This article was downloaded by: [114.79.28.

90]
On: 04 October 2014, At: 17:48
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

Soil Science and Plant Nutrition

Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/tssp20

Determination of Total Boron in

Soil by the Curcumin-Acetic Acid
Method After Extraction with 2Ethyl-1,3-Hexanediol
a

Hidekazu Yamada & Tomoo Hattori

Department of Agricultural Chemistry. Faculty of

Agriculture , Kyoto Prefectural University , Shimogamo ,
Kyoto , 606 , Japan
Published online: 30 Oct 2012.

To cite this article: Hidekazu Yamada & Tomoo Hattori (1986) Determination of Total Boron
in Soil by the Curcumin-Acetic Acid Method After Extraction with 2-Ethyl-1,3-Hexanediol, Soil
Science and Plant Nutrition, 32:1, 135-139, DOI: 10.1080/00380768.1986.10557487
To link to this article: http://dx.doi.org/10.1080/00380768.1986.10557487

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information
(the Content) contained in the publications on our platform. However, Taylor
& Francis, our agents, and our licensors make no representations or warranties
whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and
views of the authors, and are not the views of or endorsed by Taylor & Francis. The
accuracy of the Content should not be relied upon and should be independently
verified with primary sources of information. Taylor and Francis shall not be liable
for any losses, actions, claims, proceedings, demands, costs, expenses, damages,
and other liabilities whatsoever or howsoever caused arising directly or indirectly in
connection with, in relation to or arising out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden.
Terms & Conditions of access and use can be found at http://www.tandfonline.com/
page/terms-and-conditions

Short Communication
Soil Set. Plant Nutr., 32 (1), 135-139, 1986

DETERMINATION OF TOTAL BORON IN SOIL BY

THE CURCUMIN-ACETIC ACID METHOD AFTER
EXTRACTION WITH 2-ETHYL-l,3-HEXANEDIOL
Hidekazu YAMADA and Tomoo HATTORI

Downloaded by [114.79.28.90] at 17:48 04 October 2014

Department of Agricultural Chemistry. Faculty of Agriculture.

Kyoto Prefectural University. Shimogamo. Kyoto, 606 Japan

Received February 12, 1985

The curcumin-acetic acid method after extraction of boron into chloroform or

methyl isobutyl ketone with 2-ethyl-I,3-hexanediol (EHD) has been used for the determination of boron in fertilizers (1) and foods (2). The extraction with EHD is so
selective to boron that it appears to be a suitable procedure for the separation of boron
from the solution of soil digests. The curcumin-acetic acid method is based on the
fact that boron in the organic phase reacts with curcumin in an acetic acid-concentrated sulfuric acid medium, and this method is simpler than the conventional curcumin
method that requires evaporation to dryness of the reagents.
To apply this technique to the determination of boron in soil we evaluated several
analytical conditions for the extraction of boron and color development in the curcumin-acetic acid method.
Experimental
J) Chemicals and reagents. Extracting solvent: dissolve 200 ml of EHD into
chloroform, dilute to 1,000 ml with chloroform. Curcumin-acetic acid solution: dissolve 0.5 g of curcumin into 250 ml of hot glacial acetic acid (60-70C) in a polyethylene
bottle. This reagent solution stored in a dark polyethylene bottle is stable for at least
2 months. Standard boron solution: dissolve 2.858 g of boric acid (HallOs) in water,
dilute to 500 mI. This stock solution contains I mg of boron per ml and is diluted
to prepare the working solutions before use.
2) Apparatus. Absorbance was read with a Hitachi 100-60 type spectrophotometer using 1 cm glass cells. Phase separating filter paper, Whatman IPS, was used
for the separation of the aqueous and organic phases.
3) Procedure. Fuse 0.2 g of fine-powdered soil sample with I.S g of sodium
peroxide, Na 20 2 , in a 35 ml nickel crucible for 20 min in an electric furnace at 550C.
Cool and place the crucible in a 100 ml polytetrafluoroethylene (PTFE, Tefion) beaker,
and add 5 ml of water in the crucible. Place a polyethylene-made watch glass on the
Key Words:

boron, 2-ethyl-l,3-hexanediol, curcumin.

135

Downloaded by [114.79.28.90] at 17:48 04 October 2014

136

H. YAMADA and T. HATTORI

beaker and allow to stand for 30 min to digest the melted product. Transfer the crucible contents into the PTFE beaker. Wash the crucible several times with water and
add the washings to the beaker. Acidify the solution in the beaker by gradual addition
of approximately 4 ml of (1 + 2)H2SO, and heat the beaker on a hot plate. After
cooling, transfer the solution in the PTFE beaker into the 50 ml polyethylene bottle
with a narrow mouth and dilute it to 25 mt with water. Add 4 ml of extracting solvent
in the bottle and shake it for 3 min. Filter the contents in the bottle with a phase
separating filter paper to separate the organic phase from the aqueous phase. To 1
ml of the filtrate (organic phase) add 1 ml of curcumin-acetic acid solution and 0.25
ml of concentrated sulfuric acid. Allow the mixture to stand for 30 min with occasional shaking and dilute it to 50 ml with 95% ethanol. After 30 min, measure the
absorbance at 550 nm with reagent blank as a reference, and determine the concentration of boron with reference to a calibration curve prepared at the same time.

Results and discussion

Elemental analysis of soils necessitates their decomposition into soluble forms by
acid digestion or fusion with various fiuxes. As boron volatilizes easily from the acidic
aqueous solution upon heating, alkali fusion is suitable for boron analysis of soil.
Alkali fusion with sodium peroxide as a fusion fiux was chosen. Soil sample could be
completely decomposed with the addition of an amount of sodium peroxide of more
than six times the weight of the soil sample. A larger flux/sample ratio is desirable
so that both the temperature and time of fusion can be kept to a minimum. But when
sodium peroxide was added in excess, the amount of sulfuric acid to acidify the solution after fusion increased and the corrosion of the nickel crucible was accelerated.
Therefore, 1.5 g of sodium peroxide was mixed with 200 mg of soil and the mixture
was fused for 20 min at 550C.
Extraction conditions of boron with EHD and conditions for color development
of the boron-curcumin complex in an acetic acid-concentrated sulfuric acid medium
were also studied. The results obtained generally agreed well with the results reported
by AOAZZI (3) and by UENO and TODA (1); thus, this paper described a few improvements in the method.
It is well known that a small amount of water contaminating the organic phase
affects the color development of the boron-curcumin complex: with only 50 ,ul of water
present in 1 ml of organic phase, the absorbance was about 85% of that without water
in the organic phase. To remove the interference from water, the filtration through
a dry filter paper or the addition of a drying agent, such as sodium sulfate anhydride
or propionic anhydride, has been tested. But when a phase separating filter paper
was used, the phase separation and the dehydration of the organic phase could be
achieved at the same time.
The volume ratio of an aqueous to an organic phase is of importance in solvent
extraction, because the recovery by extraction is closely related to the value of the
ratio. A higher ratio is desirable as a means of concentrating boron, hence lowering

Determination of Boron in Soil

0.4
e

6 03

137

'0o--<l..-

~O.2

~~

'"

.0
I-

~ 0.1

Downloaded by [114.79.28.90] at 17:48 04 October 2014

12

16

Vaq .' Vorg

Fig. 1. Effect of ratio of aqueous to organic phase on extraction of boron. The procedure is
described in the text, with varying volume of aqueous phase containing 4 pg of boron. Vaq
volume of aqueous phase; Vorg volume of organic phase.

the detection limit. AOAZZI (3) reported that when the volume ratio of the aqueous
to the organic phase was below 2: 1, boron could be quantitatively extracted (recovery>
96%) in a single extraction. Our study showed that the extractability decreased with
the increase of the ratio as shown in Fig. 1, but the decrease of the extractability was
gradual until a value of about six for the ratio was attained. Considering these results
and the sensitivity of the analysis, we used a ratio of 4 ml of organic phase to 25 ml
of aqueous phase. Under these conditions, the percentage extraction of boron was
about 91 % regardless of the amount of boron present in the aqueous phase.
The calibration curve for the determination of boron was linear over the range
of 1 to 32 pg boron in the aqueous phase. The molar absorptivity calculated from
the slope of the curve was 1.7 x 105 dms mol-1 cm-1 at 550 nm of the wavelength of
maximum absorption. The mean absorbance and its relative standard deviation obtained from five analyses of a sample containing 1 pg of boron in the aqueous phase
were 0.078 and 1.14%, respectively. These results indicate that when more than 4
ppm is present in the soil, boron content can be determined with 200 mg of soil sample.
The proposed method was applied to the determination of boron in two soils
(soils A and B) to evaluate the reproducibility and the recovery with this method.
Soil B contained about 2,220 ppm of chromium, one of the few elements interfering
with the extraction of boron with EHD. The recovery tests were carried out by
adding a known amount of boron as boric acid and determining the boron by the
proposed method. As seen in Table 1, the determined values were highly reproducible with relative standard deviations of 2.69% (for soil A) and 4.16% (for soil B)
,and satisfactory recoveries (98.3-98.9%) of boron were obtained. Consequently the
'
lowering of the recovery due to chromium could be avoided.
/'
Boron contents of the reference soil samples from the Soil Research Institute,
'Central Experimental Farm, Canada and the geochemical reference rock samples JB-I

138

H. YAMADA and T. HATTORI

Table 1. Reproducibility and recovery of added boron with the proposed method.

Sample

Sample taken (g)

Soil A

Downloaded by [114.79.28.90] at 17:48 04 October 2014

SoilB

Boron added (Jlg) as B

in the form of HaBOs

Boron found (Jlg)

0.200

7.36, 7.18, 7.04, 7.48

X=7.27 (36.3 ppm in soil)
S=0.194, CV=2.67%

0.200

5.0

12. 1, 12.3, 12. 1, 12.2

X=12.2, S=0.0957, CV=0.79%
Recovery=98.3%

0.100

2.14, 2.20, 2.24, 2.36

X=2.24 (22.4 ppm in soil)
S=0.0929, CV=4.16%

O. 100

5.0

7.24, 7.12
X=7.18, Recovery=98.9%

X, mean; S, standard deviation; CV, coefficient of variation. Soil A: collected from the plow layer of
a paddy field at Kyoto Prefectural University. Soil B: collected from the surface of virgin land formed
on serpentinite at Ooe-cho in Kyoto Prefecture.

Table 2. Analytical results of boron in reference samples.

Reference sample

Boron concentration
(ppm)

Mean
(ppm)

Reported value (4, 5)

(ppm)

Soil

SO-I
SO-3
SO-4

20.9, 24.1, 22.6

29.7, 28.9,25.9
44.7, 47.9, 46.0

22.5
28.2
46.2

204
227
4310

Rock

JB-1

8.8, 10.1, 10.9

5.9, 6.5, 6.0

9.9
6.1

8.2*

JO-l
Arithmetic mean of reported values (5).

(basalt) and JG-! (granodiorite) from the Geological Survey of Japan were determined
to evaluate the accuracy of the method. The boron contents obtained in this study
were in good agreement with the reported values (4, 5) for the reference samples (Table 2).
REFERENCES
1) UENO, Y. and TODA, T., Determination of boron in fertilizer by using curcumin-acetic acid, Hiken
Kaiho, 29, 14-20 (1976) (in Japanese)
2) FUKUI, S., HIRAYAMA, T., NOHARA, M., KOBAYASHI, K., KAWAMURA, T., IWAIDA, M., lTo, Y.,
OOAWA, S., KAKIUCHI, Y., YAMAZAKI, H., and ONO, N., Colorimetric determination of boric acid

Determination of Boron in Soil

139

in food by chelate extraction with 2-ethyl-l,3-hexanediol and by using protonated curcumin, Eisei
Kagaku, 29, 323-328 (1983) (in Japanese)
J) AOAZZI, E.J., Extraction flame photometric determination of boron, Anal. Chem., 39, 233-235 (1967)

Downloaded by [114.79.28.90] at 17:48 04 October 2014

4) STEaM, H.P., Certified reference materials, CANMET (Canada Centre of Mineral and Energy Technology) Report 80-6E (1980)
S) ANoo, A., KURASAWA, H OHMORI, T., and TAKEOA, E., 1974 compilation of data on the OSJ
geochemical reference samples JG-l granodiorite and JB-l basalt, Geochem. J., 8, 175-192 (1974)