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 copper ions adsorption" Full name : Luu Thi Thuy Linh Class : K42AEP Supervisor : Prof RueyAnDoong Dr Nguyen Thanh Hai Taiwan - 2014 i 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 INTRODUCTION LITERATURE REVIEW 2.1 The value of tea 2.1.1 Nutritional Value 2.1.2 The value of medicinal 2.1.3 The value of Economic 2.2 The role of nutrients for tea 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 RESEARCH METHODS 20 3.1 Objectives: 20 3.2 Location: 20 3.3 Project Content: 20 3.4 Methodology: 20 RESULTS 27 4.1 Soil properties 27 4.1.1 Size of soil sample: 27 i 4.1.2 Soil Organic Matter (SOM), pH of soil: 28 4.2 Adsorption 32 DISCUSSION AND CONCLUSION 34 REFERENCES 36 APPENDICES 38 ii 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 iii 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 speed: 130rpm) 18 Fig.3: Effect of pH of solution on As (III) adsorption C = 1.0 mg l-1, adsorbent dose: 25g l-1, shaker speed: 130rpm 19 Fig.4 OM process 28 Fig.5: Absorption of copper ions in the soil after 24 hours at lower concentrations 32 Fig.6: Absorption of copper ions in the soil after 24 hours at higher concentrations 33 iv LIST OF ABBREVIATIONS Temp Temperature Cu Copper US United State EU Eropean Union OM Organic Matter N Nitrogen P Photphorus Z Zinc XRD X-ray diffraction USSR Union of Soviet Socialist Republics TOC Total Organic Carbon LOI Loss on ignition Conc Concentration DI water Deionized water AAS Atomic Absorption Spectrometry SOM Soil Organic Matter v 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 vi 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 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 vii 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 Table 4: The group of higher concentration Conc (µM) Stock solution (ml) DI water (ml) 0,5 49,5 1,5 0,75 49,25 49 2,5 1,25 48,75 1,5 48,5 + After preparation of the samples, using AAS to determine concentration of copper element This method was selected because it is the fastest * Atomic Absorption Spectrometry (AAS) is a technique for measuring quantities of chemical elements present in environmental samples by measuring the absorbed radiation by the chemical element of interest This is done by reading the spectra produced when the sample is excited by radiation The atoms absorb ultraviolet or visible light and make transitions to higher energy levels Atomic absorption methods measure the amount of energy in the form of photons of light that are absorbed by the sample A detector measures the wavelengths of light transmitted by the sample, and compares them to the wavelengths which originally passed through the sample A signal processor then integrates the changes in wavelength absorbed, which appear in the readout as peaks of energy absorption at discrete wavelengths 25 The concentration is calculated based on the Beer-Lambert law Absorbance is directly proportional to the concentration of the analyte absorbed for the existing set of conditions The concentration is usually determined from a calibration curve, obtained using standards of known concentration In analytical chemistry, AAS is a technique used mostly for determining the concentration of a particular metal element within a sample AAS can be used to analyze the concentration of over 62 different metals in a solution [16] + Each sample, take 1g of soil, shake and wait 24 hours, then check the concentration for the result To measure correct result, right experimental methods, when measuring samples with ASS machine must be fluid and no solids or cloudiness So, after 24 hours, the sample will be separated from soil by sedimentation and filtration 26 RESULTS 4.1 Soil properties 4.1.1 Size of soil sample: Highly dispersive soil particles play an essential role in all the interphase interactions in soils: ion-exchange adsorption Therefore, the assessment of the effect of the particle-size distribution on the adsorption properties of soils is a vital task (Aslanov and Ryzhov, 1969) Table 5: Size of soil sample # Size Weigh (g) Percentage (%) #10 2000µm 11,577 3,3 #60 0,250 µm 119,441 34,8 #100 0,149 µm 137,012 40 #230 0,062 µm 54,317 15,8 #325 0,044 µm 19,688 6,1 Total of weigh: 343 (g) 100 Compare with the classification of soil particles by diameter that has been adopted in the USSR (Table 2) 27 In the results, particle size of soil was almost in the range from 0.5 to 0.1 (60%) To compare with Table 5, the major soil here is "fine clay." soil particle size smaller, the more flexible and higher activity, enhances the absorption of soil metals 4.1.2 Soil Organic Matter (SOM), pH of soil: * OM: *Calculate the OM of soil: Fig.4 OM process It is necessary to convert the organic matter content to total organic carbon content Traditionally, for soils, a conversion factor of 1.724 has been used to convert organic matter to organic carbon based on the assumption that organic matter contains 58% organic C (i.e., g organic matter/l 724 = g organic C)(Nelson and Sommers, 1996) However, there is no universal conversion factor as the factor varies from soil to soil, 28 from soil horizon to soil horizon within the same soil, and will vary depending upon the type of organic matter present in the sample Conversion factors range from 1.724 to as high as 2.5 (Nelson and Sommers, 1996; Soil Survey Laboratory Methods Manual, 1992) Broadbent (1953) recommended the use of 1.9 and 2.5 to convert organic matter to total organic carbon for surface and subsurface soils, respectively The process of determining organic matter experiments were done in 270 minutes, the initial sample weight is 2g, end of the experiment, the remaining sample weight is 1,891g, losing weight is 0,109g (percent 5,45%) are considered "total organic carbon" Organicmatter (%) = Total organic carbon (%) x 1,724 = 5,45 x 1,724 = 9,34 (%) 2% Organic matter is poor Over 4% O.M to 10% is ideal (Carl Rosat– Soil Consultant) With this ideal "SOM", will bring advantages for tea, specifically: Organic matter contributes to plant growth through its effect on the physical, chemical, and biological properties of the soil Availability of nutrients for tea growth Organic matter has both a direct and indirect effect on the availability of nutrients for tea growth In addition to serving as a source of N, P, S through its mineralization by soil microorganisms, organic matter influences the supply of nutrients from other sources (for example, organic matter is required as an energy source for N-fixing bacteria) 29 A factor that needs to be taken into consideration in evaluating humus as a source of nutrient is the cropping history When soils are first placed under cultivation, the humus content generally declines over a period of 10 to 30 years until a new equilibrum level is attained[11] At equilibrium, any nutrients liberated by microbial activity must be compensated for by incorporation of equal amounts into newly formed humus Effect on soil physical condition, soil erosion and soil buffering and exchange capacity Humus has a profound effect on the structure of many soils The deterioration of structure that accompanies intensive tillage is usually less severe in soils adequately supplied with humus When humus is lost, soils tend to become hard, compact and cloddy Aeration, water-holding capacity and permeability are all favorably affected by humus The frequent addition of easily decomposable organic residues leads to the synthesis of complex organic compounds that bind soil particles into structural units called aggregates[14] These aggregates help to maintain a loose, open, granular condition Water is the better able to infiltrate and percolate downward through the soil The roots of tea need a continual supply of O2 in order to respire and grow Large pores permit better exchange of gases between soil and atmosphere Humus usually increases the ability of the soil to resist erosion First, it enables the soil to hold more water Even more important is its effect in promoting soil granulation and thus maintaining large pores through which water can enter and percolate downward.[19] 30 Effect on soil biological condition Organic matter serves as a source of energy for both macro- and macrofaunal organisms Numbers of bacteria, actinomycetes and fungi in the soil are related in a general way to humus content Earthworms and other faunal organisms are strongly affected by the quantity of plant residue material returned to the soil.[11][19] Organic substances in soil can have a direct physiological effect on tea growth Some compounds, such as certain phenolic acids, have phytotoxic properties; others, such as the auxins, enhance plant growth It is widely known that many of the factors influencing the incidence of pathogenic organisms in soil are directly or indirectly influenced by organic matter For example, a plentiful supply of organic matter may favor the growth of saprophytic organisms relative to parasitic ones and thereby reduce populations of the latter Biologically active compounds in soil, such as antibiotics and certain phenolic acids, may enhance the ability of certain plants to resist attack by pathogens [14] * pH: Measurements of soil pH is 4.7, this value is the most suitable for the growth of tea plants The soil pH has a significant effect not only on the rate but also the kind of ions uptake This property is also due to its effect on cellular components that are involved in absorption, which further suggests that proteins are involved in the ion uptake As the 31 protein structure is very sensitive to pH, its function also changes if there is any change in the pH That is why the maintenance of proper soil pH is very important in agriculture 4.2 Adsorption Results of experiments test the ability to absorb copper are shown in tables and graphs Table 6: Absorption of copper ions in the soil after 24 hours at lower concentrations Conc 0.1 0.2 0.5 1.25 Before 0.307 0.313 0.319 0.325 0.329 After day 0.285 0.286 0.287 0.287 0.289 Fig.5: Absorption of copper ions in the soil after 24 hours at lower concentrations 32 Concentrations have decreased clearly, only small differences (ranged from 0.022 to 0.04) and increase when the concentration increases Table7: Absorption of copper ions in the soil after 24 hours at higher concentrations Conc Before After day 1.5 0.325 0.327 0.289 0.29 0.337 0.291 2.5 0.347 0.295 0.362 0.311 Fig.6: Absorption of copper ions in the soil after 24 hours at higher concentrations Concentrations also have decreased clearly, but the absorption value is bigger (ranged from 0.036 to 0.052) and it also increase when the concentration increases 33 DISCUSSION AND CONCLUSION After analyzing the important factors of the soil, we can conclude that soil quality is very beneficial for the development of tea Soil type is "fine clay", and it is ideal for tea Fine clay stays sodden after raining or sprinklers, it retains moisture And as they dry out quicker, because of this, tea growing in clay often deal with dry conditions better than tea in other soils Fine clay is usually very rich in nutrients too, which reduced need for fertilising Howerver, one of the disadvantages of fine clay, is that it stays wet long after rain Because of this disadvantage, the tea should be planted in areas where elevation and slope for easy water drainage, avoiding submerged for tea The pH of the soil is ideal for the growth of tea, however, it reduces the absorption capacity of the soil However, soil organic matter was the major determinant of strength of Cu adsorption This soil samples have quite high organic matter, kind of "organic soil" Not only the major determinant of strength of Cu adsorption, it also influences the supply of nutrients from other sources Although there such advantages, but the ability to absorb copper is relatively low, absorption capacity of 7% (for the lowest concentration) to 14% (for the highest concentration) But easy to see that, the higher the concentration, the higher absorb ability Since conditions of limited time, so we can not test with high concentrations But with the above results, we can see that the quality of the soil is very good, can provide high-quality tea, however, because the absorption of copper is less, so the farmers should fertilizer copper for tea regular and long-term, although only small quantities, but 34 should be maintained during the growing of tea, so tea can be achieve the best quality, bring higher profits for farmers It can be predicted that the absorption capacity of the soil copper will reach high values when testing high concentrations, however, will be limited to certain of it I am very interested and want to learn more about this issue, so in the future, I want to continue this research to obtain exact results and to provide information for agriculture and science 35 REFERENCES Vietnamese: [1] Sở nông nghiệp & PTNT Thái Nguyên (2009) Báo cáo tình hình sản xuất nơng nghiệp tỉnh Thái Nguyên năm 2003-2004-2009 [2] Đỗ Ngọc Quỹ, 2003, Cây chè Việt Nam sản xuất, chế biến tiêu thụ [3] Ngô Xuân Cường, Nguyễn Văn Tạo, (10/2004) Một số yếu tố ảnh hưởng đến chất lượng chè xanh đặc sản Tạp chí Nơng nghiệp Phát triển Nơng thơn, tr.1334 - 1336 [4] Hoàng Thảo Nguyên (2014) (TTXVN/vietnam+) [5] PGS Đỗ Ngọc Quỹ – TS Đỗ Thị Ngọc Oanh.(2001) Khoa học Văn hóa trà Việt Nam Thế Giới – Trang [211-214] [6] Nguyễn Hữu Khải, ( 2005).Cây chè Việt Nam: Năng lực canh tranh xuất phát triển Nxb Lao động Xã hội, Hà Nội, [7] KS Nguyễn Xuân Thự, (2012) http://nongnghiep.vn English [8] Rana Munns, Functional Plant Biology 36(5) 409–430) [9] Angela Lovell, (March 22, 2012) The role of copper in plant nutrition [10] Brian A Schumacher, Ph.D., (April 2002) Methods for the Determination Of Total Organic Carbon (Toc) In Soils And Sediments [11] Drozd J., Weber J (red.) (1996) The role of humic substances in the ecosystem and in environmental protection PTSH, Wrocław 36 [12] Das B and Mondal N K, (2011) Universal Journal of Environmental Research and Technology [13] Fred R Davis, Kent, Ohio, (1983) Micronutrients And Plant Nutrition [14] Fuller W.H et al (1956) Soil Sci Soc Amer Proc 20,218 [15] George Rehm, Michael Schmitt, (2002) Copper for crop production, Extension Soil Scientist, [16] R García and A P Báez, (2012) Atomic Absorption Spectrometry (AAS) Centro de Ciencias de la Atmósfera, Universidad Nacional Autónoma de México, Ciudad Universitaria, Mexico City,Mexico) [17] Pravin D Nemade, A M Kadam and H S Shankak, (2008), Department of Chemical Engineering, Indian Institute of Technology, Bombay, Powai, Mumbai, India [18] Saha, P., Datta, S., and Sanyal, S (2010) Application of Natural Clayey Soil as Adsorbent for the Removal of Copper from Wastewater J Environ Eng., 136(12), 1409– 1417 [19] Stevenson F.J (1982) Humus chemistry Genesis, composition, reactions 37 APPENDICES * The filters with layers * Measure the pH with pH meter instrument 38 * The furnace to determine the amount of organic matter in soil * Using AAS to determine concentration of copper element 39 ... 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. .. 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... 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