Author’s Accepted Manuscript

Paper-based analytical device for sampling, on-site

preconcentration and detection of ppb lead in water

Thiphol Satarpai, Juwadee Shiowatana, Atitaya

Siripinyanond

www.elsevier.com/locate/talanta

PII: S0039-9140(16)30256-9
DOI: http://dx.doi.org/10.1016/j.talanta.2016.04.017
Reference: TAL16499
To appear in: Talanta
Received date: 24 February 2016
Revised date: 4 April 2016
Accepted date: 5 April 2016
Cite this article as: Thiphol Satarpai, Juwadee Shiowatana and Atitaya
Siripinyanond, Paper-based analytical device for sampling, on-site
preconcentration and detection of ppb lead in water, Talanta,
http://dx.doi.org/10.1016/j.talanta.2016.04.017
This is a PDF file of an unedited manuscript that has been accepted for
publication. As a service to our customers we are providing this early version of
the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting galley proof before it is published in its final citable form.
Please note that during the production process errors may be discovered which
could affect the content, and all legal disclaimers that apply to the journal pertain.
Paper-based analytical device for sampling, on-site

preconcentration and detection of ppb lead in water

Thiphol Satarpai1, Juwadee Shiowatana1, and Atitaya Siripinyanond*

Department of Chemistry and Center for Innovation in Chemistry, Faculty of Science,

Mahidol University, Rama VI Road, Bangkok 10400, Thailand

*
Fax: +662-354-7151; Tel: +662-201-5195; E-mail: atitaya.sir@mahidol.ac.th

Abstract

A simple and cost effectiveness procedure based on a paper based analytical device

(PAD) for sampling, on-site preconcentration and determination of Pb(II) in water samples

was developed. The inkjet printing method was used for patterning of PAD. Colorimetric

assay was developed on a PAD for Pb(II) detection in µg L-1 level. This µg L-1 level

detection limit was achieved by in situ- and on-site preconcentration of Pb(II) onto adsorption

filter paper disc with a home-made holder before color development. Water sample was

loaded onto a circular filter paper coated with zirconium silicate in 3% sodium

carboxymethylcellulose for Pb(II) preconcentration. Subsequently, sodium rhodizonate in

tartrate buffer solution (pH 2.8) was used as colorimetric reagent for direct Pb(II) detection

on a PAD. Detection was achieved by measuring the pink color and recorded by scanner or

digital camera. ImageJ software was used for measuring grey scale values. The calibration

curve was linear in the range of 10 µg L-1 and 100 µg L-1, with a detection limit of 10 µg L-1.

The developed method was successfully applied to the determination of Pb(II) in drinking

1
Fax: +662-354-7151; Tel: +662-201-5195
-1-
water, tap water and surface water near electronic waste storage and the results were

compared with those by graphite furnace atomic absorption spectroscopy (GF-AAS) with

good agreement.

Keywords: PAD, GF-AAS, Colorimetric assay, Lead, Water sample analysis

1. Introduction

Lead, Pb(II), is a toxic element and often contaminated in food and water due to its wide

application [1]. Lead contamination commonly occurs from metal corrosion of lead-bearing

materials distributed through lead pipes in the water supply or the premise plumbing. Human

intakes lead through various routes, including respiratory and digestive systems. Current

guidelines on lead in drinking water are mostly in the range of 10-15 µg L-1. The United

States Environmental Protection Agency (EPA) has established a maximum allowable limit

of lead in drinking water to be 10 µg L-1 [2]. Exposure to lead is a public health concern,

particularly as it can affect the neuro-development of young children [3]. Drinking water in

household water represents a potential source of lead exposure for children [3]. The study of

health effect of lead, the release and removal of lead has been reported continuously since the

last 20 years [4]. Thus research on lead has become an important topic for environmental

monitoring.

Several methods for lead detection in water sample are based on instrumentation

techniques such as atomic absorption spectrometry with preconcentration techniques [5-7],

gamma spectrometry [8], atomic fluorescence spectrometry [9], stripping voltammetry [10-

14], differential pulse voltammetry [15], potentiometric stripping analysis [16],

chronopotentiometric analysis [17], immunochromatographic assay [18], high-performance

-2-
liquid chromatography (HPLC) [19], light scattering [20], laser-induced breakdown

spectroscopy [21], inductively coupled plasma optical emission spectroscopy (ICP-OES) and

inductively coupled plasma mass spectrometry (ICP-MS) [22-24] and laser

desorption/ionization mass spectrometry (LDI-MS) [25]. Furthermore, various types of

sensors including chemical, biological, and optical sensors have been developed for lead

detection with the use of UV-vis spectrophotometer, fluorescence or attenuated total

reflectance for measuring the intensity of the color change [26-29]. Nonetheless, in order to

detect lead ions in the community water or in the field, a simple and low cost technique

without the need for expensive and sophisticated instruments should be developed. It is

therefore essential to develop a simple and reliable method for lead determination in water

samples.

Paper-based analytical device (PAD) is a low-cost analytical platform. The main

component of paper is cellulose fiber which allows hydrophilic liquid as water to penetrate or

transport within its hydrophilic part using capillary forces [30]. Fabrication of the channels

on paper can be performed by modifying some hydrophilic parts to become hydrophobic as a

barrier in order to confine liquid flow within the hydrophilic channels. Therefore, liquid flow

can be designed in a controlled manner. Many fabrication techniques were used to pattern

hydrophilic-hydrophobic contrast on a paper [30]. The principles of paper fabrication can be

divided into three categories: physical blocking of the pores in paper; physical deposition of a

hydrophobizing reagent on the paper; and chemical modification of cellulose fiber surfaces

using paper sizing/hydrophobizing agents such as alkyl ketene dimer (AKD), which is an

amphiphilic compound normally used in the papermaking industry [31]. In this work, inkjet

printing technique was used to introduce AKD onto the paper, as reported by Li et al. [32],

because it is simple and requires only a computer and desktop inkjet printer, apart from the

AKD reagent. The chemical modification of cellulose on the paper occurs through the

-3-
replacement of hydroxyl group of cellulose by beta-keto ester group. Various applications of

these PADs include health diagnostics such as the analyses of nitrite ion and uric acid [33],

biochemical analysis by studying enzyme activity of alkaline phosphatase [32], biomedical

analysis by detection of nicotinamide adenine dinucleotide (NADH) [34], and environment

monitoring by detection of nitrite and nitrate [35]. Previously the detection of Pb(II) in PAD

was based on electrochemical detection [36-38] or electrochemi-luminescence detection [39]

or colorimetric detection with nanogold-based membrane after acid leaching of AuNPs by

microwave irradiation [40].

In order to monitor metal concentration in natural waters, sample collection and

preservation are often additional to the quality control aspects [41]. The collected water

sample from an environmental source must maintain concentrations of heavy metals as its

original source and the volume of water sample must be enough for handling the required

analysis. Sample preservation methods include chemical addition, pH control, refrigeration,

and freezing [42], for example. Thus, collecting a large number of water samples requires

appropriate store capacity and the sample preservation during transport to laboratory. A good

solution to this problem is to use adsorption filter paper disc for simultaneous collection and

preconcentration, without the necessity to store or preserve a large volume of sample, by

which the trace heavy metals from water sources can be kept in adsorption filter paper discs.

Use of adsorption filter paper disc for sampling and preconcentration can decrease

contamination from sample container and also avoid losing of trace heavy metals from

adsorption to the wall of the sample container during water sample collection. After

sampling and preconcentration on adsorption filter paper disc, colorimetric detection method

was carried out for detection of Pb(II) ions on the adsorption filter paper disc.

In this work, paper-based analytical device (PAD) was developed to allow sampling,

on-site preconcentration and preservation on adsorption filter paper disc for field monitoring.

-4-
Specific colorimetric assay for Pb(II) detection as sodium rhodizonate (NaR), a well-known

colorimetric test for Pb(II) [45, 46], was employed for direct Pb(II) detection on PAD. The

rhodizonate changes from orange-brown to pink upon Pb(II) binding. The adsorption filter

paper disc was made from a circular filter paper as a substrate which was coated with

zirconium silicate in 3% sodium carboxymethylcellulose as adsorbent to preconcentrate lead

ions on site on the disc, with subsequent colorimetric detection on the disc after placing it

onto PAD. The preconcentration was carried out using a home-made filter holder. Thus, the

combination between a simple preconcentration and selective colorimetric method effectively

creates a low cost paper-based device for Pb(II) detection in water samples with low

detection limit.

2. Experimental

2.1. Chemicals and reagents

All chemicals used were of analytical reagent grade. Lead (II) nitrate, sodium

carboxymethylcellulose, sodium bitartrate monohydrate and tartaric acid were purchased

from Sigma-Aldrich (MO, USA). Zirconium silicate was obtained from Yong Thai Chemical

(BKK, Thailand). Rhodizonic acid disodium salt was purchased from Acros Organics (NJ,

USA). Hydrochloric acid, nitric acid and n-heptane were purchased from RCI Labscan Co.,

Ltd. (BKK, Thailand). Deionized water with a resistivity of 18 MΩ.cm (Easypure®II model

D7031, Barnstead, Iowa, USA) was used for solution preparation. All glasswares and plastic

bottles were first soaked in diluted nitric acid and then rinsed with deionized water before

use. Polypropylene microcentrifuge tube was purchased from Plastibrand® (Wertheim,

Germany). Whatman® filter paper no. 4 was purchased from GE (Buckinghamshire, UK).

-5-
 2.2. Instrumentation

Atomic absorption measurement of Pb(II) was performed with a Perkin Elmer Model

AAnalyst 100 (Norwalk, CT, USA) equipped with an HGA-800 graphite-furnace system, an

AS-72 autosampler and a deuterium background corrector. L′vov graphite tube (Perkin

Elmer, CT, USA) was used. A Pb hollow-cathode lamp (PHOTRON, Victoria, Australia)

was used as the radiation source and operated at 8 mA. The selected wavelength was 283.3

nm and slit width was set at 0.70 nm. Atomization was set at 1900 °C for 5 s.

The paper-based analytical device was created by AKD sizing [34] using inkjet

printer (PIXMA iP3680, Canon®) and scanned using Scanner (CanoScan LiDE100, Canon®).

A peristaltic pump (ISMATEC®, Switzerland) was used to systematically control the flow

rate of lead solution passing through adsorption filter paper disc. The pH measurement was

made by Thermo Orion pH-meter model 420 equipped with glass electrode.

2.3. Preparation of adsorption filter paper disc for sampling and

preconcentration of water sample

Adsorption filter paper disc was prepared from Whatman® filter paper no.4 as a

substrate and zirconium silicate as a sorbent material. The paper was cut to a diameter of 5.5

mm. The sorbent material was prepared from 0.1 g of zirconium silicate suspended in 1 mL

of 3% sodium carboxymethylcellulose. To prepare the adsorption filter paper disc, 10 µL of

sorbent material was pipetted onto the paper substrate, and allowed to dry in an oven at 100

ºC for 1 hour. An in-house simple filter holder was made using a cap of microcentrifuge tube

(size 1.5 mL) and a plastic volumetric flask stopper (mouth size #10/19). A hole (ca. size

-6-
about 1 mm) was drilled onto the volumetric flask stopper at the center, and also another hole

was punched onto the microcentrifuge tube cap at the center. A fluoropolymer (FEP) tubing

(OD. 1/16″, ID. 0.030″) was inserted through the holes of the volumetric flask stopper and

the microcentrifuge tube cap for sample introduction. To perform preconcentration, a

circular filter paper loaded with zirconium silicate (adsorption filter paper disc) was placed

on top of the inside of the microcentrifuge tube cap and the volumetric flask stopper. Sample

solution was introduced through the fluoropolymer (FEP) tubing inlet by means of peristaltic

pump (Fig. 1).

2.4. PAD fabrication for colorimetric detection

Ink-jet printing technique with alkyl ketene dimer (AKD) sizing agent (3% in

heptane) was applied onto Whatman® filter paper no. 4 to fabricate PAD. The pattern used

for printing is illustrated in Fig. 2a. The pattern consisted of two sample reservoirs (left and

right) and one detection zone (center), all with the circular shape of 5 x 5 mm. After AKD

printing, the paper was heat-treated in an oven at 50 °C for 45 min. Then, the patterned paper

was punched to create a hole at the center reservoir and the paper was cut in the dash lines

area: one between the left and the center ports; and another one between the center and the

right ports, to allow the paper to flap, creating valves (A and B). With the paper flaps lifted

up, it was not possible for the solution to flow from one port to another, acting as valve

closing. With the paper flaps placed down, however, it was possible for the solution to flow

from one port to another, acting as valve opening. The PAD was folded at half and double-

sided tape was used to stick the paper together as shown in Fig. 2a.

2.5. Preconcentration and colorimetric detection procedure

To perform preconcentration, a 25 mL of water sample was introduced through the

adsorption filter paper disc in a simple filter holder at a flow rate of 2 mL min-1 by peristaltic

-7-
pump. After adsorption of lead ions, the adsorption filter paper disc was removed, allowed to

dry, and placed at the center of detection zone of the PAD (Fig. 2b) (For field sampling, the

adsorption filter paper disc can be kept in a well-prepared cabinet for transportation to the

laboratory for later detection). The adsorbed lead ion on the adsorbent was detected by

placing the filter paper disc in the center port of the PAD, then adding 15 µL of 0.5% sodium

rhodizonate reagent in aqueous tartrate buffer (pH 2.8) at the right reservoir. With the valve

opening, the chemical reaction of sodium rhodizonate reagent and Pb(II) ions took place,

yielding the pink color product (Reaction as shown in Fig. 3). The color was recorded by

taking a photograph with a smart phone or a scanner. The color intensity in the detection

zone was quantified by measuring as the grey intensity using image processing by ImageJ

(NIH, USA). The higher concentration of Pb(II) gave the more intense pink color, resulting

in the lower grey intensity values (values ranging from 0 to 255). To determine % remaining

Pb(II) in solution, Pb(II) in the filtrate was measured by using GF-AAS to check the mass

balances.

2.6. Interference studies

Different amounts of Co2+, Ni2+, Zn2+, Cd2+, Cr3+, Cu2+, Mn2+, Fe2+, and Ba2+ ions,

which may be present in water samples, were added to the test solution containing 60 µg L-1

Pb(II), with the Pb(II)/interferent ions ratio of 1/25, 1/50, and 1/100.

2.7. Sampling procedure

To prove the concept of lead ions preconcentration on adsorption filter paper disc

before colorimetric measurement using PAD, the analysis of lead in water samples from

-8-
various sources was performed. These samples included drinking water sample collected

from a local market in Bangkok, domestic tap water sample from Thonburi and our

laboratory (Phayathai campus, Mahidol University, Bangkok, Thailand). Surface water

samples were collected from the area near the local electronic waste storage at Khong Chai,

Kalasin, Thailand. These water samples were also spiked with 40 µg L-1 and 100 µg L-1 of

Pb(II).

3. Results and discussion

3.1. The adsorption study of lead ion onto the adsorbent

To test the potential of zirconium silicate as the adsorbent, the batch adsorption

experiments of Pb(II) on this adsorbent were conducted in a 100 mL conical flask at room

temperature (25 ºC). 100 mg adsorbent was weighed and added in the flask containing 25 mL

of Pb(II) solution (ranging from 10 to 500 µg L-1) at pH about 6.7 with a stirring time at 10

min using a magnetic stirrer. After each run, the suspension was filtered and the filtrate was

measured for the concentration of Pb(II) by using GF-AAS. The adsorption percentage

( was calculated from : where is the initial conce ntration of

Pb(II); is the residual concentration of Pb(II) in the solution. The results in Fig. 4 show

that the adsorption percentage were > 97% (n =3) for all Pb(II) concentrations studied herein.

Therefore, zirconium silicate can be used as an adsorbent on sorption of lead ions.

Furthermore the effect of lead concentration on its adsorption on the adsorbent was

studied (data not shown). The initial lead concentration ranging from 10 to 10,000 µg L-1

were prepared and were examined under optimum conditions for their sorption on the

adsorbent filter paper disc (see preparation in 2.3). The filtrate was collected for further

-9-
determination of residual concentration of lead ions in the solution by using GF-AAS and

were calculated. The results show that the percentage lead ions adsorbed decreased

with increasing initial lead concentration, which is due to less favorable sites of zirconium

silicate.

3.2. Effect of pH on adsorption of lead ions

The effect of pH in the aqueous solution on the adsorption of lead ions on the

adsorbent was investigated. A wide range of pH from 1 to 8 was examined by adjusting the

pH with hydrochloric acid and sodium hydroxide. The % remaining Pb(II) in solution was

determined by using GF-AAS, with the results shown in Fig. 5. The % remaining Pb(II) in

solution were found to be the lowest when the pH was adjusted to be between 6.0 and 7.0. At

pH lower than 6.0, lead ions cannot be adsorbed or retained on the surface of adsorbent

resulting in the high % remaining Pb(II) in solution. At pH values higher than 7.0,

precipitation of lead hydroxide occurred. Thus, lead ions were effectively adsorbed with

unmodified adsorbent in pH range 6.0-7.0, in agreement with the report by Hussain et al. [43]

and Mahmoud et al. [44].

3.3. Effect of sample flow rate on adsorbent

The effect of sample flow rate on lead adsorption was studied. After the adsorption

process was completed, the adsorption filter paper disc was removed, allowed to dry, and

placed at the center of the PAD detection zone as shown in Fig. 2b to start the colorimetric

detection by dropping NaR reagent on the right port and placing down the paper flap to allow

the reagent to flow to the detection port. In the presence of Pb(II), the red color was

- 10 -
developed. The filtrate was also collected to determine % remaining Pb(II) in solution. The

flow rates were examined in the range of 0.5-3.0 mL min-1, with the results shown in Fig. 6.

With the very slow flow rate, lead adsorption on the adsorbent increased but the color spot

upon interaction with rhodizonate became quite dispersed resulting in the higher relative

standard deviation of the grey intensity color values. With higher flow rates, the efficiency of

adsorption was reduced, resulting in higher % remaining Pb(II). The lowest % remaining

Pb(II) in solution was found in the flow rates ranging from 0.5-1.5 mL min-1. However, to

obtain the shortest preconcentration time the flow rate at 2.0-2.5 mL min-1 were considered as

they offered the well-defined spot to determine the grey intensity values with the shorter time

than using flow rate at 0.5-1.5 mL min-1. Thus, the flow rate of 2.0 mL min-1 was selected for

further experiments. With this selected flow rate, it would take approximately 13 min to

preconcentrate 25 mL of water sample, leading to the total analysis time of approximately 15

min for each sample.

3.4. Interferences

Various ions were tested for their interference effects on the preconcentration and the

colorimetric detection of Pb(II). Different amounts of these ions normally present in water

samples were added to the test solution containing 60 µg L-1 of Pb(II) and the developed

method was applied. Fig. 7 is the plot of the grey intensity values of Pb(II)-rhodizonate in

the presence of various foreign ions. Uneven background occurred for Fe2+ interference ions

which is caused by the brown color of iron hydroxide precipitate as the pH of the solution

was approximately 6.0 (see Fig. 7). To fix this problem, background subtraction before

measuring the grey intensity values was performed. The results indicated that these foreign

ions have no effect on the determination of Pb(II) on the PAD. Nonetheless, the Pb2+/Ba2+

- 11 -
ratio of 1/50 showed positive effect with sodium rhodizonate reagent, similar to the report by

Bartsch et al. [45]. Upon reacting with sodium rhodizonate, barium ion gave similar color to

Pb(II). In order to indicate if the pink color was attributed from Pb2+ or Ba2+, the left

reservoir on the PAD was loaded with 5% HCl. With the valve opening, acid could flow to

the detection port. In the presence of 5% HCl, Ba(II)-rhodizonate was decolorized, whereas

the red-pink color of Pb(II)-rhodizonate would turn into the blue color. This blue color was

proposed to come from the formation of Pb(II) complex with the alternating

tetrahydroxyquinone (THQ) ligand rather than the rhodizonate [45]. Therefore, addition of

5% HCl to the left port was performed as a confirmation test. The dark pink color should be

immediately changed to the blue color when the pink color occurred from Pb(II)-rhodizonate

complex [46]. However, the blue color may fade with time. The tolerable levels of foreign

ions are summarized in Table 1. Under the conditions used herein, the concentration levels

of these foreign ions found in natural water do not cause any interference effect on

colorimetric detection of Pb(II).

3.5. Analytical performance and determination of Pb(II) ions in real samples

The analytical features of the developed method including the linear range of the

calibration curve, limit of detection, precision, and accuracy were investigated. The linearity

of the calibration curve (grey intensity value) was found to be 10-100 µg L-1 with a

correlation coefficient of 0.969 (Fig. 8). The detection limit of Pb(II) ions was 10 µg L-1.

The precision of the developed method was less than 20 %RSD for Pb(II) in the solutions.

The accuracy was checked by using the spiked standard and validated by GF-AAS. The

developed method was applied for the determination of Pb(II) in household tap waters,

drinking waters and surface water near electronic waste storage in Thailand. The results are

- 12 -
summarized in Table 2. Pb(II) ions were not detectable in these samples by using the

developed PAD and GF-AAS. These samples were then spiked with 40 µg L-1 and 100 µg L-
1
of Pb(II) and good recoveries were obtained, suggesting that the developed PAD can be

applied to determine lead ions in these matrices. The results given in Table 2 showed good

agreement between the proposed method with those from the GF-AAS technique.

4. Conclusions

The developed method is composed of two steps: preconcentration and colorimetric

detection of lead ions. Preconcentration was performed by using an adsorption filter paper

disc placed in a home-made filter holder following sensitive colorimetric detection of Pb(II)

ions directly in situ on the PAD without elution step. An unmodified zirconium silicate in

3% sodium carboxymethylcellulose was used as adsorbent. The proposed method can detect

Pb(II) in the µg L-1 level by the naked eye after approximately 13 min preconcentration step

(for 25 mL water samples). The total analysis time of the proposed method was less than 15

min. Accuracy was tested and validated by GF-AAS with good agreement. The PAD was

successfully applied for the determination of Pb(II) in drinking water, tap water and waste

water matrices. The proposed method ensures many merits such as simplicity, cost

effectiveness, and ease in preparation and operation. The method can be further modified for

on-site and real time monitoring of Pb(II) by using plastic syringe instead of peristaltic pump

to control the flow of solution.

- 13 -
Acknowledgements

We are grateful for the scholarship given to TS and the funding for equipment from Mahidol

University under the National Research Universities Initiative. Thanks are also due to Miss

Rattaporn Saenmuangchin for collecting surface water sample near an electronic waste

storage in Thailand.

References

[1] M.C. Talio, M. Alesso, M.G. Acosta, M. Acosta, L.P. Fernandez, Sequential

determination of lead and cobalt in tap water and foods samples by fluorescence,

Talanta 127 (2014) 244-249.

[2] Drinking water contaminants: Standards and Regulations, EPA

«http://water.epa.gov/drink/contaminants/index.cfm» (accessed 30.06.11).

[3] G. Ngueta, M. Prevost, E. Deshommes, B. Abdous, D. Gauvin, P. Levallois, Exposure

of young children to household water lead in the Montreal area (Canada): The

potential influence of winter-to-summer changes in water lead levels on children’s

blood lead concentration, Environ. Int. 73 (2014) 57-65.

[4] J. Hu, Y. Ma, L. Zhang, F. Gan, Y.S. Ho, A historical review and bibliometric

analysis of research on lead in drinking water field from 1991 to 2007, Sci. Total

Environ. 408 (2010) 1738-1744.

[5] S.W. Wadhwa, M. Tuzen, T.G. Kazi, M. Soylak, B. Hazer, Polyhydroxybutyrate-b-

polyethyleneglycol block copolymer for the solid phase extraction of lead and copper

in water, baby foods, tea and coffee samples, Food Chem. 152 (2014) 75-80.

- 14 -
[6] E. Sahmetlioglu, E. Yilmaz, E. Aktas, M. Soylak, Polypyrrole/multi-walled carbon

nanotube composite for the solid phase extraction of lead (II) in water samples,

Talanta 119 (2014) 447-451.

[7] H. Xu, Y. Wu, J. Wang, X. Shang, X. Jiang, Simultaneous preconcentration of

cadmium and lead in water samples with silica gel and determination by flame atomic

absorption spectrometry, J. Environ. Sci. 25(Suppl.) (2013) S45-S49.

[8] Z. Grahek, M.R. Macefat, S. Lulic, Isolation of lead from water samples and

determination of 210Pb, Anal. Chim. Acta. 560 (2006) 84-93.

[9] Q. Zhou, N. Zhao, G. Xie, Determination of lead in environmental waters with

dispersive liquid-liquid microextraction prior to atomic fluorescence spectrometry, J.

Hazard. Mater. 189 (2011) 48-53.

[10] V.B. Santos, E.L. Fava, N.S.M. Curi, R.C. Faria, O.F. Filho, A thermostated

electrochemical flow cell with a coupled bismuth film electrode for square-wave

anodic stripping voltammetric determination of cadmium (II) and lead (II) in natural,

wastewater and tap water samples, Talanta 126 (2014) 82-90.

[11] Z. Bi, P. Salaun, C.M.G. van den Berg, Determination of lead and cadmium in

seawater using a vibrating silver amalgam microwire electrode, Anal. Chim. Acta.

769 (2013) 56-64.

[12] F.C. Vicentini, T.A. Silva, A. Pellatieri, B.C. Janegitz, O.F. Filho, R.C. Faria, Pb (II)

determination in natural water using a carbon nanotubes paste electrode modified

with crosslinked chitosan, Microchem. J. 116 (2014) 191-196.

- 15 -
[13] R.G. Kempegowda, P. Malingappa, A binderless, covalently bulk modified

electrochemical sensor: Application to simultaneous determination of lead and

cadmium at trace level, Anal. Chim. Acta. 728 (2012) 9-17.

[14] E.E. Bellido, M.D.G. Riano, M.G. Vargas, Sensitive adsorptive stripping

voltammetric method for determination of lead in water using multivariate analysis

for optimization, J. Hazard. Mater. 166 (2009) 1326-1331.

[15] M.K. Bojdi, M.H. Mashhadizadeh, M. Behbahani, A. Farahani, S.S.H. Davarani, A.

Bagheri, Systhesis, characterization and application of novel lead imprinted polymer

nanoparticles as a high selective electrochemical sensor for ultra-trace determination

of lead ions in complex matrixes, Electrochim. Acta. 136 (2014) 59-65.

[16] C.R.T. Tarley, V.S. Santos, B.E.L. Baeta, A.C. Pereira, L.T. Kubota, Simultaneous

determination of zinc, cadmium and lead in environmental water samples by

potentiometric stripping analysis (PSA) using multiwalled carbon nanotube

electrode, J. Hazard. Mater. 169 (2009) 256-262.

[17] R.O. Kadara, I.E. Tothill, Development of disposable bulk-modified screen-printed

electrode based on bismuth oxide for stripping chronopotentiometric analysis of lead

(II) and cadmium (II) in soil and water samples, Anal. Chim. Acta. 623 (2008) 76-

81.

[18] Y. Tang, Y.F. Zhai, J.J. Xiang, H. Wang, B. Liu, C.W. Guo, Colloidal gold probe-

based immunochromatographic assay for the rapid detection of lead ions in water

samples, Environ. Pollut. 158 (2010) 2074-2077.

- 16 -
[19] Q. Hu, G. Yang, J. Yin, Y. Yao, Determination of trace lead, cadmium and mercury

by on-line column enrichment followed by RP-HPLC as metal-tetra-(4-

bromophenyl)-porphyrin chelates, Talanta 57 (2002) 751-756.

[20] K.J. Tan, C.Z. Huang, Y.M. Huang, Determination of lead in environmental water

by a backward light scattering technique, Talanta 70 (2006) 116-121.

[21] S.T. Jarvinen, J. Saarela, J. Toivonen, Detection of zinc and lead in water using

evaporative preconcentration and single-particle laser-induced breakdown

spectroscopy, Spectrochim. Acta. B. 86 (2013) 55-59.

[22] L. Zhao, S. Zhong, K. Fang, Z. Qian, J. Chen, Determination of cadmium (II), cobalt

(II), nickel (II), lead (II), zinc (II), and copper (II) in water samples using dual-cloud

point extraction and inductively coupled plasma emission spectrometry, J. Hazard.

Mater. 239-240 (2012) 206-212.

[23] D. Lariviere, K.M. Reiber, R.D. Evans, R.J. Cornett, Determination of 210Pb at ultra-

trace levels in water by ICP-MS, Anal. Chim. Acta. 549 (2005) 188-196.

[24] Z.Y. Huang, F.R. Chen, Z.X. Zhuang, X.R. Wang, F.S.C. Lee, Trace lead

measurement and on-line removal of matrix interference in seawater by isotope

dilution coupled with flow injection and ICP-MS, Anal. Chim. Acta. 508 (2004)

239-245.

[25] H.Y. Wu, B. Unnikrishnan, C.C. Huang, Membrane-based detection of lead ions in

seawater, urine and drinking straws through laser desorption/ionization, Sensor

Actuat. B. 203 (2014) 880-886.

[26] H.H. Cai, D. Lin, J. Wang, P.H. Yang, J. Cai, Controlled side-by-side assembly of

gold nanorods: A strategy for lead detection, Sensor Actuat. B. 196 (2014) 252-259.

- 17 -
[27] N. Yildirim, F. Long, M. He, C. Gao, H.C. Shi, A.Z. Gu, A portable DNAzyme-

based optical biosensor for highly sensitive and selective detection of lead (II) in

water sample, Talanta 129 (2014) 617-622.

[28] J. Richardson, A. Drake, C.L. Miller, J. Hand, T. Morgan, I. Lagadic, Lead detection

in environmental water sample using an organoclay film-based attenuated total

reflectance sensor, Sensor Actuat. B. 158 (2011) 271-277.

[29] S.M. Taghdisi, S.S. Emrani, K. Tabrizian, M. Ramezani, K. Abnous, A. S. Emrani,

Ultrasensitive detection of lead (II) based on fluorescent aptamer-functionalized

carbon nanotubes, Environ. Toxicol. Phar. 37 (2014) 1236-1242.

[30] D.D. Liana, B. Raguse, J.J. Gooding, E. Chow, Recent advances in paper-based

sensors, Sensors 12 (2012) 11505-11526.

[31] X. Li, D.R. Ballerini, W. Shen, A perspective on paper-based microfluidics: Current

status and future trends, Biomicrofluidics 6 (2012) 011301-011313.

[32] X. Li, J. Tian, G. Garnier, W. Shen, Fabrication of paper-based microfluidic sensors

by printing, Colloid Surf. B: Biointerfaces 76 (2010) 564-570.

[33] X. Li, J. Tian, W. Shen, Quantitative biomarker assay with microfluidic paper-based

analytical devices, Anal. Bioanal. Chem. 396 (2010) 495-501.

[34] J.L. Delaney, C.F. Hogan, J. Tian, W. Shen, Electrogenerated chemiluminescence

detection in paper-based microfluidic sensors, Anal. Chem. 83 (2011) 1300-1306.

[35] B.M. Jayawardane, W. Shen, I.D. McKelvie, S.D. Kolev, Microfluidic paper-based

analytical device for the determination of nitrite and nitrate, Anal. Chem. 86 (2014)

7274-7279.

- 18 -
[36] G. Lisak, J. Cui, J. Bobacka, Paper-based microfluidic sampling for potentiometric

determination of ions, Sensor Actuat. B. 207 (2015) 933-939.

[37] Z. Nie, C.A. Nijhuis, J. Gong, X. Chen, A. Kumachev, A.W. Martinez, M.

Narovlyansky, G.M. Whitesides, Electrochemical sensing in paper-based

microfluidic devices, Lab Chip 10 (2010) 477-483.

[38] P. Rattanarat, W. Dungchai, D. Cate, J. Volckens, O. Chailapakul, C.S. Henry,

Multilayer paper-based device for colorimetric and electrochemical quantification of

metals, Anal. Chem. 86 (2014) 3555-3562.

[39] M. Zhang, L. Ge, S. Ge, M. Yan, J. Yu, J. Huang, S. Liu, Three-dimensional paper-

based electrochemiluminescence device for simultaneous detection of Pb2+ and Hg2+

based on potential-control technique, Biosens. Bioelectron. 41 (2013) 544-550.

[40] Y.F. Lee, C.C. Huang, Colorimetric assay of lead ions in biological samples using a

nanogold-based membrane, Appl. Mater. Interfaces 3 (2011) 2747-2754.

[41] T.R. Crompton, Determination of metals in natural waters, sediments, and soils, First

ed., Elsevier, Netherlands, 2015

[42] D. Duncan, F. Harvey, M. Walker, S. Australia, Regulatory monitoring and testing:

Water and wastewater sampling, Environment Protection Authority, Adelaide, 2007.

[43] S. Hussain, S.A. Schonbichler, Y. Guzel, H. Sonderegger, G. Abel, M. Rainer, C.W.

Huck, G.K. Bonn, Solid-phase extraction of galloyl- and caffeoylquinic acids from

natural sources (Galphimia glauca and Arnicae flos) using pure zirconium silicate

and bismuth citrate powders as sorbents inside micro spin columns, J. Pharmaceut.

Biomed. 84 (2013) 148-158.

- 19 -
[44] M.E. Mahmoud, G.M. Nabil, S.M.E. Mahmoud, High performance nano-zirconium

silicate adsorbent for efficient removal of copper (II), cadmium (II) and lead (II), J.

Environ. Chem. Eng. 3 (2015) 1320-1328.

[45] M.R. Bartsch, H.J. Kobus, K.P. Wainwright, An update on the use of the sodium

rhodizonate test for the detection of lead originating from firearm discharges, J.

Forensic Sci. 41(6) (1996) 1046-1051.

[46] M.G. Haag, L.C. Haag, Shooting incident reconstruction, second ed., Academic

Press, San Diego, 2011.

- 20 -
Figure Captions

Fig. 1. Photograph of a home-made adsorption filter paper disc holder, consisting of a

modified plastic volumetric flask stopper and a cap of microcentrifuge tube used

as adsorption filter paper disc supporter.

Fig. 2. Images showing (a) the pattern and fabrication of the PAD (Magenta color represents

hydrophobic area and white color represents hydrophilic area) and (b) the

colorimetric detection procedure after lead preconcentration with the adsorption

filter paper disc.

Fig. 3. The chemical reaction of sodium rhodizonate reagent with Pb(II) ion.

Fig. 4. The adsorption efficiency of adsorbent.

Fig. 5. Effect of solution pH on Pb(II) sorption on adsorption filter paper disc.

Fig. 6. Effect of sample flow rate on Pb(II) sorption and colorimetric detection of Pb(II).

Fig. 7. Effect of interfering ions on the determination of 60 µg L-1 Pb(II) using PAD. The

concentrations of interfering ions were 1500 µg L-1 for Cd2+, Cr3+, Cu2+, Mn2+, Fe2+ and 3000

µg L-1 for Ba2+, Co2+, Ni2+, Zn2+.

Fig. 8. Calibration curve of standard Pb(II). The linear equation was y = -0.4626x + 152.05

and correlation coefficient was 0.9695.

- 21 -
Table 1. Tolerance limits of interference ions

Tolerance limits
Interference ions (µg L-1)
Ni2+, Co2+, Zn2+ 3000
Cr3+, Cu2+, Cd2+, Mn2+, Fe2+ 1500

Table 2. Determination of Pb(II) in water samples and the analytical recovery by PAD and

GF-AAS

PAD GF-
AAS
Samples Pb(II) (µg L-1) Recovery Pb(II) (µg L-1) Recovery

Added Found a (%) Added Found a (%)

Drinking water
(D1) 0.0 ND b - 0.0 ND c -
41.2 41.2±3.8 100.0 41.2 38.2±7.8 92.6
103.0 99.1±10.4 96.2 103.0 103.2±1.1 100.2
Drinking water
(D2) 0.0 ND - 0.0 ND -
41.2 48.3±4.9 117.2 41.2 39.2±0.5 95.3
103.0 89.5±11.0 86.9 103.0 106.7±6.0 103.6
Tap water (T1) 0.0 ND - 0.0 ND -
41.2 45.1±8.1 109.5 41.2 39.2±6.9 95.3
103.0 89.2±4.4 80.5 103.0 117.2±7.1 113.8
Tap water (T2) 0.0 ND - 0.0 ND -
41.2 43.6±5.4 105.9 41.2 42.2±6.0 102.3
103.0 84.3±2.6 81.8 103.0 89.5±20.3 86.9
Waste water (A) 0.0 ND - 0.0 ND -
41.2 39.7±5.5 96.3 41.2 38.7±3.4 93.9
103.0 97.9±12.4 95.1 103.0 111.2±7.9 107.9
Waste water (B) 0.0 ND - 0.0 ND -
41.2 43.8±12.0 106.4 41.2 42.8±1.2 104.0
103.0 101.0±15.2 98.1 103.0 117.1±2.0 113.7
a
Mean ± SD (n=3)
b
Not detectable (<10 µg L-1)
c
Not detectable (<4.7 µg L-1)

Highlights

- 22 -
 Paper device was developed for on-site preconcentration and determination of Pb.
 Zirconium silicate adsorbent coated on the filter paper was used for Pb sorption.
 Rhodizonate color reaction with Pb(II) was performed directly on the paper device.
 The detection limit of 10 µg L-1 was obtained.

- 23 -
Fig. 1

- 24 -
Fig. 2

- 25 -
Fig. 3

- 26 -
Fig. 4

- 27 -
Fig. 5

- 28 -
Fig. 6

- 29 -
Fig. 7

- 30 -
Fig. 8

- 31 -
Graphical Abstract

- 32 -