applicability of the procedures to the
replicate determinations, each of a blank with the modifier analysis of real samples we analysed the National Bureau of
700 View1988,
JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, AUGUST Article Online
VOL. 3

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.

L L I necessary to decrease the pyrolysis and atomisation tempera-


tures. It is anticipated that this “streamlining” of the analytical
conditions will be considered to be a major contribution to the
simplification of work in a routine analysis laboratory and for
the minimisation of errors.
The analysis has also been found to be remarkably free from
Published on 01 January 1988. Downloaded by University of Rochester on 29/08/2013 09:18:36.

interferences, and this may, at least in part, be due to the high


................................................... ......................... ......... ...... pyrolysis temperatures which may be used with the proposed
modifier. Lead and cadmium, two elements for which many
0 5.0
interferences have been reported in the literature, were found
Ti mels to be affected to less than t-5% by all of the investigated
interferents. Iron at concentrations greater than 1 mg 1-1
Fig. 6. Influence of 15 pg of palladium on A, base-line and B,
background absorbance of thallium at 276.8 nm: ( a ) atomisation causes a spectral interference in the determination of selenium
temperature 1650 “C (integrated absorbance -0.026) and ( b atomisa- when an instrument with continuum source background
tion temperature 2000 “C (integrated absorbance -0.047;). (BG = correction is used. Another spectral interference is observed
background absorbance and BGC = background corrected absor- in the determination of copper at the 324.75-nm primary
bance) resonance line. Neither interference is observed when Zeeman-
effect background correction is used.
Our current experience indicates that the palladium nitrate -
Table 7. Qualitative (2.330) and quantitative (4.660) detection limits magnesium nitrate modifier can be applied for the determina-
(DL) for As, Cd, Cu, Mn, Pb, Sb, Se and T1 in water
tion of other elements and a wider range of matrices with
Absolute DL/pg Relative DL/pg 1-1 comparable success, providing further simplification for
Sample routine analysis and greater freedom from interferences.
Element 2.330 4.660 volume/pl 2.330 4.660
As . . . .
23 47 20 1.2 2.4
Cd . . . . 0.22 0.44 10 0.02 0.04 References
Cu . . . . 6 12 20 0.3 0.6
Mn . . . . 4.5 9 10 0.45 0.9 1. Welz, B . , CZ Chem. Tech., 1972, 1, 455.
Pb . . . . 9 18 20 0.45 0.9 2. Welz, B., and Wiedeking, E., Fresenius Z. Anal. Chem., 1973,
Sb . . . . 35 70 30 1.2 2.3 264, 110.
Se . . . . 12 23 20 0.6 1.2 3. Welz, B . , V o m Wusser, 1974, 42, 119.
T1 . . . . 16 31 20 0.8 1.6 4. Burba, P., Lieser, H. H., Neitzert. V . , and Rober, H. M.,
Fresenius 2. Anal. Chem., 1978, 291,273.
Table 8. Analysis of the NBS SRM 1643b, Trace Elements in Water 5. Hegi, H. R., Hydrologie, 1976, 38, 35.
6. Edmunds, W. M., Giddings, D. R., and Morgan-Jones, M., At.
Concentration/pg 1-1 Absorpt. Newsl., 1973, 12, 45.
7. Barnard, W. M., and Fishman, M. J., At. Absorpt. Newsl.,
Element Certified* Found 1973, 12, 118.
8. Maier, D., Sinemus, H. W., and Wiedeking, E., Fresenius 2.
As . . . . . . . . 507 53 Anal. Chem., 1979, 296, 114.
Cd . . . . . . . . 2021 19 9. Slavin, W., Manning, D. C., and Carnrick, G. R., At.
Cu . . . . . . . . 22.3k0.4 22 Spectrosc., 1981, 2 , 137.
Mn . . . . . . . . 28.522 30 10. Regan, J. G. T., and Warren, J., Analyst, 1978, 103, 447.
Pb . . . . . . . . 24.140.7 24 11. Callio, S., At. Spectrosc., 1980, 1, 80.
Sb . . . . . . . . L

ND$ 12. “Techniques in Graphite Furnace Atomic Absorption Spec-


Se . . . . . . . . 9.9k0.5 9.4 trometry,” Perkin-Elmer, Ridgefield, CT. 1985, Part No.
TI . . . . . . . . 8.1 2 0 . 2 7.6 0993-8 150.
* Certified concentrations in ng 8-1 multiplied by the density of 13. Bertenshaw, M. P., Gelsthorpe, D . , and Wheatstone, K. C.,
water, i.e., 1.017 g ml-1. Analyst, 1982;107, 163.
t Non-certified value, for information only. 14. Fletcher, I. J.. Anal. Chim. Acta, 1983, 154, 235.
$ N D = not detected. 15. Sthapit, P. R . , Ottaway, J. M . , Halls, D. J . , and Fell, G . S . ,
Anal. Chim. Acta, 1984, 165, 121.
16. Hunt, D. T. E., and Winnard, D. A., .4nalyst, 1986, 111, 785.
Standards (NBS) Standard Reference Material (SRM) 1643b, 17. Webster, J., and Wood, A., Analyst, 1984, 109, 125.5.
Trace Elements in Water. The results are summarised in Table 18. Slavin, W . , Manning, D. C., Carnrick. G. R., and Pruszkow-
8. Correlation with the certified values was satisfactory. It ska. E . , Spectrochim. Acta, Part B, 1983, 38, 1157.
should be noted, however, that the element concentrations in 19. Martin, T. D.. Kopp, J. F., and Ediger, R. D., At. Absorpt.
this sample are relatively high compared with those typically Newsl., 1975, 14, 109.
found in unpolluted surface and drinking waters. The concen- 20. Stein, V. B., Canelli, E., and Richards. A. H., At. Spectrosc.,
tations of minor elements such as Ca, Mg and Na are 35 1980, 1. 61.
21. Stein, V. B . , Canelli, E., and Richards, A. H., At. Spectrosc.,
mg 1-1,15 mg 1-1 and 8 mg 1-1, respectively, and hence so low
1980, 1, 133.
that no interferences should be expected. The same is true for 22. Welz, B., Curtius, A. J., Schlemmer, G., Ortner, H. M., and
iron which is present at a concentration of about 0.1 mg 1-1. Birzer, W., Spectrochim. Acta, Part B, 1986, 41, 1175.
23. Shan, X.-Q., and Ni, Z.-M., Acta Chim. Sinica, 1979,37.261.
Conclusion 24. Shan, X.-Q., and Ni, Z.-M., Acta Chim. Sinica, 1981,39, 575.
2.5. Jin, L.-Z., and Ni, Z.-M., Can. J . Spectrosc., 1981, 26, 219.
The proposed palladium nitrate - magnesium nitrate modifier 26. Shan, X . - Q . , Ni, Z.-M., and Zhang, L., Anal. Chim. Acta,
makes the determination of six out of the eight elements under 1983, 151, 179.
View Article Online
701
JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, AUGUST 1988, VOL. 3

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
Published on 01 January 1988. Downloaded by University of Rochester on 29/08/2013 09:18:36.

W. B., At. Spectrosc., 1981,2, 73. Accepted April 6th, 1988

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