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Abubakar Tafawa Balewa University
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ABSTRACT
A simple, sensitive, selective, and non-extractive UV-Vis
spectrophotometric method for the determination of cadmium, lead, Published Online: July 13, 2021
chromium, and arsenic in biological, soil and water samples using ISSN: 2684-4478
synthesized and characterized phenyl hydrazone; glutaraldehydephenyl
DOI :10.24018/ejchem.2021.2.3.59
hydrazone (GPH) as the chromogenic reagent was developed. GPH was
synthesized as new chromogenic analytical reagents for the direct UV-Vis
spectrophotometric determination of the selected metals of interest in a S. Echioda
slightly acidic pH of 6.5-7.5 and 20 % dimethylformamide (DMF) solution Department of Science Laboratory
to give stable coloured metal-ligand complexes. The reactions were Technology, Federal College of
instantaneous; the wavelengths of maximum absorptions were followed Agricultural Produce Technology, Kano,
Nigeria.
spectrophotometrically and noted. The reagent GPH revealed a wavelength
of maximum absorption between 360.0 (Cr) to 395.0 nm for (Pb and As) at (e-mail: samechioda@yahoo.com)
A. O. Ogunieye
a working pH of 6.5 to 7.5 room temperature (37 °C). The reagent GPH had Chemistry Department, School of
a molar absorptivity (L mol-1 cm-1) ranging from 2.213×104 (Pb) to Chemistry Education, Federal College of
2.460×104 (As), a mole ratio of metal to ligand of 2:1, the detection limit Education (Technical) Bichi, Kano State.,
(µg/g) ranging from 0.3432 (As) to 0.5250 (Pb) and the metal-ligand complex Nigeria.
was stable for 0-48 hours. The reagents had a Beer’s law validity range (mg S. Salisu
L-1) of 0.001 to 100. The Sandell’s sensitivities (µg/cm 2) ranged from Department of Science Laboratory
0000409 (As) to 0.00499 (Pb) for APDH and 0.00406 (As) to 0.00452 (Pb) Technology, Federal College of
respectively. Large excess of cations and anions as possible interferences up Agricultural Produce Technology, Kano,
Nigeria.
to 15 folds were studied and do not interfere with the determination of the A. A. Abdulrasheed
selected metals of interest. The developed method is highly selective for Cd, Department of Science Laboratory
Pb, and Cr and As and was successfully used for the determination for the Technology, Federal College of
said elements in soil, water, and biological samples. The results of the Agricultural Produce Technology, Kano,
developed methods were comparable with AAS and were found to be in Nigeria.
good agreement. The method had very high precision and very good (e-mail: samechioda@yahoo.com)
accuracy. I. Y. Chindo
Chemistry Department, Abubakar Tafawa
Balewa University, Bauchi, Bauchi State,
Nigeria.
Keywords: Chromogenic reagents, glutaraldehyde phenyl hydrazone, A. M. Kolo
selective, sensitive. Chemistry Department, Abubakar Tafawa
Balewa University, Bauchi, Bauchi State,
Nigeria.
*Corresponding Author
were of analytical grade, sourced from accredited vendors The criterion for interference is an absorbance value varying
and were used without further purification, unless stated by more than ± 5% from the expected value for the metal
otherwise. under observation alone.
A. Samples Collection and Treatment
The samples (Wastewater, Water and Soil) in triplicates III. RESULTS
were collected from Challawa Industrial Area of Kumbotso
TABLE I: DETERMINATION OF LEAD IN SOIL, WATER AND BIOLOGICAL
Local Government Area of Kano State Nigeria West Africa SAMPLES WITH THE DEVELOPED METHOD (GPH) WITH AAS AS
into polythene bags and transported to the laboratory of REFERENCE METHOD
Federal College of Agricultural Produce Technology Kano Relative
Serial Sample Concentration (µg.g-1) ±SD
p-value Error (%)
for analysis. The waste water samples collected (500.00 cm3) No Code of Pb AAS1 GPH
AAS/GPH
were filtered using a filter paper (Whatman No. 41) and then
1 F 0.007 ± 0.001 0.007 ± 0.001 0.2297 0.00
each filtered water sample was evaporated nearly to dryness 2 L 0.001 ± 0.001 0.001 ± 0.000 0.0000 0.00
with a mixture of 5.00 cm3 of concentrated H2SO4 and 10.00 3 P1 1.018 ± 0.001 1.019 ± 0.002 0.5878 +0.0
cm3 concentrated HNO3 in a fume cupboard and then cooled 4 P2 1.014 ± 0.001 1.015 ± 0.000 0.2297 +0.09
to room temperature. In order to dissolve the salts, the residue 5 B 0.001 ± 0.001 0.001 ± 0.000 0.0000 0.00
was then heated with 15.00 cm3 of distilled water. After 6 IW 0.810 ± 0.001 0.081 ± 0.001 0.2991 +0.12
cooling the solution was neutralized with dilute NH4OH 7 SW 1.924 ± 0.002 1.924 ± 0.002 0.2297 0.00
8 WS 1.173 ± 0.003 1.174 ± 0.002 0.5242 +0.08
solution and the obtained solution was filtered into 50.00 cm 3
9 WW 0.877 ± 0.002 0.877 ± 0.003 0.75041 0.00
standard flask and made up to the mark with deionized water
[1]. TABLE II: DETERMINATION OF CADMIUM IN SOIL, WATER AND
Before digestion of the soil samples, each sample was BIOLOGICAL SAMPLES WITH THE DEVELOPED METHOD (GPH) WITH AAS
AS THE REFERENCE METHOD
dried at 65.0 °C for 48.0 hours. All samples were performed
Relative
in triplicates. Five grams (5.00 g) of the samples in crucibles Serial Sample Concentration (µg.g-1) ±SD
p-value Error (%)
was placed in a pre-heated muffle furnace at 200-250.0 °C No Code of Pb AAS1 GPH
AAS/GPH
for 30.0 minutes and ashed for eight hours at 500-550.0 °C. 1 F 0.000 ± 0.000 0.000 ± 0.000 0.00 0.00
Then, the samples were removed from the furnace and 2 L 0.020 ± 0.001 0.020 ± 0.001 0.2297 0.00
cooled. A 2.00 cm3 of 5.00 mol/dm3 of HNO3 was added and 3 P1 0.014 ± 0.003 1.014 ± 0.002 0.75041 0.00
evapourated to dryness on a sand bath. The samples were 4 P2 1.021 ± 0.003 1.021 ± 0.001 1.0000 0.00
then placed in a furnace and heated to 550.0 °C for 15.0 5 B 0.000 ± 0.000 0.000 ± 0.000 0.00 0.00
6 IW 0.031 ± 0.004 0.031 ± 0.001 0.509224 0.00
minutes. The samples were removed from the furnace, 7 SW 1.055 ± 0.004 0.055 ± 0.002 0.814812 0.00
cooled and moistened with four drops of distilled water. Then 8 WS 0.008 ± 0.004 0.008 ± 0.002 0.791764 0.00
2.00 cm3 of concentrated HCl was added into the sample was 9 WW 0.009 ± 0.002 0.008 ± 0.002 0.668422 0.00
evaporated to dryness, removed, and 5.00 cm 3 2.00 mol/dm3
HCl was again added and the crucible. The solution was TABLE III: DETERMINATION OF CHROMIUM IN SOIL, WATER AND
filtered through Whatman No. 41 filter paper and the BIOLOGICAL SAMPLES WITH THE DEVELOPED METHOD (GPH) WITH AAS
AS THE REFERENCE METHOD
transferred quantitatively to a 50.00 cm3 flask by making it Relative
up with deionized water [2]. Serial Sample Concentration (µg.g-1) ±SD
p-value Error (%)
No Code of Pb AAS1 GPH
The biological samples (liver, blood and flesh from AAS/GPH
animals) and plants samples were collected from Challawa 1 F 0.033 ± 0.001 0.033 ± 0.001 0.45826 0.00
industrial of Kano State Nigeria West Africa. The blood 2 L 0.010 ± 0.002 0.010 ± 0.002 0.43902 0.00
samples of 5.00 cm3, the liver, flesh and plants samples were 3 P1 3.474 ± 0.015 3.475 ± 0.002 0.9392 +0.02
oven dried and 5.00 g were transferred into crucibles. The 4 P2 2.042 ± 0.005 2.041 ± 0.003 0.8779 -0.04
5 B 0.000 ± 0.000 0.000 ± 0.000 0.0000 0.00
samples were then ashed in the muffle furnace at 500- 6 IW 1.988 ± 0.001 1.986 ± 0.001 0.1237 -0.10
550.0 ºC for 8.0 hours in the presence of 5.00 cm 3 nitric acid. 7 SW 2.248 ± 0.003 2.247 ± 0.002 0.2438 -0.04
The contents of each crucible were cooled to room 8 WS 2.616 ± 0.004 2.615 ± 0.002 0.2710 -0.03
temperature, and 1.50 cm3 of concentrated hydrochloric acid 9 WW 1.038 ± 0.001 1.039 ± 0.001 0.2926 +0.09
was added and warmed slightly. The solutions were then
transferred quantitatively into 50.0 cm 3 calibrated flask and TABLE IV: DETERMINATION OF ARSENIC IN SOIL, WATER AND
BIOLOGICAL SAMPLES WITH THE DEVELOPED METHOD (GPH) WITH AAS
made up to the mark with deionized water [3]. AS THE REFERENCE METHOD
Relative
B. Samples Collected and their Codes Serial Sample Concentration (µg.g-1) ±SD
p-value Error (%)
No Code of Pb AAS1 GPH
F = Animal flesh, L = Animal liver, P1 = Spinach, P2 = AAS/GPH
Cabbage, B = Animal blood, IW = Irrigation water, SW 1 F 0.000 ± 0.000 0.000 ± 0.000 0.00 0.00
= Wastewater, WS = Farm land Soil, WW = Well water. 2 L 0.000 ± 0.000 0.000 ± 0.000 0.00 0.00
3 P1 0.012 ± 0.001 0.012 ± 0.001 0.00 0.00
C. Effect of Interference or Foreign Ions 4 P2 0.014 ± 0.002 0.014 ± 0.002 0.3415 0.00
The effects of foreign ions (cations; Co, Cu, Al, Fe, Hg, 5 B 0.000 ± 0.000 0.000 ± 0.000 0.00 0.00
Zn, Ca, and anions like SO42-, NO3-) on the determination of 6 IW 0.011 ± 0.001 0.012 ± 0.002 0.2297 +0.09
7 SW 1.010 ± 0.002 0.010 ± 0.002 0.5878 0.00
the heavy metals were studied using the methods of [4] by 8 WS 0.009 ± 0.004 0.010 ± 0.002 0.5878 +1.11
measuring the absorbances of the metal-ligand complex 9 WW 0.028 ± 0.002 0.028 ± 0.002 0.8000 0.00
containing 1, 5, 10 and 15.0 µg mL-1 of the metal of interest.
TABLE V: EVALUATION OF ACCURACY OF LEAD TO THE DEVELOPED TABLE VII: EVALUATION OF ACCURACY OF CHROMIUM (CR) FOR THE
METHOD (GPH) DEVELOPED METHODS (GPH)
GPH method Method GPH
Sample Pb added Sample Cr added
Found (µg/ml) Recovery (%) ± SD Found (µg/ml) Recovery (%) ± SD
- ND - F - ND -
50.0 49.99 99.98±0.2 50.0 49.99 99.99±0.2
F
100.0 99.99 99.99±0.2 100.0 99.99 99.99±0.2
500.0 499.99 99.99±0.1 500.0 499.98 99.99±0.2
- ND -
L - ND -
50.0 49.99 99.98±0.2
L
100.0 99.98 99.98±0.2
50.0 49.99 99.99±0.2
500.0 499.99 99.99±0.2 100.0 99.98 99.98±0.3
- ND - 500.0 499.98 99.99±0.2
50.0 49.97 99.94±0.3 P1 - ND -
P1 50.0 49.97 99.98±0.3
100.0 99.98 99.98±0.2
500.0 499.96 99.20±0.4 100.0 99.98 99.98±0.2
- ND - 500.0 499.96 99.98±0.3
50.0 49.99 99.98±0.3 P2 - ND -
P2
100.0 99.98 99.98±0.2 50.0 49.98 99.96±0.3
500.0 499.99 99.99±0.1 100.0 99.98 99.98±0.3
- ND - 500.0 499.97 99.99±0.2
50.0 49.98 99.96±0.3 B - ND -
B
100.0 99.99 99.99±0.2 50.0 49.98 99.98±0.2
500.0 499.98 99.99±0.1
100.0 99.96 99.96±0.3
- ND -
50.0 49.98 99.96±0.3
500.0 499.97 99.98±0.3
IW IW - ND -
100.0 99.99 99.99±0.1
500.0 499.98 99.99±0.2 50.0 49.99 99.99±0.2
- ND - 100.0 99.97 99.97±0.3
50.0 49.98 99.96±0.3 500.0 499.98 99.99±0.3
SW
100.0 99.99 99.99±0.1 SW - ND -
500.0 499.98 99.99±0.2 50.0 49.99 99.99±0.2
- ND - 100.0 99.98 99.98±0.3
50.0 49.98 99.96±0.3 500.0 499.94 99.98±0.3
WS
100.0 99.98 99.98±0.2 WS - - -
500.0 499.97 99.97±0.2 50.0 49.98 99.96±0.3
- ND - 100.0 99.98 99.98±0.2
50.0 49.98 99.96±0.3 500.0 499.98 99.99±0.2
WW
100.0 99.98 99.98±0.2
WW - ND -
500.0 499.98 99.99±0.2
50.0 49.96 99.92±0.2
Average of five replicate determinations of each Sample (n = 5).
ND = Not Detected.
100.0 99.98 99.98±0.3
SD = standard deviation. 500.0 499.94 99.99±0.2
Average of five replicate determinations of each Sample (n = 5).
ND = Not Detected.
TABLE VI: EVALUATION OF ACCURACY CADMIUM FOR THE DEVELOPED SD = Standard Deviation.
METHODS (GP)
GPH method TABLE VIII: EVALUATION OF ACCURACY OF ARSENIC (AS) FOR THE
Sample Cd added
Found (µg/ml) Recovery (%) ± SD METHODS (GPH)
- ND - GPH Method
50.0 49.99 99.99±0.2 Sample As added
F Found (µg/ml) Recovery (%) ± SD
100.0 99.99 99.99±0.2
F - ND -
500.0 499.97 99.99±0.2
50.0 49.98 99.96±0.3
- ND -
100.0 99.98 99.98±0.3
50.0 49.96 99.92±0.3
L 500.0 499.96 99.99±0.2
100.0 99.98 99.98±0.2
L - ND -
500.0 499.96 99.99±0.2
50.0 49.98 99.98±0.2
- ND -
100.0 99.97 99.97±0.3
50.0 49.98 99.99±0.2
P1 500.0 499.95 99.99±0.2
100.0 99.99 99.99±0.3
500.0 499.97 99.99±0.3
P1 - ND -
- ND -
50.0 49.98 99.96±0.3
50.0 49.99 99.99±0.2
P2 100.0 99.98 99.98±0.2
100.0 99.98 99.98±0.2
500.0 499.96 99.99±0.3
500.0 499.96 99.99±0.3
P2 - ND -
- ND -
50.0 49.98 99.98±0.2
50.0 49.99 99.99±0.2
B 100.0 99.97 99.97±0.3
100.0 99.98 99.98±0.2
500.0 499.96 99.99±0.2
500.0 499.98 99.99±0.3
B - ND -
- ND -
50.0 49.98 99.98±0.2
50.0 49.98 99.98±0.3
IW 100.0 99.97 99.97±0.3
100.0 99.98 99.98±0.3
500.0 499.98 99.99±0.2
500.0 499.98 99.99±0.2
IW - ND -
- ND -
50.0 49.98 99.98±0.3
50.0 49.98 99.99±0.2
SW 100.0 99.98 99.98±0.2
100.0 99.98 99.98±0.3
500.0 499.95 99.99±0.2
500.0 499.96 99.99±0.4
SW - ND -
- ND -
50.0 49.98 99.99±0.1
50.0 49.98 99.98±0.3
WS 100.0 99.95 99.95±0.3
100.0 99.98 99.98±0.3
500.0 499.95 99.99±0.2
500.0 499.97 99.99±0.4
WS - - -
- ND -
50.0 49.98 99.99±0.2
50.0 49.98 99.98±0.3
WW 100.0 99.94 99.94±0.3
100.0 99.98 99.98±0.2
500.0 499.98 99.99±0.2
500.0 499.97 99.99±0.3
WW - ND -
Average of five replicate determinations of each Sample (n=5).
50.0 49.96 99.92±0.3
ND = Not Detected.
100.0 99.98 99.98±0.2
SD = Standard Deviation.
500.0 499.96 99.99±0.2
Average of five replicate determinations of each Sample (n = 5).
ND = Not Detected.
SD = Standard Deviation.