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DEPARTMENT OF MECHANICAL

ENGINEERING
2009/2010
Iron oxide amended ceramic water
purifiers for point-of-use arsenic
removal from drinking water
Sean Rivers
Supervisor: Dr H. Ewing
Word count: 10,529
MEng Mechanical Engineering
i
Acknowledgements
I would like to thank my project supervisor Dr Helen Ewing, for enabling this
project and for providing guidance and advice throughout the duration. I
would also like to thank Engineers Without Borders UK and the members
and friends of Potters for Peace who helped to form the project in the
beginning. In addition I would like to express a special thanks to Prasantha
for showing me round his factory in Sri Lanka. Finally, this project would not
have been possible without input and assistance from James Kelly, Jim
Docherty, Dr John Reglinski, Gerry Johnstone, Fiona Gentles, Keith
Torrance and Prof. Robert Kalin.

















ii
Table of Contents
Acknowledgements ________________________________________________________ i
Abstract _________________________________________________________________ iv
LIST OF NOMENCLATURE & ABBREVIATIONS ________________________________ v
List of Figures __________________________________________________________ vii
List of Tables ___________________________________________________________ vii
1. Introduction _________________________________________________________ 1
1.1. Background ______________________________________________________ 1
1.2. Aims ____________________________________________________________ 1
2. Background Research _________________________________________________ 3
2.1. The Problem of Arsenic in Groundwater ________________________________ 3
2.1.1. Summary of the Arsenic Crisis in Bangladesh ________________________ 3
2.1.2. Effects of Arsenic Poisoning _____________________________________ 4
2.1.3. Chemistry of Arsenic ___________________________________________ 6
2.1.4. Mechanisms of Arsenic mobilisation in Groundwater __________________ 6
2.1.5. Arsenic Removal Technologies ___________________________________ 7
2.2. Ceramic Water Purification __________________________________________ 9
2.2.1. Point-of-use water filtration ______________________________________ 9
2.2.2. The filtrn ___________________________________________________ 10
2.2.3. Introduction to ceramics ________________________________________ 12
2.2.4. Ceramic Properties____________________________________________ 12
2.2.5. Ceramic Processing ___________________________________________ 13
2.2.6. Filtrn manufacturing process ___________________________________ 16
2.3. Iron Oxide Amended CWPs _________________________________________ 17
2.3.1. Factors affecting Arsenic sorption ________________________________ 18
2.3.2. Leaching of arsenic from filtrns _________________________________ 18
3. Methodology ________________________________________________________ 19
3.1. Manufacture of Ceramic Specimens __________________________________ 19
3.1.1. Powder Formation ____________________________________________ 20
3.1.2. Mixing ______________________________________________________ 21
3.1.3. Pressing ____________________________________________________ 21
3.1.4. Sintering ____________________________________________________ 22
3.1.5. Collodial Silver application ______________________________________ 24
3.2. Microstructure Analysis ____________________________________________ 25
3.2.1. Pycnometry _________________________________________________ 25
3.2.2. Metallography ________________________________________________ 26
3.3. Experimental Set-up _______________________________________________ 27
3.3.1. Column Apparatus ____________________________________________ 27
3.3.2. Preparation of Arsenic Spiked Water ______________________________ 28
3.4. Analysis ________________________________________________________ 28
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3.4.1. Hydraulic Conductivity _________________________________________ 28
3.4.2. Empty Bed Contact time _______________________________________ 29
3.4.3. Arsenic Removal _____________________________________________ 29
3.4.4. pH _________________________________________________________ 31
4. Results and Observations _____________________________________________ 32
4.1. Manufacture of Ceramic Samples ____________________________________ 32
4.1.1. Pressing ____________________________________________________ 32
4.1.2. Sintering ____________________________________________________ 32
4.2. Microstructure Analysis ____________________________________________ 32
4.2.1. Pycnometry _________________________________________________ 32
4.2.2. Metallurgy ___________________________________________________ 33
4.3. Experimental Set-up _______________________________________________ 37
4.3.1. Apparatus ___________________________________________________ 37
4.3.2. Influent Arsenic Analysis _______________________________________ 38
4.4. Analysis ________________________________________________________ 39
4.4.1. Hydraulic conductivity _________________________________________ 39
4.4.2. Empty Bed Contact Time _______________________________________ 40
4.4.3. Arsenic Removal _____________________________________________ 40
4.4.4. pH _________________________________________________________ 40
5. Discussion _________________________________________________________ 41
5.1. Manufacturing and Processing_______________________________________ 41
5.2. Microstructure Analysis and Hydraulic Conductivity ______________________ 41
5.3. Empty Bed Contact Time ___________________________________________ 43
5.4. Arsenic Removal by iron hydroxide amended ceramic ____________________ 45
5.5. Arsenic Detection Method __________________________________________ 46
6. Conclusions ________________________________________________________ 46
7. Future Work ________________________________________________________ 47
Literature References ____________________________________________________ 48
Appendices 53






iv
Abstract
This research was requested through the research program of Engineers
Without Borders UK by U.S. based not-for-profit organisation Potters for
Peace. This investigation aimed to determine what effect the addition of the
iron (hydr)oxide goethite (-FeO(OH)) would have in removing arsenic when
included in filtrn ceramic water filtration technology, an already established
an affordable point-of-use water filtration technology in developing countries.
Ceramic specimens were manufactured which represented the commonly
used existing ceramic filters and the new iron oxide amended filters. The
specimen were tested for total porosity and examined under microscope to
determine the distribution of iron oxide additions within the clay
microstructure, and more specifically within the pore surfaces. Arsenic
removal performance was tested by passing arsenic spiked water though the
specimen in a down-flow column test. The hydrostatic head above the
samples was altered to allow arsenic removal to be measured at different
flow rate and empty bed contact times.
Results indicated that the addition of iron oxide increased the porosity of the
ceramic after sintering. Due to the limit of magnification, micrographs of the
ceramic did not give adequate insight into the distribution if iron oxide within
pores, though they did give an insight as to why very low flow rates were
obtained by the specimen during testing. As a result of the very low hydraulic
conductivity of the manufactured specimens it was not possible to obtain
results for arsenic removal by either the control ceramic or iron oxide
amended ceramic.
A discussion is included on perhaps why the samples did not have the
hydraulic conductivity expected. Simple calculations are displayed with
existing scientific data to hypothesise required contact times for arsenic
removal by iron oxide amended filters. The resulting hypothesis is that for
this method of arsenic removal to work, long contact times with the filter is
required which will lower the quantity of water obtained sufficiently that the
device will not be user friendly.
v
LIST OF NOMENCLATURE & ABBREVIATIONS

Symbol Description Units
A Filter media surface cross sectional area cm
2

As(III) Arsenite
As(V) Arsenate
BGS British Geological Survey
CWP Ceramic water purifier
CWP-Fe Goethite amended ceramic water purifier
EBCT Empty bed contact time mins
h Hydrostatic head cm
K Hydraulic conductivity m/h
L Filter media thickness cm
NSF National Sanitation Foundation
P
%
Percentage total pore volume
POU Point of Use
PfP Potters for Peace
ppm Parts per million
ppb Parts per billion
Q Volume flow rate cm
3
/h
RDIC Resource Development International - Cambodia
REDOX Reduction-oxidation
RO Reverse osmosis
vi
T Time mins
TGA Thermal Gravimetric Analyser
V Volume cm
3

V
p
Pore volume cm
3

V
tablet
Tablet volume cm
3

W Weight g
WHO United Nations World Health Organisation
Density g/cm
3

UNICEF United Nations Children Fund

vii
List of Figures
Figure 1 Map illustrating Arsenic concentrations in Bangladesh groundwater [9] _________ 3
Figure 2 Skin legions caused by long-term arsenic consumption [3]. ___________________ 5
Figure 3 Stacked filtrns []. _______________________________________________________ 11
Figure 4 - Finished filter in container [26].____________________________________________ 11
Figure 5 Uniaxial press used in filtrn production [28]. _______________________________ 14
Figure 6 Formation of necks, grain boundaries and pores during sintering [26]. _________ 15
Figure 7 Creation of interconnected and isolated pores during sintering [26]. ___________ 16
Figure 8 Vibrating sieving table [26]. ______________________________________________ 20
Figure 9 Die, plunger and washers [26]. ___________________________________________ 22
Figure 10 Assembled die and plunger [26]. ________________________________________ 22
Figure 11 Sintering protocol from RDIC Ceramic Water Filter Handbook [24]. _________ 24
Figure 12 Column apparatus with head control and recirculation of feedwater [26]. ______ 27
Figure 13 Mounted specimen. C1-C3, left op right respectively [26]. __________________ 28
Figure 14 Specimen C1 at 50x magnification. ______________________________________ 33
Figure 15 Specimen C2 at 50x magnification _______________________________________ 34
Figure 16 Specimen C3 at 50x magnification _______________________________________ 34
Figure 17 Specimen C1 at 500x magnification. _____________________________________ 35
Figure 18 Specimen C2 at 500x magnification. _____________________________________ 36
Figure 19 Specimen C3 at 500x magnification. _____________________________________ 36
Figures 20a, b & c Specimens C1-C3 at 500x magnification, left to right respectively. ___ 37
Figure 21 Finalised experimental set-up [26]. _______________________________________ 38
Figure 22 Results of HACH arsenic testing on prepared standard solutions [26]. _______ 39

List of Tables
Table 1 Scale of Arsenic Poisoning in Bangladesh. __________________________________ 4
Table 2 Constituents of ceramic specimen. ________________________________________ 19
Table 3 Pycnometry results. ______________________________________________________ 32
Table 4 Measured hydraulic conductivity parameters. _______________________________ 39
Table 5 Comparison of hydraulic conductivity (K) values from various filtrn studies. ___ 40
Table 6 Empty bed contact times depending on specimen type and hydrostatic head. ___ 40

Iron oxide amended ceramic water purifiers for point-of-use arsenic removal from drinking water

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1. Introduction
1.1. Background
The installation of millions of shallow tube wells in Bangladesh during the
70s, 80s and 90s has been recognised as the greatest mass-poisoning in
history. Due to a well-intentioned international effort to supply the country
with safe drinking water, it is estimated up to 75million people are at risk of
ingesting unsafe levels of cancer-causing arsenic with over 20million already
exposed to varying degrees [1, 2]. This crisis far outweighs the number of
those affected in the catastrophes of Bhopal and Chernobyl [3].
72% of Bangladeshis live in rural areas [4]. For those relying on wells without
centralised treatment, the priority is on identifying the affected wells and
switching to alternate, clean water sources. Where such sources are not
easily available or testing has not been carried out, appropriate intermediate
solutions are required which work successfully on a community level.
This paper presents a study into the adaptation for arsenic removal of the
filtrn, an already existing, affordable and popular method proven to treat
biologically contaminated water in developing countries. In 2009, Brown and
Sobsey demonstrated that the filtrn was more effective at removing viruses
when amended with an iron (hydr)oxide prior to sintering [5]. Iron oxides are
known to bind with inorganic arsenic, although applying this property for
arsenic removal from drinking water has not yet been investigated [6, 7].
1.2. Aims
The objective of this research was to determine whether filtrns amended
with goethite have the potential to provide an appropriate intermediate
solution to removing arsenic from drinking water. For the filtrn to be deemed
fit for the purpose of removing arsenic it must meet the following criteria:
- Must be easy to use and maintain.
- Must be affordable.
- Must Remove all inorganic arsenic (As(III) & As(V)) to below WHO
limit of 10 parts per billion (ppb).
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- Must have a high absorption capacity (long safe operating life).
- Must have a short retention time.
- Must not produce toxic waste for disposal.
- Must hold its structural integrity in water.
- Must not leach arsenic or any other filter materials back into the filtrate
or environment upon disposal.

Due to time constraints in this undergraduate project it was not feasible to
carry out a comprehensive test of all criteria. Therefore, it was decided to test
for the most immediate indicators of this technologys potential:
- Ability to remove inorganic As(V) to within 50ppb and 10ppb..
- Minimum empty bed contact time required for removal of As(V) to
within 50 and 10ppb.
- Distribution of iron oxide within the ceramic pore surface and
microstructure.














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2. Background Research
2.1. The Problem of Arsenic in Groundwater
2.1.1. Summary of the Arsenic Crisis in Bangladesh
In the 1970s, the overwhelming majority of Bangladeshi citizens relied on
un-safe surface sources of drinking water. It was common to remove water
for drinking, food preparation and hygiene from stagnant ponds and lakes
which led to a range of water-related illnesses such as gastroenteritis,
dysentery and diarrhoea [3]. This countrywide lack of safe water supply
contributed to decreased productivity, lower family incomes, higher child
mortality and poor school attendance (especially among girls).
As part of the United Nations (UN) water supply and sanitation decade
from 1970-1980, the United Nations Childrens Fund (UNICEF) and World
Health Organisation (WHO) worked with the Bangladesh Department of
Public Health Engineering (DPHE) to install some 3 million shallow tube
wells in the country. The effort was taken over by many other government
and non-governmental organisations (NGOs) resulting in over 10 million
shallow wells delivering water to over 90% of Bangladeshis [8], In 1997 the
WHO stated that it had surpassed its goal of delivering safe water to over
80% of the country by the year 2000.

Figure 1 Map illustrating Arsenic concentrations in Bangladesh groundwater [9]
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Cases of arsenicosis (figure 2) were first detected in India in 1983 from
people arriving from West Bengal [10, 8]. Arsenic was first detected in
Bangladeshi groundwater in 1993, though the problem was not fully
acknowledged by international organisations until 1998. Agencies involved in
the shallow well projects did not test water for arsenic as they claimed they
had no reason to suspect its presence in Bangladeshs groundwater.
The scale of arsenic poisoning arsenic poisoning known so far is shown in
figure 1 and table 1. The WHO has recommended an upper limit of arsenic in
drinking water of 10g/l (10ppb) irrespective of arsenic species, in
Bangladesh the national standard is set at 50g/l (50ppb).
Table 1 Scale of Arsenic Poisoning in Bangladesh.
Population of Bangladesh 125 million [3]
Total number of tubewells in
Bangladesh
11 million [3]
Safe-level of Arsenic in drinking
water
50g/l (Bangladesh national standard)
10 g/l (WHO standard)
Number of affected districts (out of
64)
59 [1]
Percentage of Bangladesh with
contaminated groundwater
85% [1]
Population of regions with
contaminated wells
35-77 million [3]
Number of tube wells tested in 1998
by British Geological Survey (BGS)

Proportion with Arsenic > 50g/l
Proportion with Arsenic > 300g/l
2022 [3]


35% [3]
8.4% [3]

2.1.2. Effects of Arsenic Poisoning
Arsenic was used historically as an anaesthetic although it is now regarded
for its more harmful properties as a poison and carcinogen.
Medical Effects of Arsenic Poisoning include but are not limited to the
following:
- Legions
- Skin cancer
- Hypertension and cardiovascular disease
- Neurological effects
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- Internal cancers
o Bladder
o Kidney
o Lung
- Pulmonary disease
- Diabetes mellitus
- Peripheral vascular disease

There is a latency associated with arsenicosis such that the first symptoms,
being skin legions, are not normally seen for around 10 years after regularly
ingesting elevated levels (more than 10ppb) of arsenic [3]. This latency was
one of the reasons why the arsenic went undetected in the water supply of
Bangladesh and West Bengal for such a long time. Even now that arsenic is
being tested for and detected in wells, the process is a slow one and it will
not be known for years the true number of people who have been affected.

Figure 2 Skin legions caused by long-term arsenic consumption [3].
Often overlooked by engineers and scientists are the social issues
associated with physical problems. In Bangladesh, paranoia and lack of
education has led people to treat arsenicosis sufferers as lepers, with the
afflicted being ostracized by their relatives and communities. Due to fear of
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catching arsenicosis,, the healthy population deny the sufferers access to
schools, workplaces and public gatherings. Cases have been reported of
young female sufferers staying unmarried, while affected wives and mothers
are sent back to their families with their children or abandoned altogether [1].
2.1.3. Chemistry of Arsenic
Arsenic is a naturally occurring element constituting less than 1% of the
worlds surface. Its atomic number is 33 on the periodic table and it has an
atomic weight of 74.9. Inorganic arsenic is more harmful to humans than the
organic form [11]. Inorganic arsenic exists in the environment in four
common valence states, -3, 0 +3, +5, however inorganic arsenic only exists
in groundwater in two of these valence states [12]. Arsenite (As(III)), the
trivalent form, is found under anaerobic conditions and has the ions AsO
2
or
AsO
3
. Arsenate (As(V)) the pentavalent form is found under aerobic
conditions with the ion AsO
4
. As(III) is more potent and less stable than As
(V). For a time, inorganic arsenic was at the top of the USEPA list of
prioritised pollutants [16].
Due to the complexities of maintaining As(III) in an oxygen free environment
during testing, only As(V) was tested for in this investigation.
2.1.4. Mechanisms of Arsenic mobilisation in Groundwater
The mechanism(s) of arsenic mobilisation in the Ganges basin which
supplies Bangladeshs ground and surface water is a contested issue. There
are two generally suggested methods. The core existence of arsenic in
Bangladeshi groundwater is generally accepted to be due to natural arsenic
compounds present in soil sediments. Rock formations containing arsenic
higher up the Ganges suffered erosion over thousands of years, allowing
arsenic to be transported downstream and deposited to low lying floodplains
of Bangladesh in the form of arsenopyrite and attached to iron oxides. The
first mechanism is that under reducing conditions arsenic is converted to
mobile and soluble As(III). Reduction of iron also causes further release of
As(III) into groundwater [13]. The second explanation is that the due to
groundwater abstraction, and a falling water table, arsenopyrite is exposed to
oxygen which releases arsenic when oxidised [1]. The presence of iron,
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arsenic and sulphur reducing bacteria further influence the species of arsenic
and the release of arsenic from sediment compounds.
Arsenic contamination of groundwater is not limited to Bangladesh and west
Bengal. 70 countries around the world including Taiwan, Pakistan, China,
New Zealand, Hungary, USA and Canada suffer from arsenic in groundwater
reserves. It is estimated that as many as 140 million people worldwide have
been exposed to arsenic in drinking water over the WHO limit of 10g/l [14].
Though the majority of arsenic in the environment is natural, anthropogenic
sources of arsenic include coal production, pesticides, cotton production,
munitions manufacturing, semiconductors, wood preservatives, textiles and
adhesives [15].
2.1.5. Arsenic Removal Technologies
There are many method of removing arsenic technologies. The most
commonly used methods of arsenic removal are described in this section.
Oxidation Sedimentation
As As(V) is more stable and less mobile than As(III) it makes removal easier
if oxidation is used to transform arsenite to arsenate. Although fresh air is the
obvious choice for oxidation in developing countries, the process is very slow
taking up to weeks [16]. The process can be catalysed however using
bacteria, activated carbon, UV radiation, high temperatures and extreme
acids or alkalis. Potassium permanganate and hypochloride (bleaching
powder) are both commonly available in developing countries though the
former has a longer shelf life.
Sedimentation by leaving water standing in the home is an attractive solution
as it requires little effort or behavioural change. Results are mixed from with
one rapid assessment showing failure to remove arsenic to below 50ppb
[17].
Coagulation sedimentation filtration
Some very fine particles are too small to be removed by mechanical filtration
and are held in constant suspension due to their electrostatic charges
repelling one another. Coagulation filtration involves administering a
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flocculant or flocculating agent to bind such particles together into a heavier
floc which can then be removed by physical means.
Iron/aluminium salts and lime are common flocculating agents for arsenic
removal, although using lime requires pH correction prior to consumption.
Again, oxidation of As(III) to As(V) prior to coagulation increases the removal
efficiency. One disadvantage with this method is the creation of an arsenic
laced sludge during sedimentation which must be disposed of, without
leaching arsenic back into the environment and water resources.
Membrane Filtration
Membrane filtration involves using a fine mesh whose pores are too small for
contaminants to physically pass through. The use of synthetic membranes
can successfully remove bacteria, viruses and metal ions. For arsenic
removal a very small pore size is required, hence only high pressure
membrane nanofiltration and reverse osmosis (RO) are effective to a high
degree. Problems with nanofiltration and RO technology in a development
context involve supplying energy for the high pressures required and
protecting the delicate membrane from suspended solids and metals found in
groundwater such as iron and manganese.
Distillation
Distillation uses heat to evaporate water into vapour leaving contaminants
behind and subsequently condensing the vapour back into pure water. For
high yields this method requires a lot of heat energy and therefore fuel. A
simple, passive method has been invented which use solar radiation to
evaporate water in a box or still with an inclined glass lid. The water then
condenses on the glass and runs off into a collecting gutter. Of all low-cost
technologies for arsenic removal, solar distillation is the only to be accredited
by the National Sanitation Foundation (NSF) for removing 100% of arsenic
including all other heavy metals, salts, bacteria and viruses [18]. The main
downside with solar distillation is the low output per surface area required for
the stills, approx 2-3 litres/m
2
/day [19].
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Sorptive Filtration
Soprtive filtration uses the electrostatic affinity between arsenic and the
sorptive media to retain arsenic, thus removing it from drinking water.
Adsorption is the process where the adsorbate adheres to the surface of an
adsorbent. Such adsorbent media include iron hydroxides, aluminium,
activated carbon and biomass.
The critical factors for sportive media is the adsorption capacity of the media,
usually measured in milligram of adsorbent per gram of sportive media
(mg/g), and the contact time required to achieve the desired level of
contaminant removal. Removal efficiency is influenced by pH, REDOX
conditions, the presence of other inorganic and organic contaminants which
may competitor for attachment sites, and microbes which can consume or
create oxygen thus affecting REDOX conditions of the adsorbent, adsorbate
and competing compounds such as sulphur.
Sorptive filtration possibly provides the best solution to arsenic removal as it
is quick, does not require the use of coagulants and does not produce a
hazardous sludge. It must be ensured however that arsenic does not leach
from the filter media during use or after disposal due to REDOX conditions or
microbial activity.
2.2. Ceramic Water Purification
2.2.1. Point-of-use water filtration
Point-of-use (POU) is used to describe methods of water purification which
occur immediately prior to consumption rather than at a centralised or
decentralised water treatment plant. In many developing countries where
transmission infrastructure is poorly maintained, or where water is collected
by hand and stored in the home for periods of time, previously treated water
becomes vulnerable to recontamination [20, 21]. POU water treatment
avoids risks of recontamination during transport and storage of water and
has been found to reduce diarrheal diseases by over 70% [22].
POU water filtration can work well in remote rural areas, or informal
settlements with no urban planning, where piped systems are expensive to
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both install and maintain for a range of financial, institutional, technical and
social reasons. Also by making the treatment process visible, POU treatment
also causes communities to consider other health intervention such as
hygiene and sanitation.
POU filters such as porous ceramic water purifiers (CWPs) a type of
membrane filter and bio-sand filters can be manufactured by local skilled
people, using local resources, with donor funding being going directly to the
local economy. It however, would be wrong to assume that POU filters are a
perfect solution to the problem. POU treatment required behavioural change
which can be difficult in traditional cultures. Methods such as boiling water
using wood for fuel, whilst POU treatment, contributes to deforestation and
approximately 1.6 million deaths annually due to indoor air pollution [23].
An effective and sustainable POU water treatment system must fulfil a set of
criteria such as recommended by Sobsey et al, 2008 [22]:
- Ability to supply required quantity of safe drinking water
- Effective for treating a range of influent water qualities
- Method is not time intensive, allowing user to pursue other
work/leisure activities
- Low purchase and maintenance costs, making treatment
insensitive to income insecurities.
- Have spare parts affordable, accessible and easy to replace.
- Maintain usage in the long term.
2.2.2. The filtrn
The filtrn, a flowerpot shaped porous CWP (figures 3 & 4) was developed
and by U.S and Nicaragua based not-for-profit organisations Potters for
Peace (PfP), and Resource Development International Cambodia (RDIC)
[24]. Bacteria are removed by physical straining though the ceramics
micropores and contact with the colloidal silver coating a biocide which
inactivates bacteria. Colloidal silver also inhibits bacterial growth on the filter
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surface. There are currently hundreds of thousands of CWPs of filtrn design
being both manufactured and used in developing countries including
Nicaragua, Cambodia and Sri Lanka. The filtrn has received endorsement
from the UN and WHO [25].

Figure 3 Stacked filtrns [26]. Figure 4 - Finished filter in container [26].
Some reasons for the success of the filtrn are outlined below:
- The design uses locally available materials and skills which
keeps the cost of manufacture and distribution low.
- The product resembles a simple terracotta pot, which is
unobtrusive in many cultures.
- The device has good impact strength, making it less
susceptible to breakages, and increasing the life span.
- The device required minimal effort and infrequent cleaning.
Three main drawbacks with the filtrn are that:
- Storage containers are susceptible to re-contamination if not
properly kept clean.
- Drinking clean water will not prevent diseases caused by poor
hygiene and sanitation practise.
- The filtrn is not currently designed to remove heavy metals
such as Arsenic.
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2.2.3. Introduction to ceramics
Ceramics have been in use for over 10,000 years, making them one of the
oldest engineering materials known to man. The word ceramic comes from
the Greek keramos literally meaning burnt earth. It is assumed that
ceramic processing originated from a simple observation that some types of
mud solidified when left in the sun. Therefore by altering the shape of the
mud in its wet, plastic state, and applying heat though fire, it was possible to
create solid objects of a desired shape with relative ease. This ease of
producing simple components is a particular reason why the technology is
appropriate to communities in developing countries.
2.2.4. Ceramic Properties
Ceramics are an inorganic, non-metallic material group, which are largely
composed of a mixture of metallic and non-metallic compounds. For the clay
in use in this investigation the constituents are mostly silicate and alumina.
Ceramics are formed by the application of heat (and in some cases heat and
pressure). With the exception of amorphous ceramics such as glass, most
ceramics have crystalline structures. Ceramics can be divided into two main
categories depending on their properties and application: traditional and
advanced. Traditional ceramics includes terracotta, earthenware, whiteware,
porcelain and structural ceramics. Advanced ceramics include
semiconductors and technical ceramics used in aerospace applications.
The properties and application of ceramics are largely dependant on their
microstructure. Crystalline solids can exist in two forms: a single crystal, or a
collection of smaller, packed crystals. The latter form is termed
polycrystalline. Single crystals feature a perfect repetition of atoms
throughout the structure which unless produced in a very controlled
atmosphere is difficult to achieve. In polycrystalline ceramics the crystals or
grains are highly varied in size, shape and arrangement. Grains normally
occur in a size range of 1 to 50 microns. Filtrns consist of polycrystalline
ceramic.
Chemical bonds in ceramics are ionic between metals and non-metals, and
covalent between non-metals and metalloids such as Boron, Silicon and
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Arsenic [27]. Unlike metallic bonds, neither ionic nor covalent bonds leave a
free electron, which is why ceramics are typically insulators and also why
dislocations do not slide over one another. The ionic and covalent bonds also
account for the high melting point and high modulus of elasticity of the
material compared to metals. Although the properties of ceramics are
variable, low-tech ceramics are generally hard, brittle and corrosion resistant.
Ceramics tend to have a high, specific melting point.
The interface between grains is a disordered region termed the grain
boundary. Not all grain surfaces are connected however; this is what is
termed porosity, and it is of critical importance in water filtration applications.
2.2.5. Ceramic Processing
Due to the high melting point of ceramics it is not normally feasible to form
products from melt in the same way in which metals are formed. Ceramic
processing normally involves powdering the raw materials, mixing them and
moulding them prior to heating. The method of forming the unfired or green
body has a great effect on the microstructure and the final properties of the
material.
There are many methods of varying accuracy and cost available to produce
powders. The commonly used method in filtrn production is using a hammer
mill to crush constituents into a powder which is then passed through a mesh
screen to sort out particles of a specific size.
When moulding the powder, there are three main options: pressing, casting
and plastic forming. Pressing is the process used in the manufacture of
filtrns. It involves inserting the powdered material into a die and applying
pressure. The pressure causes elastic deformation, plastic deformation and
fracture of the particles, packing the powder densely and reducing empty
pore spaces between the particles.
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Figure 5 Uniaxial press used in filtrn production [28].
Pressure can either be applied uniaxially by means of a simple plunger or
isostatically by using a flexible mould and applying pressure on all sides by
means of pressurized fluid. In the case of the filtrn, pressure is applied by
the more straightforward plunger method (figure 5).
Once pressure is removed some of the energy stored in the elastically
deformed particles will cause the green body to expand, this is known as
springback. Defects can be caused by different levels of springback within
the green body which can cause shearing between layers within the brittle
body.
Because of the delicate nature of dry green bodies, it is common in ceramic
processing to use a range of additives such as binders, plasticisers and
lubricants to increase the plasticity and strength of the green body during the
forming process.
In filtrn production, water is used as a lubricant. This reduces the friction
between dry particles, allowing the particles to move and form more easily
within the die. This allows higher packing densities to be achieved at lower
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pressures and gives more uniform packing density which decreases the
chance of defects due to springback. Water also gives the green body
strength during handling, making removal and transfer to other processing
stations easier.
Sintering is the final stage in the production of ceramics. This involves
applying heat to the green body which results in compaction of the body,
removal of pore spaces and the formation of strong bonds between particles.
To allow this densification to occur, a mechanism of material transport is
required. This mechanism is the heat in the firing process which allows
diffusion and viscous flow of the ceramic [29].
Sintering occurs in thee stages.
In the initial stage particles rearrange slightly, increasing their contact with
adjacent particles. Where there is sufficient energy at these contact points to
allow material transport, bonds begin to form. These early bonds are called
necks, due to their appearance.

Figure 6 Formation of necks, grain boundaries and pores during sintering [26].
During the intermediate stage, necks grow larger, making particles less
recognisable as such (figure 6). Particle are now termed grains, with their
grain boundaries transecting the necks. Grains move closer together
leading to a decrease in pore size and total pore volume decrease equal to
the volume shrinkage of the component. The intermediate stage is deemed
concluded when pores are isolated from one another and no longer form
Necking
Grain boundaries
Pores

Key:

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continuous channels. Of course it is these channels of interconnected pores
which allow fluid flow in the filtrn. Figure 7 shows how the creation of
interconnected pore channels is aided by burnout material.

Figure 7 Creation of interconnected and isolated pores during sintering [26].
The final stage of sintering involves further grain growth and isolated pores
being removed by vacancy diffusion. This process depends the rate of grain
growth, as if grain boundaries are formed too quickly, pores may become
trapped with no path to exit.
2.2.6. Filtrn manufacturing process
As with many appropriate technologies the manufacturing process for a
filtrn depends highly on the location, and as such is not an exact science.
As clay powder and burnout materials are often sourced locally and their
chemical composition varies from location to location, there exists a degree
of experimentation and customisation required in each factorys
manufacturing process. In the factory visited in Sri Lanka, it took Prasantha
(the factory owner) 9 months of experimentation to finally get the composition
right before any filters were ready for sale.
The manufacturing process detailed below is derived from the RDIC 10 step
production process, on-line manuals from the PfP website and conversation
with a filter factory owner in Matara, Sri Lanka [3, 4, 30].
1. Preparation of raw materials: clay, laterite (optional), rice husks,
water.
2. Mix raw materials
Burnout material


Isolated pores

Water

Clay/ceramic

Key:

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3. Form clay balls for pressing
4. Press clay into pot shape
5. Surface finishing and stamping of pressed filters
6. Dry pressed filters for 2-3 days.
7. Fire filters in a kiln
8. Flow rate testing
9. Application of colloidal silver. 2mg of 3.2% solution to 300ml.
10. Package filter with receptacle, lid, spigot, and information leaflet.
Ready for sale.
2.3. Iron Oxide Amended CWPs
Research by Brown and Sobsey showed that iron oxides provide attachment
sites for virus bacteriophages, removing them from drinking water, in
laboratory tests an 8log (99.999999%) reduction in bacteriophages was
recorded [5].
Goethite (pronounced gertide) is a ferric hydroxide with the chemical
composition -FeO(OH). It is a brown mineral formed by the weathering of
iron (eq. 1) and a component in the rich red/brown lateritic soils found in
many tropical regions. [31, 32].
4Fe
2+
+O
2
+6H
2
O = 4FeOOH + 8H
+
(1)
Lateritic soils are produced where long-term high rainfall dissolves more
soluble compounds in soli leaving behind amounts of insoluble iron and
aluminium, resulting in a hard, rust-coloured soil. During field research in Sri
Lanka, lateritic soil was observed in use in building construction and as a
strength additive in CWP production. During sintering at 260-320C in an
oxidising environment goethite is transformed to hematite [33, 34, 35].
Dehydration of goethite is shown in equation (2) [36].
2FeOOH -> Fe
2
O
3
+ H
2
O (2)
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As with other iron oxides, Hematite has been demonstrated to be effective at
removing over 80% of As(V) from pH neutral drinking water [37, 7]. Clay is
also shown to absorb arsenic, though not as effectively as iron oxides [46].
2.3.1. Factors affecting Arsenic sorption
Arsenic sorption onto ferric oxides is influenced by a range of abiotic and
biotic factors. The main abiotic factors are contact time, pH, REDOX
conditions and the presence of other adsorbents. Under acidic conditions
As(V) sorption onto iron oxides is more favourable with As(III) sorption being
prevalent under more alkaline conditions [38]. As the proportions of
As(III)/(V) are determined by the oxidation state, it follows that the under
reducing conditions a high pH is preferable, while a low pH is preferable for
aerobic conditions. Competition for sorption surfaces on hematite by sulphur
also influences the efficiency of arsenic removal [39]. This has
consequences for Bangladesh where there is an abundance of pyrite (iron
sulphide) in ground sediments [40]. Dissimilatory reducing bacteria (DRBs)
are also responsible for the reduction of As(V) [41]. Recently bacteria which
oxidise As(III) to As(V) were discovered in California [42].
2.3.2. Leaching of arsenic from filtrns
Desorption or leaching of As(III) and As(V) from filtrns back into supposedly
safe drinking water is of concern. This point was raised by PfP during the
conception of this project, not just for filtrns with the purpose of removing
arsenic but also in areas where arsenic exists in laterite and clay which are
being used for filter production. Leaching of As(III) occurs quicker and to a
greater extent than As(V) possibly due to weaker bonds [43].






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3. Methodology
3.1. Manufacture of Ceramic Specimens
Three different constructions were used in order to asses the effect of the
goethite amended ceramic. C1 was un-modified porous ceramic, C2 was un-
modified porous ceramic coated with colloidal silver, and C3 contained
goethite addition and no colloidal silver coating. C1 and C2 would act as
controls to C3. The constituents of the ceramic specimen are listed in table 2.
Table 2 Constituents of ceramic specimen.
Specimen Constituents
C1 1/1 clay/sawdust by volume
C2 As for C1, with colloidal silver applied to disc
post-firing
C3 6/1 clay/goethite by mass, 1/1
(clay+goethite)/sawdust by volume.

Specimen type C1 and C2 were used as controls to the goethite amended
ceramic. The reason for having two different controls is that it was unknown
what interactions arsenic may have with the colloidal silver. Though a
solution would be to avoid any problems by just using specimen C1, this
would give an impractical comparison for any added benefits of using
goethite, as filtrns should always coated with colloidal silver. 1/6 was the
largest goethite/clay ratio reported by Brown and Sobsey to be possible
without loss of filter strength [5]. Specimens were disk shaped, 37-39mm
diameter and 10-13mm thick. The thickness of real filtrons vary from 10-
20mm [Error! Bookmark not defined.].
The sample preparation methodology was kept as close to the in field
production method and was as follows:
1) Sieve clay through a 500 m mesh.
2) Sieve sawdust through a 500 m mesh.
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3) Combine dry ingredients. 1/6 for oxide/clay by weight and 1/1 for clay
(+ oxide)/sawdust by volume.
4) Mix dry ingredients on roller bed for 10 minutes.
5) Add water, starting at 30% weight of dry ingredients.
6) Mix wet ingredients until the clay is of uniform consistency.
7) Press clay into tablets.
8) Dry samples for 2-3 days at 50 C.
9) Bake samples in furnace for 24 hours. 860-900 degrees [44]
3.1.1. Powder Formation
From researching various literature there did not appear to be a solid
consensus on the particle size of the ceramic powder prior to sintering [24,
45]. Recommendations varied between a particle size of between 30 and 60
mesh, less than 40 mesh and less than 30 mesh. For this investigation, a
mesh size of 30 (0.5mm aperture) was used as recommended by Prasantha
[30].

Figure 8 Vibrating sieving table [26].
The clay and sawdust were passed separately through a 30 mesh sieve
mounted on a vibrating sieving table (figure 8). It was found that the first
batch of sawdust obtained from the university workshops contained
aluminium particles which were not removed during sieving. As aluminium is
shown to be an effective sorptive media for arsenic it was crucial that the
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sawdust be aluminium free [46]. Aluminium free sawdust was finally obtained
from Polney sawmill in Dunkeld, Perthshire. To minimise waste, clay which
was too large to pass through the sieve on the first attempt was ground by
hand using a mortar and pestle and sieved again.
3.1.2. Mixing
When mixing the clay and sawdust, a 1/1 volume ratio was used as per the
factory in Sri Lanka. It was unlikely that this 1/1 mix would achieve the
desired porosity and hydraulic conductivity on the first attempt, however due
to setbacks caused by equipment breakdowns there was no time to carry out
an iterative process of testing and multiple hydraulic tests on samples prior to
arsenic sorption tests, so a 1/1 ratio was taken as the standard.
For each batch, 100ml of dry ingredient were sealed in a plastic flask and
placed on a roller bed for 10 minutes to ensure a homogeneous mix.
Afterwards, water was added slowly while manually stirring the mixture in a
Pyrex

dish. Approximately a 1/3 ratio of water/dry matter was required. At


the end of mixing, the dough was removed and folded by hand to ensure
uniform consistency before being weighed and divided into appropriate sized
portions, ready for pressing.
The exact composition of each batch can be seen in appendix I.
3.1.3. Pressing
Samples were pressed in a steel 40mm diameter die (figures 9 & 10) with a
uniaxial applied force of 170N applied in addition to the 2kg weight of the
plunger.
The die was a lined with a plastic shopping bag (as used in field) to prevent
the green body from sticking to the mould. As no information could be found
on the pressure applied to filters in the field, the samples were pressed with
a slowly ramping pressure and inspected at intervals. The samples normally
dried out in the hot workshop and exhibited some cracking at the
circumference during pressing due to the heat and dryness of the workshop.
Any cracking was touched-up upon inspection before being re-inserted and
pressed further until the green body achieved 100% packing in the die.
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Figure 9 Die, plunger and
washers [26].

Figure 10 Assembled die and
plunger. Washers are placed inside
the die above and below the clay
[26].
Once disks were successfully pressed they were dried for 2-3 days at 50C
in a drying oven, before being transferred to a desiccating chamber while
waiting to be sintered.
3.1.4. Sintering
The sintering protocol for the ceramic specimen was derived from the RDIC
Ceramic Water Filter Handbook as shown in figure 11 [24].
The equipment used was a Carbolite CWF 1200 furnace. In the first ramp the
clay is heated over 1 hour to one hundred degrees where it is allowed to
dwell for 2 hours. This allows any moisture still present in the ceramic to
evaporate slowly without boiling and damaging the structure of the green
body. Following this dwell, the temperature is ramped steadily up to 890C.
During this ramp the burn-out material combusts, leaving pore volumes, and
the ceramic begins the sintering process as described in section 2.2.5.
Following the long dwell the temperature is lowered to 400C gradually, rapid
cooling (quenching) of the specimen can cause thermal shock and lower the
strength of the specimen [47]. Below 400C sintering is completed and the
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temperature can be decreased as rapidly as the furnace allows without effect
to the microstructure.

Figure 11 Sintering protocol from RDIC Ceramic Water Filter Handbook [24].
3.1.5. Collodial Silver application
Colloidal silver was purchased from Sigma-Aldrich

. In practice colloidal
silver solution is often prepared in a 3.2% concentrate which is then diluted
as required to create a batch of 220mg/l solution for application. As there
was only need to make enough solution for one disc the following method
was adopted:
- Measure 50ml of water
- Weigh 11mg of colloidal silver
- Add colloidal silver to water and stir
- Brush solution on tablet surface
The calculation proof is shown in equation (3).
l g
water of Vol
Silver of Mass
ion Concentrat / 22 . 0
50
11
= = =
(3)
Following the application of the colloidal silver C2 was dried in an oven at
50C for one hour.
0
200
400
600
800
1000
0 5 10 15 20 25 30
T
e
m
p
e
r
a
t
u
r
e

(

C
)
Time (Hours)
Furnace Protocol
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3.2. Microstructure Analysis
3.2.1. Pycnometry
Pycnometry is a method which uses Archimedes principle to measure the
volume of irregular shaped objects. It was used in order to calculate the total
pore volume of the specimen types.
Archimedes principle states that when an object is placed in water, the
buoyancy force on the object is equal to the weight of mass of water
displaced. When that object is fully submerged in water, it is also true that
the volume of water displaced is equal to the volume of the object. Therefore
by comparing the weight of an object suspended in air and in water, the
buoyancy force on the object can be calculated, hence it follows that the
mass of water displaced can be calculated, which in turn will give the volume
of water displaced and therefore the bulk volume of the object.
The internal pore volume of the ceramic is calculated by placing the samples
in boiling water, which forces water into the pore volumes and causes air in
the pores to expand and vacate the pores. Upon cooling, any air left in the
pores contracts, creating a vacuum which further draws water into the pores.
By measuring the weight of water gained by the tablets during this process, it
is possible to estimate the volume of the internal pores.
The method for the pore volume investigation is detailed below. The weights
of the tablets in air and water were obtained using Mettler Toledo Excellence
XP/Xs analytical balances. The full method is explained below.
1. Dry tablet was weighed in air
2. The tablet was then weighed in water
3. Tablets were submerged in separate beakers of deionised water
and placed on a hot plate. Once brought to the boil the tablets
were boiled for 10 minutes.
4. The beaker was then removed from the hot plate and allowed to
cool to allow water to be drawn into any pore spaces by
contracting air.
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5. Tablets were then removed from the beakers, dried lightly with a
paper towel and weighed.
The pore volume can be calculated by applying equations (4)-(8).
water
water air
water
disp
tablet
W W
W
V


= =
(4)

water
air boiled
water
adsorp
pore
W W
W
V


= =
(5)

100
%
=
tablet
pore
V
V
P
(6)
100
%

|
|
.
|

\
|
|
|
.
|

\
|
=
water
water air
water
air boiled
W W
W W
P

(7)
100
%

|
|
.
|

\
|

=
water air
air boiled
W W
W W
P
(8)
3.2.2. Metallography
In order to examine the microstructure of the ceramic samples and gain an
insight into the distribution of hematite within the pore surfaces, the surface
and profile section of each three specimen types were viewed under a
microscope.
Sections of the ceramic tablet samples were cut using a Struers Accom-5
diamond saw. Using a vacuum impregnation chamber, two samples of each
tablet were mounted in resin such that a surface and cross section of each
could be viewed upon hardening. Once the resin was set, the dies were
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polished and the samples viewed at 50x and 500x using an Olympus GX51
metallurgical microscope.
3.3. Experimental Set-up
3.3.1. Column Apparatus


Figure 12 Column apparatus with head control and recirculation of feedwater [26].
The test column apparatus (figure 12) consisted of an 800mm tall, 40mm
internal diameter transparent acrylic cylinder with the specimen fixed at the
base. Ceramic specimens were mounted in a frame made from acrylic tubing
(figure 13) and used an Araldite

layer between the mounting and sides of


the specimen to prevent short-circuiting around the ceramic media. Water
was delivered into the top of the cylinder by a peristaltic pump using 4mm
internal diameter Tygon

tubing which drew water from a jerry can. The


hydrostatic head was controlled by an inverted U-bend. This consisted of a
flexible 6mm Tygon

tubing to allow easy adjustment. The inverted U-bend


fed excess water back into the jerry can for recirculation by the peristaltic
pump. Filtrate which passed through the ceramic sample was first collected
in a well created from a regulating well made from a plastic flask and spigot.
Column
Ceramic
Specimen
Inverted
U-bend
Pump
To pump
Collecting
beaker
Regulating
well
Reservoir
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This allowed the flow of filtrate into the collection beaker to be controlled
when removing the beaker for analysis.

Figure 13 Mounted specimen. C1-C3, left op right respectively [26].
A peristaltic pump was used as it prevents the arsenic from coming into
contact with any internal pump parts. This prevents arsenic binding to any
metallic pump internal parts and also means the pump does not require
cleaning after using arsenic.
3.3.2. Preparation of Arsenic Spiked Water
Sodium arsenate dibasic heptahydrate (Na
2
HAsO
4
7H
2
O) was purchased
from Sigma-Aldrich

. The chemical was of ACS reagent grade and >98%


purity. An influent quality of 300g/l of inorganic arsenic was chosen as it
was found in 1998 by the BGS that less than 10% of wells investigated in
Bangladesh had arsenic levels exceeding 300g/l [3]. The arsenic laced
water was prepared by weighing 6.3mg3 under a fume hood. This was then
added to a container containing 5 litres of deionised water. Full dosing
calculations can be seen in the appendix II.
3.4. Analysis
3.4.1. Hydraulic Conductivity
Hydraulic conductivity is a measure of the conductivity or resistivity of a
porous media to water flowing through it. It is expressed in units of speed.
The hydraulic conductivity is determined by the physical structure of the
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media such as pore size, distribution and total pore volume as well as the
effective diameter and tortuosity of pore channels. In this investigation,
hydraulic conductivity is calculated using Darcys law. Darcys law is used in
filtration theory and groundwater studies and is shown in equation (9).
l
h
kA Q
A
=
(9)

The hydraulic conductivity of the specimen was obtained by:
- Measuring the cross sectional area of the filter media
- Measuring the hydrostatic head of water above the filter media
- Measuring the volume of filtrate collected over a period of time
Experimental results are substituted into darcys law, rearranged for
hydraulic conductivity as shown in equation (10).
h A
Ql
k
A
=
(10)
3.4.2. Empty Bed Contact time
The Empty bed contact time (EBCT) is calculated as the time required for a
fluid to pass through a volume of sorptive media. For this study it indicates
the time that water is in contact with the ceramic media. The calculation for
EBCT is shown in equation (11).

Q
V
EBCT = (11)
3.4.3. Arsenic Removal
To investigate the removal capability of goethite amended ceramic, and the
contact time required for maximum removal, arsenic removal was tested at
different flow rates by altering the hydrostatic head above the filter media. As
shown in Darcys law, the flow rate is directly proportional to the hydrostatic
head. The expectation was to obtain a relationship between contact time and
arsenic removal which would allow optimisation of the filter design to remove
arsenic concentration to within desired standards while maintaining a high
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enough flow rate to enable sufficient quantities of drinking water to be
produced.
Arsenic analysis was performed using a HACH field test kit for arsenic
detection. The field kit is capable of detecting arsenic to below 10ppb which
made it a suitable method for indicating whether or not the apparatus was
successful at reducing arsenic to within the WHO recommended limit. The kit
works by oxidising hydrogen sulphide to sulphate which prevents
interference, the oxidising conditions are then neutralised. Salfamic acid and
powdered zinc produce reducing conditions which convert the inorganic acid
into arsine gas. The arsine gas is directed through the cap of the vessel and
into contact with the test strip. The test strip contains mercuric bromide which
reacts with the arsine gas to produce halogens which discolour the pad on
the test strip. Discolouration occurs from yellow to brown with increasing
concentration of arsenic in the test water. A guide to the quantity of arsenic
present is obtained from comparing the test strip with a colour chart
provided.
The methodology for using the HACH field test kit is as follows:
1. Insert the test strip under the cap holder.
2. Measure 50ml of water into the vessel.
3. Add the contents of reagent 1 (Sodium Phosphate).
4. Add the contents of reagent 2 (Ozone Monopersulfate) and swirl.
5. Wait 3 minutes.
6. Add the contents of reagent 3 (EDTA Tetrasodium Salt) and swirl.
7. Wait 2 minutes.
8. Add the contents of reagent 4 (Sulfamic Acid) and swirl
9. Add the contents of reagent 5 (Zinc) and immediately place the cap on
the beaker.
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10. Swirl and leave for 30 mins (no more than 35 mins), swirling the beaker
twice during this period.
11. Remove the test strip and compare discolouration against the colour
chart.
3.4.4. pH
The pH of both the influent and filtrate was tested with universal indicator
strips which gave a colorimetric indication of pH to within 0.5.















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4. Results and Observations
4.1. Manufacture of Ceramic Samples
4.1.1. Pressing
The first attempt at pressing samples resulted in destruction of the green
body due to a combination of excessive pressure and a high water content
which increased the plasticity of the green body to such an extend that it was
able to escape around the plungers used in the die. The methodology was
subsequently altered to use less water and apply just as little pressure as
required to obtain an adequately shaped cast from the mould. The method of
lining the mould with a plastic bag was abandoned as it hampered the filling
of corner spaces and the crinkled plastic left an uneven finish on the tablets.
4.1.2. Sintering
The sintering of the ceramic tablets was achieved without any problems.
Upon visual inspection pores appeared clean and free of soot. Both the
control and goethite amended ceramic tablets were strong enough to be
handled.
4.2. Microstructure Analysis
4.2.1. Pycnometry
Pycnometry was only carried out for C1 and C3. It was considered that
results from C1 would be representative of C2 as there was no difference in
ceramic structure between C1 and C2, and it was assumed that the
application of colloidal silver would have a negligible effect on the mass and
volume of the specimen.
Table 3 Pycnometry results.
Specimen
Dry Weight
(g)
Wet Weight
(g)
Boiled Weight
(g)
Percentage
porosity
C1 21.17343 10.5865 25.974 45%
C3 15.41695 6.38570 20.027 51%

The results in table 3 show that a 1/1 clay:burn-out ration will achieve
approximately a 50% porosity in the fired ceramic.
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4.2.2. Metallurgy
Micrographs are shown in figures 14-19 for all three specimen types at 50x
and 500x. Images are also shown of needle-like formations which were
recorded in the large pore volumes in figures 12a, b & c.

Figure 14 Specimen C1 at 50x magnification.
Solid 2
nd

phase particle
Metallic particles
Pore volume
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Figure 15 Specimen C2 at 50x magnification

Figure 16 Specimen C3 at 50x magnification
Metallic particles,
Possibly colloidal silver
Possibly hematite
particles
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It appears that the samples are consecutively brighter, possibly due to
colloidal silver in figure 15 and the addition of hematite in figure 16. The
contradiction to this observation is that metallic particles should be a bright
white, and the speckles are more of a grey colour, suggesting 2
nd
phase non-
metallic particulates.


Figure 17 Specimen C1 at 500x magnification.
Large pore
Interconnected
pores
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Figure 18 Specimen C2 at 500x magnification.

Figure 19 Specimen C3 at 500x magnification.
Possibly colloidal silver
Possibly Hematite
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As can be seen in figures 16-18, specimen C3 has more pores >10m than
C1, however as C2 is also similar no direct conclusion can be drawn as to
whether this is the effect of the goethite. The large white particle in figure 19
may be hematite as no such size of metallic or silica particles were observed
in figures 17 and 18. Further analysis would be required to determine the
nature of the particle. It was also observed that despite colloidal silver being
applied to C2 there did not appear to be any substantial visible difference at
the 500x level.

Figures 20a, b & c Specimens C1-C3 at 500x magnification, left to right respectively.
Crystalline structures were clearly visible in pores of all samples at the 50x
and 500x levels. It was originally hypothesised that this may be resin due to
inadequate suction during vacuum impregnation. However, another
hypothesis is that it is sap or another hydrocarbon left from the burnout
material. This may further explain the anomaly with the hydraulic
conductivity. The matter is discussed in full in section 5.2.
Ultimately microscopic analysis only gives part of the picture as to the
microstructure. Further methods of obtaining chemical and statistical
information is discussed in section 5.2.
4.3. Experimental Set-up
4.3.1. Apparatus
On preliminary testing of the apparatus it was found that the 6mm tygon


tubing was too thin to be used for the inverted U bend. The viscosity of water
in such a small diameter tube meant that it was not possible for partial flow at
the top of the U bend and once the U bend began draining excess water, a
siphon effect was created which drained the entire cylinder.
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Figure 21 Finalised experimental set-up [26].
The obvious solution was to use larger diameter tubing, however large
diameter, flexible, transparent tubing was only available to order in bulk at
considerable expense. Instead, a reservoir was fabricated using a
translucent plastic bottle and discarded length of opaque garden hose pipe.
In practice this method did not work well under the fume hood as it was
difficult to maintain a constant downward gradient in the 100cm of hosepipe
when coiled at low hydrostatic head heights. The final solution was to attach
a copper valve to the 6mm Tygon

tubing (figure 21). As the valve was


metallic and may influence arsenic levels in the apparatus the water was not
re-circulated and was fed straight to a drain in the fume hood.
4.3.2. Influent Arsenic Analysis
It was found when testing the prepared 300ppb arsenic water that the test
strip gave a paler stain than the colour chart. The gloss coated colour chart
also made comparison with the stick difficult. To solve this issue tests were
performed on standard solutions of 30, 150 and 300ppb. The results are
shown in figure 22.
Reservoir
Column
Ceramic
Specimen
Tap
Pump
Funnel
Collecting
beaker
Iron oxide amended ceramic water purifiers for point-of-use arsenic removal from drinking water

Sean Rivers 39

Figure 22 Results of HACH arsenic testing on prepared standard solutions [26].
4.4. Analysis
4.4.1. Hydraulic conductivity
Hydraulic conductivity experiments were originally planned to be carried out
during the arsenic removal experiments to be more efficient than running two
separate tests. However, in preliminary tests using deionised water to test
the integrity of the system, it was found for the first control that the rate of
flow through the sample was significantly less than anticipated, and the small
amount of filtrate collecting in the beaker was evaporating during collection in
the hot laboratory conditions. Under considerable time constraints the
decision was made to cancel the control arsenic experiment and at least
attempt to measure the hydraulic conductivity of the sample at a high head
this would provide more filtrate and decrease errors caused by evaporation
before moving on to the arsenic removal testing of the goethite sample. Due
to further complications which were unable to be resolved in time, no flow
rate results were gathered for the goethite sample. The results of the
hydraulic conductivity test for the control sample are given in table 4.
Table 4 Measured hydraulic conductivity parameters.
Specimen h
(cm)
V
(cm
3
)
T
(mins)
Q
(cm
3
/hr)
L
(cm)
A
(cm
2
)
K
(cm/hr)
C1 70 3.53 62 3.416 1.2 11.9 0.00491
Iron oxide amended ceramic water purifiers for point-of-use arsenic removal from drinking water

Sean Rivers 40
The hydraulic conductivity of 0.004 cm/h is approximately 40 times lower
than expected for the ceramic with 50/50 burnout/clay ratio. Results from
similar studies on filtrn hydraulic conductivities are shown in table 5.
Table 5 Comparison of hydraulic conductivity (K) values from various filtrn
studies. Units in m/hr.
Rivers Lee [48] Eriksen [49] Lantagne [49] Fahlin [49]
0.00004 0.0016265 0.03 0.004 0.001-0.003
4.4.2. Empty Bed Contact Time
It was only possible to calculate the EBCT for specimen C1 at a head of
70cm. Results are shown in table 6.
Table 6 Empty bed contact times depending on specimen type and hydrostatic
head.
Specimen h
(cm)
Pore Volume, V
(cm
3
)
Flow rate, Q
(cm
3
/h)
EBCT
(hours)
C1 70cm 4.7641185 3.416 1.39
4.4.3. Arsenic Removal
Due to the low flow rate experienced with C1 it was not feasible to carry out
experiments for C1 and C2. In the experiment with C3, sealing problems in
the apparatus caused influent water to leak into the collecting beaker,
contaminating any result. This problem was not overcome, resulting in no
results of any specimen for arsenic removal.
4.4.4. pH
Only the influent water was tested flowing the low flow rates experienced.
The influent water was found to have a pH of 5. This result is good for
arsenic sorption of As(V). pH correction would be required to obtain a neutral
water pH.




Iron oxide amended ceramic water purifiers for point-of-use arsenic removal from drinking water

Sean Rivers 41
5. Discussion
5.1. Manufacturing and Processing
The clay/goethite ratio suggested by Brown and Sobsey was successful in
producing a suitably strong ceramic for the purposed of this testing. During
cutting with the diamond saw it was noted that cutting fluid (water) caused a
brown residue to be left on anything the ceramic touched while wet. This lack
of integrity in water was a concern. It would be critical to resolve this issue on
application in the field.
During the field research in Sri Lanka, it was noted that coconut oil was used
as a lubricant for extracting the green bodies from the mould. This method is
more environmentally sustainable than the use of plastic bags as is common
practice at present. Currently RDIC do not recommend the use of any oils for
this purpose so this finding may perhaps have a positive impact on the waste
produced during the manufacturing process.
5.2. Microstructure Analysis and Hydraulic Conductivity
The results gained for the microstructure analysis of all specimen types is the
cause of some confusion. As expected, all samples were found to have a
total porosity in the region of 50%10 with the iron oxide amended ceramic
containing a higher total porosity. However, the results gained from the
hydraulic conductivity in which the conductivity was found to be
approximately 40x lower than expected appeared to contradict the findings
of the pycnometry.
As hydraulic conductivity was only calculated for C1 which had a total
porosity of 43%, it is possible that this result is not out of the ordinary. In
practice, burnout/clay ratios can be up to 60/40 rather than 50/50. Lee
showed that a small difference in total pore volume has an exponential effect
on the hydraulic conductivity [48]. It is also possible that by not screening
sawdust particles between two mesh sizes that very fine particles contributed
to the total porosity but resulted in vey small channels for water to flow
though, thus leading to the extra resistance observed.
Iron oxide amended ceramic water purifiers for point-of-use arsenic removal from drinking water

Sean Rivers 42
Another perhaps stronger hypothesis is that the needle structures observed
in the clay micrographs were not resin, but were the result of tree sap or
similar hydrocarbons present in the burn-out material which did not vaporise
and vacate the ceramic completely during the firing process. This theory
could explain why when exposed to boiling water during pycnometry, pores
could be occupied. It is possible that as the sap melted or became more
pliable with heat during the pycnometry it was possible for water to enter the
pores, however under cold conditions such as in the column tests, the sap
would solidify, preventing water from easily penetrating the pore spaces.
For this hypothesis to be investigated it would be necessary to place an
amount of the burnout material in a furnace while running the protocol shown
in figure 11. If residue was found to be left then the hypothesis is likely true. If
there is no residue left after firing it does not necessarily disprove the theory
as gases could be trapped in the pored and re-crystallise upon cooling.
In determining the composition of hydrocarbons present in the sawdust it
would be possible to use a thermal gravimetric analyser (TGA) to measure
the weight loss of the sawdust over a burn cycle. This can be compared to
data from a differential thermal analyser (DTA) which measures the energy
consumption or emission as a function of temperature. Together the two
profiles can be used to form an idea of the types of hydrocarbons present in
the sawdust. It would also be possible to run multiple TGA tests in
succession and observe whether a decrease in mass is recorded. If all the
burnout material is vaporised during initial sintering then no subsequent
change in mass would be expected by re-firing the sample.
Other methods to ascertain the nature of the structures (including second
phase particles) observed in the micrographs would be to use scanning
electron microscopy (SEM). Energy dispersive x-ray spectroscopy (SEM-
EDX) is a method which can be used to determine the elemental composition
of a compound, however this method is not suited to detecting low numbered
elements such as oxygen and hydrogen, which comprise hydrocarbons.
Although SEM-EDX can give a count of elements in an area, it does not
provide information on how the elements are arranged in compounds.
Iron oxide amended ceramic water purifiers for point-of-use arsenic removal from drinking water

Sean Rivers 43
Electron backscattered diffraction and x-ray diffraction (EBSD-XRD) is able
to provide crystallographic information on the phase of compounds.
5.3. Empty Bed Contact Time
If the hypothesis regarding the sap is correct then the EBCT would have to
be adjusted for the occlusion of pore volumes which would cause a smaller
empty bed volume and thus a shorter EBCT.
An estimation of possible EBCTs and flow rates required for an arsenic
removing filtrn is calculated below.
As filter hydraulics throughout the depth of the filter are complex [49], this
example calculation will just deal the bottom surface of the filter as it will
experience the highest hydrostatic head and thus the shortest ECBT time of
any part of the filter. This means if the required EBCT is satisfied for the filter
base, then it will be satisfied for all the filter.
Singh reported a contact time of half an hour required for maximum arsenic
removal [6]. As the body is only one seventh hematite then the following
calculation will be carried out for both EBCTs of 0.5 hours and 3.5 hours for
an arsenic removing filtrn.
As the flow rate is directly related to the EBCT, the EBCT is first calculated
for a real filtrn. By knowing the flow rate for a real filtrn (1.5-2l/hr), the flow
rate of an arsenic removing filtrn can be simply calculated by the fractions
of one EBCT over another.
The flow rate for a real filtrn specimen is calculated using the hydraulic
conductivity of 0.001m/hr from table 5 in section 4.4.1, and a filter thickness
of 12mm.
l
h
kA Q
A
=
(9)
hr cm
l
h
kA Q / 8 . 23
2 . 1
20
9 . 11 1 . 0
3
= =
A
=
Iron oxide amended ceramic water purifiers for point-of-use arsenic removal from drinking water

Sean Rivers 44
As EBCT results in section 4.4.2 were considered inaccurate the estimated
EBCT for a real filtrn of 12mm thickness is calculated. The pore volume is
taken from pycnometry measurements in table 6.
Q
V
EBCT =
(11)
min 12 2 . 0
8 . 23
76 . 4
= = = = hrs
Q
V
EBCT
The resulting flow rate for an arsenic removing filtrn can be calculated as a
fraction of equation (11) for each case.
2
1
1
2
2
1
V
V
EBCT
EBCT
Q
Q
=
(12)

where subscript 1 indicates the arsenic removing filtrn and subscript 2
represents the real filtrn. As the arsenic removing filtrn requires a longer
EBCT it can be assumed that V
1
/V
2
<1. Therefore equation (11) becomes
equation (12).
2
1
2
1
Q
EBCT
EBCT
Q <
(12)

So for an arsenic removing filtrn with a 30min contact time,
h l Q / 6 . 0 5 . 1
30
12
< <
For a 3.5hr contact time,
h l Q / 086 . 0 5 . 1
60 5 . 3
12
<

<
In summary, flow rates are seen to diminish by at least 60-94% to obtain
arsenic free water by using a filtrn with a 30min contact time for hematite
and depending on hematite coverage within pore surfaces.
Iron oxide amended ceramic water purifiers for point-of-use arsenic removal from drinking water

Sean Rivers 45
The flow rate could be improved by either using a different sorptive media
requiring a shorter contact time, or allowing a trade of between quality and
quantity of water.
5.4. Arsenic Removal by iron hydroxide amended ceramic
Though this investigation did not provide conclusive results on the ability of
goethite amended ceramic to lower arsenic concentrations it is still of value
to discuss the options possible in the technology. Iron has a chemical affinity
for binding with arsenic and there are many iron hydroxides such as goethite,
hematite, jarosite and lepidocrocite which have been shown to effectively
bind with arsenic. Goethite is generally better at arsenic removal in terms of
capacity and contact time although problems lie in sintering without
converting goethite to hematite. It could be worth looking at ways of sintering
goethite in such a way to prevent a chemical change to hematite. Though it
could be possible to try and achieve this by sintering in a reducing
environment with an argon or nitrogen blanket, this would be difficult to
replicate in a development context.
The question of leaching is of great concern. The very reason for the
groundwater poisoning of Bangladesh is due to the release of arsenic from
ferric compounds under reducing conditions coupled with the presence of
microorganisms. It would be all too easy for filtrns to be improperly cleaned,
or kept under anoxic conditions by being constantly refilled and not aerated,
thus possibly causing dangerous levels of arsenic to be released into
drinking water which people believe to be safe. Leaching can also cause
damage to the environment upon disposal.
The use of oxidising agent and flocculants would have to be either prevented
in the use of an arsenic treating filtrn or perhaps a layer of material (if the
mesh was fine enough) could be used as a barrier to prevent agglomerates
clogging the surface pores. Furthermore, following any laboratory testing
which may prove the viability of arsenic treating filtrns, a small field study
would be necessary to determine whether the technology really is
appropriate outside of controlled laboratory conditions and whether
Iron oxide amended ceramic water purifiers for point-of-use arsenic removal from drinking water

Sean Rivers 46
beneficiaries are able (and willing) to use and maintain the technology to
ensure its effectiveness.
5.5. Arsenic Detection Method
Although the HACH method was used in this investigation it was not the
preferred method. Inductively Coupled Plasma Optical Emission
Spectroscopy (ICP-OES) or ICP-Mass Spectroscopy (ICP-MS) would have
provided a much more accurate result. The draw back with these methods
compared to the HACH field kit is the expensive equipment required,
stringent sample preparation controls and expertise required to operate the
equipment. It was attempted to use Flameless Atomic Adsorption
Spectroscopy (FAAS) but the detection limit of the equipment was found to
be in the ppb scale meaning the concentrations of arsenic used in this
investigation could not be detected. For detection of arsenic to ppb scale a
carbon tube based FAAS is required which was not available at the time.
6. Conclusions
Though not directly related to arsenic removal, it was found during the field
research that coconut oil can be used as a substitute for plastic bags in the
manufacturing process, providing a more environmentally sustainable to the
problem of removing pressed filters from moulds.
It was confirmed that the addition of goethite into the ceramic at a while
maintaining the volume ratio of burnout to clay+additives led to a greater
porosity than ceramic without goethite. A 1/6 ratio of goethite/clay resulted in
the ceramic porosity to be increased from 45% to 51%.
Microscopic analysis showed the presence of a crystalline formation in the
pore structures, although it is not known what the material is or whether it is
representative of other filters.

Iron oxide amended ceramic water purifiers for point-of-use arsenic removal from drinking water

Sean Rivers 47
7. Future Work
There were areas where this study was not able obtain results on what may
potentially be an appropriate technology for arsenic removal from drinking
water. As such the author recommends the following future work.
- An investigation into the efficacy of arsenic removal by goethite
amended ceramic for As(III) and As(V) at various influent
concentrations and for various contact times.

- To obtain Freundlich and Langmuir adsorption isotherm adsorption
expressions for goethite amended ceramic.

- To determine the maximum adsorption capacity of goethite amended
ceramic.

- To perform a toxic characteristic leaching protocol (TCLP) for goethite
amended ceramic containing adsorbed arsenic (preferably after
capacity breakthrough).

- Investigation into the effect of oxic and anoxic operating conditions on
the sorption and leaching characteristics of goethite amended
ceramic.

- Methods of preserving goethite during the sintering process.

- The use of iron oxides other than hematite in filtrn production.

Iron oxide amended ceramic water purifiers for point-of-use arsenic removal from drinking water

Sean Rivers 48
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Iron oxide amended ceramic water purifiers for point-of-use arsenic removal from drinking water

Sean Rivers 53

Appendices
Appendix I - Specimen Batch Information

Table A - C1 and C2
Specimen
Number
1 2 3
Clay Weight (g) 30 32 34
Thickness (mm) 11.7-12.66 12.16-12.6 13.34-13.94
Diameter (mm) 38.74 39.24 38.8
Dried Weight (g) 22 23 24

Table B - Goethite amended ceramic specimen
Specimen
Number
1 2 3
Clay Weight (g) 25 27 29
Thickness (mm) ~10 ~11 ~13
Diameter (mm) 18 19 21
Dried Weight (g) 22 23 24









Iron oxide amended ceramic water purifiers for point-of-use arsenic removal from drinking water
Sean Rivers 54
Appendix II - Arsenic dosing
Atomic Masses for Sodium Arsenate di-basic Heptahydrate
(Na
2
HAsO
4
7H
2
O)
Table C - Mass calculation for Sodium Arsenate di-basic Heptahydrate
Element Atomic
Mass
Number
of atoms
Total
Mass
Hydrogen
(H)
1 15 15
Oxygen
(O)
16 11 176
Sodium
(Na)
23 2 46
Arsenic
(As)
75 1 75
TOTAL 313
Proportion of mass which is As: 75/313 = 0.239
For a 5l 300ppb As solution is: 0.3mg x 5 = 1.5mg of As
So, the total amount of Sodium Arsenate di-basic Heptahydrate required for
5l of 300ppb As solution is: 1.5/.239 = 6.28mg.

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