You are on page 1of 9

See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/338415724

Microfluidic Soil Nutrient Detection System: Integrating Nitrite, pH and


Electrical Conductivity Detection

Article  in  IEEE Sensors Journal · January 2020


DOI: 10.1109/JSEN.2020.2964174

CITATIONS READS

0 139

3 authors:

Sohan Dudala Satish Kumar Dubey


BITS Pilani, Hyderabad BITS Pilani, Hyderabad
7 PUBLICATIONS   3 CITATIONS    23 PUBLICATIONS   13 CITATIONS   

SEE PROFILE SEE PROFILE

Sanket Goel
BITS Pilani, Hyderabad
103 PUBLICATIONS   389 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Characterization of Underwater Solarcells View project

Microfluidic Microbial Fuel Cell View project

All content following this page was uploaded by Sanket Goel on 11 January 2020.

The user has requested enhancement of the downloaded file.


This article has been accepted for publication in a future issue of this journal, but has not been fully edited. Content may change prior to final publication. Citation information: DOI 10.1109/JSEN.2020.2964174, IEEE Sensors
Journal
IEEE SENSORS JOURNAL

Microfluidic Soil Nutrient Detection System:


Integrating Nitrite, pH and Electrical
Conductivity Detection
Sohan Dudala, Student Member, IEEE, Satish Kumar Dubey, Sanket Goel, Senior Member, IEEE

Abstract— Soil harbours innumerable microorganisms, contribution of soil in aiding human life is its role in plant
nutrients, and other crucial elements, it anchors vegetation and growth. Healthy plant growth ensures food security, essential
supplies it with the primary factors that make agriculture possible. for human life and the growth of any economy. Soil health is
Soil health is determined by quantifying nutrients and physical primarily determined by identifying and quantifying nutrients
parameters that are required to be in optimum range depending
on the cropping pattern. In line with this, the current work
and specific physical parameters. Physical parameters include
presents an integrated, low-cost, microfluidic-based system for the pH, electrical conductivity (EC) and organic carbon (OC).
detection of three such parameters namely – nitrite, pH and Nutrients are generally subdivided into macronutrients and
electrical conductivity (EC). A filtration protocol using different micronutrients. Macronutrients comprise available nitrogen
grades of Whatman filter paper was established to detect the said (N), potassium (K), and phosphorus (P), amongst many others.
parameters using a suspension of soil. A multiplexed Micronutrients consist of sulfur, zinc, boron, iron, manganese,
polydimethylsiloxane (PDMS) device was designed and fabricated
to test for EC and nitrite. The device employed a conductivity cell copper amongst others [1]–[3]. The nutrients are required to be
with copper electrodes, connected in series with a resistor, in the optimal range and their deficiency can hamper the plant
powered using an oscillating power source. Griess reaction-based growth. Most of these nutrients are available as water-soluble
photometric detection using an LED and photodiode was used to salts, and thus excess of these can easily seep into the water
quantify nitrite. A transimpedance amplifier circuit was designed table and contaminate the water leading to detrimental effects
and fabricated to amplify the photodiode output. pH detection was on human health. For instance, nitrite (NO2-), which is
achieved using a commercially available pH probe and an Arduino
pH breakout board. A low-cost 3D printed syringe pump was
commonly found in nitrogen-rich fertilizers, is water soluble
developed to achieve flow control. Atmega 328P (onboard Arduino and can contaminate drinking water [4].
Uno) was used to integrate the subsystems. A smartphone Given the requirement to safeguard and improve soil health
application was built to control the system and store geotagged by maintaining the nutrients and physical parameters in
data. Bluetooth protocol was used to communicate between the optimum range, it is necessary to gauge the persisting values of
smartphone application and Arduino. Standards and real soil the components mentioned earlier. The identification of
samples were tested using the developed microfluidic system.
existing soil health would aid in proper use of fertilizers and
Index Terms— Microfluidics, Soil Testing, Nitrite Detection, selection of the best-suited crop.
Point-of-Source platform, Three-dimensional printing In this work, the focus was laid on three parameters –
nitrogen (in the form of nitrite), pH, and electrical conductivity,
which are three critical indicators of soil health. The existing
I. INTRODUCTION methods for determination of the soil nutrients and physical
parameters are laboratory-based. They utilize lab-based
S OIL is the source of nutrients for plant growth; it acts as a
water filter for the water table and is the habitat for billions
of organisms. The primary and probably the most important
equipment (spectrophotometers, flame photometers) and
complex chemical processes to quantify the required
parameters [5], [6]. Lab-based tests are not only skill-intensive
Manuscript submitted on September 25, 2019. but also expensive and time-consuming. Microfluidic
Revised Manuscript submitted on November 17, 2019. technologies are being widely used in environmental
Revised Manuscript submitted on December 19, 2019. monitoring and detection [7] to eliminate the drawbacks of
S. Dudala and S. Goel are with MEMS, Microfluidics & Nanoelectronics
Lab, Department of Electrical & Electronics Engineering, BITS Pilani,
above mentioned lab-based tests, which not only expedite the
Hyderabad Campus, Hyderabad 500078, India (e-mail: sample testing but also decrease the required sample size.
sohandudala@gmail.com; sgoel@hyderabad.bits-pilani.ac.in) Nitrogen is an essential mineral nutrient for plant growth and
S.K. Dubey is with MEMS, Microfluidics & Nanoelectronics Lab, is abundant in fertile soil [8]. Nitrogen is utilized by plants,
Department of Electrical & Electronics Engineering and Department of
Mechanical Engineering, BITS Pilani, Hyderabad Campus, Hyderabad
primarily in the form of nitrate, nitrite, and ammonium [9]. The
500078, India (e-mail: satishdubey@hyderabad.bits-pilani.ac.in) conventional methods for the detection of total nitrogen and

1558-1748 (c) 2019 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission. See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
This article has been accepted for publication in a future issue of this journal, but has not been fully edited. Content may change prior to final publication. Citation information: DOI 10.1109/JSEN.2020.2964174, IEEE Sensors
Journal
IEEE SENSORS JOURNAL

available nitrogen utilize complex digestion process involving pH is another crucial physical parameter in soil health.
bulky and expensive laboratory equipment [5]. Nitrite, an Nutrient availability, solubility, and microbial activity are
intermediate product in the conversion of ammonium to nitrate, important aspects of soil health that depend on pH [21]. For
can also act as an indicator of nitrogen in soil. Excess nitrogen instance, the availability of micronutrients to plants increases in
in the soil can have adverse impacts. Nitrites, being water- acidic soil rather than in alkaline soils, whereas the availability
soluble, can contaminate potable water sources via agricultural of macronutrients is increased in alkaline soil [22]. Mostly, pH
drainage from septic tanks and wastewater treatment resulting of soil for effective plant growth varies between sub acidic to
in fatal effects on the human population [10]. Nitrates and sub alkaline range. Ion-sensitive field-effect transistor ISFETs
nitrites, beyond prescribed limits, have shown to have adverse have emerged as a popular choice for pH measurement [23],
effects on human health. Acute toxicity in the form of [24].
methemoglobinemia and a detrimental effect on the thyroid Electrical conductivity (EC) is an indicator of salts in the soil.
gland are a few hazardous effects, amongst many others [11]. Just as in the case of pH, EC also determines nutrient
Carcinogenic effects of nitrates and nitrites have also been availability and microbial activity, amongst other plant growth
reported in cases of chronic exposure [11]. factors. Excess nitrogen-based fertilizer use can also lead to an
Various methods exist for the detection of nitrates and increase in the electrical conductivity of the soil. As per the
nitrites, including spectrophotometric, chemiluminescence and protocol laid down by the Bureau of Indian Standards (BIS) for
spectrofluorometric methods, which have been compared based the determination of electrical conductivity of soil, a
on their advantages and disadvantages [12]. conductivity meter is used employing conductivity cell [6]. A
Chemiluminescence and spectrofluorometric methods have a parallel plate two electrode-based conductivity cell is well-
good detection limit; however, they are expensive compared to established. This macro conductivity cell has a possible
spectrophotometry. One of the popular and established miniaturization application which was employed in this work.
spectrophotometric detection methods for the detection of Table 1 provides an overview of some existing soil sensing
nitrite is using the Griess assay [12], which has also been systems [25]–[29]. Microfluidic based devices for soil nutrient
employed in our earlier work [13]. The Griess reagent is 1% testing are reported in limited numbers. In the past, work has
sulphanilamide (SA) and 0.1 % n-(1-naphthyl) ethylenediamine been done to achieve microfluidic detection of nitrite and nitrate
dihydrochloride (NED) in 5% polyphosphoric acid H 3PO4. in soil [28], [30], [31]. The method of detection employed is
Griess reagent is widely used in the detection and quantification based on impedance measurements. Impedimetric approach-
of nitro groups in a wide variety of applications, including based detection systems have good sensitivity, but the
detection of nitro group compounds in biological samples like sophisticated fabrication methods for electrodes and
blood and urine, and the detection of nitro compounds in water microfluidic channel makes the approach expensive as
[14]–[16]. Owing to the solubility of nitrite in water, a compared to Griess reagent based photometric detection.
suspension of soil in water can be made, and further filtration Recently, nutrient sensing using electrophoresis was reported
can be done. Microfluidic technologies have been widely used [29] where anions and electrical conductivity were
in microreactor applications [17]–[20]. Thus, the Griess test in simultaneously analyzed. Integrated microfluidic system for
the microfluidic environment is accomplished by mixing the simultaneous pH, electrical conductivity and nutrient detection
reagent with the sample in the microchannels. The embedded has not yet been reported.
microchannels enable the use of small volumes of reactant In this work, we report a microfluidic-based portable and a
solutions along with the advantages of large surface-to-volume standalone system for soil testing. Miniaturizing the test setup
ratio, high efficiency, and repeatability. Also, the streams in is intended to decrease chemical reagent cost and detection
microchannels primarily form laminar flow thus allowing strict setup cost, enabling point of source and portable testing,
control on time and reaction conditions. reducing the overall skill required for operation, and improving
TABLE I
OVERVIEW OF SOME EXISTING SOIL SENSING SYSTEMS
Reference Fabrication Method/ Electrical Conductivity (EC) pH Detection Nitrite (NO2-) Sensing Additional Features
Material Sensing
[23] Si wafer Pt Electrodes ISFET type - Temperature sensing, multimodal
(EC Range: 7mS/m to 5 S/m) sensor approach, signal processing circuit
available
[25] Conductive ink printing Four Pt/Au ink electrodes - - Each electrode dimension 27 mm x
on ceramic substrate (0.2 mS/cm to 4 mS/cm) 4mm, Sensor array interface circuit
used
[24] Si wafer - ISFET type - Wireless Sensor Network Employed
sensor
[26] e-beam evaporation on - - Au, Ag/AgCl electrodes Electrochemical studies done for
Si wafer with GF−TiN NFs sensor characterisation
(LOD – Nitrate: 0.01 ppm)
[27] Macroscale electrodes Zn and carbon electrodes - - Wide range DC-DC convertor used
(0.114 mS/cm to 0.744 mS/cm)
[28] Gold interdigitated - - Impedance based sensing of nutrients (N, P, K, Ca, Mg and S)
electrodes
[29] PDMS on glass with Au - - Electrophoretic sensing, soil solution extraction system incorporated,
microelectrodes 7.5 µM LOD for Nitrate ions

1558-1748 (c) 2019 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission. See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
This article has been accepted for publication in a future issue of this journal, but has not been fully edited. Content may change prior to final publication. Citation information: DOI 10.1109/JSEN.2020.2964174, IEEE Sensors
Journal
IEEE SENSORS JOURNAL

the time required to obtain results. To develop the integrated suspension was subjected to a centrifuge at 4,000 rpm for 3
device, Polydimethylsiloxane was used to create the minutes, which accelerated the mixing of water-soluble
microfluidic channel using a 3D Printed mold [32]. Griess assay components. The suspension was filtered using Whatman filter
was employed to detect nitrite using a photometric approach paper. Whatman filter paper of different grades were tested
(LED-Photodiode). Electrode-based detection with the aid of a (four times each) and compared for time taken for filtration
suitable electric circuit was utilized for quantification of (Table 2).
electrical conductivity. pH measurement was achieved using a
commercially available pH electrode. Injection of the sample
was achieved using 3D printed syringe pumps. The system was
integrated using a microcontroller, Bluetooth module, and an
android-based smartphone.

II. EXPERIMENTAL
A. Chemicals and Materials
Phosphoric acid was obtained from SRL Chemicals,
Mumbai. Sodium nitrite, n-(1-naphthyl) ethylenediamine
dihydrochloride (NED), sulphanilamide (S.A.) were procured
from Sigma-Aldrich. All solutions were prepared using Milli-Q
Fig. 1. Soil Suspension in different stages of filtration a) Suspension prior to
grade water. Griess reagent was prepared by making an aqueous filtration b) stage 1 filtration c) Suspension after final filtration
solution of 0.1 g of NED, 1 g sulphanilamide, and 5.0% A compounded filtering method (2 stage filtering) was used.
phosphoric acid. Standard solutions of different concentrations Grade No. 113 paper was first used for filtration, followed by
of nitrite were prepared in Milli-Q grade water using sodium the filtrate being subjected to filtration using Grade No. 1 filter
nitrite. Ferric chloride, sodium carbonate, sodium hydroxide paper. This effectively cut down the filtration time, and the final
were procured from Avra Laboratories. Sodium chloride was filtrate did not exhibit any cloudiness. The filtrate obtained at
purchased from SRL Laboratories, and standard solutions for the end displayed optical clarity on visual inspection. The
conductivity were prepared in HPLC grade water. Buffer suspension prior to filtration and the final filtrate is shown in
solutions of pH 7.0 and 4.0 for pH electrode calibration were Figure 1.
procured from SRL Laboratories. 4.0 molar stock solution of
potassium chloride for storing pH electrode was prepared using C. pH Detection
potassium chloride obtained from Sigma Aldrich. pH detection was carried out using a pH probe and a pH
Whatman Filter papers conforming to different grades (No. 4502C Arduino breakout board (MEMIGHTY, India).
113, No. 41, No. 3, and No. 1) were purchased from Sigma Interfacing of the breakout board to Arduino was done using the
Aldrich. Ploydimethylsiloxane (PDMS) as Sylgard 184 was power supply ports, and data was obtained via the analog input
obtained from Dow Corning. Continuous cast polymethyl ports. Bayonet Neill–Concelman (BNC) connectors were used
methacrylate (PMMA) was procured from Mitsubishi to connect the 4502C board with the pH probe. It was ensured
Chemical. Filaments of 1.75 mm diameter, both polylactic acid that the electrode was always dipped in preservation solution
(PLA) and acrylonitrile butadiene styrene (ABS), for FDM (Potassium Chloride solution), when not in use, to prevent
based 3D Printing were purchased from Novabeans (India). damage to the electrode. Reference solutions of pH 4.0 and pH
7.0 were used to calibrate the device. The hardware calibration
was done by changing the potentiometer value and measuring
B. Filtration Protocol
the pH value of the reference solution. Once a limit on hardware
It is challenging to use soil suspension flowing through calibration was reached, software calibration was employed by
microchannels in optical-based detection. Thus, mixing with defining an offset to correct any error. Post calibration, different
water and successive filtration was employed to obtain a pH standards, and sample test solutions were tested using the
solution containing water-soluble components of soil with calibrated device and corroborated using a commercially
better optical clarity. Centrifuge tubes (15 ml, Tarson) were available pH meter (OAKTON PC 700). The comparison is
used for sample collection. A fixed volume of soil sample tabulated in results and discussion section as Table 3. The
(equivalent to 5 ml) was taken. Deionized (DI) Milli-Q water maximum relative error obtained was 2.02%.
was added in order to obtain a total volume of 15 ml. The soil
D. Electrical Conductivity (EC) Detection
TABLE II
TIME FOR FILTRATION - DIFFERENT GRADE WHATMAN FILTER PAPERS For the detection of electrical conductivity, a two-electrode
Whatman Filter Paper Pore Size Filtration conductivity cell was employed. A Polydimethylsiloxane
Time (PDMS) cell was fabricated using Polylactic Acid (PLA) mold
No. 113 30 µm 16 minutes
No. 41 20-25 µm 27 minutes by fused deposition modelling (FDM) based 3D printing
No. 3 6 µm 136 minutes (Creator Pro, Flash Forge). PDMS, available in the form of
No. 1 11 µm 83 minutes polymer and curing agent, were thoroughly mixed in a 10:1

1558-1748 (c) 2019 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission. See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
This article has been accepted for publication in a future issue of this journal, but has not been fully edited. Content may change prior to final publication. Citation information: DOI 10.1109/JSEN.2020.2964174, IEEE Sensors
Journal
IEEE SENSORS JOURNAL

ratio and placed in a desiccator. The mold was left to cure at E. Nitrite Detection and Multiplexed Microchannel
room temperature for 48 hours and was later extracted [33]. In our earlier work, a proof-of-principle depicting a
Two single strand 20G wires were incorporated in the design to microfluidic device with a Y-shape microchannel was
act as electrodes. A 6 mm wide copper tape was used as presented to enable the mixing of the sample with Griess
electrodes. A conductivity cell was made with dimensions 10 reagent under pressure-driven flow [13]. Owing to the
mm x 10 mm x 6 mm. The electrode surface area was 6 mm x sequential detection of pH, EC, and nitrite, in the current work,
6 mm and was placed 10 mm apart (Figure 2a). the microfluidic device was redesigned. A geometric model of
EC of water in a parallel plate electrode conductivity cell was the microchannel was created in PTC Creo 3.0 (Figure 4). The
obtained from Equation 1. first region incorporated EC cell, and the later region
𝑌𝑥 = 𝐾 × 𝑌 (𝑆𝑐𝑚−1 ) (1) incorporated the nitrite detection region. A mold to be used for
molding PDMS was fabricated using 3D printing with a PLA
Where, filament based on the geometric model (Figure 5a). The region
𝑌 (Measured Conductance) = I/V (S) intended to be used as a detection region showed surface
𝐾 (Cell Constant) = L/A (cm-1) irregularities, which, when molded onto PDMS would interfere
A = area of electrode surface (cm2) with optical detection. Post-processing by vapor smoothing of
L = distance between electrodes (cm) the mold was carried out using Dichloromethane (DCM) (SRL
V = excitation voltage (V) Chemicals, India), to improve the surface finish and enable
I = cell current (A) good optical detection. The 3D printed moulds could be reused,
When the fabricated EC cell was connected in series with a however, to stay away from any unwarranted contamination,
9V battery and ammeter for preliminary testing, bubble each mould was used only once.
formation was observed at the cathodic side of the cell (Figure
2b). This could be attributed to the electrolysis of water. To
prevent this a 50 kHz oscillator circuit was designed and
fabricated (Figure 3). A 555 timer was employed in a stable
mode with suitable resistors and capacitors to obtain a square
wave 50 kHz frequency power source. A voltage drop of around

Fig. 4. Technical drawing of multiplexed microchannel (all dimensions in mm)


Fig. 2. a) Conductivity cell fabricated using copper tape as electrodes b) bubble
formation due electrolysis
1.7 V was observed at the output, effectively making the entire
circuit a 7.3 V oscillating power source. The output from the
oscillator circuit was connected to the conductivity cell with a
1 kΩ resistor in series. The voltage drop across the resistor was
measured at the analog input ports of Arduino by scaling them
between 0 V and 4.9 V. A program was written for Arduino to
convert this voltage drop to corresponding electrical
conductivity values.

Fig. 5. a) Mould for multiplexed microchannel b) Multiplexed channel with


Griess reagent immobilized serpentine microchannel and electrodes.
Griess reagent was immobilized in the serpentine
microchannel. The microchannel was flushed with isopropyl
alcohol (IPA) prior to immobilization. The immobilization of
Griess reagent was achieved using a micropipette and pipetting
Fig. 3. Circuit diagram of the oscillating power source. out the reagent in the microchannel. The open microchannels
were then placed in a hot air oven at 50°C for 90 minutes.

1558-1748 (c) 2019 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission. See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
This article has been accepted for publication in a future issue of this journal, but has not been fully edited. Content may change prior to final publication. Citation information: DOI 10.1109/JSEN.2020.2964174, IEEE Sensors
Journal
IEEE SENSORS JOURNAL

Fig. 7. Results from calibrated developed system. Error bars for absorbance
plotted represent standard deviations for 8 trials of 13 samples

Fig. 6. Integrated System: Circuitry and power source placed behind the vertical support bearing the syringe pump; Tygon tubing connected with 3-way stop cock to
alter flow direction for drawing and delivering the sample. a) 3D printed motor enclosures and supports: 1-stepper motor enclosure, 2-motor and lead screw coupler
support, 3,4-syringe holders; b) detection unit acts as enclosure for LED-Photodiode. The fabricated microfluidic chip is placed in a slot in the detection unit with
LED oriented at the bottom and photodiode at the top of detection region. c) GUI of the Android App.
Finally, the microchannel was bonded and sealed using double- filament (Novabeans, India). The amplified voltage was fed to
sided acrylic tape and PMMA sheet (Figure 5b). the microcontroller powered by a standalone power source (9 V
battery). The integrated system is shown in Figure 6.
F. System Integration
5 ml of sample post-filtration was collected into the sample
An injection system was fabricated to enable inexpensive and container. First the pH of the sample was recorded. Tygon
controlled injection. The system comprised of single-use tubing was used to draw sample from the container into the
Dispovan 3 ml syringes (HMD Healthcare, India) for injecting syringe through the 3DP syringe pump. A 3-way stop cock was
sample and reagent. A stepper motor (28BYJ-48) was used for used to control the direction of flow. Once the fluid was drawn
driving the fluid, and a trapezoidal lead screw was used to into the syringe, the stop cock was turned to enable the flow
convert the rotary motion of the motor to translational motion into the microfluidic channel. The detection setup fixture
enabling the movement of the plungers of syringes. A ensures that the detection region was aligned with the
microcontroller was employed to control stepper rpm thus photodiode and LED. Sample was then dispensed into the
controlling the flow rate of the injection system. microchannel. The electrical conductivity measurement was
The detection unit comprised of a PIN photodiode ambient done continuously for 10 seconds and averaged out. After the
light sensor (TEMD Series, Vishay Intertechnology, USA – electrical conductivity measurement, the microcontroller was
peak sensitivity at 540 nm) having good spectral sensitivity in programmed to switch on the LED. Readings from the
the required wavelength range and a 5 mm green LED. A photodiode were taken continuously for a period of 10 seconds
transimpedance amplifier circuit was designed using an at an interval of 250 ms and averaged.
Operational Amplifier (Texas Instruments, USA) to amplify the MIT App Inventor was used to create an android based
photodiode output to ensure linear gain, low noise, and high mobile app (Figure 6c) to control the entire testing apparatus.
repeatability. Resistor and capacitor values were calculated and Bluetooth was employed to communicate between the
selected to obtain the desired output from an amplifier in the microcontroller and the android smartphone (Samsung Galaxy
range of 0.1 to 4.9 V to prevent the noise from affecting the A7). HC-05 Bluetooth module was integrated with the
output. microcontroller. The inbuilt GPS of the smartphone was used
A printed circuit board (PCB) was fabricated using a negative to geotag the results for reference, which could be used to map
dry-firm photoresist (DFR) based photolithography process to and analyze the results over a region. The results were stored
accommodate all the components of the designed circuit. All locally on the smartphone and could be shared using existing
components of the detection unit were housed inside an techniques. Integration can also be with a cloud-based server to
enclosed 3D printed black box fabricated using the store and analyze the data as an extended application of this
commercially available acrylonitrile butadiene styrene (ABS) work.

1558-1748 (c) 2019 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission. See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
This article has been accepted for publication in a future issue of this journal, but has not been fully edited. Content may change prior to final publication. Citation information: DOI 10.1109/JSEN.2020.2964174, IEEE Sensors
Journal
IEEE SENSORS JOURNAL

III. RESULTS AND DISCUSSION microcontroller cannot comprehend these results. For the other
pH and electrical conductivity for standard known solutions readings, the maximum error is about 14%. The possible
were measured using the fabricated device (Figure 5) and a reasons for this could be additional resistance of the
commercially available device OAKTON PC 700. The results components or minor changes in distance between electrodes or
of pH and electrical conductivity are tabulated in Table 3 and the size of the microfluidic device. Nevertheless, by leveraging
Table 4 respectively. The results in Table 3 and Table 4 are other unique advantages, this device can be used for
reported after performing a minimum 3 repeats for each comparative estimation of electrical conductivity for soil
measurement. suspensions.
TABLE III
COMPARISON BETWEEN 4502C BOARD RESULTS AND COMMERCIAL PH METER Calibration was established using standard solutions with
# Solution pH Value pH Value from Error varying concentrations (0.2-4.5 ppm). Spectrophotometric
from 4502C OAKTON PC 700 (%) absorbance analysis using a UV-Vis Spectrophotometer (Jasco
1 Milli-Q Water 6.95±0.21 7.01 0.90 V-650) was performed on standard solutions. Results were
2 Test Solution 1 2.52±0.18 2.47 2.02 taken at the absorbance maxima of 542nm. The same standard
solutions were tested using the developed system. The results
3 Test Solution 2 8.6±0.12 8.56 0.47
from fabricated device and UV-Vis spectrophotometry are
4 Test Solution 3 5.63±0.14 5.67 0.76 illustrated in Table 5, which were used for calibration of the
5 pH 4.0 Buffer 4.01±0.12 4.11 1.62 device. As expected, the results (Table 5 and Figure 7) indicate
that the absorbance increases as the strength of azo dye
increases, i.e. concentration increases.
TABLE IV
ELECTRICAL CONDUCTIVITY RESULTS USING FABRICATED DEVICE AND
To establish repeatability, thirteen samples ranging from
COMMERCIALLY AVAILABLE DEVICE 0.20 to 4.50 ppm, were prepared and subjected to testing using
# Sample Reading from Reading from pH the developed system (Figure 6). The data for eight trials for
Fabricated Device Meter each of the thirteen samples (thirteen different concentrations),
(µS/cm) (µS/cm) represented good repeatability of the system with the R2 value
1 0.1% aq. NaCl 1596.1±16.9 1647.32
equal to 0.9938 representing good linearity. The limit of
2 0.075% aq. NaCl 1182.5±15.2 1234.84 detection (LOD) and limit of quantification (LOQ) were
3 0.05% aq. NaCl 780.6±11.2 823.21 estimated to be 0.07103 ppm (1.52µM/l) and 0.21524 ppm
4 0.025% aq. NaCl 392.1±5.6 414.2 (4.78 µM/l) respectively. The LOD and LOQ were estimated
using 3σ/m and 10σ/m respectively. As discussed earlier,
5 Tap Water 655.7±7.9 740.6
nitrite in an intermediate product during the conversion of
6 RO Water 455.5±5.8 531.12 ammonia to nitrate, thus a correlation needs to be established
7 DI Water 38.05 6.013 between nitrite level and total nitrogen to analyze the results
8 3.5% aq. NaCl 3805.18 5412.02 better.
Based on the fabricated system, two real samples (red sandy
pH detection subsystem displayed good results against the and black soil) were tested. The samples were collected from
sample solutions. The maximum absolute error in pH value BITS Pilani, Hyderabad Campus. Samples were selected in
between fabricated device and commercially available device order to ensure the difference in physical appearance (color,
was 2.02%. Based on the results from electrical conductivity granule size, moisture content, etc). Three test repetitions were
detection subsystem, it can be observed that the difference in done for each soil sample and the observations and results are
electrical conductivity between test samples (DI water and summarized in Table 6.
3.5% NaCl solution), is quite high. The reason behind this TABLE VI
SOIL SAMPLE TEST RESULTS
variation can be attributed to the voltage readings from
# Sample Physical Electrical pH Nitrite
Arduino. The analog inputs in Arduino could only read a signal Location Observations Conductivity Content
between 0 to 5 volts. For DI water and 3.5 % salt solution, the (µS/cm) (ppm)
limiting values have already been achieved, and the 1 D-Block Red Colour, 417.3±5.76 7±0.1 0.70±0.02
TABLE V Garden, Moist, Grass
RESULTS USED FOR CALIBRATION FROM FABRICATED DETECTION SYSTEM BPHC being grown
AND UV-VIS SPECTROPHOTOMETER
2 Construction Black, Dry, 1273.83±15.57 8±0.11 3.69±0.02
Solution Concentration Detection Spectrophotometer Site, Used for land
No. (ppm) System Output Absorbance I Block, fill
(V) (542 nm) BPHC
1 0.00 (Blank) 4.70 0.00213
2 0.20 4.31 0.01406
IV. CONCLUSION
3 0.75 3.90 0.04956
The presented work puts forth, an integrated microfluidic
4 1.50 3.05 0.08589
platform for soil testing. The device establishes nitrite detection
5 3.00 1.88 0.16479 with good repeatability. The standard deviation for
6 4.50 0.85 0.26255 measurement of lowest analyte concentration using eight trials
for thirteen samples was 0.0012. The system displayed

1558-1748 (c) 2019 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission. See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
This article has been accepted for publication in a future issue of this journal, but has not been fully edited. Content may change prior to final publication. Citation information: DOI 10.1109/JSEN.2020.2964174, IEEE Sensors
Journal
IEEE SENSORS JOURNAL

detection capability for pH and electrical conductivity with 7, pp. 6041–6059, Jul. 2011.
[18] V. Hessel, S. Hardt, and H. Löwe, Chemical Micro Process
maximum errors of 2.02% and 14%, respectively. An electrical Engineering: Fundamentals, Modelling and Reactions. John Wiley
conductivity detection method was employed with ease of & Sons, Ltd, 2005.
fabrication. Shortcomings have been identified, and [19] Y. Wang and J. D. Holladay, Microreactor Technology and Process
Intensification. ACS Publications, 2005.
enhancement will be done to improve detection range and
[20] S. C. Bera and B. Chakraborty, “A Novel Technique of Flow
accuracy. Work is being carried out to integrate detection and Measurement for a Conducting Liquid,” IEEE Trans. Instrum. Meas.,
quantification of other soil macronutrients by utilizing the same vol. 58, no. 8, pp. 2512–2517, 2009.
platform. To improve automation of the system, an automated [21] R. Gentili, R. Ambrosini, C. Montagnani, S. Caronni, and S. Citterio,
“Effect of Soil pH on the Growth, Reproductive Investment and
sample loading technique is being devised. Further, it is planned Pollen Allergenicity of Ambrosia artemisiifolia L.,” Front. Plant Sci.,
to integrate the system with IoT to establish the possibility of vol. 9, p. 1335, 2018.
real-time monitoring soil health. With the component cost of [22] Z. Lončarić, K. Karalić, B. Popović, D. Rastija, and M. Vukobratović,
“Total and plant available micronutrients in acidic and calcareous
₹4,300 (US$ 60), the current integrated system is a step towards soils in Croatia.,” Cereal Res. Commun., vol. 36, no. Suppl., pp. 331–
a complete point of source soil analysis system to replace the 334, 2008.
time, skill, and resource-intensive laboratory-based soil testing [23] M. Futagawa, T. Iwasaki, H. Murata, M. Ishida, and K. Sawada, “A
Miniature Integrated Multimodal Sensor for Measuring pH, EC and
and analysis. Temperature for Precision Agriculture,” Sensors , vol. 12, no. 6.
2012.
REFERENCES [24] C. Manjarrés, D. Garizado, M. Obregon, N. Socarras, M. Calle, and
C. Jimenez-Jorquera, “Chemical sensor network for pH monitoring,”
[1] K. M.G, K. Ritz, and S. M.J, “Soil health in agricultural systems,” J. Appl. Res. Technol., vol. 14, no. 1, pp. 1–8, 2016.
Philos. Trans. R. Soc. B Biol. Sci., vol. 363, no. 1492, pp. 685–701, [25] J. K. Atkinson and M. Sophocleous, “A novel thick-film screen
Feb. 2008. printed electrical conductivity sensor for measurement of liquid and
[2] Z. Rengel, “Soil pH, Soil Health and Climate Change BT - Soil soil conductivity,” in SENSORS, 2014 IEEE, 2014, pp. 86–89.
Health and Climate Change,” B. P. Singh, A. L. Cowie, and K. Y. [26] M. A. Ali et al., “In situ integration of graphene foam–titanium
Chan, Eds. Berlin, Heidelberg: Springer Berlin Heidelberg, 2011, pp. nitride based bio-scaffolds and microfluidic structures for soil
69–85. nutrient sensors,” Lab Chip, vol. 17, no. 2, pp. 274–285, 2017.
[3] Ministry of Agriculture & Farmers’ Wlefare (GOI), “Soil Health [27] I. Ou, K. Tsai, Y. Chu, and Y. Liao, “Self-Sustaining Soil Electrical
Card.” [Online]. Available: Conductance Measurement Using a DC–DC Power Converter,” IEEE
https://soilhealth.dac.gov.in/Content/FAQ/SOILHEALTHCARD- Sens. J., vol. 19, no. 22, pp. 10560–10567, 2019.
English.pdf. [28] L. M. Braunger et al., “Microfluidic Electronic Tongue Applied to
[4] A. Verma, A. K. Rawat, and N. More, “Extent of Nitrate and Nitrite Soil Analysis,” Chemosensors , vol. 5, no. 2. 2017.
Pollution in Ground Water of Rural Areas of Lucknow, U.P, India,” [29] Z. Xu, X. Wang, R. J. Weber, R. Kumar, and L. Dong, “Nutrient
Current World Environment, vol. 26, no. 27. 2014. Sensing Using Chip Scale Electrophoresis and In Situ Soil Solution
[5] R. K. Thakur, S. S. Baghel, G. D. Sharma, R. K. Sahu, and P. C. Extraction,” IEEE Sens. J., vol. 17, no. 14, pp. 4330–4339, 2017.
Amule, “Laboratory Manual for Biotic and Abiotic Resources [30] M. A. Ali, K. Mondal, Y. Wang, N. K. Mahal, M. J. Castellano, and
Management for Eco-friendly and Sustainable Agriculture,” 2011. L. Dong, “Microfluidic detection of soil nitrate ions using novel
[6] B. 23 Soil Engineering Sectional Committee, “Determination of the electrochemical foam electrode,” in 2017 IEEE 30th International
specific electrical conductivity of soils - method of test,” Bur. Indian Conference on Micro Electro Mechanical Systems (MEMS), 2017,
Stand., pp. 1–10, 2000. pp. 482–485.
[7] M. Yew, Y. Ren, K. S. Koh, C. Sun, and C. Snape, “A Review of [31] M. A. Ali et al., “Microfluidic impedimetric sensor for soil nitrate
State-of-the-Art Microfluidic Technologies for Environmental detection using graphene oxide and conductive nanofibers enabled
Applications: Detection and Remediation,” Glob. Challenges, vol. 3, sensing interface,” Sensors Actuators B Chem., vol. 239, pp. 1289–
no. 1, p. 1800060, Jan. 2019. 1299, 2017.
[8] N. M. Crawford, “Nitrate: nutrient and signal for plant growth.,” [32] P. S. B., S. A. Puranam, and S. Goel, “3-D Printed Integrated and
Plant Cell, vol. 7, no. 7, pp. 859–868, Jul. 1995. Automated Electro-Microfluidic Viscometer for Biochemical
[9] S. J et al., Role of Nitrogen for Plant Growth and Development: A Applications,” IEEE Trans. Instrum. Meas., vol. 68, no. 7, pp. 2648–
review, vol. 10. 2016. 2655, 2019.
[10] G. J. A. Speijers, “Nitrate and nitrite in drinking-water,” 2011. [33] I. D. Johnston, D. K. McCluskey, C. K. L. Tan, and M. C. Tracey,
[11] M. Parvizishad, A. Dalvand, A. H. Mahvi, and F. Goodarzi, “A “Mechanical characterization of bulk Sylgard 184 for microfluidics
Review of Adverse Effects and Benefits of Nitrate and Nitrite in and microengineering,” J. Micromechanics Microengineering, vol.
Drinking Water and Food on Human Health,” Heal. Scope, vol. 6, no. 24, no. 3, p. 35017, Feb. 2014.
3, pp. 1–9, 2017.
[12] Q.-H. Wang et al., “Methods for the detection and determination of
nitrite and nitrate: A review,” Talanta, vol. 165, pp. 709–720, Apr. Sohan Dudala (S’19) received the B.Tech
2017. degree from Manipal University Jaipur, India, in
[13] S. Dudala, S. K. Dubey, and S. Goel, “Fully Integrated, Automated 2016 and M.E. degree from BITS-Pilani,
and Smartphone enabled Point-of-Source Portable Platform with Hyderabad Campus, India, in 2019, both in
Microfluidic Device for Nitrite Detection,” IEEE Trans. Biomed. Mechanical Engineering. He is currently working
Circuits Syst., pp. 1–1, 2019. towards the Ph.D. degree at MEMS,
[14] M. Benhabib and X. Li, “Low-cost assays in paper-based Microfluidics & Nanoelectronics Lab,
microfluidic biomedical devices,” Microfluid. Devices Biomed. Department of Electrical & Electronics
Appl., pp. 492–526, 2013. Engineering, BITS-Pilani, Hyderabad Campus. His current research
[15] D. Giustarini, R. Rossi, A. Milzani, and I. Dalle-Donne, “Nitrite and interests include MEMS, microfluidics, Organ-on-Chip platforms
nitrate measurement by Griess reagent in human plasma: evaluation and point-of-source devices.
of interferences and standardization.,” Methods Enzymol., vol. 440,
pp. 361–380, 2008.
[16] Q. Wen and D. C. Paik, “Using the Griess colorimetric nitrite assay
for measuring aliphatic beta-nitroalcohols.,” Exp. Eye Res., vol. 98,
pp. 52–57, May 2012.
[17] Y. Asanomi, H. Yamaguchi, M. Miyazaki, and H. Maeda, “Enzyme-
immobilized microfluidic process reactors,” Molecules, vol. 16, no.

1558-1748 (c) 2019 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission. See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
This article has been accepted for publication in a future issue of this journal, but has not been fully edited. Content may change prior to final publication. Citation information: DOI 10.1109/JSEN.2020.2964174, IEEE Sensors
Journal
IEEE SENSORS JOURNAL

Satish Kumar Dubey received his M. Tech in


Thermal Engineering from Maulana Azad
National Institute of Technology, Bhopal, India
and PhD Degree from Birla Institute of
Technology and Science Pilani. He is currently
Assistant Professor in the Department of
Mechanical Engineering at BITS Pilani,
Hyderabad Campus. His research interests
include Microfluidics, Computational Heat
Transfer, Simulation of Micro and Thermal Systems, MEMS, etc.

Sanket Goel (SM’19) received the B.Sc. (H-


physics) degree from Ramjas College, Delhi
University, the M.Sc. (physics) degree from IIT
Delhi, and the Ph.D. (electrical engineering)
degree from the University of Alberta, Canada.
He headed the R&D Department and worked as
an Associate Professor, University of Petroleum
and Energy Studies, Dehradun, India, from
2011 to 2015. He is currently an Associate
Professor and Head, Electrical and Electronics
Engineering Department, BITS–Pilani, Hyderabad Campus, Hyderabad,
India. He has >80 publications, 7 patents (1 U.S. and 6 Indian) to his
credits, delivered >50 invited talks, and guided 12 Ph.D. and 9 master’s
students. His current research interests are microfluidics and
nanotechnology, materials and devices for energy and biomedical
applications. He has awards including the Fulbright-Nehru Fellowship
(2015), the Young Scientist Award (2013), the Best Students Paper
Award (2005), and the Ph.D. Thesis Award (2005). Currently, he is the
Associate Editor of IEEE Sensors Journal and IEEE Access, and holds
visiting appointment with UiT, The Arctic University of Norway.

1558-1748 (c) 2019 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission. See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
View publication stats

You might also like