Design and Development of an Onsite

Photoresistive Sensor for Detection of Arsenic

in Water

A Master’s Thesis Project Report

Submitted in Partial Fulfillment of the Requirements
for the Degree of

Master of Technology
by

CHANDARANA TARANG J.
Roll No.174107019

Under the Guidance of

Prof. Tapas Kumar Mandal

Department of Chemical Engineering

Indian Institute of Technology Guwahati
Guwahati, 781039
June 2019
 INDIAN INSTITUTE OF TECHNOLOGY GUWAHATI

DEPARTMENT OF CHEMICAL ENGINEERING

GUWAHATI, 781039, ASSAM, INDIA

Date: 22/06/2019

Certificate

It is certified that the work presented in this thesis entitled "Design and
Development of an Onsite Photoresistive Sensor for Detection of Arsenic in
Water", is a bonafide work of Mr. Tarang Chandarana (Roll No. 174107019),
has been carried out in the Department of Chemical Engineering, Indian Institute
of Technology Guwahati, under my supervision and this work has not been
submitted elsewhere for any other degree.

Prof. Tapas Kumar Mandal

Department of Chemical Engineering
Indian Institute of Technology Guwahati

i
 Acknowledgement

I wish to express my sincere gratitude to my MTP supervisor, Prof. Tapas

Kumar Mandal, Department of Chemical Engineering, Indian Institute of

Technology Guwahati, Guwahati. He has been a constant source of well needed

guidance, suggestive discussions and helpful advice.

I would like to acknowledge the support of my seniors, Mr. Rajshekhar

Ravula and Mr.Nilanjan Mandal.

Tarang Chandarana
(174107019)

ii
 Abstract

The purpose of this work is to make a portable electronic sensor to detect

arsenic contamination in ground water. By analyzing available literatures,
molybdenum blue method has been chosen for the present study. The method is
based on the reaction of As(V) with Mo(VI) under oxidizing and acidic condition.
To make solutions acidic HCl and H2SO4 are used. Acid concentration is optimized
by considering the rate of colour development and stability of the resulting
arsenomolybdate complex. Formed arsenomolybdate complex has been reduced by
ascorbic acid. Prepared sample has been tested in UV-visible spectrophotometer.
The portable photometric resistance meter has been made with the use of LED,
arduino board and photometer resistance. The resistance given by sensor was
increased with increase in concentration. The sensor is sensitive even for 8 µg/L
concentration of arsenic in solution which is lower than the maximum concentration
limit (10 µg/L) defined by WHO.

iii
Table of Contents
Certificate ............................................................................................................................................... i
Acknowledgement ................................................................................................................................. ii
Abstract ................................................................................................................................................ iii
List of Figures ........................................................................................................................................ v
List of Tables ......................................................................................................................................... v
1. Introduction ....................................................................................................................................... 1
1.1 World Wide Presence of Arsenic .................................................................................................... 1
1.2 Background of the motivation ........................................................................................................ 3
2. Literature Review .............................................................................................................................. 5
2.1 Current Status of Arsenic Detection Technology............................................................................. 5
2.1.1 Laboratory Techniques ............................................................................................................ 5
2.1.2 Field Arsenic Test Kits ............................................................................................................ 6
2.2 Chemistry of Gutzeit’s Method and Molybdenum Blue Method ................................................... 14
2.2.1 Gutzeit’s Method .................................................................................................................. 14
2.2.2 Molybdenum Blue Method .................................................................................................... 15
2.3 Knowledge Gap............................................................................................................................ 16
2.4 Objective ..................................................................................................................................... 16
3. Experimental Procedure.................................................................................................................. 17
3.1 Preparation of Reagents .............................................................................................................. 17
3.2 Reagents Mixing Order ................................................................................................................ 17
3.3 Development of portable photometric resistance meter .............................................................. 19
4. Results and Discussion..................................................................................................................... 21
4.1 Results by Spectrometric Analysis ................................................................................................ 21
4.2 Results of Spectrometric Analysis for Optimization of Acid Concentration .................................... 22
4.3 Results Obtained by Portable Photometric Resistance Meter ....................................................... 25
4.4 Calibration Curve ......................................................................................................................... 27
Conclusions and Future Aspects ......................................................................................................... 30
Appendix I ........................................................................................................................................... 32
Appendix II .......................................................................................................................................... 34
Appendix III ........................................................................................................................................ 35
References ............................................................................................................................................ 36

iv
 List of Figures

Figure 1: Issue of arsenic contamination across the world ...................................... 1

Figure 2: Diseases Caused by Arsenicosis ............................................................. 2
Figure 3: Toxicity of different compounds of arsenic ............................................. 3
Figure 4: Color Chart ............................................................................................14
Figure 5: Reagents Order of Mixing .....................................................................18
Figure 6: Portable Photometric Resistance meter ..................................................19
Figure 7: Voltage Divider Circuit .........................................................................20
Figure 8: Effect of concentration on absorbance intensity .....................................21
Figure 9: Comparison of absorbance at different time intervals for different
concentrations of acid ...........................................................................................23
Figure 10: Comparison of maximum absorbance wavelength at different time
intervals for different concentrations of acid .........................................................24
Figure 11: Comparison of multimeter and resistance meter readings for 50 ppb
arsenic concentration sample ................................................................................25
Figure 12: Comparison of the results obtained by multimeter and resistance meter
using 3 kΩ and 5 kΩ resistance for 10 ppb arsenic concentration sample .............26
Figure 13: Resistance vs Time Curve for 8 ppb Arsenic Concentration ................26
Figure 14: Absorbance vs Time curve for 10 ppb samples ....................................34
Figure 15: Absorbance vs Time curve for 50 ppb samples ....................................34

List of Tables

Table 1: Comparison Between AAS,ICP-MS and AFS .......................................... 5

Table 2: Portable Arsenic Test Kits Based on the Gutzeit Reacton ........................ 7
Table 3: Logarithmic Regression Results ..............................................................27
Table 4: Polynomial Regression Results ...............................................................28
Table 5: Linear Regression Results ........................ Error! Bookmark not defined.

v
 1. Introduction

1.1 World Wide Presence of Arsenic

Contamination of arsenic affects regions in all over the world. Countries
affected by arsenic contamination are Bangladesh, China, India, Mexico,
Myanmar, Nepal, Pakistan, Vietnam, and parts of the USA (Figure 1) [1-2].
Arsenic is mainly more severe in tube wells of Bangladesh and India, a large no.
of research studies and field surveys are based on to detect arsenic contamination
in these areas and reduce it to a lower limit.

Figure 1: Issue of arsenic contamination across the world [2]

1
 As per the studies around 32-79 million Bangladesh’s people, or 29-63%
of the nation’s population, can be affect by arsenic exposure [3]. The arsenic
contamination in Bangladesh is described as “the largest mass poisoning of a
population in history” [3-4]. A research studies show that around 12,000
Bangladesh’s people in last 10 years, from 2000-2009, showed that nearly 15-
25% of all deaths in the nation are based on arsenic exposure [5]. As per surveys,
it is said that in few areas of Bangladesh contamination of arsenic is around 2,500
µg/L. The exposure of this high amount is based on natural high percent
composition of the element is because of ground deposits [1, 6-7]. As leaching of
arsenic is a continuous process, it is anticipated that well testing must also be
carried out in a continuous manner.

Figure 2: Diseases Caused by Arsenicosis [7]

Poisoning of arsenic is due to the large constant exposure to high levels of

arsenic is known as arsenicosis. Symptoms of this condition include diseases of
blood vessels in the legs, skin lesions and hard patches on the soles of feet and
palms of hands, skin and internal organ cancers, diabetes, high blood pressure,
and reproductive disorders [7-11]. Arsenicosis severity is mostly dependent on
the dose and number of years of exposure to arsenic [5, 10-15]. The World Health
Organization (WHO) defined the maximum contamination limit (MCL) of
arsenic in drinking water, in 1993, is 10 µg/L [12]. This limit was decided based
on the projected health effects of lifetime exposure to arsenic [3]. There are
different arsenic compounds. Toxicity of all the compounds of arsenic is not

2
same. It is shown in following Figure 2.

Figure 3: Toxicity of different compounds of arsenic [16]

In this study the As(III) and As(V) arsenic species to be of greatest interest
for primary analyte detection because they are the most common forms of arsenic
in water, and pose high toxicity to humans (Figure 3) [16].

1.2 Background of the motivation

It was found that 6-11 million tube-wells in Bangladesh need to be tested for
arsenic detection [17]. The current arsenic contamination in drinking water of
Bangladesh is around 50 µg/L [1, 18]. Due to the social and economic conditions
of Bangladesh, it is not possible to closely follow the provisional WHO standard
of 10 µg/L. India and Bangladesh are now using the system of painting the well
to indicate its arsenic levels. Since, for arsenic, the primary mode of entry into the
body is through ingestion and inhalation rather than absorption; ‘unsafe’ wells can
still be used for non-consumption purposes such as washing clothes [7].

Generated laboratory techniques like atomic absorption spectroscopy

(AAS), and atomic fluorescence spectroscopy (AFS), inductively coupled plasma
mass spectrometry (ICP MS), can easily measure arsenic levels below 10 µg/L
[19-22]. These high sensitive techniques are expensive, bulky and require highly
trained technicians for their operation and maintenance. As an additional
disadvantage, these detection techniques also involve labeling and shipping of
samples to facilities. Nations like Bangladesh do not have the facilities to perform
these techniques reliably and with high throughput.

3
 Because of these issues, the United Nations International Children's
Emergency Fund (UNICEF), the WHO and other organizations use portable test
kits for arsenic detection. Around more than one million tube-wells in Bangladesh
and India were tested and labelled by portable arsenic test kits [23]. Most of the
kits in market are based on the Gutzeit’s reaction, known since the 1900s.in this
test colorimetric analysis is based on the reaction of arsine gas with mercuric
bromide embedded on a paper strip. These both reactants are hazardous and toxic
to the user. General studies gave the results of high rate of false negative and false
positive and are not reliable for the detection of arsenic contamination under 70
µg/L [18, 23-24]. Due to this, many people continue to drink contaminated waters
from ‘clean’ sources. In addition to this, many people in these regions are still
waiting for testing of their water resources that it is drinkable or not [25].

It was supposed that around 1% of people, who drink water in excess of 50

µg/L of arsenic, would die mostly due to an arsenic-related cancer [7]. The
development of an arsenic sensor with the sensitivity same as in the laboratory
method is not a cost effective till date. So concerned authority is facing a lot of
difficulties to provide the minimum service of health care for the community.
Many groups are working on the advancement of alternate analytical methods for
arsenic detection. However, a comprehensive solution is yet to be developed. To
address this serious issue of the nations, we tried to make a new portable arsenic
sensor, which is highly sensitive, quick and reliable, transferrable, health and
environmental risk free and ease of use to a local expert [26-28].

4
 2. Literature Review

2.1 Current Status of Arsenic Detection Technology

2.1.1 Laboratory Techniques

Table 1 shows the comparison between laboratory techniques. Based on

that we can say these techniques are more sensitive, accurate and use lower
sample sizes. But these techniques cannot be useful for onsite detection. The cost
of detection is also a very high so it cannot be possible to use these techniques in
developing nations like Bangladesh. Furthermore, these techniques need trained
personnel.

Table 1: Comparison Between AAS, ICP-MS and AFS

AAS ICP-MS AFS

LOD (µg/L) 0.0008 - 1 0.0004 – 1 0.0004 – 10

Sample Size (µL) >1,000 5 – 250 25 –220

Time Required ~ 35 minutes ~ 25-30 ~8-13

seconds minutes

Cost (USD) ~ $50,000 ~ $180,000 ~ $55,000

Easy to use for a Difficult initial Easy to use

Skill Requirement trained method for a trained
technician development technician
even for a
trained
technician

References [20-23] [20-23] [20-23]

5
2.1.2 Field Arsenic Test Kits

Table 2 shows the comparison between different tests kits that are used as
field detection kits. Tests kits like NIPSOM, merck and GPL are not useful for
lower detection limits where, Quick As and Hach EZ are quietly favorable
because of their lower detection limit. But any of the test kits not satisfies the
LOD defined by WHO.

Advantages of these test kits are that these kits are portable, lower in cost
and they can be used by local technicians. But drawbacks are like that are not
useful to measure lower detection limit (10 µg/L) that is defined by WHO, human
eye is not sensitive to yellow colour, evolved yellow colour fades with time,
mercuric halide strips are sensitive to hydrogen sulphide.Another measure
drawback is that these kits are work based on gutzeit reaction because of that
arsine gas is generated which is more toxic and hazardous.

6
 Table 2: Portable Arsenic Test Kits Based on the Gutzeit Reacton

Portable Arsenic Test Kits Based on the Gutzeit Reaction

AAIH
NIPSOM Merck GPL AAN Quick As Hach EZ Arsenator
&PH

Theoretical
10 10 10 50 10 5 10 0.5 – 2
LOD (µg/L)
Practical LOD
> 20 > 50 > 50 > 20
(µg/L)
It can be
Not reliable Can detect correct 80-
Can detect
< 70 µg/L. solutions 90%of the
solutions
Results with more time
Not reliable Not reliable Not reliable Not reliable with more
Reliability are not arsenic Not much
< 70 µg/L. < 70 µg/L. < 70 µg/L. < 70 µg/L. arsenic than
matched than 15 reliable at
15 µg/L
with lab µg/L higher
.
results concentrati
ons

Cost per sample $ 2.5 $2 –2.5 $0.45, $0.40 $1.00 – $1.00 – $5.00-10
$0.5-1
(USD) 2.00 2.00

Time per sample

6-7 25-35 25 25-35 25 - 45 15-25
(min)
Colour Colour Colour Colour Colour Colour Colour
sensitivity sensitivity sensitivity sensitivity sensitivity sensitivity sensitivity Ability to
Skills required to yellow; to yellow; to yellow; to yellow; to yellow; to yellow; to yellow; make
by technician Quick Quick Quick Quick Quick Quick Quick accurate
workabl workabl workabl workabl workabl workabl workabl dilutions.
e. e. e. e. e. e. e.
change change change change change change Digital
change
of of of of of of ly
Data type of color
readabl
color color color color color color
(binary)
(range) (range) (range) (range) (range) (range) e
[31-
Reference [23,29] [23,29] [23,29] [23,29] [23,29] [30] [30]
32]

7
 Okazaki et al. [34] used modified molybdenum blue spectrophotometric
method with the use of a soluble membrane filter and CaCO3-column for
determining arsenic contamination in ground water in the presence of phosphate.
They used CaCO3-column to remove phosphate by passing sample in it. Here,
AS(III) was oxidized to As(V). As(V) converted into a heteropoly acid anion.
The blue anion collected on a membrane filter as an associated with N-
dodecyltrimethylammonium ion by filtration. They dissolved the filter in 2 mL
of 2-methoxyethanol. The maximum absorbance of their sample was around at
810 nm against a reagent blank. Before the reaction in column they reduced As(V)
to As(III). The Relative Standard Deviations in measurement was around 2.9%
for 10 µg/L of As. As per their study low phosphate and iron concentration not
affected the arsenic detection.

Hu et al. [35] worked to achieve the requirement of regular field testing.

They tried to make the fast colorimetric method with a wide dynamic detection
range and high sensitivity. They used the KMnO4 and C𝐻4 𝑁2 𝑆 for oxidation of
As(III) and for reduction of As(V) respectively. The LOD of their method is
around 8 μg/L with a linear range (R2 = 0.998) of four orders of magnitude in
total arsenic concentration. They determined the contamination of arsenic in
groundwater samples and results are near to the HPLC and AFS. As per their
study good recovery of total arsenic, AS(III) and AS(V) were got for groundwater
samples for a total arsenic concentration range around 100–800 μg/L. They
showed that large amount of As(III) can only be present in industrial water and
results for that samples are consistent with the HPLC and AFS results. As per
their study there is no interference of any other ions.

Das et al. [36] tried to make a colorimetric sensor for As(V) based on a
polymer hydrogel. Their technique is depend on the generation of a blue colored

8
antimonyl–arseno–molybdate complex in the presence of ammonium molybdate,
potassium antimonyl tartrate and ascorbic acid. They encapsulated all their
reagents in a polymer hydrogel made of polyvinyl alcohol, acrylamide and
glutaraldehyde. They dip coated the Plastic detector strips with this hydrogel. As
per their work Scanning electron microscopy (SEM) represented the highly
porous structure of the polymer hydrogel allowing adsorption of As(V) confirmed
by EDX, TEM and FTIR analysis. In this technique they used lower volume of
sample (10 ml). In their method the sensor strips are selective in presence of
phosphate concentration of less than 100 μg/L and iron concentration of around
3 mg/L. The paper says that the modifications in the RGB (red, green, and blue)
values of color spots on the As(V) colorimetric dipstick sensor with various
concentrations of As(V) creates a pattern. They said that the higher B (blue)
colour values showed the low concentration range of As(V) while the R (red)
values showed the higher concentrations. The strip used to measure As(III) is also
used for detection of total arsenic. As per paper Phosphate interference is
observed by a simple improvement in the procedure. When they applied this
method to natural groundwater with arsenic contamination, the results were as
good as laboratory techniques.

Dasgupta et al. [26] made the quick, ease in use and sensitive light-
emitting diode (LED)-based photometric method for the different determinations
of ppm–ppb levels of As(III) and As(V) in drinkable water in the presence of ppm
contamination of phosphate. Their detection method was based on the formation
of arsenomolybdate complex by ammonium molybdenum blue method, followed
by reduction. They injected the As(III) into the medium and it is oxidized in-line
with KBrO3 to As(V) and forms Molybdenum blue that is detected by an LED-
based sensor. As per their study if all arsenic in the sample is prereduced to
arsenite (with the use of cysteine), the system measures total arsenic. By this

9
detection limit is less than 8 gm/L As, and the linear range extends to 2.4 mg/l.
They eliminated the Potential interference from dissolved silica and Fe(III) by the
addition of NaF to the sample.

Kiso et al. [37] tried to make the technique to detect 0.01 mg/L level of
arsenic by visible determination. They made the compact column that is packed
with the polyvinylchloride particles that were coated by a quaternary ammonium
salt. They derived molybdenum blue using arsenate by improved reaction
conditions. They introduced molybdenum blue solution (20 mL) into the
detection tube by a syringe to form color band. They have used the sodium
dichloroisocyanuric acid as oxidizing agent and then measured the concentration
of arsenite. As per their study the length of the colour band in the detection tube
is directly related with the total arsenic concentration in the range of 0.01–0.1
mg/L, and the relative standard deviations in the concentration range is around
1%. As per paper’s conclusion arsenic is successfully detected at concentration
around 0.01 mg/L using this detection tube.

Carvalho et al. [38] used the spectrophotometric method, based on the

determination of the absorbance of arsenomolybdate and phosphomolybdate
together at 925 nm, and of phosphomolybdate alone after treatment with L-
cysteine and acetone at 875 nm. They mentioned that L-cysteine quickly reduces
arsenate to arsenite and the addition of acetone diminishes the reaction time for
color development to less than 15 minutes at room temperature, which makes the
method a faster alternative to the existing phosphate and arsenate molybdenum
blue methods. As per paper the detection limit for determinations of arsenate in
the presence of phosphate is 0.2 µM in the presence of arsenate and of phosphate
or arsenate alone is 0.04 µM. Their method’s Recoveries are nearly 100%. As per

10
conclusion this method can be used for analysis of total inorganic arsenic after
oxidizing As(III) to As(V) and offers a simple, rapid and inexpensive way to
distinguish inorganic arsenic species in solutions containing up to 40 µM As.

Watanabe et al. [39] used the flow injection method and the molybdenum
blue method and found the presence of arsenic in steel. With the use of a Teflon
(PTFE) filter tube concentration method, they precipitated arsenic with beryllium
hydroxide. After that the precipitate reacted with ammonium molybdate solution
and arsenomolybdate complex was generated. The arsenomolybdate complex
was reduced with ascorbic acid. The generated molybdenum blue complex was
determined by UV-visible spectrophotometric method at 840 nm. The LOD of
arsenic was around 0.7 μg/L.

Matsunaga et al. [40] detected arsenic based on a molybdenum-loaded

chelating resin. The generation of colour is proportional to the amount of arsenic
present when it passed through the resin. They determined that color development
took time around 20 min at 40 °C. Their detection range was 75 μg/L at shorter
time span and 7.5 μg/L at longer time range.

Based on the knowledge that intensity of the blue colour generation is

because of the reaction of groundwater with the molybdenum blue complex, they
tried to do experiment with aim to observe colour changes on clearly viewable
media such as a resin. To get a constant absorbance of molybdenum by a resin,
they found that the solution required more time for stirring. Moreover, they found
that even after long time (around three hours) of stirring, arsenic was not easily
bound to molybdenum. Their research team found that it needs more expensive
equipment and apparatus. Because of these limitations their analysis would still
need more improvement for practical use in field.

11
 Tsang et al. [41] modified the molybdenum blue method for quick and
accurate detection of arsenate and phosphate in aqueous solution at
concentrations below 10 μg/L. They used the reagents like potassium antimony
tartrate, ammonium molybdate, sulfuric acid. They modified the composition of
these reagents which are react with molybdenum solution to generate the
molybdenum blue. To determine the phosphate, As(III) and As(V) concentration
they used sodium dithionite as a reducing agent. This scheme was developed by
Johnson and Pilson. As per paper this is the first time that any research group has
used sodium dithionite for quick, complete and selective reduction of As(v). As
per their study because of these two important changes this colorimetric method
is useful to detect arsenic level up to 10 μg/L which is defined by WHO.

Lenoble et al. [42] used the colorimetric method to detect low level of
arsenic(V) in groundwater using the fact of similar properties of arsenic and
phosphate. In their research they include the testing of time influence, sunlight,
temperature and anions like sulfate and silicate on the formation of complex.
They said that optimum time of complex formation is around one hour at 15-20
°C and this time is slightly less in daylight. As per their study with decreasing
temperature the rate of formation is decreased and any of the ions are tested at a
concentration same as generally found in groundwater. The LOD their method is
20 mg/L As(V). Their simpler, quick and sensitive method for determination of
arsenic is suitable for onsite detection, mostly for groundwater that contains low
phosphate concentration. They compared the five oxidants that are regularly used
in industry. As per their research H2O2 and MnO2(s) are not good options as a
oxidation of As(III) because for complete oxidation it requires in large amount.
NaOCl and KMnO4 are good options because they allowed complete oxidation
of As(III) even with small amount of it.in case of KMnO4 very low amount is

12
required for complete oxidation than the NaOCl. In the spectrometric
determination they got the maximum absorbance at wavelength of 870 nm.

Dhar et al. [43] used the Johnson and Pilson method but increased the
concentrations of potassium iodate, ascorbic acid, and antimony potassium
tartrate. All these were used in the pretreatment or reduction of the samples and
the formation of a colored product. One of the characteristics of this technique is
that they used the phosphate as catalyst for generation of arsenomolybdate
complex. They explained the presence of phosphate in groundwater with
concentration around 3-30 μmol/L.

By analyzing literatures, it has been found that there are mainly two
methods for onsite detection of arsenic. Gutzeit’s method is based on the gas
phase route and molybdenum blue method is based on the liquid phase route.
Because of the generation of arsine gas in Gutzeit’s method it is not a good option
to select it for onsite detection.

13
 2.2 Chemistry of Gutzeit’s Method and Molybdenum Blue
Method

2.2.1 Gutzeit’s Method

This process initially converts Arsenate to Arsenite with the addition of

potassium iodide and stannous chloride. Arsenite reacts with the addition of zinc
and hydrochloric acid to produce arsine gas. The reaction of the amount of arsine
gas produced with mercuric bromide paper produces a color change relative to
the arsenic concentration in the water sample. The resulting color is compared to
a color chart of varying shades from light yellow to brown to black in increasing
arsenic concentration [16,26]. Figure 4 is an example of a semi-quantitative color
chart used in the field (1 mg/l = 1000 ppb). Depending on the test kit the method
detection limit can range from 5 to 100 ppb.

4AsCl3 + 3NaBH4 → 4AsH3 + 3NaCl + 3BCl3 (1)

Zn3As2 + 6H+ → 2AsH3 + 3Zn+2 (2)

Figure 4: Color Chart [16]

14
 2.2.2 Molybdenum Blue Method

The theory of heteropoly MoO3 groups which forms large structure was
not known until 1892. In 1892 Blomstrand said that these groups form a large
structure. He had no proof to confirm it. Researchers known about these large
structures but they were unable to explain behind it. By 1903, researchers had
found more than 750 similar kinds of compounds. In 1929 Linus Pauling defined
several rules to detect the presence of these large structures.

An emerging laboratory-based colorimetric method is being investigated

for adaptation to field use. It involves arsenic chemistry that forms a highly
colored reaction called the molybdenumblue colorimetric method [27-28].
Arsenate reacts with molybdenum oxide which forms a complex that is then
reduced to give off a blue color. The intensity is in relation to the concentration
of arsenic in the sample. The results are read using an inexpensive electronic
device by removing operator variability but increasing the need for training [29].

By the reaction of As(v) solution and ammonium molybdate solution

(𝑉𝐼) −3 (𝑉𝐼) −3
𝐴𝑠𝑀𝑜12 𝑂40 forms. This 𝐴𝑠𝑀𝑜12 𝑂40 anion has an ability to gain more
electrons because of that deeply coloured valence complex is formed. This has a
structure like keggin structure. By reduction of this keggin structure, it converts
into another form of keggin structure. The reduction is a reversible process and
structure of the anion is not changed. The intensity of the blue colour is directly
proportional to the amount of arsenic present in the solution.

𝐴𝑠𝑂4−3 + 12Mo𝑂4−2 +27𝐻 + → 𝐻3 𝐴𝑠𝑂4 (𝑀𝑜𝑂3 )12 + 12 𝐻2𝑂 (3)

(𝑉𝐼) (𝑉𝐼) (𝑉) (4)

𝐻3 𝐴𝑠𝑀𝑜12 𝑂40 + 𝑅𝑒𝑑𝑢𝑐𝑡𝑎𝑛𝑡 → [𝐻3 𝐴𝑠𝑀𝑜8 𝑀𝑜4 𝑂40 ]−3

15
 2.3 Knowledge Gap

By review of literatures, we can say that available techniques based

on the molybdenum blue method are required a long time for accurate arsenic
detection and shows arsenomolybdate complex stability for a very small time. It
is also clear that available field test kits are not reliable and are not useful for
onsite detection of arsenic up to the lower concentration limit that is defined by
WHO (10 μg/L). Research groups are trying to make a technique that is low in
cost, easy to use and can operate by local technicians.

2.4 Objective

The objective is to reduce the time required for arsenomolybdate complex

formation, increase the stability of it and develop a sensor that can be useful for
onsite detection of arsenic up to the LOD defined by WHO (10 μg/L) using
ammonium molybdenum blue method and make such that untrained personnel
can use it easily.

16
 3. Experimental Procedure

3.1 Preparation of Reagents

Arsenic solutions were prepared by serial dilution of stock solution. 1 ppm

of arsenic stock solution was prepared by dissolving 0.001 gm of sodium arsenite
in 1000 ml of deionised water. After that different concentrations (10 ppb and 50
ppb) of arsenic solutions were prepared by diluting 1 ppm of solution. For
preparing the solution of ammonium molybdate heptahydrate we have added 8.9
gm of ammonium molybdenum heptahydrate to 100 ml of water and stirred it for
some time to have uniform concentration throughout the solution. KMnO 4
reagent plays a very crucial role in the reaction. Since aresnomolybdate complex
forms only with the As(V) and not with As(III) and hence it is very important to
convert all As(III) into As(V) to find the exact concentration of arsenic in the
sample. To prepare the KMnO4 solution we have dissolved 0.8 gm of KMnO4 to
100 ml of water. The role of Ascorbic acid in the reaction is to provide H+ ion in
reaction to initiate the formation of β-Keggin from α-Keggin. The ascorbic acid
solution was made by dissolving 11.1 gm of ascorbic acid into 100 ml of water.
Different concentrations (2M, 3M, 4M, etc.) acid solutions were prepared by
diluting concentrated acid. Volumetric glassware and micropipettes were used for
small volume (500 μl, 1ml) measurements of solutions.

3.2 Reagents Mixing Order

The four fundamental reagents of our molybdenum blue method are

KMnO4, ammonium molybdate heptahydrate, HCl or H2SO4 and ascorbic acid
were mixed with an arsenic solution of different concentrations in various
combinations and observed the colour changes.

17
 Reagent 3:
Reagent 1: Reagent 2: HCl+Ammonium Reagent 4:
Arsenic solution KMNo4 molybdate Ascorbic acid
heptahydreate

Reagent 4:
Reagent 1: Reagent 2: Reagent 3: HCl Ammonium Reagent 5:
Arsenic solution KMNO4 molybdate Ascorbic acid
heptahydreate

Reagent 3:
Reagent 1: Reagent 2: Ammonium Reagent 4:
Reagent 4: HCl
Arsenic solution KMNO4 molybdate Ascorbic acid
heptahydreate

Figure 5: Reagents Order of Mixing

The aim of this experiment is to determine the best way to mix the four
reagents with the arsenic solution. Through compatibility testing, it becomes
evident that this was an inappropriate choice as KMnO4 and HCl or H2SO4 cannot
be pre-mixed with one another. The results obtained by this experiment shows
that why experiments with these reagents grouped together did not produce the
expected reaction results.

18
 3.3 Development of portable photometric resistance meter

 Required Materials

a) Arduino board
b) Bread board
c) LED (Light source)
d) Resistance
e) Multimeter
f) LCD display
g) 3 D printed box

For making a photo resistance meter Arduino board was fitted in a 3-D
printed box. We have connected this Arduino board with light a source. Photo
resistor was connected with the multimeter. A photoresistor is a resistor that
works based on the intensity of light incident on it. The resistance of a
photoresistor decreases with increasing incident light intensity. It is because of
photoconductivity. A photoresistor can be applied in light-sensitive detector
circuits and light-activated and dark-activated switching circuits.

Figure 6: Portable Photometric Resistance meter

19
 Figure 7: Voltage Divider Circuit

R unknnown
Vout = Vin *
R unknnown + R known

Vout V
R unknnown = * R known + out * R unknnown
Vin Vin

Vout
* R known
Vin
R unknnown = V
(1 - out )
Vin

To calculate the unknown resistance of the arsenic sample solution

simple voltage divider circuit has been used. The algorithm to calculate unknown
resistance using the Arduino board is mentioned in Appendix I.

20
 4. Results and Discussion

4.1 Results by Spectrometric Analysis

1.0

90ppb
70ppb
0.8 50ppb
30ppb
10ppb
0.6
Absorbance

0.4

820 nm

0.2

0.0
400 500 600 700 800 900
Wavelength (nm)

Figure 8: Effect of concentration on absorbance intensity

Prepared sample solution was analyzed into UV-visible spectrophotometer

to confirm the formation of arsenomolybdate complex i.e. Keggin. From the
analysis we can see that we have a peak in the absorbance v/s wavelength curve
in between 800 − 850 𝑛𝑚 for different concentration of sample solution. Also the
graph shows that as the concentration of the solution increases intensity of
absorbance increases which indicates that the concentration of arsenic is
proportional to the absorbance of light.

21
 4.2 Results of Spectrometric Analysis for Optimization of Acid
Concentration

The MB reaction requires a strong acid, with reported pH values generally

below 1 to ensure the appropriate formation of arsenomolybdate complex.
However, the choice of acid can negatively impact the reaction. Oxidising acids
interfere with the reduction process, and anion interactions with Mo(VI) species
can affect the formation of arsenomolybdate complex. The most commonly used
acids are H2SO4 and HCl. The effect of acidity on the rate of colour development
and on the stability of the resulting arsenomolybdate complex has been reported
and was investigated for our modified molybdenum blue method. So, It is
important to optimize the concentration of the acid to reduce the time required
for arsenomolybdate complex and to increase the stability of arsenomolybdate
complex.

0.5 0.6
2M HCl 3M HCl
2M H2SO4 3M H2SO4
0.4 0.5

0.4
0.3
Absorbance

Absorbance

0.3
0.2

0.2
0.1

0.1
0.0

0.0
0 20 40 60 80 100 120 140 160 180 200 0 20 40 60 80 100 120 140 160 180 200
Time (min) Time (min)

22
 0.7
4M HCl 0.75 4.5M HCl
4M H2SO4 4.5M H2SO4
0.70
0.6
0.65

0.60
0.5
0.55

Absorbance
Absorbance

0.4 0.50

0.45

0.3 0.40

0.35
0.2 0.30

0.25
0.1
0 20 40 60 80 100 120 140 160 180 200 0 20 40 60 80 100 120 140 160 180 200

Time (min) Time (min)

0.75
0.75 5M HCl 6M HCl
5M H2SO4 0.70 6M H2SO4
0.70
0.65
0.65
0.60
0.60
Absorbance

0.55
Absorbance

0.55

0.50 0.50

0.45 0.45

0.40 0.40

0.35 0.35

0.30 0.30
0 20 40 60 80 100 120 140 160 180 200
0 20 40 60 80 100 120 140 160 180 200
Time (min)
Time (min)

Figure 9: Comparison of absorbance at different time intervals for different

concentrations of acid

The above graphs indicate that as the concentration of acid increases time
required for the complex formation decreases. For lower concentration of acids
time required for the complex formation is very high (more than 3 hr) and for
higher concentration of acids it takes around 30 min.

23
 835
5 M HCl 4.5 M H2SO4
830
6 M HCl 6 M H2SO4
830
7 M HCl 7 M H2SO4
820
Peak Wavelength(nm)

825

Peak Wavelength(nm)
820
810
815
-----------------------------------------------------------------------------------
810 800

805 --------------------------------------------------------------------------------
790
800

795 780
0 1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7
Time(hr) Time (hr)

Figure 10: Comparison of maximum absorbance wavelength at different time intervals

for different concentrations of acid

The above graphs indicate that for the higher concentration of acids peak
wavelength of arsenomolybdate complex shifts below 800 after 4 to 5 hr. This
shift comes because the solution becomes bit turbid and it shows slight colour
change from the blue colour. It indicates that for the higher concentration of acid,
arsenomolybdate complex holds stability only for 4 to 5 hr.

Based on Figure 10 and 11 it is clear that as acid concentration increases

the time required for the complex decreases but the stability of the complex also
decreases. From the graphs, it is evident that around 4.5M is the optimized
concentration for H2SO4 and around 5M is the optimized concentration for HCl.

Heating the samples at around 50 °C to 65 °C also affects the rate of

complex formation. Appendix II shows that by heating the samples at 50 °C to
65 °C, how it affects the rate of arsenomolybdate complex formation.

24
 4.3 Results Obtained by Portable Photometric Resistance Meter

3.85

3.80

3.75
Multimeter
Resistance Meter
Resistance (k)

3.70

3.65

3.60

3.55

3.50

3.45

0 20 40 60 80 100 120 140 160 180 200

Time (min)

Figure 11: Comparison of multimeter and resistance meter readings for 50 ppb arsenic
concentration sample

Once the formation of Keggin was confirmed using the UV-Vis

spectroscopy, multimeter readings of different sample solutions were taken at
different temperatures and at different time intervals. We found that as the
concentration of arsenic was increasing, the resistance reading of the multimeter
was also increasing showing that the concentration is proportional to the
resistance to the light due to increase in the intensity of the blue coloured complex
formed causing resistance to the light passing through it. For calculating the
resistance in photometric resistance meter simple voltage divider circuit has been
used. To calculate the unknown resistance of 50 ppb sample solution 5 kΩ
resistance has been used.

25
 2.15

2.10

2.05

Resistance (k)
2.00 Multimeter
Resistance Meter (3 k)
1.95 Resistance Meter (5 k)

1.90

1.85

1.80

0 20 40 60 80 100 120 140 160 180 200

Time (min)

Figure 12: Comparison of the results obtained by multimeter and resistance meter using
3 kΩ and 5 kΩ resistance for 10 ppb arsenic concentration sample

Above graph shows that results obtained using the 3 kΩ resistance for 10
ppb concentration arsenic solution gives better results than the results measured
by the 5 kΩ resistance. It shows that the accuracy of the resistance meter will be
poor if the value of the known resistance is very high or very small than the
unknown resistance. Resistance meter is sensitive for 8 ppb arsenic concentration
also. Below figure shows the Resistance vs Time Curve for 8 ppb Arsenic
concentration.

1.82

1.80

1.78
Resistance (k)

1.76

1.74

1.72

1.70

1.68

0 20 40 60 80 100 120 140 160 180 200

Time (min)

Figure 13: Resistance vs Time Curve for 8 ppb Arsenic Concentration

26
 4.4 Calibration Curve

To find the concentration of arsenic in any random sample, we first needed

the calibration curve which can be used to calculate the concentration based on
the resistance reading of the sample. Using the known concentration sample
solution readings we have found that the best calibration curve fitting is given by
a straight line (Linear Fitting) or polynomial fitting on the experimental data.

7.5
7.0
6.5
6.0
5.5
5.0
Resistance (k)

4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
-0.5
0 20 40 60 80 100 120
Concentration (ppb)

Figure 12: Logarithmic curve fitting

Table 3: Logarithmic Regression Results

Equation y=A*ln(x)-B
Reduced 0.14455275
Chi-Sqr
Adj. R- 0.92929776
Square
Value Standard
Error
resistance A 1.34626613 0.15064623
resistance B 1.19174944 0.5578958

27
 8.0
7.5
7.0
6.5
6.0
5.5
5.0
Resistance (k)

4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
-0.5
0 20 40 60 80 100 120
Concentration (ppb)

Figure 13: Polynomial curve fitting

Table 4: Polynomial Regression Results

Equation y = Intercept + B1*x^1 + B2*x^2

Adj. R- 0.99531317
Square
Value Standard
Error
resistance Intercept 1.51100887 0.09657946
resistance B1 0.04839941 0.00479698
resistance B2 -9.50E-05 4.45E-05
resistance B2 -9.50E-05 4.45E-05

Table represents the polynomial equation, value of constants in polynomial

equation. Standard error present in the constants and value of R2 is also shown in
the table.

28
 8.0
7.5
7.0
6.5
6.0
5.5
5.0
Resistance (k)

4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
-0.5
-1.0
0 20 40 60 80 100 120
Concentration (ppb)

Figure 14: Linear curve fitting

Equation y = a + b*x
Adj. R- 0.99198
Square
Value Standard
Error
resistance Intercept 1.66079 0.08683
resistance Slope 0.03842 0.00141

The above table shows the equation of curve fitted in the figure 14, value
of R2, intercept and slope of the curve. Standard error in intercept and in slope is
also given in table. Matlab can be used for more accurate results. Algorithm of
regression in Matlab is given in Appendix III.

29
 Conclusions and Future Aspects

Conclusions
The basic aim of this research work is to reduce the time required for
arsenic detection, increase the stability of arsenomolybdate complex and to
measure usefulness of electronic sensors in relation to the arsenic recognition of
traces and tried to make a simple and portable sensor, which can potentially be
used for regular testing in arsenic affected areas. From the results it is evident that
for H2SO4 around 4.5 M is the optimized concentration and for HCl around 5M
is the optimized concentration. Result shows that optimized concentration of HCl
gives better stability of arsenomolybdate complex than optimized concentration
of H2SO4. This work is driven by the need for better portable arsenic sensors for
routine arsenic monitoring in areas such as Bangladesh, and it is expected that
with the development of better technology may lead the lowering of their current
arsenic maximum concentration limit of 50 μg/L can be reduced to WHO-
suggested standard of 10 μg/L. The portable test kits based on the Gutzeit reaction
are not reliable and safe. I believe that using colorimetric methods with electronic
sensor we can make ideal sensors, in which LOD can reach the safe arsenic limit
of 10 μg/L.

In addition, the results of my review show that, despite the many different
possible techniques for determination of arsenic, colorimetric techniques are the
most classic, feasible and easy for simple regional testing. Because of that, my
research work has been focused on making of a simpler, portable electronic
colorimetric sensor based on the chemistry of molybdenum blue and other
advantage is that it is not generating the toxic compounds like Gutzeit’s test.

By application of colorimetric techniques and basic electronics we tried to

make portable, ease of use and good detection range photometric sensor.

30
Future Aspects
In this study interference of phosphate is not tested so future work can be
based on to see how there will be a change in results because of phosphate
interference. The cost of Arduino is slightly higher so next objective is to reduce
it by some modification. Another objective is to check how the device will give
the results for other metals. It can be tried to increase the LOD of photometric
resistance meter by using the small valued known resistances.

31
Appendix I

Algorithm to Calculate Unknown Resistance of Sample:

int analogPin= 0;
int a= 0;
int Vinput= 5;
float Voutput= 0;
float Rknown= 3 k;
float Runknown= 0;
float var= 0;
void setup()
{
Serial.begin(9600); }
void loop()
{
a= analogRead(analogPin);
if(a)
{
var= a * Vinput;
Voutput= (var)/1024.0;
var= (Vinput/Voutput) -1;
R2= R1 * var;
Serial.print("Voutput: ");
Serial.println(Voutput);
Serial.print("Runknown: ");
Serial.println(Runknown);
delay(1000); }}

32
Algorithm for LCD Output:-
#include <LiquidCrystal.h>
LiquidCrystal lcd(12, 11, 5, 4, 3, 2);
int analogPin= 0;
int a= 0; int Vinput= 5;
float Voutput= 0;
float Rknown= 3 k;
float Runknown= 0; float var= 0;
void setup()
{
lcd.begin(16, 2); }
void loop()
{
a= analogRead(analogPin);
if(a)
{
var= a* Vinput;
Voutput= (var)/1024.0;
var= (Vinput/Voutput) -1;
Runknown= Rknown * var;
lcd.setCursor(0, 0);
lcd.print("Voutput: ");
lcd.print(Voutput);
lcd.setCursor(0, 1);
lcd.print("Runknown: ");
lcd.print(Runknown);
delay(1000); } }

33
 Appendix II

For onsite detection of arsenic, heating a sample at 50 °C to 60 °C is not

feasible but for the detection of arsenic in the laboratory, heating the samples at
50 °C to 60 °C can be used to reduce the time required for complex formation.

0.65
0.30 50 C Temperature
65 C Temperature
0.60
0.25 50 C Temperature
65 C Temperature
0.55
0.20
Absorbance
Absorbance

0.50
0.15
0.45
0.10
0.40
0.05
0.35

0.00
0 20 40 60 80 100 120 140 160 180 200 0 20 40 60 80 100 120 140 160 180 200

Time (min) Time (min)

Figure 14: Absorbance vs Time curve for 10 ppb Figure 15: Absorbance vs Time curve for 50 ppb samples
samples

The above Figure 14 and 15 shows that heating a 10 ppb arsenic

concentration sample at 50 °C to 65 °C does not affect the time required for the
complex formation but heating a 50 ppb arsenic concentration sample at 50 °C to
65 °C, the time required for the arsenomolybdate complex formation significantly
decreases.

34
Appendix III

Interpolation Code:
Newton Interpolation:
Script File:
concentration=[10 30 50 70 90]';
n=length(concentration);
resistance=[ 2.07 2.82 3.81 4.34 5.1 ];
p=newtintpol(concentration,resistance,n)
Function File:
function [p] = newtintpol(concentration,resistance,n)
p=zeros(n,n);
p(:,1)=resistance;
for q=2:n
for s=1:(n-q+1)
p(s,q)=(p(s+1,q-1)-p(s,q-1))/(x(s+q-1)-x(s));
end
end
end

35
 References

1) Petrusevski, B., Sharma, S., Schippers, J. C., & Shordt, K., (2007). Arsenic
in drinking water. Delft: IRC International Water and Sanitation Centre,
17(1), 36-44.
2) Kemper, K., & Minnatullah, K., (2005). Towards a More Effective
Operational Response-Arsenic Contamination of Groundwater in South
and East Asian Countries (2/2). World Bank, Water and Sanitation
Program.
3) Smith, A. H., Lingas, E. O., & Rahman, M., (2000). Contamination of
drinking-water by arsenic in Bangladesh: a public health emergency.
Bulletin of the World Health Organization, 78, 1093-1103.
4) Kinniburgh, D. G., (2001). Arsenic contamination of groundwater in
Bangladesh.FinalReport.http://www.bgs.ac.uk/research/groundwater/heal
th/arsenic/Bangladesh/reports. html.
5) Argos, M., Kalra, T., Rathouz, P. J., Chen, Y., Pierce, B., Parvez, F., ... &
Sarwar, G., (2010). Arsenic exposure from drinking water, and all-cause
and chronic-disease mortalities in Bangladesh (HEALS): a prospective
cohort study. The Lancet, 376(9737), 252-258.
6) Cicero, L.A., (2009). Scientists solve puzzle of arsenic-poisoning crisis in
Asia. Stanford Report.
7) WHO, (2001). Water-related diseases: Arsenicosis
8) Yang, C. Y., Chang, C. C., Ho, S. C., & Chiu, H. F. (2008). Is colon cancer
mortality related to arsenic exposure? Journal of Toxicology and
Environmental Health, Part A, 71(8), 533-538.
9) Chen, C. J., Chuang, Y. C., You, S. L., Lin, T. M., & Wu, H. Y. (1986). A
retrospective study on malignant neoplasms of bladder, lung and liver in
blackfoot disease endemic area in Taiwan. British journal of cancer, 53(3),
399.
10) Ferreccio, C., González, C., Milosavjlevic, V., Marshall, G., Sancha, A.
M., & Smith, A. H. (2000). Lung cancer and arsenic concentrations in
drinking water in Chile. Epidemiology, 673-679.
11) Wu, M. M., Kuo, T. L., Hwang, Y. H., & Chen, C. J. (1989). Dose-response
relation between arsenic concentration in well water and mortality from
cancers and vascular diseases. American journal of epidemiology, 130(6),
1123-1132.
12) World Health Organization. (2004). Permethrin in drinking-water:
background document for development of WHO guidelines for drinking-
water quality.
13) Morales, K. H., Ryan, L., Kuo, T. L., Wu, M. M., & Chen, C. J. (2000).

36
 Risk of internal cancers from arsenic in drinking water. Environmental
health perspectives, 108(7), 655.
14) Tsuda, T., Babazono, A., Yamamoto, E., Kurumatani, N., Mino, Y.,
Ogawa, T., ... & Aoyama, H. (1995). Ingested arsenic and internal cancer:
a historical cohort study followed for 33 years. American Journal of
Epidemiology, 141(3), 198-209.
15) Sohel, N., Persson, L. Å., Rahman, M., Streatfield, P. K., Yunus, M.,
Ekström, E. C., & Vahter, M. (2009). Arsenic in drinking water and adult
mortality: a population-based cohort study in rural Bangladesh.
Epidemiology, 824-830.
16) Samanta, G., Chowdhury, T. R., Mandal, B. K., Biswas, B. K.,
Chowdhury, U. K., Basu, G. K., ... & Chakraborti, D. (1999). Flow
injection hydride generation atomic absorption spectrometry for
determination of arsenic in water and biological samples from arsenic-
affected districts of West Bengal, India, and Bangladesh. Microchemical
Journal, 62(1), 174-191.
17) Flanagan, S. V, Johnston, R.B. & Zheng, Y., (2012). Arsenic in tube well
water in Bangladesh: health and economic impacts and implications for
arsenic mitigation. Bulletin of the World Health Organization, 90(11),
pp.839–46.
18) Jakariya, M., Vahter, M., Rahman, M., Wahed, M. A., Hore, S. K.,
Bhattacharya, P., ... & Persson, L. Å. (2007). Screening of arsenic in
tubewell water with field test kits: evaluation of the method from public
health perspective. Science of the Total Environment, 379(2-3), 167-175.
19) Klaue, B. & Blum, J.D., (1999). Trace Analyses of Arsenic in Drinking
Water by Inductively Coupled Plasma Mass Spectrometry : High
Resolution versus Hydride Generation spectrometer ( ICPMS ) was
applied to the determination chloride interference , the accompanying
reduction in. Analytical Chemistry, 71(7), pp.1408–1414.
20) United States Environmental Protection Agency Office of Water, (1999).
Analytical Methods Support Document For Arsenic In Drinking Water.
21) Wahed, M. A., Chowdhury, D., Nermell, B., Khan, S. I., Ilias, M., Rahman,
M., ... & Vahter, M. (2006). A modified routine analysis of arsenic content
in drinking-water in Bangladesh by hydride generation-atomic absorption
spectrophotometry. Journal of Health, Population and Nutrition, 36-41.
22) Behari, J.R. & Prakash, R., (2006). Determination of total arsenic content
in water by atomic absorption spectroscopy (AAS) using vapour
generation assembly (VGA). Chemosphere, 63(1), pp.17–21.
23) Rahman, M. M., Mukherjee, D., Sengupta, M. K., Chowdhury, U. K.,
Lodh, D., Chanda, C. R., ... & Shahidullah, S. M. (2002). Effectiveness
and reliability of arsenic field testing kits: are the million dollar screening
projects effective or not? Environmental science & technology, 36(24),
5385-5394.

37
24) Arora, M., Megharaj, M. & Naidu, R., (2009). Arsenic testing field kits:
some considerations and recommendations. Environmental geochemistry
and health, 31 Supply 1, pp.45–8.
25) George, C. M., Graziano, J. H., Mey, J. L., & Van Geen, A. (2012).
Impact on arsenic exposure of a growing proportion of untested wells in
Bangladesh. Environmental Health, 11(1), 7.
26) Dasgupta, P. K., Huang, H., Zhang, G., & Cobb, G. P. (2002).
Photometric measurement of trace As (III) and As (V) in drinking water.
Talanta, 58(1), 153-164.
27) Melamed, D., (2005). Monitoring arsenic in the environment: a review of
science and technologies with the potential for field measurements.
Analytica Chimica Acta, 532(1), pp.1–13.
28) Feldmann, J. (2009). Onsite testing for arsenic: Field test kits. In Reviews
of Environmental Contamination Volume 197 (pp. 61-75). Springer, New
York, NY.
29) Johnson, D. L., & Pilson, M. E. (1972). Spectrophotometric determination
of arsenite, arsenate, and phosphate in natural waters. Analytica Chimica
Acta, 58(2), 289-299.
30) Pande, S.P., Deshpande, L.S. & Kaul, S.N., (2001). Laboratory and field
assessment of arsenic testing field kits in Bangladesh and West Bengal,
India. Environmental monitoring and assessment, 68(1), pp.1–18.
31) Steinmaus, C. M., George, C. M., Kalman, D. A., & Smith, A. H. (2006).
Evaluation of two new arsenic field test kits capable of detecting arsenic
water concentrations close to 10 μg/L. Environmental science &
technology, 40(10), 3362-3366.
32) Kinniburgh, D.G. & Kosmus, W., (2002). Arsenic contamination in
groundwater: some analytical considerations. Talanta, 58(1), pp.165–80.
33) Safarzadeh-Amiri, A., Fowlie, P., Kazi, A. I., Siraj, S., Ahmed, S., &
Akbor, A. (2011). Validation of analysis of arsenic in water samples
using Wagtech Digital Arsenator. Science of the Total Environment,
409(13), 2662-2667.
34) Okazaki, T., Wang, W., Kuramitz, H., Hata, N., & Taguchi, S. (2013).
Molybdenum Blue Spectrophotometry for Trace Arsenic in Ground Water
Using a Soluble Membrane Filter and Calcium Carbonate Column.
Analytical Sciences, 29(1), 67-72.
35) Hu, S., Lu, J., & Jing, C. (2012). A novel colorimetric method for field
arsenic speciation analysis.
36) Das, J., & Sarkar, P. (2016). A new dipstick colorimetric sensor for
detection of arsenate in drinking water. Environmental Science: Water
Research & Technology, 2(4), 693-704.

38
37) Kiso, Y., Asaoka, S., Kamimoto, Y., Tanimoto, S., & Yokota, K. (2015).
Detection tube method for trace level arsenic. Journal of Environmental
Chemical Engineering, 3(1), 40-45.
38) Carvalho, L., De Koe, T., & Tavares, P. (1998). An improved molybdenum
blue method for simultaneous determination of inorganic phosphate and
arsenate. Restoration, 1(1).
39) Watanabe, K., Osawa, T., Iwata, J., & Itagaki, M. (2006).
Spectrophotometric determination of arsenic in steels by FIA using filter-
tube concentration method. Bunseki Kagaku, 55(4), 251-257.
40) Matsunaga, H., Kanno, C., & Suzuki, T. M. (2005). Naked-eye detection
of trace arsenic (V) in aqueous media using molybdenum-loaded chelating
resin having β-hydroxypropyl-di (β-hydroxyethyl) amino moiety. Talanta,
66(5), 1287-1293.
41) Tsang, S., Phu, F., Baum, M. M., & Poskrebyshev, G. A. (2007).
Determination of phosphate/arsenate by a modified molybdenum blue
method and reduction of arsenate by S2O42−. Talanta, 71(4), 1560-1568.
42) Lenoble, V., Deluchat, V., Serpaud, B., & Bollinger, J. C. (2003). Arsenite
oxidation and arsenate determination by the molybdene blue method.
Talanta, 61(3), 267-276.
43) Dhar, R. K., Zheng, Y., Rubenstone, J., & Van Geen, A. (2004). A rapid
colorimetric method for measuring arsenic concentrations in groundwater.
Analytica Chimica Acta, 526(2), 203-209.

39
40