Asian Journal of Organic & Medicinal Chemistry ISSN Online: 2456-8937

Vol. 7 No. 2 (April-June, CRNSS 2022) UGC CARE APPROVED JOURNAL

Acid-base Modified Biosorbent for Heavy Metal Removal - A Review

Bharat N. Shelke1,2, Manohar K. Jopale2,3, Manoj R. Gaware4 and Amol H. Kategaonkar5,*
1
Department of Chemistry, M.V.P. Samaj's Arts, Science and Commerce College, Ozar (Mig) Nashik-422206,
India
2
Department of Chemistry, M.V.P. Samaj's G. M. D Arts, B. W. Commerce and Science College, Sinnar,
Nashik-422103, India
3
Department of Chemistry, M.V.P. Samaj's Arts, Commerce & Science College Jawahar Road,
Tryambykeshwar, Nashik-422212, India
4
Department of Chemistry, M.V.P. Samaj's K. P. G. Arts, Commerce & Science College Takeghoti, Igatpuri,
Nashik-422402, India
5
Post Graduate Department of Chemistry, M.V.P. Samaj's K.S.K.W. Arts, Science and Commerce College,
CIDCO, Uttamnagar, Nashik 422008, India

ABSTRACT
The heavy metals Cu, Cd, Ni, Cr, Pb, As and Bi removal by modified low cost adsorbents were reviewed in the
current article. The present study focuses on enhancement of adsorption of metal by acid-base modification of
low cost adsorbent. An acid modification were carried out by H2SO4, HNO3, H3PO4, citric acid and tartaric acid
while base modification were carried out by NaOH, K2CO3 and KOH. The review represents various parameters
such as activation agent of adsorbent by acid-base, type of adsorbent, characterization methods viz. SEM, EDS,
FTIR, BET and maximum adsorption capacity of heavy metals. Adsorption method is found superior for
removal of pollutant from waste water than any other conventional method. The adsorption of metal on
adsorbent surface occurred by physical sorption, chemical sorption, complexation, ion exchange and through
pore diffusion process. Agricultural waste adsorbents are found good alternative due its negligible cost, easy
availability and maximum adsorption capacity.

KEYWORDS: Heavy metals; Adsorbent; Acid-base treatment; SEM; BET

INTRODUCTION
Heavy metals are major toxic pollutants specially found in waste water discharges from different industries. The
process of metal extraction from ore such as mining, roasting, pulverizing, refining greatly contributes the
heavy metal accumulation into the waste water while the fertilizer industry, tanneries, pesticides, batteries,
electroplating and paper industries also introduces heavy metal into the environment 1. Heavy metals such as
Cadmium (Cd), Chromium (Cr), Copper (Cu), Cobalt (Co), Lead (Pb), Zinc (Zn), Arsenic (As) Vanadium (V)
and Nickel (Ni) shows adverse effect on animals as well as aquatic life2. The effluent of industrial waste
containing large amount of toxic heavy metals without prior treatment causes hazardous effect to aquatic life.
Many of the heavy metals are non-biodegradable and hence accumulate in the food chain which reduces the
human life3. Cadmium (Cd) is carcinogenic and responsible for Itai-Itai disease, anemia, dyspnea, Chromium
causes lungs tumor and allergic dermatitis, Copper (Cu) gives liver illness, diarrhea, headache, Mercury affects
on kidney, nervousness, unconsciousness, Nickel (Ni) causes anaphylaxis and damages red blood cells, lead
(Pb) affects on appetite loss, kidney failure, high blood pressure, anemia and Zinc (Zn) causes restlessness and
metal fume fever4.

Nowdays numerous techniques are available for the removal of heavy metals such as precipitation, oxidation,
reduction, ultrafiltration, reverse osmosis, electro dialysis and ion exchangers5. Due to increase in processing
cost, low efficiency, low sensitivity, all these techniques have certain limitations for heavy metal removal from
waste water. Adsorption is an advantageous technique over the all of these methods due to low cost and greater
removal efficiency of metal from waste water6. An activated carbon adsorbent used for heavy metal removal
shows greater removal efficiency and easy operating process but due to its high cost it have some limitation.
The adsorbent prepared from fly ash, sludge, industrial waste, zeolites and agricultural waste has great
significance for heavy metal removal 7-8.

In the current review article, the surface modification for various low cost adsorbents by acid-base treatment is
explored. The absorption efficiency of adsorbent can be enhanced by activation viz. physical method and

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Asian Journal of Organic & Medicinal Chemistry ISSN Online: 2456-8937
Vol. 7 No. 2 (April-June, CRNSS 2022) UGC CARE APPROVED JOURNAL

chemical method9. The present work summarizes the effect of modification of various adsorbents by treatment
with sulphuric acid, hydrochloric acid, nitric acid, tartaric acid, phosphoric acid while with base sodium
hydroxide, potassium hydroxide, potassium carbonate and calcium hydroxide.

Sulphuric
acid
(H2SO4)
Potassium Nitric
carbonate acid
(K2CO3) (HNO3)

Sodium Phosphoric
hydroxide acid
(NaOH) Activation (H3PO4)
of adsorbent
by acid-base

Potassium Citric
hydroxide acid
(KOH) (C6H8O7)

Calcium Tartaric
hydroxide acid
(Ca(OH)2) (C4H6O6)

Figure 1. Activation of adsorbent by various Acid-Base treatment

Modification of adsorbent by acid treatment: The removal of Cu from agricultural waste adsorbent like
bagasse on activation with citric acid was investigated by Meenal Gupta et al. 10. Sulphuric acid treatment for
various adsorbents namely areca catechu 11, Cynodon Dactylon 12, Henna leaves 13, Cashew nut14 were carried
out and found maximum adsorption capacity for Cu 1.33 mg/g, 90.35 mg/g, 3.65 mg/g and 406.6 mg/g
respectively. An azadirechta indica leaf 26 on phosphoric acid treatment shows higher adsorption capacity 110.9
mg/g for Cr removal while Macadamia activated carbon15 on treatment with sulphuric acid, phosphoric acid and
nitric acid shows 25.75 mg/g, 25.43 mg/g and 38.59 mg/g respectively. Sorghum bicolor 19 and Cassava peel 28
adsorbents on sulphuric acid modification for Cr shows maximum adsorption capacity 25.64 mg/g and 10.07
mg/g respectively. The adsorption efficiency of toxic metal Cd was investigated by sulphuric acid treated
cashew nut shell 14, phosphoric acid treated azadirechta indica leaf 26 and sulphuric acid modified cassava peel
28
. Lapsi seed stone 21 on activation with mixture of sulphuric acid-nitric acid shows maximum adsorption
capacity 69.49 mg/g for Ni ion while Sorghum bicolor 19, Doam seed coat 20 on sulphuric acid treatment has
adsorption capacity 47.62 mg/g and 13.51 mg/g respectively.

Ponnusamy Senthil Kumar et al.14 studied on removal of Zn by using low cost adsorbent Cashew nut shell. The
prepared adsorbent was characterized by FTIR and SEM. The maximum adsorption capacity was found 455.7
mg/g while the Palm midrib 23 on citric acid and tartaric acid treatment and azadirechta indica26 on phosphoric
acid treatment shows 5.72 mg/g and 133.3 mg/g respectively. Sartape Ashish et al. explored the use of coconut
shell adsorbent 22 on activation with sulphuric acid for the removal of Bi and the activated adsorbent was
characterised by FTIR, SEM and BET surface area analyser. The amount of removal of Pb were investigated on
sulphuric acid activated maize tassel 25, phosphoric acid treated azadirechta indica leaf 26, nitric acid activated
baggasse, palm pit, saw dust 27, sulphuric acid treated cassava peel 28. An elemental analysis and Boehm method
were applied to characterise the prepared adsorbent.

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Asian Journal of Organic & Medicinal Chemistry ISSN Online: 2456-8937
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Cu Henna
Zn Palm midrib
Cu Areca catechu Leaves
Cu Baggasse
shell Cr Cassava peel
Cr Henna Leaves
Ni Doum seed coat
Ni Sorghum bicolor
Pb Baggasse
Cr Macadamia Cr Activated carbon
activated carbon Pb Palm pit

Pb Maize Tassel
Pb Sawdust

Ni Lapsi seed stone Ni Oil palm

Cu Palm

Cr Macadamia Pb Cassava peel

activated carbon
Cr Macadamia
Cr Sorghum bicolor activated carbon

Figure 2. Heavy metal adsorption capacity between 0.078 to 47.62 mg/g by different acid treated adsorbents

Cr Olive stone Cu Cynodon Dactylon

Ni Lapsi seed stone Cr Azadirechta indica
leaf
Ni Cashew nut shell
Ni Azadirechta indica
leaf
Zn Cashew nut shell
Zn Azadirechta indica
leaf

Cd Azadirechta indica
leaf

Cu Azadirechta indica
leaf
Cd Cashew nut shell
Pb Azadirechta indica
leaf
Cu Cashew nut shell Bi Coconut shell

Figure 3. Heavy metal adsorption capacity between 69.49 to 456.3 mg/g by different acid treated adsorbents

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Asian Journal of Organic & Medicinal Chemistry ISSN Online: 2456-8937
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Table 1. Biosorption of heavy metals by acid treated low cost adsorbents

Heavy Adsorbent Modifying Characterizations Maximum Ref
metal agent adsorption
capacity mg/g

Cu Baggasse Citric acid FTIR, SEM 5.35 10

Cu Areca catechu shell H2SO4 FTIR, SEM 1.33 11

Cu Cynodon Dactylon H2SO4 FTIR, XRD, SEM 90.35 12

Cu Henna Leaves H2SO4 -- 3.65 13

Cr Henna Leaves H2SO4 -- 0.078 13

Cu Cashew nut shell H2SO4 FTIR, SEM 406.6 14

Cd Cashew nut shell H2SO4 FTIR, SEM 436.7 14

Zn Cashew nut shell H2SO4 FTIR, SEM 455.7 14

Ni Cashew nut shell H2SO4 FTIR, SEM 456.3 14

Cr Macadamia activated H2SO4 FTIR, TGA, EDAX, 25.75 15

carbon BET

Cr Macadamia activated H3PO4 FTIR, TGA, EDAX, 25.43 15

carbon BET

Cr Macadamia activated HNO3 FTIR, TGA, EDAX, 38.59 15

carbon BET

Cr Activated carbon HNO3 EAS, Boehm method 13.74 16

Cr Olive stone H2SO4 FTIR 71 17

Ni Oil palm H3PO4 -- 19.6 18

Cr Sorghum bicolor H2SO4 BET, FTIR 25.64 19

Ni Sorghum bicolor H2SO4 BET, FTIR 47.62 19

Ni Doum seed coat H3PO4 FTIR, 13.51 20

Ni Lapsi seed stone H2SO4 FTIR, Boehm 28.25 21

method

Ni Lapsi seed stone H2SO4 and FTIR, Boehm 69.49 21

HNO3 method

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Bi Coconut shell H2SO4 SEM, FTIR, BET 250 22

Zn Palm midrib Citric acid SEM 5.72 23

and tartaric
acid

Cu Palm H3PO4 FTIR, BET 21.23 24

Pb Maize Tassel H2SO4 XRD, FTIR 37.31 25

Pb Azadirechta indica H3PO4 BET 205.6 26

leaf
Cu Azadirechta indica H3PO4 BET 185.8 26
leaf

Cd Azadirechta indica H3PO4 BET 154.5 26

leaf
Zn Azadirechta indica H3PO4 BET 133.3 26
leaf
Ni Azadirechta indica H3PO4 BET 120.6 26
leaf
Cr Azadirechta indica H3PO4 BET 110.9 26
leaf
Pb Baggasse HNO3 Element analysis, 13.7 27
Boehm method,

Pb Palm pit HNO3 Element analysis, 15.20 27

Boehm method

Pb Sawdust HNO3 Element analysis, 17.5 27

Boehm method

Pb Cassava peel H2SO4 Nitroperchloric 24 28

digestion method,
FAAS

Cd Cassava peel H2SO4 Nitroperchloric 7.05 28

digestion method,
FAAS

Cr Cassava peel H2SO4 Nitroperchloric 10.07 28

digestion method,
FAAS

Modification of adsorbents by base treatment: Bagasse 10, green vegetable waste 29, rice husk 30 and orange
peel 31 have been used as adsorbent for removal of Cu from its solution. Green vegetable waste was modified by
potassium hydroxide while other adsorbents were modified with sodium hydroxide. The author carried out the
FTIR, SEM, EDS, TGA and BET characterization for the activated biosorbent material. Green vegetable waste
biosorbent shows higher adsorption capacity 75 mg/g in comparison with other adsorbent. The removal of Cd
by sodium hydroxide treated biosorbent such as sawdust, wheat straw, corn stalk 32 and rice husk 33 shows
adsorption capacity 40.78, 38.75, 30.40, 8.50 mg/g respectively. Rice husk 33 on modification with potassium
hydroxide and calcium hydroxide changes adsorption capacity 8.24 mg/g and 10.46 mg/g respectively.

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Asian Journal of Organic & Medicinal Chemistry ISSN Online: 2456-8937
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Cu Baggasse, 2.06
V seaweed, 12.3
Cu Green vegetable
Hg Rice husk, 55.87 waste, 75
Pb Cluster stalk , 58 Cu Rice husk, 48.84

Cu Orange
Cr Bamboo waste,
peel, 50.25
59.23

Cd Sawdust, 40.78
Cr corncob, 29.46

Cr Corn straw,
30.15
Cd Wheat straw,
38.75
Cr sawdust, 34.07
Cd Corn stalk, 30.4

Ni apricot, 101.01 Cd Rice husk, 8.5

Cd Rice husk, 10.46
Cd Rice husk, 8.24

Figure 4. Heavy metal adsorption capacity between 2.06 to 101.01 mg/g by different base treated adsorbents.

S. Erdogan et al. utilised potassium carbonate treated apricot 34 adsorbent for the removal of Ni ion. The
prepared biosorbent was characterised by BET and FAAS and shows maximum adsorption capacity 101.01
mg/g. The study of adsorption of Cr by potassium hydroxide activated sawdust, corn straw and corncob 35 were
carried out by Shujauddin Khushk et al. The higher adsorption capacity 59.23 mg/g was observed by bamboo
waste 36 while corncob shows minimum adsorption capacity 29.46 mg/g. The sawdust and corn straw shows
maximum adsorption capacity 34.07 mg/g and 30.15 mg/g respectively. Francisco Jose Alguacil et al. explored
the use of cluster stalk 37 on potassium hydroxide activation for Pb ion adsorption.

The poisonous Hg metal adsorption has been investigated by Zhiyuan Liu et al. by rice husk 38 adsorbent on
activation with potassium hydroxide. The material was characterised by SEM, FTIR, BET and XPS. The
maximum amount of Hg removal by rice husk was found 55.87 mg/g. The seaweed 39 is used as low cost
adsorbent on modification with potassium hydroxide and found 12.3 mg/g of maximum adsorption capacity for
Vanadium removal.

Table 2. Biosorption of heavy metals by base treated low cost adsorbent

Heavy Adsorbent Modifying Characterization Maximum Ref.
metal agent adsorption
capacity mg/g
Cu Baggasse NaOH FTIR,SEM 2.06 10
Cu Green vegetable KOH SEM, TGA, DSC, 75 29
waste FTIR
Cu Rice husk NaOH FTIR, SEM, EDX 48.84 30
Cu Orange peel NaOH FTIR, SEM, BET 50.25 31
Cd Sawdust NaOH FTIR, SEM, BET, 40.78 32
XRD
Cd Wheat straw NaOH FTIR, SEM, BET, 38.75 32
XRD

Cd Corn stalk NaOH FTIR, SEM, BET, 30.40 32

XRD

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Cd Rice husk NaOH FTIR 8.50 33

Cd Rice husk KOH FTIR 8.24 33

Cd Rice husk Ca(OH)2 FTIR 10.46 33

Ni apricot K2CO3 BET, FAAS 101.01 34

Cr sawdust KOH SEM, BET, FTIR 34.07 35

Cr Corn straw KOH SEM, BET, FTIR 30.15 35

Cr corncob KOH SEM, BET, FTIR 29.46 35

Cr Bamboo waste KOH FTIR 59.23 36

Pb Cluster stalk KOH FTIR, BET 58 37

Hg Rice husk KOH SEM, FTIR, BET, 55.87 38

XPS

V seaweed KOH SEM, EDS, FTIR, 12.3 39

BET, XPS

From the literature review it is observed that many researchers applied the acid and base activation method to
activate the adsorbent. S. Abdic et al. (2018) studied on the heavy metal removal by modified and unmodified
tangerine peel adsorbent 40. The author reported that 40% of adsorption efficiency enhanced by adsorbent
modification. The sulphuric acid is most commonly used acid activating agent for activation of adsorbents. An
acid and base activation method is simple, effective, time saving and economical than any other chemical
method. The activation of functional group on adsorbent surface found successful and which is identified by
adsorbent characterization.

CONCLUSION
In the current review, the biosorption of heavy metal on acid-base treated adsorbents have been studied.
Agricultural waste material used as low cost adsorbent for heavy metal removal was found highly efficient and
environmental healthy. It was observed that the modified adsorbent by acid-base chemical treatment shows
better adsorption efficiency than non-modified adsorbents. An acid-base treatment has been most widely used
for surface modification because of its specific impact on surface to adsorb target pollutant. Due to surface
modification, the increase in pore volume and pore size generates more active sites for adsorption which is
characterized by BET surface area analysis. A new functional group binding sites are formed due to activation
which results into more uptake of metal ion from solution. The researcher were studied the presence of different
functional groups on adsorbent surface and characterized by FTIR while the surface morphology were studied
by SEM analysis. The amount of adsorption of metal ion depends on various factors such as adsorbent dose, pH
of the solution, temperature, modifying method and nature of adsorbent. These type of modified adsorbent is
helpful for industrial waste water treatment and will used to reduce the environmental pollution.

ACKNOWLEDGEMENT
We would like to offer special thanks to Dr. Pawan Tambade, who although no longer with us, continues to
inspire by his example and dedication to us he served over the course of his career.

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