Nadirah binti Ismail
1st Assessment (2013/2014)
Supervisors:
Assoc. Prof Dr Zaiton Abdul Majid
Assoc. Prof Dr Zaharah Ibra...
Proposed Title
Isotherm, Kinetics and Thermodynamic Studies
on Adsorption of Chlorpyrifos Using Modified
Ananas Comosus (P...
Chlorpyrifos
1 or more
aromatic ring

Persistent

Organic
Pollutants

Variable numbers
of halogen
substitutions

Lack of polar
function...
the spraying of pesticides into our
external space results in only 5%
of the pesticide reaching the target
pest. The rest ...
Methods for pesticides removal

Photodegradation

Membrane filtration

Ozone treatment

Combined Ozone and UV
Disadvantages of conventional
treatment

Cost

Pesticides not
removed during
physical treatment
Adsorption
• The binding of molecules or particles to a surface.
• Happens at the surface of the substance.
• Physical ads...
Lignocellulosic materials

Lignocellulose refers to plant
biomass. It is the most abundantly
available raw material on the...
High C

Cellulose

A good
adsorbent for
pesticides

Good adsorbent

Lignin

Good adsorption
capacity

Develops
micropores
...
Adsorption
• Physicochemical process.
• Enable microorganism communities to adsorb
some toxic materials from solutions.
• ...
Problem Statement
• The application of PLP to adsorb pesticides
have not entered the scientific literature
extensively
• A...
Hypothesis
• PLP that comprises of lignin, cellulose and
hemicelluloses embedded with immobilized
bacteria has the potenti...
Objectives of study


To characterize the lignocellulosic materials in PLP for adsorption of
Chlorpyrifos



To evaluate...
Significance of study
• Chlorpyrifos has been detected in unfiltered river water
sample taken from Sungai Sayong, Kulai, J...
Novelty of study
• The adsorptive interaction of
Chlorpyrifos, lignocellulosic material, biofilm
in PLP has not been inves...
Knowledge Gap
• Adsorbent

• Biodegradation

Organoclay
Calcium alginate +
Pseudomonas

Bacillus cereus
Enterobacter sp
Kl...
-Hydrolysis may occur at several
reactive centres in the pesticide
molecule, in the presence of
OH- or H2O acting as
nucle...
FINDINGS
• Part 1: Preparation of adsorbent
Collection of pineapple leaves

Pre-treatment

Wash

Dry and sieve
Storage

Dessicator
Wash

Dry

Grind & Sieve

(d)

Pineapple leaf

Pineapple leaf powder
Chemical treatment of adsorbent
Rewash with
Deionized water

0.1M nitric
acid 1hour

Methanol
1hour

• Methanol to remove ...
• Part 2 : Characterization of adsorbent
1) Functional groups

Fourier Transform Infra Red Spectroscopy
2) Surface Area

B...
SEM of raw & treated PLP
Lignocellulosic biomass has a
complex and rigid cell wall
structure which consists of three
princ...
Fiber and elemental analysis
Parameter

Composition (%)

Cellulose

26.15

Hemicellulose

53.45

Lignin

6.93

Carbon

40....
Surface area of PLP
• Surface area - 8.61m²/g *(Carbonaceous materials
10-15 m²/g)
Pore size - 5.948 Angstroms
(micropores...
X-ray fluorescence
(XRF) of PLP
No

Parameter

Results (%)

1

Potassium Oxide

4.94

2

Calcium Oxide

2.60

3

Chlorine
...
Ash content of PLP
• Ash is the inorganic residue remaining after
the water and organic matter have been
removed by heatin...
FTIR of raw PLP

Hydroxyl groups,
Presence of –OH
groups

Aromatics
groups in
lignin
Carbonyl group in
hemicellulose
FTIR of modified PLP

Presence of –OH groups. The acid
pre-treatment increases the concentration of
the hydroxyl groups on...
pH at zero point of charge of
modified PLP
(pH at which the net surface charge is = 0)

12

pH drift method
10

8

6

pH f...
Part 3 : Isolation, Screening and
Biofilm development
1) Isolation

Microclear, soil, cultured drink
2) Screening

Chlorpy...
Gantt Chart
Thank You
Proposed title
• Isotherm, kinetics and thermodynamic studies
on combined adsorption and biodegradation
of Chlorpyrifos us...
• Pesticides ingredients:Active
ingredients
intended to kill
the target pest

Inert ingredients
used as bulk
carriers for
...
Pineapple Leaf Powder
Optical & Phase Contrast Microscope
images
Reactive Red dye adsorbed
onto PLP

Reactive Black 5 dye adsorbed
onto PLP
SEM of raw & modified PLP

Unmodified PLP

Modified PLP
* Crystalline and amorphous
structures- XRD
Adsorbent Modification
(Biologically Inspired Design = Biomimetics)
• What? : Biomimetics is the study of the structure
an...
Triolein -embedded PLP
composed of the supporting PLP and the surrounding trioleincellulose acetate membrane.
Pesticides /...
Hydrophilic
membrane
structure
(polyamide)
Lindane

Dieldrin
Atrazine

Hydrophobic
nucleolus
(triolein)
Nitrobenzene
Chlorpyrifos degradation

The degradation pathway of chlorpyrifos in aquatic environments involves the
breakdown of the th...
FTIR
• The region to the right-hand side of the diagram (from
about 1500 to 500 cm-1) usually contains a very
complicated ...
Lignin

macroporous
structure

Cellulose

microporous
materials

Lignocellulosic
Cellulose
Lignin
Adsorption kinetics
• The rate of adsorption of a molecule onto a
surface
Adsorption isotherm
• For a better understanding of binding
mechanism of the sorption system, between
liquid and solid
• L...
• Freundlich isotherm equation is based on the
assumption that cations and anions are
adsorbed onto the same surface
simul...
Thermodynamic studies
• To study the effect of temperature
• Positive values of entalphy ∆H – endothermic
• Positive value...
1st assessment ph d 30 dec dr zaharah
1st assessment ph d 30 dec dr zaharah
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1st assessment ph d 30 dec dr zaharah

  1. 1. Nadirah binti Ismail 1st Assessment (2013/2014) Supervisors: Assoc. Prof Dr Zaiton Abdul Majid Assoc. Prof Dr Zaharah Ibrahim Chemistry Department Faculty of Science, Universiti Teknologi Malaysia
  2. 2. Proposed Title Isotherm, Kinetics and Thermodynamic Studies on Adsorption of Chlorpyrifos Using Modified Ananas Comosus (Pineapple) Leaf Powder
  3. 3. Chlorpyrifos
  4. 4. 1 or more aromatic ring Persistent Organic Pollutants Variable numbers of halogen substitutions Lack of polar functional groups
  5. 5. the spraying of pesticides into our external space results in only 5% of the pesticide reaching the target pest. The rest runs off into water and dissipates in the air. Pesticide Movement Active ingredients + wetting agents, solvents, buffers, pres ervatives & emulsifiers 1 photochemical degradation 3 weaken the ecosystem damaging soil microbes biodegradation 2
  6. 6. Methods for pesticides removal Photodegradation Membrane filtration Ozone treatment Combined Ozone and UV
  7. 7. Disadvantages of conventional treatment Cost Pesticides not removed during physical treatment
  8. 8. Adsorption • The binding of molecules or particles to a surface. • Happens at the surface of the substance. • Physical adsorption : forces of attraction between the molecules are of the weak type. Can be easily reversed by heating or decreasing the pressure • Chemical adsorption :forces of attraction between the molecules are very strong. Chemical bonds present on the surface.
  9. 9. Lignocellulosic materials Lignocellulose refers to plant biomass. It is the most abundantly available raw material on the earth, It is composed of carbohydrate polymers (cellulose and hemicellulose) and an aromatic polymer (lignin).
  10. 10. High C Cellulose A good adsorbent for pesticides Good adsorbent Lignin Good adsorption capacity Develops micropores Develops macropores Dyes, pesticides, phen ols, surfactant Towards phenols and nitrogen containing compounds
  11. 11. Adsorption • Physicochemical process. • Enable microorganism communities to adsorb some toxic materials from solutions. • Allows it to passively concentrate and bind contaminants onto its cellular structure. • EPS in microbial aggregates have many available sites for the adsorption. The adsorption of organic pollutants by microbial aggregates may be attributed to the fact that there are some hydrophobic regions in EPS.
  12. 12. Problem Statement • The application of PLP to adsorb pesticides have not entered the scientific literature extensively • Adsorption is a difficult subject because adsorption may occur via several different mechanism. • Understanding adsorptive interactions between Chlorpyrifos, lignocellulosic material (PLP) and biomass/biofilm
  13. 13. Hypothesis • PLP that comprises of lignin, cellulose and hemicelluloses embedded with immobilized bacteria has the potential to remove Chlorpyrifos from aqueous solution via several adsorptive interactions.
  14. 14. Objectives of study  To characterize the lignocellulosic materials in PLP for adsorption of Chlorpyrifos  To evaluate the adsorptive interaction of interaction between chlorpyrifos with biofilm coated PLP  To determine the composition, thickness and efficiency of biofilm for the removal of Chlorpyrifos
  15. 15. Significance of study • Chlorpyrifos has been detected in unfiltered river water sample taken from Sungai Sayong, Kulai, Johor. • To solve the disposal problem of agricultural waste • The adsorption behaviour of chlorpyrifos onto lignocellulosic material is essential in predicting their potential to be adsorbed or desorbed from the adsorbent. • Development of biofilm onto lignocellulosic material in PLP will enhance the Chlorpyrifos removal and degradation.
  16. 16. Novelty of study • The adsorptive interaction of Chlorpyrifos, lignocellulosic material, biofilm in PLP has not been investigated in any research.
  17. 17. Knowledge Gap • Adsorbent • Biodegradation Organoclay Calcium alginate + Pseudomonas Bacillus cereus Enterobacter sp Klebsiella sp Serratia sp Chlorpyrifos (None) -Heavy Metal -Hydrocarbon -PAH Dyes • Biofilm
  18. 18. -Hydrolysis may occur at several reactive centres in the pesticide molecule, in the presence of OH- or H2O acting as nucleophilic reagents *Cell membranes, many classes of lipids and lipoproteins, pesticide accumulation Gram negative, LPS Chlorpyrifos Sorption may occur through hydrogen bonding from the hydroxyl surfaces toward oxygen atoms in the organic molecules. carbonyl oxygen of the carbon surface acting as the electron donor and the aromatic ring of the adsorbate acting as the acceptor. hydroxyl groups on the polymer surfaces, which probably have a positive effect on cell adherence. Surface of lignocellulosic material
  19. 19. FINDINGS
  20. 20. • Part 1: Preparation of adsorbent Collection of pineapple leaves Pre-treatment Wash Dry and sieve Storage Dessicator
  21. 21. Wash Dry Grind & Sieve (d) Pineapple leaf Pineapple leaf powder
  22. 22. Chemical treatment of adsorbent Rewash with Deionized water 0.1M nitric acid 1hour Methanol 1hour • Methanol to remove inorganic and organic matter from the surface of sorbents.
  23. 23. • Part 2 : Characterization of adsorbent 1) Functional groups Fourier Transform Infra Red Spectroscopy 2) Surface Area Brunauer, Emmett and Teller 3) Elemental Analysis C,H,N,S 4) Surface images Field Emission Scanning Electron Microscope (FESEM)
  24. 24. SEM of raw & treated PLP Lignocellulosic biomass has a complex and rigid cell wall structure which consists of three principal biopolymers, namely cellulose, hemicellulose, and lignin. Unmodified PLP Rough inhomogeneous surfaces have multiple sitetypes available for adsorption Modified PLP
  25. 25. Fiber and elemental analysis Parameter Composition (%) Cellulose 26.15 Hemicellulose 53.45 Lignin 6.93 Carbon 40.49 Hydrogen 6.45 Nitrogen 1.60 Sulfur 0.56 •Soft wood • Carbonaceous material- suitable for adsorption
  26. 26. Surface area of PLP • Surface area - 8.61m²/g *(Carbonaceous materials 10-15 m²/g) Pore size - 5.948 Angstroms (micropores) • * micropores are directly accessible from the external surface of the fiber. Thus, Chlorpyrifos can reach adsorption sites through micropores. May ease the adsorption process.
  27. 27. X-ray fluorescence (XRF) of PLP No Parameter Results (%) 1 Potassium Oxide 4.94 2 Calcium Oxide 2.60 3 Chlorine 1.66 4 Sulphur Trioxide 1.34 5 Magnesium Oxide 1.07 6 Silicon Dioxide 1.05 Inorganics and minerals * it can block the porosity of the carbon matrix and can preferentially adsorb water due to its hydrophilic character, in this case reducing the adsorption of the lipophilic Chlorpyrifos.
  28. 28. Ash content of PLP • Ash is the inorganic residue remaining after the water and organic matter have been removed by heating • 8.7% • Low ash content and have advantage in preparing adsorbent with high specific surface area
  29. 29. FTIR of raw PLP Hydroxyl groups, Presence of –OH groups Aromatics groups in lignin Carbonyl group in hemicellulose
  30. 30. FTIR of modified PLP Presence of –OH groups. The acid pre-treatment increases the concentration of the hydroxyl groups on the support. Carboxyl groups,
  31. 31. pH at zero point of charge of modified PLP (pH at which the net surface charge is = 0) 12 pH drift method 10 8 6 pH final pH initial 4 At this value (7.2), the adsorbent is neutral, while it turns positively charged at lower pH values or negatively charged at higher pH values 2 0 0 2 4 6 8 10 12
  32. 32. Part 3 : Isolation, Screening and Biofilm development 1) Isolation Microclear, soil, cultured drink 2) Screening Chlorpyrifos tolerance, degradation, removal 3) Biofilm developemnt & degradation Biofilm thickness, biofilm composition, isotherm, kinetics, thermodynamic 4) Surface images Field Emission Scanning Electron Microscope (FESEM)
  33. 33. Gantt Chart
  34. 34. Thank You
  35. 35. Proposed title • Isotherm, kinetics and thermodynamic studies on combined adsorption and biodegradation of Chlorpyrifos using lignocellulosic material in Ananas comosus (Pineapple) leaf powder.
  36. 36. • Pesticides ingredients:Active ingredients intended to kill the target pest Inert ingredients used as bulk carriers for active ingredients PESTICIDES • not really “inert” at all; they are actually more toxic than the active ingredients. • This inert information is usually not required to be displayed on the product label by the authorities.
  37. 37. Pineapple Leaf Powder Optical & Phase Contrast Microscope images
  38. 38. Reactive Red dye adsorbed onto PLP Reactive Black 5 dye adsorbed onto PLP
  39. 39. SEM of raw & modified PLP Unmodified PLP Modified PLP
  40. 40. * Crystalline and amorphous structures- XRD
  41. 41. Adsorbent Modification (Biologically Inspired Design = Biomimetics) • What? : Biomimetics is the study of the structure and function of biological systems as models for the design of materials. It is widely regarded as being synonymous with biomimicry • Why? : Pesticides can bioconcentrate: The primary "sink" for some pesticides is fatty tissue ("lipids"). Some pesticides, such as DDT, are "lipophilic", (fat loving) meaning that they are soluble in, and accumulate in, fatty tissue such as edible fish tissue and human fatty tissue.
  42. 42. Triolein -embedded PLP composed of the supporting PLP and the surrounding trioleincellulose acetate membrane. Pesticides / non polar NEPs Triolein layer PLP CA = useful polymer, used to combine triolein and PLP. Triolein has a high accumulating capacity for trace lipophilic chemicals. Naturally found in fatty tissues, cheap. is a symmetrical triglyceride derived from glycerol and three units of the oleic acid
  43. 43. Hydrophilic membrane structure (polyamide) Lindane Dieldrin Atrazine Hydrophobic nucleolus (triolein) Nitrobenzene
  44. 44. Chlorpyrifos degradation The degradation pathway of chlorpyrifos in aquatic environments involves the breakdown of the thiophosphoric esters, forming 3,5,6-trichloropyridinol (TCP) and desethyl chlorpyrifos (DEC) as main metabolites.
  45. 45. FTIR • The region to the right-hand side of the diagram (from about 1500 to 500 cm-1) usually contains a very complicated series of absorptions. These are mainly due to all manner of bending vibrations within the molecule. This is called the fingerprint region. • It is much more difficult to pick out individual bonds in this region than it is in the "cleaner" region at higher wavenumbers. The importance of the fingerprint region is that each different compound produces a different pattern of troughs in this part of the spectrum.
  46. 46. Lignin macroporous structure Cellulose microporous materials Lignocellulosic
  47. 47. Cellulose
  48. 48. Lignin
  49. 49. Adsorption kinetics • The rate of adsorption of a molecule onto a surface
  50. 50. Adsorption isotherm • For a better understanding of binding mechanism of the sorption system, between liquid and solid • Langmuir adsorption isotherm is based on the following assumptions. • i) Adsorption is a monolayer coverage. • ii) All the sites available on the adsorbent surface are equivalent and the surface is perfectly uniform.
  51. 51. • Freundlich isotherm equation is based on the assumption that cations and anions are adsorbed onto the same surface simultaneously. • This situation results in the formation of attractive forces between adsorbed cations and anions on the surface. • Multi-layer adsorption can occur
  52. 52. Thermodynamic studies • To study the effect of temperature • Positive values of entalphy ∆H – endothermic • Positive value of entropy ∆S confirms possibility of favorable adsorption • Negative value of free energy ∆G – removal to be spontaneous

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