LEACHING POTENTIAL OF THE NANOPARTICLES CONTAINING

PRODUCTS FROM THE MUNICIPAL LANDFILLS AND THEIR

SUBSEQUENT GROUND WATER POLLUTION

By

Riya Rathore (2015CEV2190)

Under guidance of

Dr. B.J. Alappat

&

Dr. Arun Kumar

Department of Civil Engineering

Submitted

in fulfillment of the requirement of the degree of

MASTER OF TECHNOLOGY

To the
Indian Institute of Technology, Delhi
November 2016

1
 CERTIFICATE

This is to certify that the report entitled, “LEACHING POTENTIAL OF THE

NANOPARTICLES CONTAINING PRODUCTS FROM THE MUNICIPAL
LANDFILLS AND THEIR SUBSEQUENT GROUND WATER POLLUTION”
Submitted by RIYA RATHORE (2015CEV2190), to the Department of Civil
Engineering, Indian Institute of Technology Delhi is a bona fide record of work carried
out by her under my supervision and guidance. The contents of this report, in full or in
parts, have not been submitted to any other University or Institute for the award of any
degree or diploma.

Date: Dr. Arun Kumar

Department of Civil Engineering

Indian Institute of Technology Delhi

Prof. B.J. Alappat

Department of Civil Engineering

Indian Institute of Technology Delhi

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 ACKNOWLEDGMENT

I would like to express my deep gratitude to my guide, Assistant Professor (Dr.) ARUN
KUMAR, Civil Engineering Department, IIT Delhi and co-guide Professor (Dr.) B.J.
ALAPPAT, Civil Engineering Department, IIT Delhi for providing me the opportunity to
work on such an innovative project and to learn and explore this field under their
guidance. The practical and invaluable advice of my guides kept me going through the
critical phases of my project.

I am also grateful to Dr. BHANU NANDAN, Department of Textile Technology, IIT

Delhi and Mr. Sajan Singh and Mr. Labeesh Kumar Rajput for their immense support.

I would like to thank all my teachers for sharing their knowledge related to subject,
which helped me in my research. I must thank Dr. Sanjay Kumar Gupta and all of my
fellow classmates and lab mates for their help and support and I needed all through my
research period. I would like to specially acknowledge the technical as well as emotional
support provided by all my seniors particularly Dr. Divya Singh, and Dr. Tropita Piplai
during whole of my stay at IIT Delhi.

The acknowledgement would be incomplete if I do not mention the support, love, faith
and confidence shown by my family members. This journey would have been impossible
without them.

Last but not the least, I would like to thank the Almighty, the faith in whom keeps me
going on the path of life, through all thick and thin.

Riya Rathore
2015CEV2190

3
 ABSTRACT

The widespread use of Nano particles in the commercial products will result in the
unknown release of Nano materials into the environment. Especially silver nanoparticles
which are used in textiles have received a lot of attention in recent years with the
increasing production, use and its potential environment implications. The scientific
consensus is that producing, using and disposing the engineered nanomaterials lead to
environment release of nanoparticles so the characterization and quantification of the Ag
released from the products should be determined to assess the risk of advancement of
nanotechnology.

The environmental impacts of silver nanoparticles are largely dependent in its transport
and mobility. Thus, understanding of the transportation of silver nanoparticles is of
especial importance for the benign use and risk management.

The aim of our study is to determine the amount and form of silver released during the
washing and biodegradation of the fabrics with the different ways of incorporation into or
onto fabrics. The effect of pH, surfactants and oxidizing agent was evaluated. The
biodegradation of the sample was simply done was buried the fabrics into the test soil.
The result show that the amount and type of silver released depend upon on type of silver
incorporated into the textiles. Bleaching agents like hydrogen peroxide accelerate the
leaching. The degradation of the silver loaded fabrics was comparatively slower and
depends upon the soil water conditions.

4
Contents
CHAPTER 1 INTRODUCTION ................................................................................................... 10
1.1 Background .......................................................................................................................... 10
1.2 Nanoparticles ........................................................................................................................ 11
1.3 Nanoparticles Types and Classification ............................................................................... 11
1.4 Applications of nanoparticles: .............................................................................................. 11
1.5 Fate of the Nanoparticles in the Environment ...................................................................... 12
CHAPTER 2 LITERATURE REVIEW .......................................................................................... 13
2.1 Silver loading and release from the fabrics .......................................................................... 13
2.2 Knowledge Gaps .................................................................................................................. 17
2.3 Need of current study ........................................................................................................... 17
CHAPTER 3 OBJECTIVE AND SCOPE...................................................................................... 18
3.1 Objectives ............................................................................................................................. 18
3.2 Scope .................................................................................................................................... 18
CHAPTER 4 METHODOLOGY ................................................................................................... 19
4.1 Flow Chart ............................................................................................................................ 19
4.2 Methodology ........................................................................................................................ 19
4.2.1 Literature review ........................................................................................................... 19
4.2.2 Experimental section ..................................................................................................... 20
4.2.2.1 Experiment 1: Ion analysis and washing experiment on the nanoparticle containing
socks available in the market .................................................................................................. 20
4.2.2.2. Experiment 2: Effect of pH, chemical agent and agitation on ion release during
Washing of the fabrics: ........................................................................................................... 26
4.2.2.3 Experiment 3: change in the fabric characteristics during the burial of the fabric in the
soil pot .................................................................................................................................... 29
CHAPTER 5 RESULTS AND DISCUSSIONS .............................................................................. 31
5.1 Loading of Ag on fabrics ...................................................................................................... 31
5.2 Ion release during washing ................................................................................................... 32
5.2.1 Release of silver ion during first washing ..................................................................... 32
5.2.2 Release of silver ion during second washing................................................................. 33
5.3 Characterization of unloaded, loaded and washed samples ................................................. 34
5.3.1 SEM and EDX analysis for the unloaded cotton fabric ................................................. 34
5.3.2 SEM and EDX analysis for the In-situ loaded cotton fabric ......................................... 35
5.3.2 SEM and EDX analysis for the Ex-situ loaded cotton fabric ........................................ 36
5.3.3 SEM analysis for the washed fabrics ............................................................................. 37

5
 5.3.4 TEM analysis of the prepared AgNO3 solution and the washed water ........................ 38
5.4 Results of burial study ......................................................................................................... 40
5.4.2 Change in the colour of the samples (Remaining) ............................................................ 40
CHAPTER 6 CONCLUSION AND FUTURE WORK .................................................................. 42
6.1 Conclusion ........................................................................................................................... 42
6.1.1........................................................................................................................................ 42
6.1.2 Effect of pH, chemical agent and agitation on the release of NPs during washing ...... 42
6.1.3 The effect on the characteristics of the fabrics during the burial in the soil ................. 43
6.2 Implications of the study ...................................................................................................... 43
6.2.1 Toxicity of Ag NPs releasing during washing to domestic waste water ....................... 43
6.2.2 Toxicity of Ag NPs releasing during washing to the ground water .............................. 43
6.3 Future work .......................................................................................................................... 44

REFERENCES

6
 LIST OF FIGURE
FIGURE TITLE OF FIGURE PAGE NO.
NO.
Fig.1.1 Silver nanoparticle molecules 11
Fig. 4.1 Overall schematic flow chart of work 19
Fig. 4.2 Schematic of treatment of silver nanoparticles to cotton 21
fabric using AgNO3+ TSC and AgNO3+ UV methods.
Fig. 4.1 prepared scoured cotton sample 22
Fig. 4.2 Preparation of solution 22
Fig. 4.3 Mechanical agitator 22
Fig. 4.4 Padding machine 23
Fig. 4.5 Digester for drying the samples 23
Fig. 4.6 The system of heating, mixing and agitating the 24
solution
Fig. 4.7(a) Acid digester with samples digesting 25
Fig. 4.7(b) Atomic Absorption Spectrometer 26
Fig. 4.8(a) Sample immersed in the washing solution 27
Fig. 4.8(b) Samples putting in the orbital shaker 27
Fig. 4.9(a) Scanning Electron Microscope 30
Fig 4.9(b) Transmission Electron Microscope 30
Fig. 5.1 shows the change in the colour of the cotton sample 31
after loading
Fig. 5.2 Electron microscopy of the unloaded fabrics with EDX- 34
spectra of the particles.
Fig. 5.3 Electron microscopy of the loaded silver nanoparticles 35
in the fabrics with EDX- spectra of the particles.
Fig. 5.4 Electron microscopy of the loaded silver nanoparticles 36
in the fabrics with EDX- spectra of the particles.
SEM images for the washed In-situ fabric 37
Fig. 5.6 SEM images for the washed Ex-situ fabric 37
Fig.5.7 TEM images for the In-situ samples 38
Fig.5.8 TEM images for the Ex-situ samples 38

7
Fig.5.9 TEM images for the In-situ samples 39
Fig.5.10 TEM images for the Ex-situ samples 39

Fig.5.11 SEM images showing degradation of the In-situ loaded 41

cotton fabric
Fig.5.12 SEM images showing degradation of the Ex-situ loaded 41
cotton

8
 LIST OF TABLES

TABLE TITLE OF THE TABLE PAGE

NO. NO.
Table no. 4.1 combination of the various washing parameter

Table no 5.1 Amount of silver loaded on the fabrics 28

Table no 5.2 Silver ion release during first washing for In-situ sample 31
Table no 5.3 Silver ion release during first washing for Ex-situ sample 32
Table no 5.4 Silver ion release during second washing for In-situ sample 32
Table no 5.5 Silver ion release during second washing for In-situ sample 33
Table no 5.5 Ion analysis of the degraded cotton fabrics 40
Table no.6.1 Distribution of the work throughtout the year 45

9
CHAPTER 1 INTRODUCTION

1.1 Background
The field of nanotechnology is one of the most active research areas in the modern
science. Impressive application prospects of Nano sized materials in a wide variety of
technical applications and consumer products (e.g. pharmaceutical, biomedical, cosmetic,
electronic, energy, environmental) have led to a significant increase in engineered
nanomaterial (ENM) production, manufacture and use of ENM containing products. Nano
silver is the most common commercialized nanomaterial and is used in more than 200
products. Indeed, these consumer products (socks, bandages, underwear, storage boxes
etc.) are surprisingly efficient in reducing odors and eliminating unwanted
microorganisms (Dura´n N et al., Kim et al., 2007).

Unfortunately, precise estimation of the release of silver from the products are hampered
by the lack of information available of the content and the form of silver in products and
its release. To assess the risk posed by these in particular needs a better understanding of
the materials, mobility, bioavailability, and toxicity in the environment, which are
strongly linked to the properties of the particles as they are actually released. Some data
are available on the release of ionic silver due to washing from the fabrics but on the
release due to disposal of the material at the end of its useful life when it has lost
approximately 10% weight.

These studies investigate the amount of nanoparticles such as silver loaded in the
different consumer products and the amount and type of nanomaterial released during its
use and after disposal. The effect of pH and other chemical agent was taken in evaluation.
The sample with washing and without washing was degraded in the two type of soil one
is the garden soil and another one is the soil from the landfill and change in the properties
of the fabrics and amount of silver remaining were observed.

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1.2 Nanoparticles
A nanoparticle is a microscopic particle with at least one dimension less than 100 nm. It
has a greater surface area per weight than larger particles that causes them more reactive
to some other molecules.

1.3 Nanoparticles Types and Classification

Types of nanomaterial:

 Natural- Mineral and mineral oxide, Biological particles, ocean particles

 Incidental- Combustion particles, vehicle, construction, pollution particles
 Engineered particles- Carbon-based NMs,, metal-oxide, Nanotube

Fig.1.1 Silver nanoparticle molecules

1.4 Applications of nanoparticles:

The properties of the conventional material are changed drastically when formed by
nanoparticles. This is typically because nanoparticles have a greater surface area per
weight than larger particles which makes them to be more reactive than the other
molecules. Nanoparticles are used in many fields. The list below introduces several of the
uses under development.

 Nanoparticles are now being used in the manufacturing of scratchproof

eyeglasses, crack- resistant paints, anti-graffiti coatings for walls, transparent

11
 sunscreens, stain-repellent fabrics, self-cleaning windows and ceramic coatings
for solar cells.

 Nanotechnology can be applied in the field of production, processing, safety and

packaging of food. It is possible that nanotechnology will allow the modification
of the molecular forms of food to provide more capability, lower costs and greater
sustainability than at present.

 Nanomaterial is also being used in medicine and biology in a various ways,

including the direct application of products into patients.

 Nano silver is currently the most widely used ENP in consumer products with 259
out of 1015 commercially available nanoparticle based products. Nano silver is
currently used as an antibacterial agent e.g. in clothing, washing machine, wound
dressing and cosmetic products.

 Nano silver is one of the most promising NP for future applications due to its
antimicrobial, antifungal and partially antiviral properties. (Mueller and Nowack,
2008)

1.5 Fate of the Nanoparticles in the Environment

The potential environment impacts of these nanomaterials are of concern once ther enter
into the environment. According to the nanomaterial market research report released in
2010, annual global nanomaterial demand is increasing by 21% and by 2025, it is
expected to reach over $ 43 billion in sales. (In Global Information, Inc. Market reports
2010) Due to the world wide application of the nanomaterial, there are chances of release
into the environment during production, transport and use. So it is very necessary to
quantify the amount of NP release due to various activities.

(Benn and westerhoff, 2008; Zhang et al., 2008) has recommended that nanopartilces
might enter the subsurface environment from wastewater reuse by directly leaching and
from the agricultural biosolids. To impart the effective risk assessment it is necessary to
predicts the concentrations and distributions of them in the environment.

12
 CHAPTER 2 LITERATURE REVIEW
To assess the prevailing information and the current gaps literature review of the released
report and journal articles was carried out. Multiple literature papers for understanding
the loading, release and behavior of the nanoparticles under various conditions were
reviewed.

2.1 Silver loading and release from the fabrics

S Topic Material used Parameters Methods used Results
N varied
o.

1 Nanoparticle Socks, - Acid digestion and Released in nanoparticles

silver released H2O2(30%), ICP-OES. and ionic silver species.
into water HNO3(65%),
from Glass fiber filters, Washing in bottle Before washing amount
commercially 1L bottle, under shaking of silver- 2 to 1360 ug/g.
available Orbital shaker, mechanism.
sock fabrics 25mmsyring filter After 24h washing silver
or 45mm vaccum SEM, TEM & EDX released- 1 to 70 ug/g
benn M. and pump apparatus,
Westerhoff P., ISE
2007
2 The Behavior Fabrics, pH, Acid digestion and Silver was labeled as
of Silver H2O2(30%), surfactants, ICP-OES. silver NP-powder & NP
Nano textiles HNO3(65%), oxidizing suspension.
during Buffers, agents, SEM, TEM & EDX.
Washing. background ions, temperature Initial silver- 8 and
+
perborate, TEAD, ISE for free Ag ion 2660 mg kg1 in
Geranio L., sufactants, concentration. nanotextiles, and 21600
Heuberger detergents mg/kg in a silver coated
M., and ISO-method for textile.
Nowack B., washtests using a
2009 Washtec-P Roaches % of total Ag released ar

13
 washing machine. pH10/0.1g/L solution- 5
to 35%.
ultrasonication for
homogenization. Silver released as Ag+ and
particulate fraction.
Cellulose nitrate filter
(45um, whatman) for The release of Ag+ from
centrifugation Ag-NPs at pH 10 during
washing is about 10× less
than at pH 7.

Significant release after

addition of oxidants.

3 Characterizati Textiles ( socks, Bleaching Ag analysis by ICP- Silver labeled in extra

on of silver T-shirt, trousers) agents OES and XRF, thin silver wire, nano
release from Detergents, particles and ionic form.
commercially washing machine Washing by ISO
available matching ISO method, Initial silver content- 1.5
functional standard and 2925 mg Ag/kg
(nano) textiles (Washtex-P Fractionization of textile.
Roaches; motor silver released by
Lorenz C., speed 40 ± 2 rpm, centrifugation, Ag released- 0.32 and
Windler L., steel vessels 38.5 mg/L into the
von Goetz N. (75 ± 5 mm Confirmation by washing solution and
and Lehmann diameter, 125 ± SEM-EDX between 0.36 and
R.P., 2012 10 mm height, 22.7 mg/L into the rinsing
550 ± 50 mL)), solution.
Polyethylene
balls, Silver released mainly in
0.45 um Ti/Si–AgCl nano
cellulose-nitrate composites, AgCl
filter, nanoparticles, large AgCl

14
 particles, nanosilver
sulfide and metallic nano-
Ag and agglomerated
form.

4 Comparative Fabrics - Cotton, AAS for Silver released as silver

study of Wool and Nylon quantification. ion, silver NP and silver
leaching of (size 5cm*5cm), colloides.
silver Pure Millipore Washing based on
nanoparticles water and double agitation mechanism % loading - % leaching
from fabric distilled water, for either 60 min Cotton- 30 – 12
and effective 100 mL glass using a stirrer/or Nylon- 10 – 14
effluent bottle, centrifuged for 30 min Woolen- 10- 24
treatment at approximately 50
r/min.
Pasricha A.,
Jangra S.L. et SEM-EDX.
al., 2010

5 In situ Cotton fabrics, Temp., Loading was done in

production of Silver nitrate, Reducing loading bath.
silver np on cetyl trimethyl agents,
cotton fabric ammonium Detergents, Washing done by
bromide using soaped solution
El-Shishtawy (CTAB), Triton at 800C for 30 min.
M., Abdullah X-100, glucose
M. et al., 2010 and sodium Characterization by
hydroxide SEM,EDX,FTIR,TEM

6 Antimicrobial Socks fabrics Synthesis of silver No washing done only

activity of Silver nitrate, tri- npby chemical wet antibacterial efficiency
nanosilver- sodium citrate reduction method was checked.

15
 coated socks and neem (Ag-chem) and by
fabrics against (Azadirachta biological method,
foot indica) leaves using A. indica
pathogens (neem) leaves (Ag-
neem)
Jayagouri P.,
Meeta G. & Quantification by
Roonal L., AAS
2010
Confirming the
presence of silver np
by UV-spectroscopy,
TEM,
Colloids and Quantification and In-situ method is more
Surfaces A: AgNO3, TSC, In- situ characterization by effective and gives more
Physicochemi cotton, UV lamp method and AAS and SEM, uniformly distribution of
cal and Ex-situ EDX,TEM NPs
7
Engineering method
Aspects Biodegradation of the
samples by direct
burial test

16
2.2 Knowledge Gaps

 Limited literatures are available on the release of nanoparticles from the food
packaging.
 The form and the amount of nanomaterial released from the products is not
properly explained.
 The leaching potential of the products (textiles and food packaging) under rain
water is not available.
 The leaching of the nanomaterial from the products disposed off on the landfill is
not available.
 The released of the nanomaterial due to biodegradation is not found in the
literatures.

2.3 Need of current study

Need of the study was found by on the basis of gap identified. The leaching potential is
needed to predict the further transport of the nanoparticles into the environment such as
ground water etc.

Different type of nanoparticles are using extensively in the consumer products and
various other items. Thus there are more chances to reach the nanoparticles in the
environment through different path i.e. air, ground water, surface water and soil. So the
study is needed to find out the amount of nanoparticles induced in the products and
release of them during the life cycle of the products. Also need for the identification of
the various factors which can influence the leaching potential of the nanoparticles. No
studies have been done regarding the leaching of nanoparticles under the rain water and
due to biodegradation and from the products going to the landfill. And then further the
ground water pollution potential of those released nanoparticles.

17
CHAPTER 3 OBJECTIVE AND SCOPE

3.1 Objectives
The project consist the following objectives:
 To understand the leaching potential of the nanoparticles containing products
(Textiles) available in the market.
 To understand the leaching potential of the nanoparticles containing fabrics loaded
in the lab itself.
 To understand the different release scenarios such as release during use or
chemical leaching and release after disposing on the landfill due to degradation.
 Estimation of the ground water pollution due to release of Nano materials.

3.2 Scope
 To understand the better approach of the loading of NPs on the fabric.
 To focus on the influence of the various kind of the factors on the release of the
nanoparticles.
 To focus on the types and amount of nanomaterial released from the products and
their environmental fate.
 To understand the leaching under the rain water or due to biodegradation.
 To develop a simple relationship that may be used to the predict the release of
nano particles and their subsequent ground water potential.

18
CHAPTER 4 METHODOLOGY

4.1 Flow Chart

Fig. 4.1 Overall schematic flow chart of work

4.2 Methodology
I have adopted following methodology to achieve the objectives of the study:

4.2.1 Literature review

 Different type of consumer products available in market containing nanoparticles (such
as textiles, food packaging, hospital waste, paints, tube tires, metals etc.) were listed
out and the detailed study were done through the various literature available regarding
the amount, type and release of Nano materials in those products.
 Two products were taken under the consideration namely fabrics (socks and bandage)
and food packages. The various literatures available on the type of Nano material
induced in those products, their quantity, characterization and the release of the Nano
materials under different conditions were studied.

19
 Learning and the understanding of the effect of the various factors on the leaching of
the nanoparticles such as effect of pH, temperature, surfactants. Oxidants etc.
 Method of Biodegradation of the fabrics were studied.
 Finding the outputs and the limitation of the literatures.

4.2.2 Experimental section

4.2.2.1 Experiment 1: Ion analysis and washing experiment on the

nanoparticle containing socks available in the market

The fabrics (socks) containing silver nanoparticles were purchased from the market and
check for the amount of silver available in it and the release during the washing but due to
very less amount of silver the detection of silver release could not be possible.

4.2.2.2 Experiment 2: Loading Ag NPs in the laboratory

Another approach to find the release of Ag NPs from the fabrics is to load the NPs in the
laboratory itself and then observing the release. The loading was done by both In-situ and
Ex-situ approaches. Methods to treat samples were selected based on minimum usage of
chemicals and the least number of steps involved in the loading process.

20
 Fig. 4.2 Schematic of treatment of silver nanoparticles to cotton fabric using
AgNO3+ TSC and AgNO3+ UV methods.( Perera S.; Bhushan B.; Bandara R, 2013)

1. In-situ method (UV method): In the UV method, cotton fabric samples were first
immersed in AgNO3solutions, padded and dried in the oven at 500C for 10 min. The
silver ions in the AgNO3 solution were diffused and absorbed in the cotton fibers
with the help of the polar hydroxyl groups in the fiber structure. Later, the treated
samples were irradiated using a UV lamp at a distance of 100 mm for 1h to
synthesize silver nanoparticles in situ on the cotton surfaces.
a) Preparation of the sample: To prepare the sample for the loading the
scouring of the cotton sample with sodium hydroxide was done to remove the
impurities from the raw cotton. The scoured cotton sample for loading is
shown in the fig. 4.1.

21
 Fig. 4.1 Prepared scoured cotton sample

b) Preparation of the AgNO3 solution & immersion of sample: Analytical

grade silver nitrate powder (AgNO3,mol.weight169.87) and tri-sodium citrate
powder (C6H5Na3O7·2H2O, mol. weight 294.10) were procured from Sigma
Aldrich. Deionized (DI) water was employed for the preparation of solution.
AgNO3, 1.5 × 10−3mol/l solution was prepared using DI water and UV was
used for the preparation of nanoparticles. And then sample were immersed in
it and kept in the agitator for uniform submergence. The fig. 4.2 shows the
preparation of the solution and the fig. 4.3 shows the mechanical agitator
operating at the speed of 100rpm.

Fig. 4.2 Preparation of solution Fig. 4.3 Mechanical agitator

c) Padding and drying: The cotton sample was taken out of the solution and
the padded in the laboratory padding machine (shown in fig. 4.4) for the
squeezing out of the excess water and for the uniformly distribution of the
silver. And then sample was dried in the digester at 1000C for 15 minutes as
shown in the fig. 4.5.

22
 Fig. 4.4 Padding machine

Fig. 4.5 Digester for drying the samples

d) Synthesis of AgNPs by UV lamp: The samples were irradiate by the UV

lamp at a distance of 100mm for 1 h to synthesis the silver nanoparticles on
the surface of the cotton samples.

2. Ex-situ method (TSC method): The following steps are involved in this method
a) Preparation of the solution: In the TSC method, AgNO3 1.5 × 10−3mol/l
solution was prepared with DI water and heated to boiling at 70◦C, and 10 ml of

23
 prepared 36 × 10−3mol/l TSC solution were added drop by drop. During the
process, the solution was mixed vigorously by mechanical agitator and heated
until a pale yellow color appeared. Reduction of silver ions (Ag+) to silver
nanoparticles was evident in the colloid synthesis process, as the colorless
solution became pale yellow with the formation of the silver nanoparticles. The
system of preparing the solution is shown in the fig. 4.6.

Fig. 4.6 The system of heating, mixing and agitating the solution

b) Immersion of the samples in the solution: Now the solution was removed from
the heating and stirred until cooled to room temperature. Cotton fabric samples
were immersed in the prepared silver Nano colloids heated at 50◦C and stirred
rapidly for 30 min.
c) Padding and of the samples: The cotton samples subsequently were padded on
a laboratory padding machine. The padding process was done to ensure that the
solution was coated evenly, and the excess chemicals were removed from the
samples.
d) Curing of the samples: The padded samples were air dried and finally cured at
120◦C for 3 min in a pre-heated curing oven.

24
4.2.2.1.3 Ion Analysis:

Modified digestion method is to be adopted for the digestion of the fabrics and the
quantification is done by either AAS or ICP-MS. In this method 3 air dried samples of
cotton fabric of weight 500mg were taken (unloaded, loaded by In-situ method and by
Ex-situ method) and each was submerged in the 5ml solution of the ultrapure reagent
grade nitric acid and 5ml of deionized water. Then a watch glass is placed over the
digestion beaker and heated at approximately 1500C and allowed to react. Nitric acid was
added in 2 mL aliquots until the material was digested. The digestion solution was
allowed to cool and then 3mL of 30% hydrogen peroxide was added to complete the
digestion process. Again the digestion beaker was heated to 100 °C, and hydrogen
peroxide was added in 1 mL aliquots until effervescence was minimal, which is the
indication of the completion of the digestion. The digestion solution was then cooled,
filtered through a glass fiber filter and diluted to 50 mL. The digestor with the digesting
sample is shown in the fig. 4.7(a)Silver was quantified by Atomic Absorption
Spectroscopy (AAS) shown in the fig. 4.7(b).

Fig. 4.7(a) Acid digester with samples digesting

25
 Fig. 4.7(b) Atomic Absorption Spectrometer

4.2.2.2. Experiment 2: Effect of pH, chemical agent and agitation on ion

release during Washing of the fabrics:

In general the release of silver from the loaded fabrics was studied by varying the
different factors such as pH, temperature, time, effect of detergents, surfactants, oxidants
etc. were taken into the consideration. The experiment was divided into two parts one is
release under gentle agitation (100-150 rpm) and protected from the light and another one
in under the still water condition. For agitating the samples orbital incubator shaker was
used as shown in the fig. 4.8(b). Bleaching agents hydrogen peroxide, sodium perborate,
peracetic acid (PAA) were used to have the effect of chemical agents on the release. The
choice of chemical agents is dependent on their use in the laundry detergents. The DI
water is used for the washing. The washing experiment was performed for fabric loaded
by both the approaches for 24 hour and both the results are comparable. The time was so
chosen to give the opportunity for the fabric to leach the silver. The combination of the
different parameters is shown in the table 4.1.
Following are the steps of washing method done:

1) The silver loaded cotton sample were dried at 700C in the oven.
2) The samples were put in the glass bottles having 100ml of the washing solution.
Washing solution was prepared by adding the detergents (4gL-1) and pH was
adjusted in all the required range.

26
 3) Then samples were washed for 1 hour or 24 hour with agitation in orbital shaker
and without agitation and then fabrics were taken out and oven dried at 700C and
placed in the new bottle for the next washing.
4) The excess water is collected in the another bottle to check the release of silver,

Washing should be done according to the ISO 105-C06 but due to unavailability of ISO
washing machine we followed the method as followed by the Benn M. and Westerhoff
P., (2007) in his research. The samples immersed in the washing solution are shown in
the fig. 4.8(a) Reduction in loading of silver after each washing is also checked by acid
digestion to know to loss of silver.

Fig. 4.8(a) Sample immersed in the washing solution

Fig. 4.8(b) Samples putting in the orbital shaker

27
Table no. 4.1: combination of the various washing parameter

Amount of silver released in washing (In µg/g)

For 24 h or 1 h washing with For 24 h or 1 h washing
agitation without agitation
S pH Without With without With
No. chemical chemical chemical chemical
agents agents agents agents
1 4 (Acidic)

2 7 (Neutral)

3 12 (Basic)

4.2.2.2.1 Separation nanoparticles and silver ionic species: To separate the

nanoparticle form of silver from ionic silver and to quantify both the forms three methods
can be used.

1. Centrifugation
2. Membrane filters
3. Silver ion specific electrode (ISE)

28
4.2.2.3 Experiment 3: Change in the fabric characteristics during the
burial of the fabric in the soil pot

The cotton samples were kept on the soil pot to observe the natural degradation of the
fabrics and loss of the silver due to degradation. For this purpose the direct burial method
was used for the biodegradation of the fabrics. (Arshad K. & Mujahid M., 2011) The
samples of size 5cm×5cm were buried in the soil in the beaker of capacity 1000mL for
different time interval. After 17 days the samples were again digested to know the amount
of silver remaining and the characterization (SEM, TEM, EDX, FTIR) was also done to
know the extent of degradation. The temperature was maintained at 300C. The parameters
which affect the degradation is the availability of the oxygen, moisture content,
temperature, presence of micro-organisms etc.

4.2.2.3.1 Total organic carbon analysis of the samples

Total organic carbon of the samples was determine before and after the biodegradation to
know the extent of degradation as loss in the organic carbon will show the degradation of
the samples.

4.2.2.3.1 Visual insepesction

The change in colour of the fabric can be observed visually which indicates the
degradation of the fabrics.

4.2.2.3.1 Characterization

Scanning and transmission electron microscopy (TEM) were used to confirm the presence
and to know the size of silver nanoparticles in the cotton samples. Energy dispersive X-
ray analysis (EDX) was performed to confirm the elemental presence of silver. X-ray
powder diffraction (XRD) was used for phase identification of a crystalline material.
Electron microscope is a high vacuum microscope with secondary electron and
backscattered electron detectors with maximum resolution of 3 nm is used to investigate

29
the changes that occurred in the samples with the passage of time. Fig. shows an electron
microscope that is analyzing the sample.

Fig. 4.9(a) Scanning Electron Microscope

Fig 4.9(b) Transmission Electron Microscope

30
CHAPTER 5 RESULTS AND DISCUSSIONS

5.1 Loading of Ag on fabrics

Loading of loading shows that the in-situ method is more effective to load more amount
of silver and the silver is in the Nanoparticles form and Ex-situ method the amount of
silver loaded is comparatively less but silver is in the nano-colloid form. (Perera S.;
Bhushan B. et. al., 2013)

Table no 5.1 Amount of silver loaded on the fabrics

Acid digestion analysis of cotton fabrics

S Loading method Mass of Average Total silver

Avg
No. silver per g fabric mass in cotton
amount of
of fabric (μg (g) sample (mg) silver (mg)
Ag/g fabric)
1 In-situ method 570 20 11.4
10.6
2 In-situ method 490 20 9.8
3 Ex-situ method 390 20 7.8
7.4
4 Ex-situ method 350 20 7.0
5 Control - 20 - -

5.1.1 Change in Colour of the sample

(a) Raw cotton (b) Scoured cotton (c) AgNPs loaded cotton
Fig. 5.1 shows the change in the colour of the cotton sample after loading

31
5.2 Ion release during washing:

The samples were washed in different conditions and for the duration of 24h.The results
show that the release of silver is significant during the first washing and it is accelerated
by the addition of oxidants (hydrogen peroxide, peracetic acid) in it. The release is
maximum in the acidic medium. The leaching was comparatively less when the pH was
lower. So the influence of pH and oxidants can be easily seen on the release of silver.

5.2.1 Release of silver ion during first washing

During the first washing of fabrics results show the significant release of the silver ions.
Lower pH is important factor for the more release. The results are summarized in the
table no. 5.2 and 5.3 for both In-situ and Ex-situ method.

Table no 5.2: silver ion release during first washing for In-situ sample

Amount of silver released during first washing (In µg/g)

For 24 hour washing with For 24 washing without
agitation agitation
S pH Without With without With
No. detergent detergent detergent detergent
1 4 (Acidic) 370 405 220 310

2 7 (Neutral) 290 295 205 274

3 12 (Basic) 150 212 110 146

Table no 5.3: silver ion release during first washing for Ex-situ sample

Amount of silver released in first washing (In µg/g)

For 24 hour washing with For 24 washing without
agitation agitation
S pH Without With without With
No. detergent detergent detergent detergent
1 4 (Acidic) 276 395 301 287

2 7 (Neutral) 220 195 149 198

32
 3 12 (Basic) 199 210 178 140

5.2.2 Release of silver ion during second washing

The results of second washing show the very less release of silver as significant release
has been taken place.

Table no 5.3: silver ion release during second washing for In-situ sample

Amount of silver released in second washing (In µg/g)

For 24 hour washing with For 24 washing without
agitation agitation
S pH Without With without With
No. detergent detergent detergent detergent
1 4 (Acidic) 87 59 24 56

2 7 (Neutral) 109 86 14 26

3 12 (Basic) 46 12 11 19

Table no 5.4: silver ion release during second washing for Ex-situ sample

Amount of silver released in second washing (In µg/g)

For 24 hour washing with For 24 washing without
agitation agitation
S pH Without With without With
No. detergent detergent detergent detergent
1 4 (Acidic) 25 76 34 56

2 7 (Neutral) 69 89 43 12

3 12 (Basic) 41 75 55 16

33
5.3 Characterization of unloaded, loaded and washed samples

5.3.1 SEM and EDX analysis for the unloaded cotton fabric

This analysis confirms the absence of silver metal in the unloaded cotton fabrics. Fig. 5.2
(a) and (b) shows the SEM and EDX images which shows that no silver is present in the
unloaded sample.

Fig. 5.2 Electron microscopy of the unloaded fabrics with EDX- spectra of the
particles.

34
5.3.2 SEM and EDX analysis for the In-situ loaded cotton fabric

SEM images show the coating of the particles on the surface of the fabrics and the EDX
results confirms the presence of elemental silver in the samples. The shape of
nanoparticles is very irregular and the range of the size is also very high. This may be due
to the non-uniform coating of the nanoapatilces on the surface of the fabrics.

cps/eV
Object 2170

3
Ag
N
C O Al Si Ag

0
0 1 2 3 4 5 6 7 8 9
keV

Fig. 5.3 Electron microscopy of the loaded silver nanoparticles in the fabrics with
EDX- spectra of the particles.

35
5.3.2 SEM and EDX analysis for the Ex-situ loaded cotton fabric

SEM images show the coating of the particles on the surface of the fabrics and the EDX
results confirms the presence of elemental silver in the samples. Similar to In-situ method
the size and shape of the nanoparticles coated are irregular.

cps/eV
Object 2171

3
Ag
N
C O Mg Si Ag

0
0 1 2 3 4 5 6 7 8 9
keV

Fig. 5.4 Electron microscopy of the loaded silver nanoparticles in the fabrics with
EDX- spectra of the particles.

36
5.3.3 SEM analysis for the washed fabrics

After washing the fabrics, they were again checked for the presence of silver. SEM
analysis of the fabric were done and SEM images shows the nanoparticles coated on the
fabrics. Since EDX analysis could not be possible due to lack of time, so the presence of
elemental silver could not be confirmed. But from the previous analysis and from the
SEM images it can be said that silver is present in the washed samples. Fig. 5.5 and
Fig.5.6 shows the silver coated on the fabrics.

Fig. 5.5 SEM images for the washed In-situ fabric

Fig. 5.6 SEM images for the washed Ex-situ fabric

37
5.3.4 TEM analysis of the prepared AgNO3 solution and the washed water

The characterization of the solutions containing silver nanoparticles was done by the
transmission electron microscope. Which shows the size and shape of the NPs in the
prepared solution and the washed water solution.

5.3.4.1 For Prepared AgNO3 soluiton

TEM images show that the size of NPs is in the range of 100-4000 nm for the sample
prepared In-situ and is in the range of 20-600 nm for the sample prepared Ex-situ. They
are uniformly shaped for the prepared solution.

Fig.5.7 TEM images for the In-situ samples

Fig.5.8 TEM images for the Ex-situ samples

38
5.3.4.2 For washed water solution

TEM analysis of the silver nanoparticles in the wash water of fabrics indicates the
presence of silver material with diameters of 200-4000nm. These particles are bigger than
the original synthesized nanoparticles. A few are irregularly shaped, like the particles in
the SEM image of impregnated fabrics. The increase in size may be due to the
agglomeration. There is a possibility that some of the silver released might be in
precipitate form.

Fig.5.9 TEM images for the In-situ samples

Fig.5.10 TEM images for the Ex-situ samples

39
5.4 Results of burial study

The samples were kept for degradation in the soil for 17 days and then after it was tested
for the amount of silver remaining, visual colour changes and characterization was also
done to know the extent of degradation.

5.4.1 Ion Analysis

After putting the samples in the soil for 17days the amount of silver was again quantified
to know whether there is any leaching of nanoparticles due to degradation of the fabrcis.
Results show that there is not much significant difference in the amount of silver present
in the samples after degradation. Some variation may due to the non uniform distribution
of the AgNPs on the fabrics. For the actual confirmation of the change in the amount of
silver it is required that the distribution of the NPs should be uniform on the surface of the
fabrics and sufficient time should be given for the degradation of the fabrics. Table no 5.5
shows the result of Ion analysis.

Table no. 5.5: Ion analysis of the degraded cotton fabrics

Acid digestion analysis of degraded cotton fabrics

S No. Loading method Mass of silver Average fabric Total silver
per g of fabric mass (g) in cotton
(μg Ag/g sample (mg)
fabric)
1 In-situ method 476 20 9.52

2 Ex-situ method 395 20 7.9

5.4.2 Change in the colour of the samples

Degraded sample loaded sample

40
5.4.3 Characterization of the degraded cotton fabric

5.4.3.1 SEM analysis

SEM images show the disturbed structure of the fabrics that means degradation of the
fabrics has been taken place. The paricles are coated to fabrics that may either silver
nanoparticles or dust particles or both. Since EDX could not be preformed so the presence
of silver was confirmed nut the ion analysis shows the significant amount os silver
present in it. Fig. 5.7 and Fig.5.8 shows the SEM images of the degraded In-situ and Ex-
situ samples.

Fig.5.11 SEM images showing degradation of the In-situ loaded cotton fabric

Fig.5.12 SEM images showing degradation of the Ex-situ loaded cotton

41
CHAPTER 6 CONCLUSION AND FUTURE WORK

6.1 Conclusion
6.1.1 Effect of the method of loading on the shape, size and uniformity of the AgNPs

The results show that In-situ method (UV method) of loading is simple, effective and
provided uniform size distribution of the NPs on the fabrics whereas in Ex- situ method
(TSC method) in which silver is in the nano colloidal form tends to agglomerate. The
results of Ion analysis show that the absorption of nano silver is more effective in In-situ
method.

6.1.2 Effect of pH, chemical agent and agitation on the release of NPs during
washing

The investigation shows that the types and amount of silver released during washing is
mainly affected by the process and the amount of loading. During washing the synergetic
effect of mechanical stress and chemical agents enhance the release of nanoparticles from
the textiles. The effect of pH can be easily seen as in acidic range the release increases.
Similarly the addition of chemical agents influence the release of silver ions. Agitation
also helps in the quick release of the silver rather than still water conditions.
Approximately 50% of the silver release during the first washing in most of the cases.
The release became very less during the second washing.

The results of characterization show the presence of silver but in very non-uniform shape
and size and this variation is more in Ex-situ method. This non-uniformity may be due to
lack of skills of loading. The coarser fraction of particles size ≥ 500 is predominant.
TEM results show the uniformity in the particles of prepared solution of AgNO3 but
agglomeration of the particles of the washed solution. So from this it can be inferred that
during washing with water and silver may change its form and can form precipitate with
the other ions present in the water such as chloride etc.

42
6.1.3 The effect on the characteristics of the fabrics during the burial in the soil

When the unwashed sample is kept in the soil for the biodegradation the structure of the
cotton disturbed. Which can be seen from the SEM images. The colour of the sample
changed from light yellow to light brown which is the evidence of the degradation. The
Ion analysis shows that Silver is still present in the high amount in the fabrics so it can
been said that no or very negligible leaching has been taken place. Since the sample was
degraded only for 17 days so there is a possibility that there is no leaching in this short
period of duration so to observe leaching long term degradation is required.

6.2 Implications of the study

6.2.1 Toxicity of Ag NPs releasing during washing to domestic waste water

During the washing of the fabrics containing silver nanoparticles may release the
significant amount of silver nanoparticles which will mix with the domestic waste water
and which can either join ground water or surface water or will go to waste water
treatment plant. So the release amount of NPs is necessary to know the extent of toxicity
to the environment.

6.2.2 Toxicity of Ag NPs leaching on landfill to the ground water

After the end of the life when fabric is disposed on the landfills, if silver is still present in
the fabrics which was not removed during its use due to washing can be leached out due
to the biodegradation of the fabric by micro-organisms.Which will further transport
towards the ground water and can pollute it.

Since nanoparticles are the hazardous materials because of their potential health impacts
so there is a need for the study of the exposure of nanoparticles into the environment.
Thus our current study reflects some light on the direction to understand the risk on the
environment due to silver nanoparticles exposure. However more studies are required in
this direction.

43
6.3 Future work

The study shows the release of coarser fraction of silver nanoparticles size greater than ≥
500nm. The composition and characteristics of the AgNPs aggregate, precipitate are
needed to be investigated in the next project work. The form of silver released during
washing is needed to be characterized. Methods such as capillary electrophoresis and
size-exclusion chromatography have the potential to separate nanomaterials from ionic
species, but the detection methods suited for environmental matrices and relatively low
concentrations are limited.

The biodegradation of the samples in simple garden as well as in landfill soil is necessary
to know the leaching of the nanoparticles due to breakdown of the fabrics naturally due to
micro-organisms. Long term study is needed to be conducted to understand the leaching
potential of the nanoparticles from the fabrics disposed on the landfills.

TIME PLAN

Table no. 6.1 gives us a brief idea of the distribution of the work throughtout the year
during the course of the present study

44
Work to be done May June July Aug Sep Oct Nov Dec Jan Feb Mar April May
2017
2016 2016 2016 2016 2016 2016 2016 2016 2017 2017 2017 2017

Literature review D D D D D D

Lab exp on D D D
market socks for
Ion analysis,
washing &
characterization
loading of D TD
AgNPs on
fabrics in
laboratory
Ion analysis, D D TD TD TD TD
washing &
characterization
for loaded
fabrics
Burial study of D TD TD TD TD TD TD
the fabrics

Table no.6.1 Distribution of the work throughtout the year

45
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