The use soil as the adsorbent to understand the capacity toward copper ions adsorption

THAI NGUYEN UNIVERSITY OF AGRICULTURE AND FORESTRY NATIONAL TSING HUA UNIVERSITY  GRADUATE REPORT Title: "The Use soil as the adsorbent to understand the capacity toward copp

THAI NGUYEN UNIVERSITY OF AGRICULTURE AND FORESTRY

NATIONAL TSING HUA UNIVERSITY



GRADUATE REPORT

Title:

"The Use soil as the adsorbent to understand the capacity

toward copper ions adsorption"

Dr Nguyen Thanh Hai

Taiwan - 2014

ACKNOWLEDGMENT

First of all, I would like to express sincere thanks to the school board Thai Nguyen University of Agriculture and Forestry, Faculty of International Training and Development; advanced program, thank the teachers who has imparted to me the knowledge and valuable experience during the process of learning and researching here

In the process of implementing and completing thesis, I have received the enthusiastic help of the teachers of National Tsing Hua University I would like to express my special thanks to Prof Ruey An Doong and Dr Nguyen Thanh Hai who has spent a lot of time, created favorable conditions, enthusiastic to guide me to complete this thesis

I sincerely thank my friends in the laboratory facilitated, and provided the information and data necessary for my implementation process and helped me finish this thesis

In the process of implementing the project, due to time, financial and research levels of myself is limited so this project is inevitable shortcomings So, I would like to receive the attention and feedback from teachers and friends to this thesis is more complete

I sincerely thank you!

Taiwan, 2014

Students perform

Luu Thi Thuy Linh

Table of Contents

LIST OF TABLES iii

LIST OF FIGURES iv

LIST OF ABBREVIATIONS v

1 INTRODUCTION 1

2 LITERATURE REVIEW 3

2.1 The value of tea 3

2.1.1 Nutritional Value 4

2.1.2 The value of medicinal 6

2.1.3 The value of Economic 7

2.2 The role of nutrients for tea 9

2.3 Role of copper in tea 11

2.3.1 Function of Copper: 12

2.3.2 Deficiency Symptoms: 13

2.3.3 Toxicity 14

2.4 Researches about the absorption of soil 15

2.4.1 Application of Natural Clayey Soil as Adsorbent for the Removal of Copper from Wastewater 15

2.4.2 Calcareous Soil as a New Adsorbent to Remove Lead from Aqueous Solution: Equilibrium, Kinetic and Thermodynamic Study 15

2.4.3 Adsorption of arsenic from aqueous solution on naturally available red soil 16

3 RESEARCH METHODS 20

3.1 Objectives: 20

3.2 Location: 20

3.3 Project Content: 20

3.4 Methodology: 20

4 RESULTS 27

4.1 Soil properties 27

4.1.1 Size of soil sample: 27

4.1.2 Soil Organic Matter (SOM), pH of soil: 28

4.2 Adsorption 32

5 DISCUSSION AND CONCLUSION 34

6 REFERENCES 36

APPENDICES 38

LIST OF TABLES

Table 1: Layers with different size 21

Table2: Classification of soil particles in the USSR 21

Table 3: The group of lower concentration 24

Table 4: The group of higher concentration 25

Table 5: Size of soil sample 27

Table 6: Absorption of copper ions in the soil after 24 hours at lower concentrations 32

Table7: Absorption of copper ions in the soil after 24 hours at higher concentrations 33

LIST OF FIGURES

Fig.1: XRD diffractogram studies of red soil 17

Fig.2: Effect of adsorbent dose on As (III) adsorption (C0 = 1.0 mg l-1, pH: 7.2, shaker

USSR Union of Soviet Socialist Republics

TOC Total Organic Carbon

LOI Loss on ignition

DI water Deionized water

AAS Atomic Absorption Spectrometry

SOM Soil Organic Matter

Thai Nguyen University of Agriculture and Forestry

Degree Program: Bachelor of Environmental Science and Management

Student name: Luu Thi Thuy Linh

Student ID: DTN 1053110124

Thesis Title: The Use soil as the adsorbent to understand the capacity toward copper

ions adsorption

Supervisor (s): Prof Ruey An Doong

Dr Nguyen Thanh Hai

Abstract:

Soil adsorption and plant adsorption are synergistic It has a major role for the plant

This research assesses the role of tea in soil ‘s absorption of copper They aremetal elements necessary for tea, they affect the growth of leaves and buds, in ethylene sensing, cell wall

metabolism, oxidative stress protection and biogenesis of molybdenum cofactor The

topics also evaluates soil’s properties and their role for tea as well as the impact insoil’s absorption capacity Specifically, the soil type is "fine clay", it needs to use filters with

multiple different sizes to accurately assess soil properties This soil type has high flexibility,

good moisture retention, increased absorption capacity of the soil Thevalue of "OM" is

measured by Loss on ignition (LOI), Total Organic Carbon (TOC) accounted for 9.34%,

which is high value They provide essential nutrients for tea, and promote the absorption sale

of soil However, the pH value of the soil is low, only 4.7, this value is appropriate with the

tea, but it reduces the absorption capacity of the soil The ability of soil to absorb increased

copper concentration increases, however, this value is very low, only about 7% to 14% for

concentrations of 0.1 to 3 The method used was Atomic Absorption Spectrometry (AAS ),

here is the testing machine, which gets the fastest and most accurate result of the

concentration The explanation for this problem may be that the influence of pH is major, but

there was not enough time to conduct research with higher concentrations It hadto be

evaluated in subjects with low concentrations It means low ability to absorb copper that

increases with increasing concentration but value is low

Keywords: Adsorption, Copper(II), soil, tea

Number of pages: 39

Date of Submision: January 15th

1 INTRODUCTION

Tea is one of the major export products of Vietnam At present, Vietnam tea

producing area ranked 5th and the 7th largest output in the world, tea products are

available in 92 countries around the globe The tea markets for Vietnam are Middle East,

South Asia, Eastern Europe, Taiwan [4]

Thai Nguyen is a mountainous province in the North Midlands, with favorable

natural conditions of climate, soil, potential agricultural and forestry development Thai

Nguyen’s tea has a long tradition In particular, Tan Cuong tea is famous in the whole

country and is considered to have high quality and safety

However, Vietnam's tea is considered to underperform compared to with its

potential Its yield is lower than that of other placesin the world Moreover, the quality

and competitiveness of the Vietnamese tea products are low and unstable Difficulties

such as technical standards, product quality, food safety, and convenience are significant

This situation is due to many causes such as the low level of intensive farming, the

cultivation techniques, rapidly changing natural conditions and ecology as well as

volatitle economic conditions and market requirements for higher quality

The best quality of tea is affected by cultivation methods, climate, soil quality,

nutrient requirements In particular, soil and nutrient have close relationships with each

other The capacity of soil to store nutrientsand supply for tea is important in maintaining

good and lasting quality

Thus it is important to assess this capability of planting soil, and apply it to tea

cultivation techniques, in order to provide guaranteed quality tea products At the same

time, it can contribute information about the soil In this case, copper is selected as a

proxy to evaluate the absorption capacity of the soil The reason is its essential role with

tea, and copper is the metal that soil can absorb quite strong Therefore, I propose

Research: "The Use soil as the adsorbent to understand the capacity toward copper ions

adsorption"

2 LITERATURE REVIEW

2.1 The value of tea

Tea is a crop brings economic benefits, an ideal drink has many medicinal values,

besides planting, the tea processing is also a long-standing culture of the traditional

Vietnamese until now

According to the study of biology, Vietnam is one of the homeland of tea in the

world Tea is a perennial plant, with long-term economic life, high economic efficiency

Tea planting once, can be harvested 30-40 years or longer Nowadays the world has

about 40 tea cultivation countries Tea is cultivated most concentrated in Asia, then to

Africa [1]

Tea cultivation in Vietnam has been a long time, but tea is planted and exploited in

a large area was began more than 50 years In plantations of tea, tea is the main source of

income, contributing significantly to improve and enhance the life of people The

production and provided of tea can satisfy demand for the domestic and export demand

Because of that, compared with other crops in Vietnam, tea is one of the most dominant

trees in both climate and labor resources

Due to the condition of land and suitable climate, so the tea is planted scattered in

most mountainous and midland provinces of Vietnam In the south, the tea is planted

mainly in the provinces of Lam Dong and Gia Lai, in the north, the provinces of Thai

Nguyen, Phu Tho, Tuyen Quang, Son La, Ha Giang, Yen Bai and Lao Cai

At present, Vietnam is a country ranked 5th in the world for the production and

export of tea, after India, China, Kenya, Sri Lanka, and on par with Indonesia

2.1.1 Nutritional Value

The nutritional components in tea include amino acids, vitamins, minerals,

hydratcarbon, protid and lipid [6]

a Amino acids

A major component in the organization of human cells is protid; in which amino

acid is the composition of protid There are 25 kinds of amino acids in the human body,

including 8 types that the human body can not synthesize, must rely on outside food

supplements

Free amino acid content in tea is 2-5% Amino acids effects with human

physiology as cardiac, diuretic, blood vessel relaxation bloom

b Vitamin

Vitamins are organic compounds essential for metabolic processes in the human

body It is a coenzyme participating nutrient composition as protid, lipid, glucide

Although the body only needs a very small amount, but humans can not create, so need to

supplements from foods as the external suppliers

In fresh tea leaves have more vitamins Vitamin can soluble in lipids (such as A1,

A2, D1, D2, D3, D4, K1, K2) and vitamin soluble in water (such as B1, B2, B6, B12, PP,

pantotenic, C, P) For the vitamin soluble in water, when mixing tea with boiling water,

can extracted up to 80% vitamin

c Minerals

Minerals are indispensable quality of the human body; some kinds can participate

in tissue composition and skeletal muscle; some kind involved in maintaining osmotic,

acid-base balance and metabolism in the body In tea has more than 40 minerals,

including macro elements such as K, Ca, Na, P, Mg, Cl and secondary and trace elements

such as Si, Fl, Al, Cd, Fe, Mn, Co, Zn, Se, As, Mo

If want to determine the mineral composition of tea, must determine the

composition of the the ashes of tea Ashes is the material remaining after tea calcined at

high temperatures of 500-600 ° C Ashes divided into 2 groups, soluble and insoluble in

water Groups that do not dissolve in water again divided into 2 small groups , soluble

and insoluble in dilute hydrochloric acid

d The glucide (hydratcarbon)

Glucide is a kind of nutrients mainly for humans, to maintain a stable body

temperature Glucide is a group of organic compounds important and common in plants

Glucide content accounted 85-90% in many plants, but in the tea leaves are low, not

exceeding 20% by weight of dry matter, this drink contain less sugar, suitable for people

with diabetes

2.1.2 The value of medicinal

Tea is a crop to bring economic benefits, an ideal drink has many medicinal

values.[2] Here are a few utility to drink tea:

1 Tea can reduce tired, promote metabolism, maintain the function of the heart,

blood vessel, gastric

2 Tea effective in preventing tooth decay, according to the documents of the

United Kingdom, children drinking tea can reduce tooth decay up to 60%

3 In the tea consists of trace elements is useful to human body

4 Tea leaves have the effect of inhibiting melanoma Drink tea to control the

growth of cancer cells

5 Drink tea to control cell aging, anti-aging effects of tea leaves is more than 18

times with the vitamin E

6 Drinking tea helps excitement of the central nervous system, strengthening

advocacy

7 Drinking tea against obesity, especially green tea has the obvious effect,

enhance beauty

8 Drinking tea destroys bacteria, prevention is sinusitis, sore throat, intestines

9 Drinking tea protects hematopoietic function In tea leaves contains

anti-radiation Drinking tea while watching television will reduce the impact of radiation from

monitor, protect eyesight

10 Drinking tea maintain balance acidity and alkalinity in the blood

11 Tea can prevent crush, drinking hot tea after 9 minutes, skin temperature

decrease 1 2ºC, makes the body cool, refreshing

2.1.3 The value of Economic

In term of tea production for export, Vietnam is ranked 5th in the export of tea

Recently, the competent authorities have agreed directives about branding Vietnamese

tea, including Tan Cuong tea is part of that brand Vietnamese tea brand will be protected

in 77 countries and territories worldwide The branding Vietnamese tea has a very

important role and increasing the value and competitiveness of Vietnam's tea products[4]

Currently, the area of specialty tea in the commune has grown to more than 300

ha; some production facilities, large tea business in commune like Tien Yen, Huong

Thang, Tien Dat has annual revenues billion per year from processing and specialty tea

business

Usually income from tea to the average value over 120 million / ha / year and now

has more than 200 households with incomes from 100 million / year from the production

of tea This year, Tan Cuong has achieved new standards of rural communities have very

large contribution from tea plants [1]

To promote the potential strength of tea, Thai Nguyen city is planning to expand

the tea growing areas in Tan Cuong include communes as Tan Cuong, Phuc Triu, Phuc

Xuan with a total area of about 1,300 hectares of tea; in which more than 1,000 hectares

of tea business, the average production about 14,000 tons / year, the value of hundreds of

billion of income [4]

At Dai Tu district, some communes as Hung Son, La Bang Phu Thinh Phu

Xuyen has increased to more than 5.400ha tea area, mainly the new tea varieties, high

quality, yield nearly 50,000 tons / year, reached the value of income from 80 to 100

million / ha / year.[1]

From craft of making tea, the province has more than 30 manufacturing

enterprises, trading and export of tea, more than 80 villages was recognized Although

there are more than 80% of processed in traditional crafts but for about 3 years now,

every year, the exporting enterprises of tea reached more than 10 million dollars profit.[1]

Some tea regions like Tan Cuong, Phuc Xuan (Thai Nguyen City), La Bang (Dai Tu),

Trai Cau (Lap Minh, Dong Hy), Tuc Tranh (Phu Luong) has produced some tea

products of high value with prices ranging from 600,000 to 2,500,000 VND / kg dry tea

leaves, consumption market are quite stable[5]

In addition to contributing to the economy through export of tea, still brings the

contribution due to tourism Foreign tourists like to visit the area of Thai Nguyen tea

Every year, Thai Nguyen also attracted tens of thousands of tourists to the tea village So

we can see the role of tea is huge for the economy of Vietnam

Besides the advantages of tea, there exist many weaknesses as products of

Vietnam's tea exports with low quality, there are many defects and no credibility on the

world market The average selling price is only 50-70% the world tea Exports to major

markets such as the US, EU, Japan has a low price.[5]

The question is, why our tea has a lower price, difficult to develop in major

markets

Thus, to improve the price of tea in Vietnam, we have to produce high quality tea

The quality of tea depends on many different factors, including the requirements for

nutrients is the most important

2.2 The role of nutrients for tea

Tea is grown mainly from grafted branch, the new tea varieties are cultivated well,

it can productive over 3 tons of dried buds / ha / year With such a large of biomass, tea

also requires a large amount of nutrients

* Nutritional requirements: The study results showed that: To get the dry tea

leaves 2 tons / ha, nutrient requirements for tea are as follows: 144kg N; 71kg P2O5; 42

kg K2O; 24kg MgO; 40 kg CaO; 4.828g Fe; 9.557g Mn; 760g Zn; 760g Cu and 520g B

When the yield up to 3 tons of dry buds/ha, the nutritional requirements for tea will

increase 2 times the amount of nutrients listed above [7]

Thus, macronutrients requirement for tea including nitrogen (N) greater than 2

times the phosphorus (P2O5) and more than 4 times potassium (K2O), and also need to

the secondary nutrients such as Mg, Ca, and micronutrients such as Fe, Mn, Zn, Cu, B

* Nutrient requirements for Nitrogen: Nitrogen is a nutrient factors leading to

improved productivity of tea Provide adequate protein, fast-growing of tea stems, leaves,

bud, budding, sprouting in the leaf axils.[11] Without Nitrogen, the tea will be stunted,

branches, leaves less developed, less shoots and buds, low productivity

* Nutritional requirements for phosphate: phosphate has an important role for the

growth and development of tea Phosphate promote the development of the roots of tea

from newly planted time to entering the production phase and phosphate are also

involved in the synthesis of nutrients for growth and development of tea and for the buds

and leaves

Phosphate also involved in the process of accumulation of dissolved minerals in

the water Lack of phosphate, tea will slow growth, poor branching capability The

process of re-creating small roots delayed absorption leads to poor nutrition, make tea

yield unstable

* Nutritional requirements for potassium: comparison with N and P are both less

abundant potassium, but potassium roles are very important for the rapid transport of

nutrients from the soil to photosynthesis and synthesis nutrition, especially in the buds

and young leaves, potassium also regulate the balance of nitrogen in tea Without

potassium, tea will be weak, slow down growth, disease resistance poor The results of

the study of inorganic fertilizers showed rate N: P: K suitable is 2.0: 1.0: 0.5, depending

on the soil conditions in each region.[3]

* Nutritional requirements for calcium: Although tea appropriate with pH from 4.5

to 5, but the fact, tea-planting soil in the northern mountainous provinces are mostly very

acidic, with a pH <4, so calcium have an important role in reducing acidic, creating an

environment suitable to the requirements of the land of tea, while also participating

synthetic nutrients for tea growing.[3]

* Nutritional requirements for magnesium: Mg has a particularly important role to

improve the efficiency of photosynthesis, tea have large biomass, mainly in buds and

leaves, so the new chlorophyll determines yield and quality tea Without magnesium, less

leaves tea, little buds, and little foil, usually dark green leaves, small buds leads to poor

yield Mg enough for tea will make increasing of chlorophyll, making the tea

development of many buds, leaves thick, shiny, accumulation of nutrients in the buds,

increase productivity and quality tea

* Nutritional requirements for micronutrients including zinc, iron, manganese,

copper and bo effective participation of the enzyme structure to catalyze the formation

of minerals, vitamin compounds in buds and leaves, decided to the taste and quality of

tea If there are deficiency of micronutrients will make a decline in the tea quality [3][7]

Recognizing that, although tea need a small amount of copper, but the role of

copper is important for the tea

2.3 Role of copper in tea

Copper is an essential metal for tea It plays key roles in photosynthetic and

respiratory electron transport chains, in ethylene sensing, cell wall metabolism, oxidative

stress protection and biogenesis of molybdenum cofactor Thus, a deficiency in the

copper supply can alter essential functions in metabolism However, copper has

traditionally been used in agriculture as an antifungal agent, and it is also extensively

released into the environment by human activities that often cause environmental

pollution.[15] Accordingly, excess copper is present in certain regions and environments,

and exposure to such can be potentially toxic to tea, causing phytotoxicity by the

formation of reactive oxygen radicals that damage cells, or by the interaction with

proteins impairing key cellular processes, inactivating enzymes and disturbing protein

structure

2.3.1 Function of Copper:

Copper is an important component of proteins found in the enzymes that regulate

the rate of many biochemical reactions in tea Tea would not grow without the presence

of these specific enzymes There are some functions of Copper[15]:

- Promotes seed production and formation

- Plays an essential role in chlorophyll formation

- It functions as a catalyst in photosynthesis and respiration

- It is a constituent of several enzyme systems involved in building and converting

amino acids to proteins

- Copper is important in carbohydrate and protein metabolism

- It is important to the formation of lignin in cell walls which contributes to the

structural strength of the cells

- Copper affects the flavor, the storage ability, and the sugar content of tea

Factors Affecting Availability [9]

 Root Growth: Copper is the most immobile micronutrient, therefore anything

that inhibits new root growth will inhibit Cu uptake

 Soil pH: Acid soils increase Cu uptake and High pH inhibits uptake

 Organic Matter: Copper is readily and tightly complexed by organic matter,

therefore high soil organic matter levels reduce Cu availability

 Flooding: Waterlogged soils can reduce Cu availability while they are saturated,

however after they are drained the Cu will become available again

 Cu: Zn Balance: High Zn levels will reduce Cu availability

 Cu: N Balance: High N uptake in the presence of marginal Cu levels can lead to

a reduction of Cu transport into the growing tips of tea

 Cu: P Balance: High soil and tea P levels can reduce Cu uptake due to reduced

soil exploration by mycorrhizas associated with tea roots

 N Stress: Low N availability decreases the vigor of tea to an extent that it may

fail to take up adequate amounts of many other nutrients Copper uptake can be affected

in this way

2.3.2 Deficiency Symptoms:

Symptoms vary depending on the crop Typically the symptoms start as cupping

and a slight chlorosis of either the whole leaf or between the veins of the new leaves

Within the chlorotic areas of the leaf, small necrotic spots may form, especially on the

leaf margins As the symptoms progress, the newest leaves are smaller in size, lose their

sheen and in some cases the leaves may wilt The death of the growing points often leads

to excessive tillering in cereal crops and excessive branching in dicots (non-grass crops)

In some case show a blue-green color before advancing to chlorosis Excessive wilting,

lodging and reduced disease resistance result from the weak cell walls caused by Cu

deficiency The apical meristems may become necrotic and die inhibiting the growth of

lateral branches Flower color is often lighter than normal Copper is found to be evenly

distributed in the plant, but is relatively immobile Therefore, a constant supply is needed

throughout the growing season.[15]

Excess potassium, phosphorus or other micronutrients can indirectly cause copper

deficiency Also if the pH of the growing medium is high, this can induce a copper

deficiency as it is less available for tea uptake

2.3.3 Toxicity

Excess copper in the growing medium can restrict root growth by burning the root

tips and thereby causing excess lateral root growth High levels of copper can compete

with the uptake of iron and sometimes molybdenum or zinc The new growth can

become initially greener than normal, then exhibit symptoms of iron deficiency or

possibly other micronutrient deficiencies If not corrected, copper toxicity can reduce

branching and eventually plant decline follows.[13]

Copper, like most micronutrients is more available when the growing medium pH

is low, so if copper toxicity is occurring, test the pH of the growing medium [8] Also

certain fungicides have copper as their active ingredient, so it is essential to rinse the

foliage off before testing the tissue

With the roles mentioned above, copper (Cu) contributed much to the growth of

tea and bring good quality In the other hand, soil and tea has nutrient relationship with

each other The ability of soil to absorb copper as possible, the tea has been providing

longevity and efficiency [15]

Absorption capacity of the soil is assessed with many different properties of soil

In which, each factor has a very important role to absorption, and the role of tea Many

articles, research about absorption capacity of different metals of different types of soil

Each soil has its own properties and has the different absorb ability for different

substances To do good research, the articles references and relevant contribution to the

experimental methods and different results, great support in the process of doing research

2.4 Researches about the absorption of soil

2.4.1 Application of Natural Clayey Soil as Adsorbent for the Removal of Copper from Wastewater [18]

Use of clayey soil has been explored in the laboratory scale experiment as a low

cost adsorbent for the removal of copper from wastewater The influence of metal ion

concentration, weight of adsorbent, stirring rates, influence of temperature, pH are also

evaluated and the results are fitted using adsorption isotherm models From the

experimental results it is observed that almost 90–99% copper can be removed from the

solution using clay at optimized pH 5.5

2.4.2 Calcareous Soil as a New Adsorbent to Remove Lead from Aqueous Solution: Equilibrium, Kinetic and Thermodynamic Study[17]

Natural calcareous soil of Indian origin was tested and evaluated as a possible

adsorbent for removal of lead from its aqueous solution using batch sorption technique