Abstract

Heavy metal pollution may be found in a variety of settings, including those used for battery acid recycling,
electroplating, military bases, shooting ranges, brownfield redevelopment, and mining.
In order to stabilise heavy metals in polluted soil, the chemical stabilization procedure employs non-hazardous
chemical binders.
Stable metal-reagent compounds are incorporated into the treated soils, which prevent metal leaching heavy
metals will be constantly stagnant

.  

14

b a
12

10
c

d
6

2
e ef ef
fg ef fg
h gh gh gh gh gh
0
CK A B C D E F G H J I K L M N O
A

Metal-phosphate complexes and zeolite found in the treated soils are sufficiently stable that they prevent
metals from leaking into groundwater and the surrounding environment.
Easy implementation is also another perk of phosphate compound and zeolite chemical stabilization and well
friendly.
Its adaptability makes it a good choice for usage in a broad variety of metals-contaminated locations. The
reagents may be sprayed topically over an active shooting range in moist form to keep the metals stabilised.
 CHAPTER ONE

The proportion of Pb content of various forms in soil

100 B4
B3
B2
80 B1

62% 64%
65%
72% 73% 72% 72% 71%
73%

60 82%
78%
83% 83% 82% 81%

92%

40
2%
2% 3%

1% 1% 2%
3%
4% 4%

20 2%
2%
35% 1%
2% 1% 2% 33% 33%
27% 26% 27%
23% 25% 23%
20%
17% 16% 16% 18%
1% 15%

6%

0 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0%

CK A B C D E F G H I J K L M N O
Treatment
 B4
B3
B2

100 B1

The proportion of Cd content of various forms in soil

23%

33%
35%
80 41%
0% 49%
5% 50% 51%
56% 57% 56%
59% 59% 58%
61%
64%
66% 0%
5% 1%
4%
60 1%
5%

0%
1% 0%

1% 0%
0% 14% 13%
40 0% 19%
12% 1%
1%
11%
0%

72% 0% 12%
11% 13%
0% 11%
13%
12% 61% 60%
9%
54%

20 35% 35%
32% 32% 32%
30% 30% 29% 28%
24% 26%
23%

0
CK A B C D E F G H I J K L M N O
Treatment

1.0INTRODUCTION

1.1Background of Study

Heavy metal poisoning of the world's soils is a major environmental issue. The environmental risks posed by
Cd and Pb are the greatest by these pollutants. Cd levels are greatly increased by consuming rice. The
environmental risks of Pb are low since it is resistant to chemical and microbiological degradation (Zeng et al.,
2012).
The complexity of the soil environment increases the challenge of heavy metal management. Binding heavy
metals with inert molecules reduces their toxicity and mobility, hence reducing their environmental impact
(Houben et al., 2012). Reports of heavy metal stabilization in situ are available (Pani and Singh, 2019; Wang et
al., 2021). This method uses soil amendments to immobilize metals with the goal of decreasing metal activity.
The stabilizing method may be used in a variety of research fields.

1.2 Heavy Metals

Lead and cadmium (Cd and Pb) amongst other heavy metals are a persistent source of contamination around
the world The greatest environmental threats come from cadmium and lead. Renal failure, osteoporosis,
cancer, and chronic celiac disease have all been related to prolonged exposure to Cd and Pb. Metal smelting,
secondary metals production, lead battery manufacture, pigment and chemical production, gasoline, and lead-
contaminated garbage are the primary sources of lead.
Oxides, hydroxides, and elemental lead are common forms of discharged lead that remain in the soil and water.
Cd(OH)2 and CdCO3 are the most abundant forms of cadmium High pH favors cadmium's form, whereas low
pH favors Cd2+ and aqueous sulphate species.
Due to their high CEC (cation-ion exchange capacity) and widespread availability, zeolites are widely used as
adsorbents for the immobilization of contaminants in soils and water bodies. Zeolites are alumina silicates with
a three-dimensional network of SiO4 - AIO4 tetrahedral linked together by common Oxygen atoms.

The intricacy of the soil ecosystem makes it hard to regulate heavy metal contamination. Soil that has been
polluted with lead or cadmium may be stabilized and cleaned up using any number of technical methods.
Isolation, immobilization, toxin removal, separation, and extraction are only few of the procedures that fall
under this category.
Mining wastes, wastewater discharges, sludge, spills, etc. are only some of the numerous potential origins of
these heavy metal pollutants.
Metals may also be dispersed into the atmosphere through duct emissions of air vapor streams or from rubbish
dumps.

1.3 Overview of Zeolite Use for Stabilization

Previous studies have shown that exchangeable Pb (lead) content drastically fell in contaminated soil owing to
adding zeolite (natural and synthetic). The advantages of using zeolite for stabilization include low cost,
availability in different parts of the world, ion exchanges, immobilization/ encapsulation, precipitation, and
complexation properties. These limitations range from long-term metal binding to long-term zeolite stability,
and variation.
1.4 Problem Statement
The stabilization technology is a proven technique used to immobilize metals and reduce metal activities in the
soil and water bodies. How quickly does lead and cadmium levels in the contaminated soil drop after zeolite
and potassium dihydrogen phosphate have been added?

Metal mobility in soil and groundwater is affected by the chemical and physical features of the polluted matrix.

Adsorbed pollutants on soil surfaces, soluble contaminants in the soil structure, and chemically fixed
contaminants as solid compounds are the three main types of soil contamination.

1.5 Aim and Objectives

1.5.1 Aim
This study aims to experiment with the Stabilization of Lead, Cadmium in Soil using Potassium Dihydrogen
Phosphate and Zeolite

1.5.2 Objectives
1. To outline the processes that take place during the stabilization process of Cd and Pb contaminated
soil using zeolite and Potassium Dihydrogen Phosphate. 
2. To examine how as the soil's pH rises, so does the concentration of organic matter in solution.
3. To experiment with the effect stabilization of Lead, Cadmium in Soil using Potassium Dihydrogen
Phosphate and Zeolite
CHAPTER TWO

LITERATURE REVIEW

2.1 Literature Review

Several chemical and electrochemical treatment technologies, such as subsurface barriers, immobilization,
solidification/stabilization, soil replacement extraction, etc. for cleaning up metal-contaminated soils, but they
change the soil's texture and could not really make it safer. The most common entry points are the respiratory,
digestive, and dermal systems of lead exposure and absorption (ATSDR, 2007). The high rate of hand-to-
mouth action in young children makes them more vulnerable to infection.
Dissolved lead in water is primarily affected by the pH, mineral surfaces, and dissolved salt content.

“Li Wang, Yonghua Li, Hairong Li, Xiaoyong Liao, Binggan Wei, Bixiong Ye, Fengying Zhang, Linsheng
Yang, Wuyi Wang, and Thomas Krafft (2014)” investigate the use of hydroxyapatite and potassium chloride to
stabilise lead and cadmium in polluted soils. Both chile (Capsicum annum) and rape (Brassica rapachinensis)
were grown in pot tests to see how well the stabilization worked.
The findings were as follows:
The best combination reduced total lead and cadmium concentrations in the plants by 69 and 44%,
respectively; (3) leachable lead and cadmium concentrations in the edible sections of both vegetables dropped
by 97.27 and 35.96%, respectively, for soil HF1 and soil HF2.
All of these are used to treat mining areas polluted with lead and cadmium.
As reported by (Ray, Pal, Mandal, & Mandal, 2015). Zeolite's porous structure is made up of cages that are
about 12 angstroms in diameter, connected by channels that are 8 angstroms wide, and composed of 12
tetrahedral rings (Nakhli, Delkash, Bakhshayesh, and Kazemian, 2017).
The general empirical formula that refers to a zeolite structure is M2nO. Al2O3. xSiO2.yH2O. 
The cations strontium (Sr) and cesium (Cs), as well as heavy metals, anions like chromate (CrO42+), and the
many organic contaminants described previously may all be absorbed or exchanged by zeolites (Youssefi, and
Waring, 2015).
Some notable physical and chemical qualities of zeolites are high cation selectivity for only ammonium,
potassium, and cesium ions, low density (2.1-2.2 g/cm3), strong molecular sieving capabilities, and a large
void volume (50%) (USGS, 2020).

In terms of pore size According to Flanigen (Flanigen, 2001), zeolites can be broken down into four distinct
groups based on the size of their pores: There are four sizes of pore diameters: I very tiny (0.3–0.45 nm), ii)
medium (0.5–0.6 nm), iii) big (0.6–0.8 nm), and iv) very large (0.8–1.2 nm) (0.8–1.0 nm diameter with 14
rings).

Bio-transformation and stability of arsenic (As) in contaminated soil utilising arsenic oxidizing bacteria and
FeCl3 amendment is the subject of an article by Santosh K.& Ian R. Jenkinson (2017).

2.1 Stabilization of Lead and Cadmium  

Lead and cadmium are both toxic heavy metals that have many practical applications. Namely, Ibhazehiebo,
Iyawe, and Ighoroje (2007). Toxic heavy metals include lead and cadmium.
The greatest environmental threats come from cadmium and lead.

Lead is a cumulative toxicant that is especially dangerous to young children and pregnant women, and it is also
extremely toxic to people and the environment. There is no known safe amount of lead exposure. Cadmium
(Cd) is a relatively rare metal that occurs naturally as CdS or CdCO3.

2.2 Zeolite

The word zeolite refers in comparison to "boiling stones" due to their capacity to foam up at temperatures of
roughly 200 °C. The mineral zeolites have been officially recognised for the first time in 1756 by Alex Fredrik
Cronstedt, a Swedish mineralogist (Polat, Karaca, Demir, and Naci-Onus, 2004). However, zeolite production
was started commercially in the 1960s (Polat, Karaca, Demir, and Naci-Onus, 2004. 

Zeolites are aluminosilicate with a three-dimensional network of SiO4 – AIO4tetrahedra linked together by
common oxygen atoms, they are very effective adsorbents used to immobilize contaminants in soils and water
bodies due to their CEC (cation-ion exchange capacity) and natural abundance. 
2.3Impacts of Zeolite Application in Industries

Zeolites change the soil's water-holding capacity and air porosity by decreasing its bulk density, which is
especially noticeable in soils with a light texture (Ramesh, Reddy, Biswas, and Subbarao, 2011).
Yet, this does not have a major impact on the overall porosity (Ramesh, Reddy, Biswas, and Subbarao, 2011).
It's possible that zeolites can store water indefinitely. Drought-induced abiotic stressors may be reduced and
plant resilience increased by retaining soil moisture for longer, especially during dry seasons.

According to Gholizadeh-Sarabi and Sepaskhah(2013), zeolites treatment greatly raised the saturated hydraulic
conductivity in fine and medium-texture soil, but drastically decreased it in coarse-texture soil at the same rate.

2.4 Environmental Impact

As compared to soil that hasn't been treated with zeolites, the amount of carbon that is sequestered and stored
in the soil thereafter is much higher (Filcheva, and Chakalov, 2002). N mineralization and subsequent soil
management strategies are strongly associated with “soil organic matter even in the light fraction”. Zeolites are
effective molecular gas sieves due to their narrow channels. According to a study conducted in 2012), zeolite-
treated soil reduced GHG emissions from duck dung by about 27% compared to untreated soil. Reduced N2O
emissions may be attributed to zeolite's ability to impede the growth of nitrifying bacteria inside its structure.

2.5Remediation of Contaminated Soil

One of the most pressing issues in contemporary farming is soil degradation caused by heavy metals. Heavy
metal pollution in the soil is a result of human activities such as fast industrialisation and the indiscriminate use
of fertilizers. Heavy metal ion retention may also be affected by the soil's sorption capability. In the year 2000,
researchers found that when zeolite was applied to soil, cadmium and lead levels in wheat decreased
dramatically. In addition, clinoptilolite zeolite has been widely documented to efficiently regulate the solubility
of heavy metals including cadmium (by 72%) and lead (81%). (Chen, Lee, and Liu, 2000).

2.6 Wastewater Treatment

Heavy metals, oils, and organics found in the vast volumes of wastewater produced by industrial growth
coupled with rapid urbanization have a detrimental effect on water quality (Wang, and Peng, 2010). Effective
methods such as solvent extraction, ion exchange, and adsorption are often employed to get rid of these
impurities. The most widely used adsorbents are zeolites because of their cheap cost, environmental
friendliness, and high selectivity for hazardous cations (Abatal, et al. 2019). Al3+, Cd2+, Cu2+, Ni2+, Pb2+,
and Zn2+ are some of the metallic cations that the clinoptilolite is particularly efficient against in copper mine
effluent (Yousef, El-Eswed, and Al-Muhtaseb, 2011). In terms of heavy metal selectivity, clinoptilolite is most
effective at removing Pb2+, followed by Cd2+, Cu2+, Co3+, Cr3+, Zn2+, and finally Ni2+ (Babel, and
Kurniawan, 2003). Clinoptilolite has the most benefit in

Water Pollution Control It has a broad pH and temperature range (25-60 °C) and agitation speed (1-4) for
heavy metal adsorption (0, 100,200, 400 rpm). Zeolite is an effective adsorbent of cations due to its high cation
exchange capacity and large surface area.

2.7 Limitation of Zeolites

It's important to remember that despite zeolites' wide range of potential uses in farming, they also have certain
drawbacks that must be taken into account. The high dispersivity of fine-grained synthetic zeolites is a cause
for concern when it comes to their use. After being mined, natural zeolites are processed using isolation
techniques such as crushing and pelletizing to get their useable form.
As zeolite soil makes up less than one percent of India's entire landmass and China accounts for more than half
of the world's natural zeolites production, supply and demand issues may drive up prices. Hence, the consistent
supply of zeolites for agricultural uses over the globe is another key limitation. (Bhattacharyya, Chandran,
Ray, Pal, Mandal, and Mandal, 2015).
CHAPTER THREE

RESEARCH METHODOLOGY

3.1 Introduction

In this chapter, the researcher describes the procedures for carrying out the study. These include Material and
Methods, stabilization experiment protocol, Pot experiment protocols, and Detection and analysis methods.

3.2 Materials and methods

A soil sample was collected from Liaoning province, China is where the sample was collected and the soil
sample is from an industrial area, 
(45o36’N 84o53’E), China. The sample was characterized for pH. 

3.3 Materials

plastic bucket, plastic test tube, centrifuging machine, Oscillating machine, contaminated soil sample, electric
pH meter, zeolite, potassium dihydrogen phosphate, silver, water bath poly bag,

The soil tested: Cd, Pb compound polluted the soil of a smeltery in Haicheng City. Stabilizers: potassium
dihydrogen phosphate and zeolite. 

3.4 physical and chemical properties of the contaminated soil

  
Soil sample pH Moisture content (%)Cd (mg/kg Pb (mg/kg)
Haicheng Heavy
Pollution 8.21 3.35% 583.6 15081.1

14

b a
Leaching concentration of Cd(mg/L)

12

10
c

d
6

2
e ef ef
fg ef fg
h gh gh gh gh gh
0
CK A B C D E F G H I J K L M N O
Treatment
 14

b a
12

10
c

8
Leaching concentration of Pb (mg/L)
d
6

2
e ef ef
fg ef fg
h gh gh gh gh gh
0
CK A B C D E F G H J I K L M N O
(Treatment)
3.5 Method 

3.7 Stabilization Culture Test

The experiment consisted of 16 treatments, each of the samples was repeated three times: A 0, A 5, A10, and
A15 with four doses of potassium dihydrogen phosphate, The percentage of potassium dihydrogen phosphate
were 0%, 5%, and 10%, 15% respectively, Four levels of zeolite treatment BO, B2.5, B5, B7.5, representing
the application of 0, 2.5%, 5%, 7.5% to the soil weight 200g respectively, were applied to the soil, the
experimental procedure as mentioned above. 200g air-dried soil was poured into a plastic bucket, and then two
different stabilizers of zeolite and potassium dihydrogen phosphate were fully mixed, the soil sample was left
indoor natural conditions under the stabilization of 28 days, during the period by weight to supplement water
was been added to soil to keep the treatment moist At the end of culture, the speciation and concentration of
Cd and Pb were determined.
3.8 Table of sampling 
Zeolite and potassium dihydrogen phosphate
 
A. Z.15g K.30g G. Z. 15g K.0g
M. Z.0g K.20g
B. Z.10g K.30g H. Z.0g K.30g
N. Z. 5g K.0g
C. Z.5g K.30g I. Z.0g K.10g
O. Z.15g K.10g
D. Z.5g K.20g J. Z.15g K.20g
CK. Z.0g K.0g
E. Z.10g K.10g K. Z.5g K.10g
F. Z.10g K.20g L. Z.10g K.0g
Z means = Zeolite while K means Potassium dihydrogen phosphate. Grams / kilo grams

 
 

3.9 Toxicity characteristic leaching procedure 

4.0 TCLP toxic leaching test

The toxicity Leaching Test was established by the Environmental Protection Agency (EPA) in the United
States to measure the amount of heavy metals leached out. Migration impact analysis is often performed to
determine how easily heavy metals may be mobilized and leached from solid and liquid wastes.
The Acetic Acid Slow Flush Technique (HJ / T300-2007) was created to examine heavy metal leaching
characteristics from soil in accordance with the TCLP approach.
The preparation method and application conditions of the extracting are shown in Table 1.
1.0g of stabilized soil sample was poured into 50mL of plastic tube container and is been centrifuged after the
appropriate extracting of soil pH was selected, 20ml of deionized water was added into the test tube and then it
oscillated for 20 hours at room temperature, the sample was removed and placed into the centrifuging machine
for 3800 r/min for 10 min the water was poured into a fresh plastic tube for analysis, 20ml of deionized water

was added to the Sediment soil in the previous container while the same procedure took place as twice.

4.1 BCR, Test of metal concentration 

The stabilized soil sample of 1.0 grams was weighed in 40ml of a test tube and centrifuged at 3000r for 20min,
after being shaken in an oscillating machine at room temperature for 16 hours after the extraction. The
supernatant was stored in a polyethylene container at 4° C for testing. 
20ml of deionized water was added to the residue and it was shaken for 15min for cleansing, and then it was
centrifuged at 3000r / for 20min, Reducible state which is Hydroxylamine Hydrochloride solution of 40ml
0.5mol/L was added to the solid residue 1, and then it oscillated at room temperature for 16h, then it was
centrifuged for 20min at 3000r /min after the extraction. The supernatant was stored in a polyethylene
container at 4°c.
 The residue was cleaned and 20ml of deionized water was added to it and then shaken for 15 min, and the
supernatant was emptied after centrifugation at 3000r / min for 20min, leaving the solid residue.

4.2 Oxidizable state of BCR test

10mL 30% H202 solution was slowly added to solid residue 2, and the lid was digested at room temperature
for 1h, during which time it oscillated
occasionally, then it was heated using a water bath to 85 °C for 1h, and it was removed and heated after the
solution has nearly dried. Then 10mL 30%H202 solution was added and the lid was covered and then heated
for 0.5h, during the occasional concussion, the cover was removed and the heating was continued til the
solution was nearly dried. After the temperature cool at room temperature, then 50mL 1mol/L ammonium
acetate solution (pH=2), was added and is been shaken at room temperature for 16h, in an oscillating machine,
after extraction, it was then centrifuged at 3000r/min for 20min. The culture medium was taken in a
polyethylene container and stored in a 4 °C refrigerator to be tested. 

4.3 Multi-stage pH extraction test    

8.0grams of stabilized soil sample was poured into a centrifuging test tube, the liquid to solid ratio of 10: 1,
and deionized water was added to it, and the values of the extracts were adjusted by HNO3 and KOH 2.0 ±
0.5,4.0 ± 0.5 5.5 ± 0.5, 7.0-0.5, 8.0-0.5 and 9.00.5, 10.5 ± 0.5, 12.0 
± 0.5,13.0 ± 0.5. 

4.4 stabilized pH of the soil

2.0 4.0 5.5 7.0 8.0 9.0 10.5 12.0 13.0

2.0 4.09 5.5 6.90 7.96 9.09 10.46 12.0 12.75

1.9 3.89 5.43 7.01 7.92 8.80 10.49 11.79 12.99
2.09 3.99 5.57 7.01 7.97 8.89 10.47 11.78 13.04

5. 

Conclusions

Lead and cadmium stabilization rates were shown to rise with the addition of
Khpo4 and zeolite in an experimental setting. The rates were greatest at 50 g/kg
zeolite and 9 g/kg Khpo4.
Chili's edible portion had a lead content that was below the National Safety
Vegetables Standard. Lead and cadmium are more easily absorbed by rape than by
chili. In addition, we discovered that solanaceous vegetables had lower lead and
cadmium absorption rates than leafy greens.

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