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Communications in Soil
Science and Plant Analysis
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Analytical methods and

quality assurance
a
Aline Renée Coscione , João Carlos de
b c
Andrade , Bernardo van Raij & Monica
d
Ferreira de Abreu
a
Instituto de Química , Universidade Estadual
de Campinas , CP 6154, Campinas, SP,
13083–970, Brazil
b
Instituto de Química , Universidade Estadual
de Campinas , CP 6154, Campinas, SP,
13083–970, Brazil E-mail:
c
Meio Ambiente , EMBRAPA , CP69, Jaguariúna,
SP, 13820–000, Brazil
d
Instituto Agronômico , Centro de Solos e
Recursos Agroambientais , CP 28, Campinas, SP,
13001–970, Brazil
Published online: 11 Nov 2008.

To cite this article: Aline Renée Coscione , João Carlos de Andrade , Bernardo
van Raij & Monica Ferreira de Abreu (2000) Analytical methods and quality
assurance, Communications in Soil Science and Plant Analysis, 31:11-14,
2027-2037, DOI: 10.1080/00103620009370560

To link to this article: http://dx.doi.org/10.1080/00103620009370560

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 COMMUN. SOIL SCI. PLANT ANAL., 31(11-14), 2027-2037 (2000)

An Improved Analytical Protocol for the Routine

Spectrophotometric Determination of Exchangeable Aluminum
in Soil Extracts with Xylenol Orange
Aline Renée Coscione,a João Carlos de Andrade,a,* Bernardo van Raij,b and Monica
Ferreira de Abreuc
Downloaded by [New York University] at 06:05 01 June 2015

a
Universidade Estadual de Campinas, Instituto de Química, CP 6154, 13083-970, Campinas -
SP, Brazil
b
EMBRAPA Meio Ambiente, CP69, 13820-000, Jaguariúna-SP, Brazil
c
InstitutoAgronômico, Centro de Solos e Recursos Agroambientais, CP 28, 13001-970,
Campinas - SP, Brazil
*
Corresponding author [e-mail: dandrade@iqm.unicamp.br].

ABSTRACT

The proposed analytical protocol is applicable to potassium chloride and ammonium chloride
soil extracts. It makes use of ethanol as a reaction accelerator. Full color development is achieved
after a standing period of 2 hours and the absorbance measurements were performed at 555 run,
against the blank. Under these conditions the interference of other elements usually found in the
soil extracts were not important. The calibration graphs, in the range from 0 to 1.0 mg L-1 Al+3
were fitted by 2nd order polynomial regressions. The protocol was tested with 10 representative
soil samples from the State of São Paulo (Brazil), containing exchangeable aluminum varying
from 30 to 200 mg Al kg-1 of soil and variable amounts of iron. All samples were run in triplicate
and the results averaged. The correlation among the proposed procedure and the measurements
obtained by ICP-AES were [A1,XO] = 0.96[Al,ICP] - 7.38 with r2=0.9950 and [Al,XO] =
1.06[Al,ICP] - 6.43 with r2=0.9970, for the KCl and NH4Cl extractions. For absorbance readings
above 0.9 or below 0.1 it is advisable to repeat the determinations by taking sample aliquots of
1.00 or 10.00 mL, respectively. This analytical approach proved to be appropriate for routine
work.

INTRODUCTION

Although not a plant nutrient, aluminum determination in soils is of great importance for
soil fertility evaluation, due to its acid character and to its phytotoxic effects (Me Lean, 1965;
Wright, 1989). Prior to its determination, this element is extracted from soils by shaking the soil
samples with an extracting solution, usually a 1 mol L"1 KC1 solution. Ammonium salt solutions

2027

Copyright © 2000 by Marcel Dekker, Inc. www.dekker.com

 2028 COSCIONEETAL.

(e.g. NH4C1) have also been proposed as an alternative to the KC1 solution, since their use
eliminates clogging effects on nebulizers and reduces the corrosive action on the spectrometers.
This point is of special interest when other exchangeable cations, such as Ca, Mg and Na,
simultaneously extracted with aluminum, are to be determined in the same extract. (Stuanes et
al., 1984; Shuman and Duncan, 1990). In addition, the use of ammonium salts also enables the
determination of K in such extracts, improving the routine work.
However, since the commonly used titration/backtitration procedure (Yuan, 1959; Me
Lean, 1965) for the determination of both the exchangeable acidity and the exchangeable
aluminum is not recommended for NH4C1 extracts and as the determination of aluminum by
backtitration in KC1 extracts was also found not to be appropriate (Coscione et al., 1998), other
simple routine procedures, such as the spectrophotometnc ones, should be considered for the
determination of aluminum, mainly in ammonium salt extracts.
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Many chromogenic reagents have been proposed for spectrophotometnc determination of

aluminum with the eriochrome cyanine R (ECR) (Jones and Thurman, 1957), catechol violet
(CV) (Dougan and Wilson, 1974) and ammonium aurintricarboxylic (Aluminon) (Chenery,
1948; Jayman and Sivasubramaniam, 1974) methods being the most referred procedures. A
procedure using xylenol orange (XO) as color reagent was also proposed for aluminum
determination in soil extracts (Pritchard, 1967), despite its lower sensitivity compared to the ECR
and CV methods. These color reagents have poor selectivity, enabling complexation with other
metals in solution, giving colored species. Even at low concentration, iron is by far the most
important interfering element. Masking or extraction steps are employed to overcome its effects,
but the addition of these steps to the analytical procedure may increase costs and method
complexity, which could also affect the resulting precision and accuracy of the method.
Phosphate, sulfate and fluoride are also major anionic interfering species, due to their ability to
complex aluminum ions to some extent, producing a decrease of the color reaction intensity.
Some authors prefer to avoid such methods, especially if speciation studies are involved in water
analysis, arguing that the reaction pathways and stoichiometries are not yet defined (Bertsch and
Bloom, 1996; Bloom and Erich, 1996).
The Aluminon method is particularly tolerant to phosphate interference but it is very
sensitive to variations in the temperature and requires the use of a stabilizer colloid to protect the
Al-Aluminon complex (Chenery, 1948; Jayman and Sivasubramanian, 1974). The detection is
made at 530 run at a pH of 4.2, adjusted with acetate buffer. Iron interference can be minimized
by using ascorbic acid in place of thyoglicollic acid (Jayman and Sivasubramanian, 1974).
Both the ECR and CV methods have similar sensitivities at pH 6.0 and 6.1, respectively.
Almost saturated hexamethyltetramine (HMTA) is used as buffer, since neither phosphate nor
carboxylic acids can be used for this purpose prepared (Doug and Wilson, 1974; Royset, 1985).
A high concentration of HMTA is necessary to compensate its low buffering capacity on the
alkaline side. The pH variations are not critical for the CV method and the reactions are quite
rapid, although the color intensity increases slowly on standing. Since the detection is made at
585 run, iron interference can be reduced or eliminated by complexation with 1,10-phenantroline
(Doug and Wilson, 1974). On the other hand, a strict pH control is of ultimate importance for the
ECR method, since the color reagent absorbs strongly at lower pHs and the complex formation is
slower at higher pHs. Detection is made at 537 run. The color starts to develop within few
minutes but the complex is stable only after 90 min., variations in absorbance being reported for
shorter reaction times (Onishi, 1986; Doug and Wilson, 1974). No heating is required. Small
deviations of Beer's law were reported for concentrations around 0.2 mg L'1 of Al (Doug and
Wilson, 1974) and the use of stabilizers, such as polycyclic ketoamines or surfactants, can
improve method sensitivity and the stability (Hill, 1966; Royset, 1985).
With respect to the xylenol orange procedure proposed by Pritchard (1967), detection can
be made either at the maximum absorbance of the Al-XO complex, 555 run, or at an
 DETERMINATION OF EXCHANGEABLE ALUMINUM 2029

isoabsorptive point, 536 nm (Otomo, 1963). At this wavelength the absorbance readings are less
sensitive to the concentration of the color reagent. An acetate buffer is commonly used to adjust
the pH to the range from 3.2 to 3.8. The presence of interfering Fe(II) and Fe(III) species is
eliminated by masking with EDTA, but the procedure is time dependent. The reaction rate
between Al and XO is quite slow, requiring heating for faster color development, with slight
color fading on standing (Tikhonov, 1965). Later it was found that the use of ethanol as reaction
accelerator eliminated the heating step in semi-automated procedures (Dodson and Jennings,
1972), opening a new perspective for batch analysis procedures. Considering this feature, the
apparently disadvantageous XO procedure may be of especial interest for routine batch
determination of the exchangeable aluminum in soils. The higher Al-XO complex stability, with
respect to larger time, temperature and pH ranges, permits devising a more robust analytical
procedure, while the development of the color reaction at lower pH results in a lower degree of
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sulfate and phosphate interference. Fluoride was not considered, since is not usually present in
this kind of matrix. In addition, its lower detection would also permit the application of the
method to a larger range of aluminum concentration in the soil extracts, making this color
reagent more attractive for soil analysis purposes.
Thus, this work reports both the investigation of the detailed behavior of the Al-XO
reaction under batch conditions and the development of an analytical protocol for the
determination of aluminum in either 1 mol I/'NH4C1 and KC1 soil extracts.

MATERIAL AND METHODS

The Standard Solutions

Aluminum, iron, sulfate and phosphate standards (Merck) were used to prepare the
1000 mg L'1 stock solutions, by appropriate dilution with deionized water to IL. Aliquots of these
stocks were taken to prepare the working solutions both for the ICP-AES and for the
spectrophotometric calibrations, as well as for the interference studies.

The Soils Samples

Ten representative soils from Säo Paulo State, Brazil, containing exchangeable aluminum
varying form 30 to 200 mg Al kg'1 soil and variable amounts of iron were selected. The
extraction and analysis of all soil samples were made in triplicate, forming a 30-sample set.
Information about these soils are given in Table 1.
The soils were extracted by shaking 5.00 g of air dried soil with 50.00 mL of the
extracting solution on a mechanical shaker (220 rpm) for 15 minutes. The soil extracts were
filtered through quantitative filter paper. Aliquots were taken for the determination of the
exchangeable aluminum by the reported analytical protocol, as well by ICP-AES. These later
results were used as reference, in comparison with those obtained for the exchangeable
aluminum determined by spectrophotometric method. The content of iron, total sulfur and total
phosphorus in these extracts were also determined by ICP-AES. Volume based soil sampling,
instead of mass soil sampling, may be used in routine work. Solutions containing 1 mol L'1 of
KC1 or NH4C1 were used in the extraction.

The ICP-AES Measurements

A Jobin-Yvon Inductively Coupled Argon Plasma Atomic Emission Spectrometer (ICP-

AES), model JY50P, was employed for the analysis of the soil extracts obtained by using either
NH4C1 and KC1 solutions as soil extractants. The ICP operating frequency was 40.68 MHz, at a
 2030 COSCIONE ET AL.

TABLE 1. Characteristics of the soils used for testing the analytical protocol proposed for
the determination of exchangeable aluminum.
pHin Other exchangeable cations and CEC
Soil Classification 0.01 mol L"1 (mmolc dm"3 soil)
number Ca¿* Mg2* CEC(3)
CaCl 2
r
1 Oxisol 4.5 11 5 0.5 55
2 Inceptisol 3.8 1 1 1.0 189
3 Inceptisol 4.2 4 3 1.4 130
4 Inceptisol 5.8 6 5 0.8 122
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5 Ultisol 4.5 19 10 1.3 58

6 Ultisol 5.9 41 16 8.9 84
7 Oxisol 4.0 1 1 0.5 55
8 Ultisol 3.8 1 1 0.8 55
9 Inceptisol 3.8 4 4 0.9 108
10 Oxisol 3.8 1 1 0.6 102
' Cation Exchange Capacity at pH 7

power of 1000 W, with a torch argon flow rate of 12 L min.'1, using the aluminum atomic line at
308.21 run for detection. For iron, sulfur and phosphorus, the atomic lines at 259.94, 180.672
and 178.225 nm were used for detection, respectively. A N2 purge gas flow rate of 0.6 L min."1
was used throughout the analysis.
The calibration of the ICP-AES operating conditions was accomplished by using working
solutions prepared under the same conditions as used for the extractions. Samples were analyzed
using the average of 3 exposures of 5 seconds each and a sample flow rate of 1.5 mL min."1.
Standards were checked periodically for drift and «standardization was performed whenever
variations higher than + 5% were observed.

The Interference Studies

Interference studies were performed for iron (up to 1.0 mg L'1), sulfate (up to 25 mg L"1)
and phosphate (up to 20 mg L"1) ions at three different levels of aluminum (0.2, 0.5 and
0.8 mg L"'), under simulated conditions achieved for measurements with 1 mol L"' NH4C1
extracts. No significative differences in absorbance were observed by changing the extracting
solution to 1 mol L"1 KC1.

The Analytical Protocol

Based on the results discussed below, it was possible to propose the following analytical
protocol for routine batch spectrophotometric determination of exchangeable aluminum in soils,
using xylenol orange.
 DETERMINATION OF EXCHANGEABLE ALUMINUM 2031

Reagents

1. Standard Al working solution (50 mg L"'): Pipette 5.00 mL of the 1000 mg L'1 Al stock
solution into a 100 mL volumetric flask. Dilute to the mark with deionized water.

2. HC1 solution (1 mol L"1): Add slowly 8.5 mL of concentrated HC1 to 50 mL of deionized
water. Dilute to 100 mL with deionized water.

3. Xylenol orange, 0.15% (m/v): Dissolve 0.15 (+ 0.02) g of xylenol orange tetrassodium salt
with 50 mL of deionized water into a 100 mL volumetric flask. Add few drops of 1 mol L"1 HC1
solution until obtain a clear orange solution. Avoid excess of acid.

4. Sodium acetate/acetic acid buffer solution, pH 3.4 (2 mol L'1): Dissolve 14.0 (+ 0.1) g of
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sodium acetate in 300 mL of water. Add 90.0 (± 0.1) mL of glacial acetic acid. Dilute to 900 mL
with water. Verify if the pH is in the range 3.4 ± 0.1 by using a pH meter. If necessary, add few
drops of 1 mol L'1 HC1 solution or small portions of 0.1 g of sodium acetate until reach the
required pH range. Dilute to IL with water.

5. Ethanol, PA (min. 99,5% purity)

Procedure

Transfer to 50 mL volumetric flasks 10.0 (± 0.5) mL of buffer solution (reagent 4), and
25.0 (± 0.5) mL of ethanol (reagent 5). Always using the same pipette, add 1.0 mL of the
xylenol orange solution (reagent 3) to each of the volumetric flasks used in the analysis. Mix
carefully. In sequence, add 2.00 mL aliquots of the 1 mol L*1 KC1 or NH4C1 soil extracts to each
flask and dilute to the mark with water. The same procedure must be followed for the calibration
curve which should be run within the sample set being analyzed by substituting the soil extracts
aliquot by 2.00 mL of the pure extracting solution used in the extraction step. The range of the
calibration curve is obtained by pipetting 0 (blank), 0.20, 0.40, 0.60, 0.80 and 1.00 mL of the
standard aluminum work solution (reagent 1) to obtain 0, 0.20, 0.40, 0.60, 0.80 and 1.00 mg L"'
Al solutions. Dilute to the mark with water and stir carefully.
The color development is almost fully achieved after a standing period of 2 hours. The
absorbance measurements should be performed at 555 nm against the blank, using a 10 mm
pathlength cell. For absorbance readings above 0.9 or below 0.1 it is advisable to repeat the
determinations by taking sample aiiquots of 1.00 or 10.00 mL, respectively. The aluminum
concentration in the samples can be obtained by simple calculations after fitting the calibration
graph to a 2nd order polynomial regression. If sipper or any flow device is used to fill the
spectrophotometric cell, it is necessary first to pump a 50 % v/v aqueous-ethanol solution into
the cell and wait for baseline stabilization. This will prevent the formation of bubbles during the
protocol run, which will affect the absorbance readings.

Calculation

mg Al +3 kg'' soil = 10xmgL' xdf

df = dilution factor = volume of extracting solution (50.00 mL)/ extract aliquot(mL)

RESULTS AND DISCUSSION

One of our aims was to extend the analytical procedure to as large a range of Al
concentration as possible. In addition, methods with absorbance optima at lower pHs, such as
 2032 COSCIONEETAL.

that of XO, are expected to be less affected by sulfate and phosphate interference, since these Al-
complexes are less stable at more acid pHs (Royset, 1985). Other points also to be considered are
the low absorption of the reagent at wavelengths closer to the Al-XO complex absorption
maximum and its relatively low sensitivity to pH variations in the pH range of 3.2 - 3.8. The
proposed procedure does not require previous reagent purification, although good quality
products are recommended.
The main disadvantage of the xylenol orange method described in the literature
(Pritchard, 1967) is the low reaction rate of the Al-XO complex formation, but this can now be
overcome by using a 50% (v/v) aqueous ethanolic solution as a reaction accelerator, as suggested
by Dodson and Jennings (1972) for semi-automated procedures. No relevant comments on the
effect of the ethanol in the reaction mechanism were found, but this approach proved to be also
effective for batch procedures. Under this condition, the reaction is almost completed within the
Downloaded by [New York University] at 06:05 01 June 2015

first two hours of standing and it seems to be independent of the Al concentration, as can be seen
from Figure 1. After two hours, the absorbance readings remains practically constant, with a
slight increasing tendency. This small increase can be properly corrected by running the
calibration curve along with the real samples. This paired procedure enable us to leave the
sample set standing for up to 120 hours without loss of precision.
For the purposes of this work, the procedure using KC1 solution was considered as the
reference, since its widely accepted as a soil extracting solution in routine soil analysis. Initially,
both the KC1 and NH4C1 extracting solutions were used at theirs natural pHs values. Experiments
with lower pH values for the NH,C1 extracting solution indicated no significant differences in the
quantities of Al found down to pH 3.8, using ICP determinations.
The action of the major and potential method interfering species, iron, phosphate and
sulfate ions, were evaluated at three different levels of aluminum in the final solution, namely
0.2,0.5 and 0.8 mg L'1. The most important interference effects are caused by iron, both Fe(II) as
Fe (III), as shown at Figure 2. However, the level of this element in the final solution, obtained
after diluting the sample extract aliquots to 50.00 mL in volumetric flasks, is low enough to not
be considered as a severe interfering specie, even when a less favorable situation is faced, as is
the case of samples 5 and 6 in Table 2, where ten milliliters of soil extract were taken for the
determination of aluminum.
Correlation of the results between ICP-AES and the proposed spectrophotometric
procedures, given below, clearly indicate that no additional step should be required to prevent the
interference of iron on the aluminum results. Phosphate did not interfere at lower Al levels, but a
small decrease in the absorbance is observed for both higher concentrations of Al (e.g. 0.8 mg L"
') and phosphate (e.g. 20 mg L"1). However, this variation in absorbance showed not to be
significant up to about 5 mg L"1 of P, which is much more than the usually observed phosphate
concentrations in 1 mol L'1 KC1 or NH4C1 soil extracts, as indicated in Table 2. Sulfate did not
interfere at least up to the 25 mg L"1 level. Further, the procedure described in this work extended
the working range of the calibration graph up to 1.0 mg L"' of Al, although fitted by 2nd order
polynomial regression, as shown in Figure 3 by using 1 mol L'1 NH4C1 solution according to the
procedure stated in the experimental section. Although Pritchard (1967) has reported the xylenol
orange methodology, with detection at 550 nm, over be linear at the range from 0 - 0.6 mg L'1 Al,
the non-linear calibration curves found in this work are consistent with the studies of Tikhonov
(1965), Tikhonov and Petrova (1973) and Otomo (1963).
A similar equation, A=0.386[AP3]2 + 0.570[Al+3] - 0.007, with a regression coefficient
r =0.9994, was found when employing 2.00 mL of the conventional 1 mol L"1 KC1 solution
2

instead of the NH4C1 solution. These results indicate that a specific calibration curve has to be
run, according to the extracting solution used. Although non-linear calibration curves may be
pointed out as a disadvantage for analytical method comparisons, this seems not to be the case.
Nowadays, common 2nd order polynomial regression routines are incorporated in most scientific
calculators and many spectrophotometers, making their use easy in laboratory calculations.
 DETERMINATION OF EXCHANGEABLE ALUMINUM 2033

10
0.8-
u Al:0.9mgL"'
c
as
•° 0.6-
o
* • • •
"° 0.4-
Al : 0.6 mg L'1
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• • • • •
0.2-

Al : 0.3 mg L"1
nn-
20 40 60 80 100 120
time / (hours)

FIGURE 1. Stability of aluminum - xylenol orange complex, under the

experimental conditions of this paper.

1.0-

0.8-

0.6-
o

0.4-

0.2-

Al : 0.2 mg L
0.0
0.0 0.2 0.4 0.6 0.8 1.0
Iron / (mg L" )
FIGURE 2. Interference effects caused by iron in the spectrophotometric
determination of Al with xylenol orange. Details in the
experimental section.
 TABLE 2. Aluminum and its major intefering species contents found
in KC1 extracts, by ICP-AES measurements.
Soil Fe S ( SO42) P(PO
number m g kg' 1 mgL-1 mg kg'1 mgL"1 mg kg'1 mgL" 1
soil soin." soil soln.(*» soil soln.(<)
1 2.7 0.01 12.3 0.05 2.6 0.01
2 9.8 0.02 21.5 0.04 3.5 0.01
3 5.1 0.02 17.8 0.07 4.2 0.02-
4 4.1 0.02 20.6 0.08 4.2 0.02
5<»> 2.2 0.05 17.8 0.36 5.5 0.11
6<"> 2.4 0.05 22.0 0.42 6.0 0.12
Downloaded by [New York University] at 06:05 01 June 2015

7 3.8 0.01 15.0 0.06 4.5 0.02

8 6.1 0.02 20.0 0.08 1.0 0.00
9 10.1 0.04 27.9 0.11 3.0 0.01
10 4.1 0.03 27.5 0.11 1.3 0.01
(<)
Values calculated for the final solution used for the
spectrophotometric determination of Al, from the values found by
ICP-AES measurements. Lower values were found at NH4C1 soil
extracts.
''^ Cases where ten milliliters of soil extract were taken for the
determination of aluminum.

1.0-

u
0.8 H
c
03

"S 0.6-
o Y=A + B,[A1] + B2[A1]'
Parameter Value
•° 0.4-
A 0.001
0.2- B, 0.548
B, 0.396

0.0-
r = 0.9995
0.0 0.2 0.4 0.6 0.8 1.0 1.2

. FIGURE 3. Calibration curve and its 2nd order polynomial equation for
the batch spectrophotometric determination of aluminum
with xylenol orange.
 DETERMINATION OF EXCHANGEABLE ALUMINUM 2035

350-

300-
Extracting solution : NH4C1 I

250-

[A1,XO] = A + B[A1,ICP]
Parameter Value SE
Downloaded by [New York University] at 06:05 01 June 2015

-6.43 2.34
1.06 0.02

r = 0.9970

50 100 150 200 250 300

[Al,ICP]/(mgkg soil)

FIGURE 4. Correlation for the determination of aluminum by ICP-AES

compared to the suggested analytical protocol. For details on
the calculation of the standard errors (SE), see discussion.

The proposed procedure, using 2.00 rtiL of the soil extracts, is effective whitin the range
from 25 to 230 mg Al+3 k g ' of soil without any further manipulation. However, it is
recommended to repeat the procedure whenever the absorbance readings are lower than 0.1
(equivalent to about 0.15 mg L'1 of Al+3 at the final solution) or higher than 0.9 (equivalent to
about 0.95 mg L"1 of Al+3 at the final solution) by taking 10.00 mL or 1.00 mL aliquots of the
sample extract, respectively. This can extend the range of the method from 10 to 500 mg Al+3 kg"1
of soil, which corresponds to 1.11 to 55.6 mmolc Al+3kg"' of soil or 0.11 to 5.56 meq Al+3/ (100 g
of soil).
Good correlations among ICP-AES and spectrophotometric measurements were obtained
for the Al determination using both KCl an NH4C1 as extracting solutions. The correlation curve
for the NH4C1 extracts, (Figure 4) is given by [Al.XO] = 1.06(± O.O2)[A1JCP] - 6.43(+2.34) with
a regression coefficient of r2 = 0.9970. That obtained for KCl extracts, given by the equation
[A1,XO] = 0.96(± 0.01)[Al,ICP] - 7.38(±1.06), with a regression coefficient of ^=0.9950, is very
close to that of the NH4C1 extract. All correlations were obtained by the least squares resolution,
and the standard errors (SE) were calculated by the variance-covariance matrix and the standard
deviation for the regression. All the coefficients presented were shown to be significant at a 95%
confidence level for the F-test.
In conclusion, the proposed analytical protocol proved to be appropriate for the routine
determination of aluminum with either KCl or NH4C1 soil extracts in soil fertility studies. Under
the operational conditions described, no significant interferences were found.
 2036 COSCIONEETAL.

ACKNOWLEDGMENTS

Thanks are due to Conselho Nacional de Desenvolvimento Científico e Tecnológico

(CNPq) and to Fundaçâo de Amparo a Pesquisa do Estado de Säo Paulo (FAPESP) for
supporting the research activities of J.C. de Andrade and B.v. Raij. The authors also
acknowledge Prof. C. H. Collins for reading the manuscript and CNPq for a fellowship to
A.R.Coscione.

REFERENCES

Bertsch, P. M. and P. R. Bloom. 1996. Aluminum. pp. 517-550, IN: Bigham, J. M. (ed.).
Methods of Soil Analysis. Agronomy, Part 3, Chemical Methods. Soil Science Society of
Downloaded by [New York University] at 06:05 01 June 2015

America, Inc. and American Society of Agronomy, Inc. Madison, WI, USA.

Bloom, P.R. and M.S. Erich. 1996. The quantification of aqueous aluminum. pp. 1-27, IN: G.
Sposito (ed.) Geochemistry of aluminum. CRC Press, Boca Raton, Florida,USA.

Chenery, E. M. 1948. Thioglycollic acid as an inhibitor for iron in the colorimetric determination
of aluminum by means of Aluminon. Analyst. 73: 501-503.

Coscione, A. R.; J. C. de Andrade and B. van Raij. 1998. Revisiting titration procedures for the
determination of exchangeable acidity and exchangeable aluminum in soils. Commum. in
Soil Sci. Plant Anal. 29(11-14): 1973-1982.

Dodson, A. and V. J. Jennings. 1972. Semi-automated determination of aluminum with xylenol

orange. Talanta. 19:801-803.

Dougan, W. K. and A. L. Wilson. 1974. The absorptiometric determination of aluminum in

water. A comparison of some chromogenic reagents and the development of an improved
method. Analyst. 99:413-430.

Hill, U. T. 1966. New direct spectrophotometric determination of aluminum in steel, spelter and
iron ores. Anal Chem. 38:654-656.

Jayman, T.C.Z. and S. Sivasubramaniam. 1974. The use of ascorbic acid to eliminate
interference from iron in the Aluminon method for determining aluminum in plant and soil
extracts. Analyst 99:296-301.

Jones, L.H. and D. A. Thurman. 1958. The determination of Al in soil, ash and plant material
using eriochrome cyanine RA. Plant and Soil. 9(2): 131-142.

McLean, E. O. 1965. Aluminum. pp. 978-998. IN: C. A. Black et al. (ed.). Methods of Soil
Analysis. Agronomy, Part 2, n°9. American Society of Agronomy, Madison, WI, USA.

Onishi, H. 1986. Photometric determination of trace metals - Part IIa. Aluminum. pp. 1-75. 4th
edition. John Wiley & Sons, New York, NY, USA.

Otomo, M. 1963. The spectrophotometric determination of aluminum with xylenol orange. Bull.
Chem. Soc. Jpn. 36:809-813.
 DETERMINATION OF EXCHANGEABLE ALUMINUM 2037

Pritchard, D. T. 1967. Spectrophotometric determination of aluminum in soil extracts with

xylenol orange. Analyst. 22:103-106.

Royset,O. 1985. Comparison of four chromogenic reagents for the flow-injection determination
of aluminum in water. Anal. Chim. Acta. 178:223-230.

Shuman, L.M. and R.R. Duncan. 1990. Soil exchangeable cations and aluminum measured by
ammonium chloride, potassium chloride and ammonium acetate. Commun. Soil Sci. Plant
Anal. 21:1217-1228.

Stuanes, A.O. ; G.Ogner, and M. Opem. 1984. Ammonium nitrate as extractant for soil
exchangeable cations, exchangeable acidity and aluminum. Commun. Soil Sci. Plant
Downloaded by [New York University] at 06:05 01 June 2015

Anal. 15:773-7 78.

Tikhonov, V. I. 1965. Photometric determination of aluminum by means of xylenol orange. J.

Anal. Chem. USSR. 20:1009-1013 [in russian: Zh. Anal. Khim. 20:941-1013].

Tikhonov, V. I. and Petrova, L. F. 1973. Increasing the accuracy of the photometric

determination of aluminum by means of xylenol orange by measuring the absorbance at the
isobestic point. J. Anal. Chem USSR. 28:1259-1261 [in russian: Zh. Anal. Khim. 28:1413-
1415].

Wright, R. J. 1989. Soil aluminum toxicity and plant growth. Commum. in Soil Sci. Plant Anal.
20(15& 16): 1479-1497.

Yuan, T. L. 1959. Determination of exchangeable hydrogen in soils by a titration method. Soil

Sci. 88:164-167.