MICROFLUIDIC PLATFORMS FOR WATER QUALITY

MONITORING

AIM

 Detection of metal ions using portable microfluidic sensor.

 Caliberation of metal ions using image analysis
 Paper based Fabrication and development of microfluidic sensor.
 To demostrate these devices as a chemical sensor

WHY THIS TOPIC?

 Low cost, high portable analytical sensors

 Understanding of flow in capillary channels
 Integration of nanoparticles in microfluidic devices for advanced applications
 Micro/nano scale systems are more ‘attractive’ than their macro counterpart
 Huge reduction in fluid volumes (109 - 1012 from l to µl/nl/pl)
 Small sample volume requirements
 Economical use of expensive reagents
 Less waste generation
 Low fabrication costs, allowing cost-effective disposable chips
 Faster analysis (scale effect)
 High throughput screening
 Ease of design modification
 Readily automated
 ABSTRACT

Water is an essential element for the life on the earth. The demand of water for human
consumption and for agricultural and industrial purposes is drastically increasing, so that one of
the most easily available resources is becoming insufficient. Thus, wastewater becomes a
valuable resource, and not a waste to be disposed of. Indeed, a lot of water, after industrial use, is
discharged in rivers, lakes or sea. Water contamination by heavy metals constitutes a large health
hazard.At present, electroplating companies discharge their effluent with either
minimal or no treatment of heavy metals. Some metals which are commonly used for
electroplating are copper, chromium, nickel, lead, cadmium, tin, zinc etc. Current estimation
methods for particulate metals are both cost and time intensive. Furthermore, analysis cost per
sample limits the number of samples that can be collected. In order to address this challenge, a
method has been developed using low-cost analytical devices with colorimetric detection to
measure particulate metals in water. Substrate for these devices are inexpensive, disposable, easy
to use, store, and transport, has a high surface area for visualization, and can be for multiplexed
analyte detection. We demonstrate the fabrication and functionalization of these devices and
their application in heavy metal detection in water samples. The devices would enable the user to
efficiently analyse the contaminants at the point of interest.
Literature survey

For Copper
A Bathocuproine Reagent-paper for the Rapid Semi-quantitative Determination of Copper
in the 1 to 70p.p.m. Range BY PETER HULTHE (Department of Analytical Chemistry,
University of Gothenburg, S-402 20 Goteborg 5, Sweden
Abstract
A procedure for the preparation of a reagent-paper for the semiquantitative determination
of copper is described. The reagent-paper contains sodium chloride, hydroquinone for the
reduction of copper(I1) to copper(1) and bathocuproine as a colour indicator. The size of the
spot is proportional to the copper concentration in the 10 to 70 p.p.m. range. Beyond this
range the calibration curve is slightly bent.

For Arsenic
Test for arsenic speciation in waters based on a paper-based analytical device with
scanometric detection Francisco Pena-Pereira, Lorena Villar-Blanco, Isela Lavilla, Carlos
Bendicho*
Analytical and Food Chemistry Department, Faculty of Chemistry, University of Vigo,
Campus As Lagoas-Marcosende s/n, 36310 Vigo, Spain

Abstract
A rapid, simple and affordable method for arsenic speciation analysis is described in this work.
The
proposed methodology involves in situ arsine generation, transfer of the volatile to the
headspace and its reaction with silver nitrate at the detection zone of a paper-based analytical
device (PAD). Thus, silver nitrate acts as a recognition element for arsine in the paper-based
sensor. The chemical reaction between the recognition element and the analyte derivative
results in the formation of a colored product which can be detected by scanning the detection
zone and data treatment with an image processing and analysis program. Detection and
injection zones were defined in the paper substrate by formation of hydrophobic barriers,
thus enabling the formation of the volatile derivative without affecting the chemical stability
of the recognition element present in the PAD. Experimental parameters influencing the
analytical performance of the methodology, namely color mode detection, composition of
the paper-based sensor and hydride generation and mass transfer conditions, were
evaluated. Under optimal conditions, the proposed method showed limits of detection and
quantification of 1.1 and 3.6 ng mL1 respectively. Remarkably, the limit of detection of the
method reported herein was much lower than the maximum contaminant levels set by both
the World Health Organization and the US Environmental Protection Agency for arsenic in
drinking water, unlike several commercially available arsenic test kits.The repeatability,
expressed as relative standard deviation, was found to be 7.1% (n 1⁄4 8). The method was
validated against the European Reference Material ERM®-CA615 groundwater and
successfully applied to the determination of As(III), As(V) and total inorganic As in different
water samples.

For Iron, Nickel and Copper

Microfluidic Paper-Based Analytical Device for Particulate Metals

Mallory M. Mentele,† Josephine Cunningham,† Kirsten Koehler,‡ John Volckens,‡
and Charles S. Henry*,†
†
Department of Chemistry and Department of Environmental and Radiological Health
Sciences, Colorado State University, Fort Collins, Colorado 80523, United States

A microfluidic paper-based analytical device (μPAD) fabricated by wax printing was designed
to assess
occupational exposure to metal-containing aerosols. This method employs rapid digestion of
particulate metals using microliters of acid added directly to a punch taken from an air
sampling filter. Punches were then placed on a μPAD, and digested metals were transported
to detection reservoirs upon addition of water. These reservoirs contained reagents for
colorimetric detection of Fe, Cu, and Ni. Dried buffer components were used to set the
optimal pH in each detection reservoir, while precomplexation agents were deposited in the
channels between the sample and detection zones to minimize interferences from competing
metals. Metal concentrations were quantified from color intensity images using a scanner in
conjunction with image processing software. Reproducible, log−linear calibration curves were
generated for each metal, with method detection limits ranging from 1.0 to 1.5 μg for each
metal (i.e., total mass present on the μPAD). Finally, a standard incineration ash sample was
aerosolized, collected on filters, and analyzed for the three metals of interest. Analysis of this
collected aerosol sample using a μPAD showed good correlation with known amounts of the
metals present in the sample. This technology can provide rapid assessment of particulate
metal concentrations at or below current regulatory limits and at dramatically reduced cost.
For bisphenol A
Paper-based Microfluidic Device for Bisphenol A Based
Chemical Reaction and Image Analysis
Hyung-Geun Park1, Ja-Young Kim1 & Min-Kyeong Yeo1,*
Received: 15 June, 2015 / Accepted: 07 September, 2015 / Published online: 12 November,
2015
C The Korean BioChip Society and Springer 2015

Abstract

Bisphenol A (BPA) is a representative xenoestrogenic endocrine disruptor that is widely used

in consumer products and remains in wastewater. Asimple detection tool is urgently needed
that can be used with the naked eye for environmental monitoring in situ. Therefore we
studied modification methods of phenol and ferric reagents on a paper-based micro-
fluidic device. The reaction between BPA and ferric reagent mixtures was examined using two
types of ferric reagent mixtures (ferric chloride/ferricyanide and ferric nitrate/ferricyanide) at
various ferric reagentmixture ratios(1 : 9, 3 : 7, 5 : 5, 7 : 3 and 9 : 1) and con-
centrations (BPA 100, 300, 500 and 1000 μg/mL and 1-5% ferric reagent mixtures).
Verification of this paper-based microfluidic device was analyzed with a UV
spectrophotometer.

For Cobalt

Abstract

Determination of cobalt in water samples using solidified floating organic drop

microextraction coupled with graphite furnace atomic absorption spectrometry Jing
Lana,b* and Zongshan Zhaob a College of Chemistry and Pharmaceutical Sciences, Qingdao
Agricultural University, Qingdao, 266109, P. R. China b Key Laboratory of Marine Chemistry
Theory and Technology, Ministry of Education, Ocean University of China, Qingdao, 266100,
P. R. China.

A simple, rapid and inexpensive method of the solidified floating organic drop extraction
(SFODME) technique coupled with graphite furnace atomic absorption spectrometry (GFAAS)
has been developed for the determination of cobalt in water samples. 8-Hydroxyquinoline
was used as a complex agent and 1-undecanol was used as the extraction solvent. The factors,
including solvent types, solution pH, extractant volume and interfering ions, were
investigated and optimised. Under the optimum conditions，the calibration graphs were
linear in the range 0.05–10.0 ng mL-1 cobalt, the limit of detection was 0.02 ng mL-1, the limit
of quantification was 0.05 ng mL-1 and the relative standard deviation for 10 replicate
measurements of 3 ng mL-1 cobalt was 2.8%. The proposed method was successfully applied
for the determination of cobalt in different water samples and the results were satisfactory .
FABRICATION OF MICROFLUIDIC PLATFORM

 Substrate

6mm whatman filter paper of grade 1 is punched

Using double sided tape the paper dot is sticked and then reagent is coated.

 Channels

Whatman filterpaper of grade 1 is taken amd is cut at different width and same length
It is sticked on the hydrophobic paper

Schematic representation of paper based microfluidic device

RATIO OPTIMIZATION

The ratio between copper and DPC has to be optimized .The optmized ratio is
5:7 i.e the DPC to copper ratio.

SPOT TEST

The spot test for copper and DPC is done on whatman filter paper grade 1.
The test was done from 0.01 to 100 ppm of copper solution.
RGB Analysis

RGB Analysis is done using Photoshop software and later Intensity Vs

concentration graph is plotted.

120
100
80 y = 0.2086x + 88.557
Intensity

R² = 0.9598
60
40
20
0
0 20 40 60 80 100 120
Concentration (ppm)

10 to 100 ppm

180
160
140
120 y = 0.0495x + 99.768
Intensity

100 R² = 0.8731
80
60
40
20
0
0 200 400 600 800 1000 1200
Concentration(ppm)

100 to 1000 ppm

Detection of Nickel

 Nickel is one of heavy metal ions which forms a complex with

DMG(Dimethyl Glyoxime) and gives a stable pink colour with the complex.

 An alcoholic solution of dimethyglyoxime (DMG) is used as the

precipitating reagent during the experiment because DMG is only slightly
soluble in water.
 It is therefore crucial to avoid the addition of too large an excess of the
reagent because it may crystallize out with the chelate. It is also important
to know that the complex itself is slightly soluble to some extent in
alcoholic solutions.
Ratio optimization

Ratio optimization is another important step as the intensity of colour changes based on the
ratio of reagent to metal ratio.
With reference to RSM Studies various ratios were studies.
Optimized ratio which was found was 3:5 reagent DMG To Nickel .

Spot test

With hard cotton cloth as chosen substrate with various concentration of nickel , spot test
were performed .
Detection of Cobalt

 For detection of Cobalt , a new complex is been reported that is complex between
Cobalt and DMG and the complex colour is orange to yellow.
 CH3C(NOH)C(NOH)CH3 - Structure of DMG
 Co[ONC(CH3)C(CH3)NOH]2 – Structure of complex of Cobalt and DMG

RGB Analysis

120

100
y = 2.3371x + 87.543
80 R² = 0.9437
Intensity

60

40

20

0
0 2 4 6 8 10 12
concentation(ppm)

180
160
140
120 y = 0.4052x + 112.49
R² = 0.9301
Intensity

100
80
60
40
20
0
0 20 40 60 80 100 120
concentation(ppm)
 200
180
160
140 y = 0.0411x + 141.54
R² = 0.9621
120
Intensity

100
80
60
40
20
0
0 200 400 600 800 1000 1200
concentation(ppm)

UV of Ni-DMG

3
2.5
Absorbance

2
1.5

1
0.5
0
400 450 500 550 600 650 700 750 800 850
wavelength(nm)

5 ppm 10 ppm 50 ppm 70 ppm 100 ppm

Interference studies

Comparison of various intensities of metals and Nickel and DMG interaction

120

115

110
Intensity

105

100

95

90
Co Ni Cu Zn Ar Fe
metals
RSM Studies

 Response surface methodology (RSM) explores the

relationships between several explanatory variables and one or
more response variables.
 This was used to reduce the number of ratio optimization steps
to be done and by that studies we found out 3:5 i.e. DMG to
Nickel ratio is the optimized value.
REFERENCES

 [1] Andres W. Martinez, Scott T. Phillips, Manish J. Butte, and George M. Whitesides,
“Patterned Paper as a Platform for Inexpensive,
 Low-Volume, Portable Bioassays”, Angew. Chem. Int. Ed. 2007, 46, 1318 –1320.
 [2] Yong He, Wen-bin Wu and Jian-zhong Fu, “Rapid fabrication of paper-based
microfluidic analytical devices with desktop
 stereolithography 3D printer“, RSC Adv., 2015, 5, 2694–2701.
 [3] Rui Hua Tang, Hui Yanga, Jane Ru Choic, Yan Gongc, Shang Sheng Feng, Belinda
Pingguan-Murphye, Qing Sheng Huang, Jun
 Ling Shia, Qi Bing Mei, and Feng Xu, “Advances in paper-based sample pretreatment
for point-of-care testing”, Critical Reviews .