The distribution and speciation of heavy metal in the agricultural contamination site by tessier method

THAI NGUYEN UNIVERSITY UNIVERSITY OF AGRICULTURE AND FORESTRY Logo 2 university THAN THI NHU ANH The Distribution and Speciation of Heavy Metal in the Agricultural Contamination Site

THAI NGUYEN UNIVERSITY

UNIVERSITY OF AGRICULTURE AND FORESTRY

(Logo 2 university)

THAN THI NHU ANH

The Distribution and Speciation of Heavy Metal in the Agricultural

Contamination Site by Tessier Method

BACHELOR THESIS

Study Mode: Full-time

Major: Environmental Science and Management

Faculty: Departement Environment and Soil Science

Batch: 2013-2017

Thai Nguyen, ………

Thai Nguyen University of Agriculture and Forestry

Degree Program Environmental Science and Management

Student name Than Thi Nhu Anh

Student ID DTN1353110012

Thesis Title The Distribution and Speciation of Heavy Metal in the

Agricultural Contamination Site by Tessier Method Supervisor(s) Prof Dr Yao-Tung Lin - National Chung Hsing University,

ACKNOWLEAGEMENT

Firstly, I would like to say thanks to the cooperation between Thai Nguyen University of Agriculture and Forestry and National Chung Hsing University for providing me an amazing opportunity to internship in Taiwan It brings me great pleasure to work and submit my thesis for graduation

I would like to express my profound gratitude to Prof Dr Yao- Tung Lin, the facilitator, facilitator, suggestion and critic of the building that contributed greatly to the development of my ideas throughout the project and teach me about the synthesis

of new knowledge about soil science and many other techniques and methods Used in the field of the environment Without their help and devotion, I will not be able to achieve this stage without your guidance, I may not have this thesis

I sincerely thanks to Assoc Prof Dr Nguyen The Hung for her advices,

assistance, sharing experiences before and after I went to Taiwan, helping me to understand and complete proposal and thesis

I am also thankful to (Your name ) and my friends in lab … They have been very helpful in providing me with constructive feedback and suggestions on my project and helping me to successfully complete some of my experiments and reports

I also thank to my family for providing me emotional, unceasing encouragement and physical and financial support At last, I would like to thank all those other persons who helped me in completing this report Because of my lack knowledge, the mistake is inevitable, I am very grateful if I receive the comments and opinions from teachers and others to contribute my report

Sincerely,

Thân Thị Như Anh

TABLE OF CONTENT

LIST OF FIGURES 1

LIST OF TABLES 2

LIST OF ABBREVIATIONS 3

PART I INTRODUCTION 4

1.1 Research rationale: 7

1.2 Research questions 9

1.3 Limitations 10

PART II LITERATURE REVIEW 11

2.1 Heavy metals speciation in the soil 11

2.2 The source of heavy metals in the soil environment: 12

2.1.1 :Industrial production 12

2.1.2 Agricultural suction 13

2.1.3 Urban waste 13

2.3 The impact of heavy metal to plant and human health 15

2.3.1 Zinc toxicity 15

2.3.2 Copper toxicity 15

2.3.3 Nikel toxicity 16

2.3.4 Chromium toxicity 17

2.4 Heavy metals toxicity 18

2.5 The metal speciation offected by environmental conditions: 22

2.5.1 Sequential extraction process: 23

2.6 The term definition of speciation 24

PART III MATERIALS AND METHODS 26

3.1 Chemical and instruments 26

3.1.1 Chemical materials 26

3.1.2 Intrusment 27

3.1.3 Reagent 28

3.2 Soil and sediment collection 28

3.2.1 Sample pretreatment 29

3.2.2 Metal speciation using Tessier et al (1979) scheme 26

3.2.3 Quality control 27

PART IV RESULTS

4.1 Quality control 27

4.2 Heavy metal speciation 28

4.3 Heavy metal distribution 28

4.4 Conclusion 29

4.5 Acknowledgments 26

PART V DISCUSSION AND CONCLUSION Error! Bookmark not defined

5.1 Discussion Error! Bookmark not defined

5.2 Conclusion Error! Bookmark not defined 5.3 Acknowledgments Error! Bookmark not defined

PART I INTRODUCTION 1.1 Research rationale:

Economic and social development have produced many benefits – raising standards of living and improving quality of life across the world – it has also resulted in the depletion of natural resources, the degradation of ecosystems and environmental issues Environmental pollution is a controversial issue not only in Vietnam but also in the world Soil is an important part of the environment, an invaluable resource naturally given to human Soils is a special production material that is unique in labor, a constituent element of the Earth's ecosystem Due to the rapidly growing population also development of the industry, urbanization, employment and transport It is the main reason makes the land resource is heavily exploited and environmental degradation is becoming more and more serious As such, depending on the way people treat the land, the soil can develop in a good way as well as can develop in a bad way Therefore, protecting the soil environment and maintaining the long-term productivity of the soil is one of the key strategies in the sustainable use of natural resources

The contamination of sediments, soils, and biota by heavy metals are of major concern, especially in many industrialized countries, because of their toxicity, persistence and bio-accumulative nature Sediment samples have been found to be carriers of most metals and some elements may be recycled through biological and chemical reactions within the water column Metals and metalloids accumulated in sediments, sludge and soils may therefore pose an environmental problem concerning possible metal transfer from these samples to the aquatic medium, and thereby including them in the food chain The total metal content in polluted environmental samples is a poor indicator of

chemical forms of binding between trace metals and solid phases of the samples Different metal extraction methods for environmental samples have been extensively studied in many countries Metal ions in sediments are partitioned between the different phases, i.e., organic matter, oxyhydroxides of iron, aluminum and manganese, phyllosilicate minerals, carbonates and sulphides In addition, metal ions are retained in these solid phases by different mechanisms (ion exchange, outer- and inner-sphere surface complexation (adsorption), precipitation or co-precipitation) Although the separation of various chemical forms of heavy metals is very difficult, the use of sequential extraction method proves to be an important and effective approach

Trace element speciation in soils is often accomplished by a variety of different empirical single as well as sequential extractions These extraction tests are commonly used to study the mobility of metals in soils and sediments by mimicking different environmental conditions or dramatic changes on them A variety of leaching techniques are used to emulate

differing environmental conditions, with strong acids being used to determine total

Single leaching and combined sequential extraction schemes have been developed to estimate the relative phase associations of sedimentary metals in various aquatic environments The most widely utilized protocol is the Tessier et al (1979)

procedure However, many schemes were developed base on the concept of Tessier et al (1979) method Therefore, this research was followed Tessier method for estimate the heavy metal speciation and distribution in soil and sediment

1.2 Research’s objectives

1) To investigate the total concentration and species distribution of heavy metal (i.e Cr,

Cu, Zn and Ni) in contaminated soil and sediment in irrigation channels

2) To determine the heavy metal speciation distribution in contaminated soil and sediment in irrigation channels

1.2 Research questions

1) How to know the heavy metal speciation that affected by environmental conditions

2) What is the main speciation of heavy metal in the soil and sediment

3) What is the heavy metal concentration in the soil and sediment

4) How to assess the heavy metal contaminate in soil and sediment

1.3 Limitations

The author got the good experience for exchange student to department of Soil and Environmental science, National Chung Hsing University, Taiwan Therefore, all of the research schedule, method, results and discussion were followed from the experiments that have been done in Taiwan The limitation of the studied were:

1) The period for exchange student was shot time (6 months) Because the author need to lean ever thing for research such as how to collected the soil and sediment sample,

sample pretreatment, chemical preparation, metal analysis, and quantification of heavy metal by Atomic absorption spectrophotometer (AAS)

2) The problem of language for communication

PART II LITERATURE REVIEW 2.1 Heavy metal speciation in soil:

The term heavy metal refers to any element with a high specific gravity (d>5 g

cm-3) and exhibits toxicity at low concentrations However, the toxicity of specific gravity also depends on the types of their existence in the soil When studied the

accumulation of heavy metals in the soil that only considers the total content, it can not properly assessed to appreciate their toxicity to the crop as well as to the variability of the soil Heavy metals are defined as metallic elements that have a relatively high density compared to water with the assumption that heaviness and toxicity are inter-related Most

of the heavy metals were founf in transition metals, some metalloids lantharides and actinides Now a day, the heavy metals contain 22 elements, however the most importance element in soil was mercury (Hg), cadmium (Cd), lead (Pb), chromium (Cr) and arsenic (As), etc They also include other heavy metals of certain biological toxicity, such as zinc (Zn), copper (Cu), nickel (Ni), stannum (Sn), vanadium (V), and so on

Figure 1 The periodic table of elements that contained the specific gravity

2.2 The source of heavy metals in the soil environment:

Soil parent material is the factor from the natural to release the heavy metal into the soil and environment by rock or mineral weathering However, this process, the

amount of metal entering the soil is negligible, with the majority of metals entering the soil due to human production activities These activities include:

2.2.1 Industrial production:

Most of the environmental pollution caused by the factory Waste leaking or waste release to the natural resources such as river may cause the heavy pollution size The material of individual factories were different that depending on the production

Table 1 The industrial type that correlated with heavy metal production

Manufacturing of microchips Cu, Ni, Cd, Zn, Sb

2.2.2 Agricultural suction:

Agriculture areas are site that were risked for heavy metal contamination by the agricultural practice from pesticide, chemical fertilizer, fungicides, plant hormone, or irrigation water that contamination

Table 2 Sources caused agricultural contamination

Chemical phosphate fertilizers As, Cd, Mn, Zn

Fungicides Cu, Mn Zn

Irrigation water Discharge to Cd, Pb, Se or depend on water

sources

2.2.3 Urban waste:

This factor caused heavy metal contamination in the environment by the activities of the human Many thing in the urban waste caused contaminate in the environment Urban waste is the used and left-over materials in urban systems comprising of household garbage included kitchen waste, green waste, street sweepings, sanitation residues The disposal of urban waste is of great concern as it poses serious management problems particularly in developing countries It causes pollution of land, water and air, which threatens public health with the waste forming the breeding ground for various pathogen-carrying vectors such as mosquitoes, rodents, pigs and others Moreover, the urban waste is known to contain hazardous persistent pollutants such as heavy metals, being detrimental to the ecosystem including human beings

Table 3 Sources caused agricultural contamination by urban waste

Figure 2 Sources of heavy metal pollutions

2.3 The impact of heavy metal to plant and human health:

With the excessive accumulation of heavy metals in the soil environment that has caused terrestrial vegetation to be lost, many species can not survive in areas with too much heavy metal content Heavy metals accumulated in the soil into agricultural products, food and heavy metal food chains in the soil will accumulate in plants and in the human body If the human body accumulates large amounts of heavy metals, it will cause many serious illnesses affected human health and life

2.3.1 Zinc toxicity:

For plants: Zinc (Zn) excess is toxic to plants when Zn accumulation in soil is too high Zn excess also causes chlorophyll loss Too much Zn accumulation in the plant causes some linkage to the level of Zn residues in the human body and contributes to the development of Zn accumulation in the environment, especially in the soil environment For humans: Zn is essential nutrients and it will cause illnesses if deficient as well as

redundant In the human body, Zn usually accumulates mainly in the liver, which is the main accumulation of micronutrients in the body, about 2 grams of Zn is filtered daily by the kidneys Zn is also toxic to the immune system Zn deficiency in the body causes impotence symptoms, testicular atrophy, dermatitis, liver disease and some other symptoms

2.3.2 Copper toxicity:

For crops: According to research results of many projects, copper (Cu) has a very important role in the development of crops Plants lacking Cu often exhibit abnormal photosynthesis rates, indicating that Cu is related to the degree of oxidation of the plant

In Cu deficient plants, Oxidation of Ascorbic Acid is slow, Cu forms a large number of organic compounds with proteins, amino acids, and other substances we commonly find

in fruits In addition to the effects of Cu deficiency, overgrowth of Cu also occurs in the presence of poisoning which can lead to death of the plant The reason for this is due to the use of fungicides, pesticides, which cause the Cu material to sink in the soil year after year, even the application of Cu sulfate is equally harmful For humans: Cu is only toxic

to animals: for people 1g/kg body weight was fatal, 60-100 mg/kg cause nausea Cu has serious health consequences due to deficiency as well as redundancy

2.3.3 Nikel Toxicity

Nickel (Ni) is generally uniformly distributed in the soil profile and typical soil nickel contents vary widely based on the parent rock, with elevated levels at surface soils been associated with soil- forming processes and anthropogenic contamination principally ascribed to agricultural and industrial activities The toxic effects of nickel

compounds to interact with at least 13 essential elements namely calcium, chromium, cobalt, copper, iodine, iron, magnesium, manganese, molybdenum, phosphorus, potassium, sodium and zinc Therefore, prolong exposure to oxides and sulphides of nickel is associated with possible risk to lung and nasal tumours, while systematic effects whose initial symptoms are mild nausea, headache, dyspnoea, and chest pain could be ascribed to nickel carbonyl; these symptoms may disappear or consequently results in severe pulmonary insufficiency Also, arising from exposure to nickel containing mists and dusts are asthma, pneumoconiosis and irritation of nasal membranes Although, Ni is ubiquitous in the environment, but its functional role as a trace element for animals and humans is not yet recognized Therefore, it becomes trace metal of concern because of its major route of exposure which is either through the dietary intake or ingestion through the food chain which may arise principally from the nickel accumulation in crops, fruits and vegetables grown on contaminated soils and their consequence consumption by animals or man

2.3.4 Chromium toxicity

Chromium (Cr) waste slag containing potentially hazardous levels of Cr(VI) compounds was used as fill material at more than 160 residential, industrial, and recreational sites Persons living or working in the vicinity of the sites may have been exposed through inhalation, ingestion, or skin contact with contaminated soils and dusts Community exposure from this fill occurred in a variety of ways Wind erosion of the soil could have made slag particles airborne, increasing the opportunity for inhalation of chromium Chromium compounds leached by rainwater could have migrated through cracks in soil, asphalt roadways, and masonry walls, forming high-content chromium

crystals on their surfaces In soil and roadways, these particles might have been eroded

by wind and foot traffic and carried as chromium-laden dust into homes and workplaces Children playing in areas where the slag was used as fill might also have been exposed through skin contact with chromium-contaminated dust, dirt, and puddles and /or ingestion of contaminated soil Other environmental sources of chromium are cement-producing plants (cement contains chromium), the wearing down of asbestos linings that contain chromium, emissions of chromium-based automotive catalytic converters, and tobacco smoke The general population is exposed to chromium by eating food or food supplements, drinking water, and inhaling air that contain chromium The mean daily dietary intake of chromium from air, water, and food is estimated to be <0.2-0.4, 2.0, and

60 micrograms, respectively One study found increased blood chromium level after total hip replacement using metal-metal pairings where metal ions of the alloys are released

2.4 Heavy metal toxicity

Some debate exists as to exactly what constitutes a "heavy metal" and which

on atomic weight; others, on a specific gravity of greater than 4.0, or greater than 5.0 The actinides may or may not be included Most recently, the term "heavy metal" has been used as a general term for those metals and semimetals with potential human or environmental toxicity. This definition includes a broad section of the periodic table under the rubric of interest Regardless of how one chooses to define the category, heavy metal toxicity is an uncommon diagnosis With the possible exceptions of acute iron toxicity from intentional or unintentional ingestion and suspected lead toxicity, emergency physicians will rarely be alerted to the possibility of metal exposure Yet, if unrecognized or inappropriately treated, heavy metal exposure can result in significant morbidity and mortality

Many of the elements that can be considered heavy metals have no known benefit for human physiology Lead, mercury, and cadmium are prime examples of such "toxic metals." Yet, other metals are essential to human biochemical processes For example, zinc is an important cofactor for several enzymatic reactions in the human body, vitamin B-12 has a cobalt atom at its core, and hemoglobin contains iron Likewise, copper, manganese, selenium, chromium, and molybdenum are all trace elements that are important in the human diet Another subset of metals includes those used therapeutically

in medicine; aluminum, bismuth, gold, gallium, lithium, and silver are all part of the medical armamentarium Any of these elements may have pernicious effects if taken in quantity or if the usual mechanisms of elimination are impaired The toxicity of heavy metals depends on a number of factors Specific symptomatology varies according to the metal in question, the total dose absorbed, and whether the exposure was acute or chronic The age of the person can also influence toxicity For example, young children are more susceptible to the effects of lead exposure because they absorb several times the

percent ingested compared with adults and because their brains are more plastic and even brief exposures may influence developmental processes The route of exposure is also important Elemental mercury is relatively inert in the gastrointestinal tract and also poorly absorbed through intact skin, yet inhaled or injected elemental mercury may have disastrous effects.

Some elements may have very different toxic profiles depending on their chemical form For example, barium sulfate is basically nontoxic, whereas barium salts are rapidly absorbed and cause profound, potentially fatal hypokalemia Exposure to metals may occur through the diet, from medications, from the environment, or in the course of work

or play Where heavy metal toxicity is suspected, time taken to perform a thorough dietary, occupational, and recreational history is time well spent, since identification and removal of the source of exposure is frequently the only therapy required A full dietary and lifestyle history may reveal hidden sources of metal exposure Metals may be contaminants in dietary supplements, or they may leech into food and drink stores in metal containers like lead decanters Persons intentionally taking colloidal metals for their purported health benefits may ultimately develop toxicity Metal toxicity may complicate some forms of drug abuse Beer drinker’s cardiomyopathy was diagnosed in alcoholics in Quebec, and later Minnesota, during a brief period in the 1970s when cobalt was added to beer on tap to stabilize the head More recently, a parkinsonian syndrome among Latvian injection drug users of methcathinone has been linked to manganese toxicity

Currently, millions of people living in and around Bangladesh are at risk for organ dysfunction and cancer from chronic arsenic poisoning from the water supply In an

effort to bypass ground water sources rife with bacterial contamination, tube wells were sunk throughout that area, deep into the water table.Bedrock rich in arsenic gives these deeper water stores—and the crops they irrigate—a high concentration of arsenic, and toxicity is epidemic throughout the area Childhood lead poisoning linked to the ingestion

of old paint chips in the North American setting is another good example of environmental contamination Metals have been used as instruments of murder Arsenic

is perhaps more rightly classified as a metalloid, but it is consistently the single substance most commonly thought of as a poison Metals have also been used in warfare as chemical weapons Again, arsenic was the primary component of the spray known as Lewisite that was used by the British during trench warfare in World War I Exposure produced severe edema of the eyelids, gastrointestinal irritation, and both central and peripheral neuropathies In total, however, occupational exposure has probably accounted for the vast majority of heavy metal poisonings throughout human history Hippocrates described abdominal colic in a man who extracted metals, and the pernicious effects of arsenic and mercury among smelters were known even to Theophrastus of Erebus (370-

develop slowly over time and may be difficult to recognize clinically In the United States, Occupational Safety and Health Administration (OSHA) regulations guide the surveillance of workers at risk and suggest exposure limits for metals of industrial importance

Figure 3 The symptom of heavy metal disease in human

2.5 The metal speciation affected by environmental conditions:

In the environment, its was contain the conditions that affected to the speciation such as organic ligand, sorption, desorption, organic coating, Fe and Mn oxides, microorganism activity, etc This factors almost affected to the metal speciation and distribution

Figure 4 Schematic illustration of a variety of molecular environmental science processes

affecting contaminant elements in soils

2.5.1 Sequential extraction process:

The sequential extraction process (SEP) is a continual multistep analysis used for evaluating various element-binding forms (Vojtekova et al 2003) The SEP aims to imitate the manner in which the weakly-bound to the strongly-bound selected target phase is released with a crystalline structure that is affected by environment conditions (Tessier et al 1979) The SEP approach gives information about the metal fractionation which takes place throughout the various lattices within a given soil sample While techniques may vary slightly (Tessier et al 1979; Shuman 1983; Ure et al 1993; Krishnamurti et al 1995), the SEP approach defines up to eight separate categories for speciation: exchangeable, carbonate, easily oxidizable, easily reducible, moderately reducible, oxidizable oxides and sulfides, poorly-reducible, and residual forms While the SEP approach was developed in order to analyze trace metals (Tessier et al 1979), it can also be legitimately applied to estimate heavy metals (Nielsen et al 2015; Xia et al 2016;

Gope et al 2017; Xu et al 2017) Furthermore, the approach has been shown to be effective in estimating non-trace elements including iron (Larner et al 2006), aluminum (Dai et al 2011), magnesium (Luo et al 2011), and also phosphorus (Wang et al 2013)

Figure 5: Sequential extraction process

2.6: The term definition of speciation:

Exchangeable; the element performed on sediments or on their major constituents (clays,

hydrated oxides of iron and manganese, humic acids) have demonstrated the adsorption of trace metals; changes in water ionic composition (e.g., in estuarine waters) are likely to affect sorption-desorption processes

Bound to Carbonates; Trace metal concentrations can be associated with sediment

carbonates; this fraction would be susceptible to changes of pH

Bound to Fe and Mn Oxides; Fe and Mn oxides exist as nodules, concretions, cement

between particles, or simply as a coating on particles; these oxides are excellent

scavengers for trace metals and are thermodynamically unstable under anoxic

conditions (i.e., low Eh)

Bound to Organic Matter; trace metals may be bound to various forms of organic

matter or living organisms, detritus, coatings on mineral particles, etc The complexation and peptization properties of natural organic matter (notably humic and fulvic acids) are well recognized, as is the phenomenon of bioaccumulation in certain living organisms Under oxidizing conditions in natural waters, organic matter can be degraded, leading to a release of soluble trace metals

Residual; once the first four fractions have been removed, the residual solid should

contain mainly primary and secondary minerals, which may hold trace metals within their crystal structure These metals are not expected to be released in solution over a reasonable time span under the conditions normally encountered in nature