Fresenius' Journal of

Fresenius J Anal Chem (1995) 352:572-576

(~) Springer-Verlag 1995

Determination of total chromium in sediments by FAAS

A. Sahuquillo 1, R. Rubio 1, G. Rauret 1, B. Griepink 2
1Departament de Quimica Analitica, Universitat de Barcelona. Avd. Diagonal 647, E-08028 Barcelona, Spain
2DGI-Commission of the European Communities (CEC), Rue de la Loi, B-2000 Brussels, Belgium

Received: 26 October 1994/Revised: 13 January 1995/Accepted: 17 January 1995

Abstract. The determination of chromium by flame sary. Especially parameters such as: flame-type, possible
atomic absorption spectroscopy (FAAS), e.g. as per- interfering effects of common anions and cations and
formed for environmental matrices, is still a controversial reagents added, require a systematic investigation.
matter as can be concluded from a literature review. Most Literature reveals that interferences are circumvented
controversy is due to the measurement conditions or the by selecting flame conditions and masking agents. Two
effect of the interferences; other conditions such as diges- types of flame are widely mentioned, air-acetylene and
tion seem to be less critical. Consequently, this paper nitrous oxide-acetylene flames.
reports a systematic study of the instrumental settings for It is suggested I-2-18] that a slightly fuel-rich air-
the two flame modes that are most widely used: air-acety- acetylene flame has a higher sensitivity as compared
lene and nitrous oxide-acetylene. In connection with the to a lean flame. In such a case, interferences are elimi-
study of experimental conditions, possible interferences nated by proper masking agents. Doubt exists on the
are investigated involving nineteen cations and some an- reproducibility and therefore correctness of the calib-
ions in different ratios Cr:interferent. Different releasers ration [19].
to overcome interferences are considered. The results are The nitrous oxide-acetylene flame has a lower sensitiv-
critically compared with current literature. For the opera- ity, but is also less prone to interferences [-6, 7, 19-29].
tional conditions the quality parameters such as the The robustness of the method towards interferences
linear range, detection limits, precision and accuracy should not be overestimated [-7, 30, 31]; some elements
are established. Although the nitrous oxide-acetylene are causing larger interfering effects in the nitrous
flame is mostly recommended, this study reveals that oxide-acetylene flame than in the air-acetylene flame [-9].
a better choice can be the use of a fuel-rich air-acety- As said before, the various publications often have
lene flame with the addition of 1% 8-hydroxyquino- contradictory conclusions. It seems that interferences of
line (oxine) as protective agent. The method is applied cations depend on the anions they were associated with in
to and validated by four sediment certified reference ma- the particular study [-321.
terials. The difficulty of achieving accuracy in the Cr deter-
mination is also reflected in the number of CRM's with
a certified value for Cr [-33].
The literature reviewed 1-11 and many intercom-
parisons reveal that a systematic study of flame condi-
Introduction tions and suppression of interfering effects was necessary;
such a study was undertaken within framework of the
Cr is both an essential and toxic element for living organ-
BCR-Programme, nowadays Measurement and Testing
isms. Therefore, the determination of this element in en-
Programme (MAT) of the European Commission. This
vironmental matrices is frequently performed.
study was performed on both species of Cr occurring in
As the determination is carried out routinely at levels
daily practice.
of lag g - 1, FAAS is the technique of final determination of
choice. The many publications [11 on the operational
conditions of FAAS for both Cr(VI) and Cr(III) reflect the
fact that there is controversy as to the best experimental Experimental
conditions for the final determination. Therefore a sys-
tematic approach to find the optimal conditions is neces- Apparatus
The single-beam atomic absorption spectrometer Perkin-
Elmer 1100 B with a continuous deuterium background
correction was used. A 10 cm single-slot burner made of
Correspondence to: A. Sahuquillo titanium and a 6 cm single-slot burner made of tungsten
 573

were applied as burner heads for the air-acetylene and the with double-deionized water and the solution was ana-
nitrous oxide-acetylene flames, respectively. lysed.
The linear range was established using three different For the open attack, 0.5 g of sediment was digested to
instruments: the model described above; a Philips near dryness with 5ml of 14moll -1 HNO3 in a sand
PU9200X and a Philips PUSP900 atomic absorption bath. 6 ml of 23 moll- i HF and 2ml of 12 tool 1-1 HC104
spectrometer. were added and the whole evaporated to dryness. The
In all cases, a hollow-cathode chromium lamp was operation was repeated with 4 ml of 23 tool 1- ~ HF and
used as radiation source. 2ml of 12moll -1 HC104 until the sample was com-
pletely digested. A further 4 ml of HC104 was added and
the mixture again evaporated to dryness; finally 5 ml of
Reagents 14 moll 1 HNO3 was added. The final residue was dis-
solved by adding 10ml of hot 3moll -~ HNO3. The
Stock solutions of 1000 mg1-1 of Cr were prepared as solution was made up to 50 ml and analysed.
follows:
Cr(VI) solutions: K2Cr207 (Merck, pro-analysis) pri-
mary standard, dissolved in 0.03 moll-~ HNO3 (Merck,
Suprapur). Results and discussion
Cr(III) solutions as nitrate salt: Cr(NO3)3"9H20
Study of flame conditions
(Carlo Erba, pure) dissolved in 0.03moll -1 HNO3
(Merck, Suprapur). From the literature review [1] it was concluded that the
Cr(III) solutions obtained by reduction of K2Cr207 most important instrumental parameters which affect
(Merck, pro-analysis) with H202 10 moll-~ (Fluka, pro- both the interferences and the sensitivity of the measure-
analysis) in H2SO 4 (Merck, Suprapur) and removal of the ments were the stoichiometry of the flame and the burner
excess of H202 by boiling. height. These variables were optimized simultaneously,
Stock solutions of 100 rag l- z were prepared weekly using the well-established Simplex approach. This was
and more diluted working solutions were prepared daily; carried out considering the mean value of 10 absor-
the acidity in HNO3 was always 0.29 moll- 1 bance readings of a standard solution of 5mg1-1
For the study of cation effects the following salts were (in 0.29 moll-1 HNO3) for each new vertex. It was per-
used: NaC1, NaHCO3, KC1, LiCI, CaC1;'2H20, CaSO4" formed in two different working sessions.
2H20, MgC12"2H20, MgSO~, FeCI3"6H20, MnSO~-H20, The ranges of the studied variables were: oxidant/fuel
Ni(NO3)2"6H20, NH4VO3, (NH,~)6MoTO24"4H20, ratio 1.5-10 in air-acetylene flame and 0.69-1.93 in
COC12"6H20, K2TiO(C2Og)2"2H20, CuC12"2H20, nitrous oxide-acetylene flame; the burner height was var-
Cd(NO3)2, ZnSO4"H20, Pb(NO3)2, HgSO~, Na2HAsO4" ied between 0 and 15 mm for both flames.
7H20 and A1K(SO,,)2"12H20, all of analytical grade. The Simplex procedure was stopped when the increase
The effect of anions was studied with the following of response had become negligible in five consecutive
concentrated acids of Suprapur quality (Merck): HC1, vertices, that is a variation of 5% in absorbance. Seven-
H2SO,~, HNO3, HC104 and H3PO4. teen movements of the Simplex were necessary for each
The certified reference materials (CRM) used for the of the standard solutions tested. Final optimum
validation of the method were: a river sediment from NBS conditions are the same for both Cr(III) and Cr(VI) stan-
(CRM-1645), a pond sediment from NIES (CRM-n°2), dard solutions: an oxidant/fuel ratio of 1.5 for air-acety-
a river sediment from BCR (CRM-320) and a lake sedi- lene flame and 0.69 for nitrous oxide-acetylene flame
ment from BCR (CRM-280). (fuel-rich flames) and a burner height of 3 mm for both
For the acidic digestions of the sediments, 14 tool 1- i flames.
HNO3, 12 moll -1 HC104 and 23 moll -1 HF (all Merck Other variables which influence the chromium deter-
Suprapur) were used. mination to a lesser extent were additionally studied:
All the solutions were prepared using double-de- slit-width (2, 0.7 and 0.2 nm were the instrument settings),
ionized water (Culligan Ultrapure GS 18.3 Mf~ resistivity) background correction (deuterium lamp on and off) and
and in a class 100 clean room, in accordance with the wavelength (357.9 and 425.4 nm). These variables were
USA Federal Standard 209 b/d norm, with vertical air established from sequential assays, i.e. obtaining absorb-
flow [35]. ance readings in the concentration range of 0.2 to
60 mgl- 1 and considering the conditions which gave the
best sensitivity.
The slit-width of 0.2 nm gave a slightly higher sensitiv-
Procedure for the determination of Cr in sediments ity and as expected, the use of a deuterium lamp was not
0.5 g of sediment was digested in a stoppered Teflon found useful due to its low emission at the wavelength of
centrifuge tube for 4 h with 4 ml 14 tool 1- ~ HNO3, 1 ml work.
12mo11-~ HC104 and 5ml 23mo11-~ HF at The wavelength of 357.9 nm gave the highest sensitiv-
140 _+ 10 °C. After cooling to room temperature, 30 ml of ity, but the use of 425.4 nm could be suitable for the
a saturated solution of boric acid was added and the final determination of higher concentrations of Cr because of
solution was centrifuged. If there was a considerable resi- its larger linear range (0.2-20 mgl- 1 for the air-acetylene
due at this point, the attack was repeated in open Teflon flame and 0.2-60 rag l-1 for the nitrous oxide-acetylene
beakers. If not, the sample volume was made up to 50 ml flame).
574

Study of the interferences Normalised slope values with respect to HNO3

1,2
Under the established conditions we studied the inter-
ferences. The absorbance obtained for standard solutions 1
with addition of interferent were plotted against absorb-
ance readings of the standards of the calibration graph in o,8
0.29 mol 1- ~ HNO3. A slope of 1 and an intercept of 0 (at
95% significance level) indicated that the two series corn- 0,6
pared were equal [361, or in other words the interferent
did not affect the calibration graph. To obtain regression 0,4-
data, a robust method was applied because in this case,
the error should be considered in both X- and Y-axis o,2--
[37, 381.
The cations studied as source of possible interference 0 ,
C D E F G H
were Na, K, Li, Ca, Mg, Fe(III), Mn(II), Ni(II), V(V), A B
Mo(V), Co(II), Ti(IV), Cu(II), Cd, Zn, Pb(II), Hg(II), a
As(V) and A1. These cations were chosen as they are
usually present in environmental samples such as waters,
sediments and soils. The interferent effect was studied in Normalised slope values with respect to HNO3
different Cr:interferent concentration ratios (1:1000, 1,2
1:100 and 1:1).
Ten cations (Ca, Mg, Fe(III), Mn(II), Ni(II), V(V),
1 ?\ /-,\
Mo(V), Co(II), Ti(IV) and Hg(II)) showed interferences in
0,8
the air-acetylene flame for both Cr(VI) and Cr(III) stan-
dard solutions. With this flame, interferences resulted in o,6-
a signal decrease.
Six cations showed interferences in the nitrous 0,4-
oxide-acetylene flame with Cr(VI) standard solutions
(Mg, Ni(II), V(V), Mo(V), Ti(IV) and Cd). Fourteen ca- 0,2-
tions caused interferences with Cr(III) nitrate (Na, K, Li,
Ca, Mg, Mn(II), V(V), Mo(V), Ti(IV), Cd, Zn, Hg(II), o- i ) i i i 7

As(V) and A1) and seventeen cations (Na, K, Li, Ca, Mg, A B C D E F G H
Mn(II), Ni(II), V(V), Mo(V), Ti(IV), Cu(II), Cd, Zn, b
Pb(II), Hg(II), As(V) and A1) with Cr(III) obtained by Fig. la, b. Effect of releasers in the air-acetylene flame, a Upon Fe, Ni,
reduction, to a different extent. The presence of these Co and Mn. b Upon Mg, V, Ca and Ti. A: HNO3; B: Interferent; C:
cations resulted in a signal increase, except for Ni which Interf. + NH+C1; D: lnterf. + Na2SO4; E: Interf, + La(NO3)3; F: In-
depressed the signal. terf. + K2S208; G: Interf. + Sr(NO3)2; H: lnterf. + oxine
The anions studied were chlorides, nitrates, sulphates,
perchlorates and phosphates. These are the anions which
can be present in environmental samples after acidic di-
V, Ca and Ti. A recovery higher than 60% was obtained
gestions. This study was carried out with Cr(VI) and
for Co, Ca, V, Fe and Mn adding NH4C1 (0.19 moll-l),
Cr(III) (as nitrate) solutions. Whereas for the air-acetylene
for Ni, Mn, Ca and V adding Na2SO4 (0.07 mol 1-1), for
flame any of the anions studied affected the measurement,
Fe, Co, Ni, V and Ca adding La(NO3)3 (0.03 moll 1) and
for the nitrous oxide-acetylene flame under the previous
for Mn, Co, Ni, and Ca adding Sr(NO3) 2 (0.05 moll-l).
established conditions, SO ] - and PO43- produced a sig-
The addition of K2S208 (0.02 moll -1) gave a recovery
nal decrease upon both Cr(III) and Cr(VI) solutions.
higher than 80% of the slope value for Fe, Mn, Ni, Ti and
V and a recovery of 60% for Co and Ca. The best results
were obtained with the addition of oxine (0.07 moll- 1),
Study of interference suppressors which effectively recovered the 60% of the slope for all the
cations tested and the 80% for Fe, Ni, Co, Mn, V and Ca.
The main releaser agents mentioned in the literature Oxine can act as a protective agent forming complexes
(NH4C1 [3], Na2SO4 [9, 32], La(NO3)3, Sr(NO3)2, 8- with the interfering cations and preventing their chemical
hydroxyquinoline (oxine) [5] and K 2 8 2 0 8 ) w e r e assayed interaction with chromium in the vaporisation step.
as suppressors for the air-acetylene flame. Oxine is therefore the most recommended suppressor for
To ascertain the usefulness of the releaser agents as- the air-acetylene flame.
sayed, the slope values found with addition of interferent We initially tested the addition of a potassium salt
and releaser agent were normalized with respect to the (1000mg1-1) as ionization suppressor for the nitrous
slope value obtained in 0.29 moll- ~ HNO3. oxide-acetylene flame. For Cd, Ca and Mg the enhancing
As the behaviour of Cr(VI) and Cr(III) solutions with effect remains for both Cr(VI) and Cr(III) standard
respect to interferences were the same, the releasers were solutions. 0.02 moll- 1 K2S208, 0.07 moll- 1 oxine and
only tested for Cr(VI) solutions. Figures la and lb show 0.04 moll -~ (NH4)aS208 were tested as suppressors for
the effect of the releasers upon Fe(III), Ni(II), Co(II), Mg, Cd, Mg, Ni, Ca and Mn. (NH4)2S208 gave the best
 575

Table 1. Recovery study of total Cr with three synthetic waters by The coefficient of variation was calculated from 30 ab-
FAAS sorbance readings obtained on three non-consecutive
Conc. Water % Recov. % Recov. % Recov. days for each type of Cr solution studied and considering
(mgl - 5) direct 0.5% K2S208 1% oxine the 90 overall readings for the final calculation. The coef-
ficient of variation obtained was 4.3% for the lowest
0.4 Soft 105.4 92.5 96.6 concentration level and 3.7% for the highest concentra-
Hard 93.2 96.2 93.1 tion level.
Very hard 81.l 96.2 89.7
Tap 70.4 94.8 92.4 Accuracy. A recovery study was performed with synthetic
soft 110.1 103.9 96.1 waters of different hardness as well as with a tap water
Hard 107.8 105.0 99.2 spiked at the same concentration levels as for the pre-
Very hard 104.1 105.8 96.4 cision study. The concentration was calculated from the
Tap 141.0 101.0 99.5 absorbance readings obtained directly and with the
addition of 0.02 m o l l -1 K2S2Os or 0.07 m o l l -1 oxine. In
each case, calibration graphs were plotted with Cr(VI)
results, although the enhancing effect of the cations was standard solutions and blank solutions in the correspond-
not completely removed. ing reagents. The addition of both releaser agents signifi-
F r o m the results obtained it can be concluded that cantly improves the recovery, as shown in Table 1.
the use of a nitrous oxide-acetylene flame with the
stoichiometry used in this study does not prevent system-
atic errors owing to interferences. Moreover, this flame
provides lower sensitivity than the air-acetylene flame (2.5 Validation of the method for chromium determination in
times less sensitive). Therefore the fuel-rich air-acetylene sediments
flame with addition of 0.07 mol 1-1 oxine is the method of The method proposed was validated for four sediments, in
choice. which the chromium content was certified (NBS-1645,
NIES-n °2, BCR-320 and BCR-280). The digestion of the
NBS sediment was performed in a closed Teflon tube,
Quality parameters whereas for the other three sediments it was necessary to
Linear range, detection limits, precision and accuracy continue the digestion in open Teflon beakers. The pro-
cedures are described in the experimental section, The
were determined using the proposed conditions men-
results obtained expressed as chromium content in dry
tioned above.
mass are shown in Table 2. They are given with their 95%
Linear range. A series of Cr standard solutions ranging confidence intervals. The results obtained without sup-
from 0.2 to 20 rag 1-1 were measured in two working pressor were the mean of six replicates whereas the results
sessions and with three different instruments. There was obtained with suppressor were performed in triplicate.
no difference between the instruments used and we did The method proposed, using a fuel-rich air-acetylene
not observe the problem mentioned by T h o m p s o n [19] as flame with the addition of 0.07 m o l l - 1 oxine, gave very
the non-linear behaviour of Cr(III) solutions and the lack good results in all cases.
of reproducibility. The linear range was from 0.2 to
5 m g l -~ Cr(VI) and from 0.2 to 6 mg1-1 Cr(III).
Limit of detection. Detection limits were expressed as the Conclusions
chromium concentration in solution corresponding to
F o r the determination of Cr by FAAS, the use of a fuel-
three times the standard deviation of blank solution
rich air-acetylene flame with a burner height of 3 m m is
(0.29moll -1 HNO3). For the air-acetylene flame, the
recommended. The addition of 0.07 m o l l - 1 8-hydroxy-
detection limit (LOD) was 0.04 mg 1-1 for the three chro-
quinoline (oxine) as a suppressor is recommended to
mium standard solutions tested.
avoid interferences from the cations assayed.
Precision. The precision was calculated at two different The use of a nitrous oxide-acetylene flame at the
concentrations within the linear range: 0.4 and 4 m g l 1. stoichiometry with highest sensitivity is not supported

Table 2. Analysis of sediments for total

chromium (CRM) Certified Certified Without 0.5% K2S;O8 1% oxine
material value suppr.
(rag kg 1)
River sediment 29600 _+2800 27700 _+1180 32310 ± 544 28700 + 2780
NBS SRM-1645
Pond sediment 75 + 5 55 + 6 59 ± 2 70 +_2
NIES CRM-n °2
River sediment 138 ± 7 122 ± 8 121 _+ 1 132 ± 6
BCR CRM-320
Lake sediment 114 + 4 101 _+2 111 _+2 112.4 _+1.5
BCR CRM-280
576

because enhancing effects for almost all of the cations 14. Belloni NL, Malla ME, Roso E (1988) Bol Soc Quire Peril
studied were found. Depressing effects were also found for 187-200
SO4z - and P O e3-. Moreover, the sensitivity achieved with 15. Mostafa MA (1991) Analusis 19:363-366
this flame is approximately one third of that found with 16. Shaw ML, Verma DK, Ferguson KL (1991) Appl Occup
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J (1992) Quire Anal 11 : (1), 25-33
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out this work. Acta 52 : 386-389
22. Wilson L (1968) Anal Chim Acta 40:503-512
23. Thomerson DR, Price WJ (1971) Analyst 96:321-329
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