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سنسور گاز1

A low-cost gas sensor utilizing surface-mount light-emitting diodes (LEDs) has been developed for colorimetric detection, featuring a simple microcontroller circuit that minimizes power consumption and cost. The sensor demonstrates high sensitivity and signal-to-noise characteristics, particularly for ammonia detection in the low-parts-per-billion range using a chemochromic film. This innovative approach eliminates the need for traditional photodiodes and analog-to-digital converters, making it suitable for battery-powered applications.

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0% found this document useful (0 votes)
14 views6 pages

سنسور گاز1

A low-cost gas sensor utilizing surface-mount light-emitting diodes (LEDs) has been developed for colorimetric detection, featuring a simple microcontroller circuit that minimizes power consumption and cost. The sensor demonstrates high sensitivity and signal-to-noise characteristics, particularly for ammonia detection in the low-parts-per-billion range using a chemochromic film. This innovative approach eliminates the need for traditional photodiodes and analog-to-digital converters, making it suitable for battery-powered applications.

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ali khorami
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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IEEE SENSORS JOURNAL, VOL. 6, NO.

4, AUGUST 2006 861

Low-Cost Surface-Mount LED Gas Sensor


Roderick L. Shepherd, William S. Yerazunis, Senior Member, IEEE, King Tong Lau, and Dermot Diamond

Abstract—A low-cost chemical sensor comprising surface- but there are no other components requiring additional power,
mount light-emitting diodes (LEDs) has been developed for col- so this is the only power draw associated with the detector
orimetric gas detection. The device consists of a pair of LEDs itself. The system provides a simple low-cost battery-powered
connected to a simple PIC microcontroller circuit and in the most
basic form, requires the use of only two input–output (I/O) pins sensing platform with very good sensitivity and signal-to-noise
on the chip. The key features of this sensor are the use of a LED (S/N) characteristics. Initially, we developed this system for
rather than a photodiode for light detection and an all-digital light communication and light sensing applications that made use of
detection protocol that leads to a reduction in cost and power con- the bidirection properties of LEDs [6]; after which, we began
sumption by avoiding the need for an analog-to-digital converter. work on all-LED colorimetric chemical sensors. To date, we
The surface-mount diodes employed are more compact than stan-
dard LEDs and are more amenable to coating by solid-state sensor have reported on the use of a fused-LED sensor for monitoring
films. Results from sensors employing a chemochromic ammonia colorimetric reactions in solution [7] and on the detection of
sensitive film are presented, and the detection of this target is Fe(II) at concentrations in the low-parts-per-billion (ppb) range
demonstrated in the parts-per-million range. The configuration is using a pair of LEDs in transmittance mode [8]. Recently, we
applicable to a wide range of colorimetric gas sensing materials. presented results on a transmission-mode solid-state gas sensor
Index Terms—Ammonia sensor, colorimetry, gas sensor, light- for ammonia, which comprises two small surface-mount LEDs
emitting diodes (LEDs), LED sensor, low-cost sensor, optical and a chemochromic polymer sensing film [9]. This paper
sensor. provides a more detailed account of the surface-mount LED
ammonia sensor and outlines the key advantages of using this
I. I NTRODUCTION approach for colorimetric chemical sensing.

L IGHT-EMITTING diodes (LEDs) are being used far more


commonly as light sources in optical chemical sensors due
to the low-cost, low-power consumption, reliability, and ever-
II. M ATERIALS AND M ETHODS
A. Sensing Protocol
increasing range of devices and wavelengths available. The
increased interest in LED sources has had a major impact on The sensing technique that we have developed is all-digital
low-cost-component-based chemical sensors, where the main in nature; hence, there is no need for conversion of an analog
goal is to achieve analytical performance without the expense signal, which is normally the case with photodiode-based op-
of more conventional instrumentation [1]–[5]. Typically, a pho- tical chemical sensors. This reduces system cost by avoiding
todiode is used for detection, good sensitivity, and a significant the need for a precision operational amplifier (OPAMP) and an
reduction in system cost. Usually, the photodiode is operated external ADC chip or a more expensive microcontroller with
at Vbias = 0 V and hence can be considered as a low-power a reasonably high-resolution built-in ADC. There is a short
sensor. However, in addition to the detector, a good-quality op- reverse-biasing step (100 µs) associated with our LED sensor,
erational amplifier and mid-to-high-resolution analog-to-digital which involves charging the diode capacitance to the supply
(ADC) are required to complete the device. These additional voltage (3 or 5 V), but this is the only power draw involved.
components not only increase system complexity and cost but While photodiode systems are typically operated at Vbias =
also add to the power requirements, which is of particular 0 V, the power consumption of any supporting chips required
importance in battery-powered systems. The sensor we have for this method of detection (OPAMP and usually external
developed requires only a simple microcontroller and a pair ADC) will be significant. Hence, the LED-based sensing ap-
of LEDs, one of which is driven in reverse-bias mode to proach is low cost with relatively low power requirements,
function as a light detector. The detector LED requires a short and our findings thus far indicate that the signal integration
reverse-biasing step (100 µs) to the supply voltage (3 or 5 V), approach used in the digitization of the photocurrent gives
excellent S/N characteristics and therefore, very low limit of
detection (LOD) in analytical measurements [8].
Manuscript received April 28, 2005; accepted September 23, 2005. This Typically, the detector LED is connected to a pair of digital
work was supported by the Science Foundation Ireland under the Adaptive
Information Cluster (AIC) Award under Grant 03/IN.3/I361. The associate input–output (I/O) pins and operated in reverse-bias mode.
editor coordinating the review of this paper and approving it for publication However, if pin availability is critical, the detector can be driven
was Dr. Erno Lindner. from a single I/O pin with the anode tied to ground. The advan-
R. L. Shepherd, K. T. Lau, and D. Diamond are with the Adaptive Sensors
Group, National Centre for Sensor Research, School of Chemical Sciences, tage of using a pair of I/O pins for detection is that the LED
Dublin City University, Dublin 9, Ireland (e-mail: [email protected]; can be operated bidirectionally and hence can be used to emit
[email protected]; [email protected]). and detect light. This has potential implications for sensors with
W. S. Yerazunis is with MERL, Cambridge Research Lab, Cambridge, MA
02139 USA (e-mail: [email protected]). communication capabilities, ranging from simple visual feed-
Digital Object Identifier 10.1109/JSEN.2006.877849 back to more complex line-of-sight data transfer. In either case,
1530-437X/$20.00 © 2006 IEEE
862 IEEE SENSORS JOURNAL, VOL. 6, NO. 4, AUGUST 2006

Fig. 2. Block diagram of the PIC16F876 LED sensing circuit.

ADC, these currently tend to be more of general-purpose con-


verters, where the resolution is only 10 bits. In many sensing
Fig. 1. Oscilloscope trace of the LED sensor discharge curve. Digital detec- applications, better resolution is required, so typically a 12-bit
tion of light is achieved by continually polling the I/O pin logic state.
or even 16-bit external ADC is employed, which adds signifi-
the diode junction is charged to the supply voltage (normally cant cost to the system and increases power usage. The current
5 V), and then the I/O pin connected to the cathode is switched PIC16F876-based circuitry provides a generic interface and
to high-impedance input mode. Photons impinging on the de- control platform that is used for the development of a range of
tector diode produce a small (in nanoamperes) photocurrent, different sensors in our laboratories, but the sensing technique
which causes the 5 V charge to decay. Using a timing routine described herein could easily be implemented on a lower cost
implemented in firmware that is programmed onto the micro- microcontroller without an ADC. The 16F876 is running at
controller, we continually poll the logic state of the input pin 5 million instructions per second (MIPS), and the resulting min-
until the logic 0 threshold (∼ 1.7 V) is reached. The time imum sensing resolution achievable at this clock speed is ap-
taken in microseconds to reach logic 0 is proportional to the proximately 5 µs. The maximum fixed sensing period typically
amount of light detected. As the amount of light received employed is 65 000 µs, which ensures that a suitable integration
increases, the diode discharges more rapidly, and hence, lower time is provided without causing any overflow problems (tim-
timing values are observed. Conversely, as the amount of light ing values are stored in a 16-bit variable max = 65535). Sig-
decreases, the time to reach logic 0 increases. An oscilloscope nificantly longer integration periods are possible by adding an
trace of a sensing cycle (Fig. 1) illustrates this process of diode additional delay in the timing routine implemented in the soft-
discharge and logic-threshold crossing. The logic voltage of the ware on the PIC. This scaling permits measurements to be made
I/O pin is plotted on the vertical axis, whereas time is plotted over hundreds of milliseconds or even seconds if required, but
along the horizontal axis in 200 µs divisions. The time-based there is an obvious tradeoff between the total integration time
measurement in this example is indicated by the horizontal line and resolution, which decreases with increased scaling.
labeled “count” and corresponds to a value of approximately If noise is considered (typically ±10 µs on the observed
1300 µs. To increase noise immunity, the measurement process discharge time), then the minimum sensing resolution is closer
is not a simple timer that stops when the first logic 0 is read. to 40 µs, but this still provides more than adequate sensitivity
Instead, repeated measurements are performed in rapid succes- for the measurements described in this paper.
sion over the maximum time interval we wish to accept. For
each measurement showing a logic 1, we increment a counter;
B. Sensor Design
if the measurement shows a logic 0, we do not change the
counter. Assuming that the noise signal is uncorrelated with the The sensor comprises two 1206-format surface-mount LEDs,
timing of the sample measurements, this gives us a significant which have overall dimensions of 3.2 × 1.6 mm and a flat
improvement in the S/N ratio and also yields a constant and lens (Fig. 3). For the sensor described in this paper, a 574 nm
deterministic output rate for the sensor–microcontroller system. green exciter LED (Kingbright KP-3216MGC) was used in
At present, data is collected via an RS232 link between the combination with a 621 nm red-orange detector LED (Lite-
device and a PC, but this could be easily replaced with a LED- On LTST-C150KAKT). The LEDs are soldered onto 2.0 mm
based wireless communication link. Molex pitch header pins for ease of connection and to allow
The circuit employed for this paper (Fig. 2) comprised a for adjustment of the air gap (Figs. 3(b) and 4). A variety
PIC16F876 microcontroller, MAX232ACP RS232 level shifter, of arrangements are possible, but for this paper, we focused
and supporting components required by the chips, including a on the design shown in Fig. 4, where the diodes are stacked
20 MHz ceramic resonator for the PIC. The microcontroller has vertically with respect to each other. For this paper, the detector
a built-in 10-bit ADC, but this feature is not required for our LED, which is coated with the chemochromic reagent film, was
sensor and hence was unused. While many reasonably priced positioned such that it faced downward, effectively reducing
microcontrollers, such as the PIC16F876, now have an internal effects arising from variations in the ambient light. In particular,
SHEPHERD et al.: LOW-COST SURFACE-MOUNT LED GAS SENSOR 863

Fig. 5. Reaction scheme of NPNA with NH3 . Ammonia forms a weak


complex with NPNA, which brings about a color change from yellow to red.

Fig. 3. (a) Schematic of the surface-mount LED ammonia sensor illus- ammonia (Fig. 5) and causes a chromic shift in the material
trating the form factor of the 1206 surface-mount LEDs and (b) configu- from yellow to red. NPNA is pH sensitive to some extent, but
ration of LEDs in the chemical sensor. (Color version available online at
http://ieeexplore.ieee.org.)
only extremely basic species shift the equilibrium. As there
are limited cross-reacting species in the gas phase with these
properties, NPNA in the solid state exhibits reasonably high
selectivity to NH3 and primary amines.

D. Ammonia Sensor Testing


The gas sensor was tested for responses to NH3 in a simple
flow cell that was fabricated in-house. A 100 ppm (v/v) NH3
standard premixed gas cylinder (Scott U.K.) was used in com-
bination with a nitrogen line for dilution to deliver ammonia
samples in the concentration range of 6.25–14.3 ppm to the
sensor. Gas flow rates were controlled by rotameters and were
in the range of 0–50 mL/min for NH3 and constant 300 mL/min
for N2 . The nitrogen flow was maintained at 300 mL/min
throughout all experiments, both during the response and re-
covery cycles, as the manual adjustment on the rotameters used
was not precise enough to allow for continual flow adjustments.
The gas flow was passed through the headspace of a water
Fig. 4. Surface-mount LED chemical sensor housed in a Molex receptacle. bubbler to maintain relatively constant humidity throughout the
Coarse baseline adjustment is made by changing the air gap between the LEDs.
experiments.
this arrangement ensures that the majority of room lighting does
not impinge directly on the detector diode. The exciter LED, III. R ESULTS AND D ISCUSSION
which was used without any additional coating on the lens,
A. NPNA Optical Response
was positioned directly below the detector at a distance of
approximately 0.5–1.0 mm. The LEDs were plugged into a The optical response of NPNA upon exposure to ammonia is
2.0 mm Molex receptacle, and the air gap between the LEDs due to shifts of the protonated-form absorbance peak (λ max =
was adjusted by simply moving the detector LED relative to 420 nm) to the deprotonated basic form (λ max = 550 nm)
the exciter (Fig. 4). This physical adjustment of the LEDs with (Fig. 6). This causes a visible color change in the material,
respect to each other allows for coarse tuning of the baseline which is yellow in air and red after interaction with ammonia.
signal, which is particularly useful when the relocation of a The green emitter LED chosen for this particular sensor has a
device involves major changes in ambient light levels. peak wavelength of 574 nm, a dominant wavelength of 568 nm,
and a spectral half-width of approximately 20 nm [10]. The
emission spectrum of the LED was measured to confirm these
C. Ammonia-Specific Colorimetric Reagent
specifications using an Ocean Optics S2000 spectrometer and
The reagent used for this paper is p-nitrophenylnitrosamine has been superimposed over the NPNA spectra in Fig. 6 for
(NPNA) and was synthesized in-house (Fig. 5). A mix of NPNA comparative purposes. It is clear that the emissive properties of
and polyvinyl chloride (PVC) in cyclohexanone was prepared, this LED overlap well with the base form of NPNA, and hence
which was subsequently drop coated onto the detector LED lens make it an ideal light source for monitoring the development
by applying a small volume from a pipette. Due to the relatively of the red NPNA/NH3 complex. As the concentration of NH3
low surface area of the LEDs used in this paper, the volume of increases, the intensity of light transmitted through the sensing
the reagent required for preparation of each sensor was kept film to the detector LED decreases, and the discharge time
to a minimum (< 5 µL). NPNA forms a weak complex with values measured by the microcontroller circuit increase.
864 IEEE SENSORS JOURNAL, VOL. 6, NO. 4, AUGUST 2006

Fig. 6. Spectra of the NPNA acid and base forms, and emission spectrum of
a 574 nm green emitter LED. The overlap between the LED source and base
form of NPNA, which develops in the presence of ammonia, is very good. Fig. 8. Average changes in the response (n = 4) of the LED ammonia sensor,
with error bars indicating the standard deviation. (Color version available online
at http://ieeexplore.ieee.org.)

be attributed to the equilibration of relative humidity (RH) in


the sensor test chamber over the course of the experiment. The
drift is most evident at the start of the test run (peak 1), with
the baseline virtually stabilizing by the last sample (peak 4).
Experiments were carried out at essentially saturated RH,
which provided a simple means of maintaining humidity close
to constant but caused some drift due to polymer swelling as
the RH stabilized. Despite some baseline instability, sensor
responses were not significantly affected, and quite reasonable
reproducibility was observed from one sample to the next.
The simple flow system used to prepare and deliver these
gas samples did not allow precise control of the NH3 flow
rates, and the influence of this on sensor reproducibility became
more evident at faster rates, where the ammonia accounted for a
larger fraction of the total flow. The larger errors associated with
the 12.5 and 14.3 ppm data points (Fig. 8) are indicative of this
flow-induced variation in the response. Despite these sources
of variation, responses were linear over the entire concentra-
Fig. 7. Response of the LED sensor to multiple samples of 9 ppm NH3 in tion range investigated, as shown in Fig. 8. The NH3 range
nitrogen. Raw data is plotted in gray, and the smoothed response is plotted
in black after a moving average filter (per = 20) was applied to the raw
studied was quite limited, as we were primarily concerned with
data. Increases in the sensor timing response are observed in the presence of determining or at least estimating the LOD. The minimum NH3
ammonia due to stronger absorbance of emitted light by the NPNA film. concentration that could be generated with the setup used was
6.25 ppm; hence, it was not possible to obtain data at lower
B. LED Sensor Responses
concentrations.
The sensor was exposed to NH3 samples in the range of The estimated LOD, which is based on the baseline noise
6.25–14.3 ppm. As mentioned earlier, an approximate lower of the raw data and an average response at 6.25 ppm NH3 of
sensing limit of this device based upon observations of the approximately 30 µs, is about 5 ppm in this particular con-
baseline noise is around 20 µs of dither in the measured nominal figuration and experimental design. We are confident that this
discharge time. Thus, at lower concentrations of the NH3 tested, can be significantly improved by applying simple filtering as
the sensor was approaching the LOD. Sensor responses to previously discussed and by varying the polymer sensing layer
multiple samples of 9 ppm NH3 are shown in Fig. 7, and as thickness, which has a significant effect on both response time
expected, increases in the sensor timing response were observed and sensitivity. Until now, we have coated the detector LED in
in the presence of ammonia. The level of noise present in the our sensors by simply drop coating a small volume of NPNA/
signal is quite significant, but despite this, the responses are polymer onto the lens and allowing this to dry. While this has
clearly distinguishable and reproducible. By applying a simple been adequate for initial prototype sensors, the ideal approach
moving average filter to data (Microsoft Excel, period = 20), to controlling the film thickness is spin coating. The surface-
there is a significant improvement in the S/N ratio [Fig. 7, (solid mount LEDs used are ideal for use with this deposition tech-
line)]. Some baseline drift was observed (Fig. 7), which can nique, as the lens structure provides a uniformly flat surface.
SHEPHERD et al.: LOW-COST SURFACE-MOUNT LED GAS SENSOR 865

Controlling the volume of the sensing material and rotation (a precision OPAMP and an expensive external ADC or a more
rate will provide a means of varying the NPNA film thick- expensive microcontroller with high-resolution internal ADC),
ness, enabling further optimization of the sensors. We plan to and as the sensing protocol employs a software-based photocur-
investigate this further in the future and are already encouraged rent measurement, the devices are highly flexible and essen-
by the results obtained using the sensor described in this tially platform independent. The sensor has been demonstrated
paper. The current surface-mount LED sensor, which is clearly for the detection of low-parts-per-million levels of ammonia,
not optimized, detected ammonia in a linear fashion in the as determined using a selective colorimetric polymer coating
5–15 ppm range. that contains NPNA, but this configuration is amenable to a
wide range of colorimetric-based gas sensing materials. Indeed,
C. System Flexibility and Portability virtually any colorimetric assay could be immobilized in some
way and deposited onto the lens of a surface-mount LED. The
One of the key features of our system is the software-based challenge is really in developing reliable sensing materials for
timing protocol. In addition to the aforementioned benefits of this purpose, with the LED sensor providing a low-cost generic
digital signals this provides, many sensing parameters can be platform upon which sensors can be developed. The portability,
controlled and updated in the software. Critical sensing prop- low cost, and low-power characteristics of these devices make
erties including integration period, minimum timing resolution, them ideal chemical sensors for WSN applications, where
average rate, sampling rate, and power saving schemes can eas- power consumption is critical.
ily be controlled at run-time in code or updated by an external
device without any change to the physical characteristics of R EFERENCES
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bidirectionally, these sensor properties can even be updated based on Berthelot’s reaction,” Sens. Actuators, B, Chem., vol. 98, no. 1,
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[2] L. Byrne, K. T. Lau, and D. Diamond, “Monitoring of headspace total
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[3] Y.-S. Lee, B.-S. Joo, N.-J. Choi, J.-O. Lim, J.-S. Huh, and D.-D. Lee,
LED-based sensors can be interfaced seamlessly with a “Visible optical sensing of ammonia based on polyaniline film,” Sens.
wide range of different microcontroller architectures and Actuators, B, Chem., vol. 93, no. 1, pp. 148–152, Aug. 2003.
[4] E. J. Cho and F. V. Bright, “Intergrated chemical sensor array platform
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efficiency is therefore paramount, and saving a few mil- 2002. [Online]. Available: www.kingbright.com
liamperes of current can significantly increase the lifetime of an [11] Mica2Dot Wireless Microsensor Mote Document Part Number: 6020-
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chemical sensors.
Roderick L. Shepherd received the B.Env.Sc. (Hons.) and Ph.D. degrees from
the University of Wollongong, Wollongong, N.S.W., Australia, in 1996 and
IV. C ONCLUSION 2001, respectively.
A low-cost colorimetric ammonia gas sensor that uses small From 2001 to 2002, he was a Research Fellow with the National Centre
for Sensor Research, Dublin City University, Dublin, Ireland, where he is cur-
surface-mount LEDs as both light source and detector has rently a Research Fellow with the Adaptive Sensors Group, working primarily
been developed. Sensor responses are monitored using a simple on wireless sensor networks and low-cost light-emitting-diode-based optical
microcontroller circuit, which is entirely digital in nature. This chemical sensors. In 2003, he was a Visiting Research Scientist with Mitsubishi
Electric Research Laboratories, Cambridge, MA. His research interests include
configuration avoids the cost and power requirements of typical chemical sensors, inherently conducting polymers, colorimetric optical sensors,
supporting components employed when using a photodiode robotics, and wireless communication.
866 IEEE SENSORS JOURNAL, VOL. 6, NO. 4, AUGUST 2006

William S. Yerazunis (SM’04) received the B.S., M.Eng., and Ph.D. degrees in Dermot Diamond received the B.Sc., M.Sc., Ph.D., and D.Sc. degrees from
systems engineering from Rensselaer Polytechnic Institute, Troy, NY, in 1978, Queen’s University, Belfast, Northern Ireland.
1979, and 1987, respectively. He is currently the Principal Investigator of a recently awarded Science
He is currently a Senior Research Scientist with Mitsubishi Electric Research Foundation Ireland (SFI) grant and the Director of the Adaptive Sensors Group,
Laboratories, Cambridge, MA, and a Visiting Scientist with Dublin City National Centre for Sensor Research, Dublin City University (DCU). The
University, Dublin, Ireland. He has worked in a number of fields including Adaptive Information Cluster (AIC) is an SFI-funded initiative that brings
optics, machine vision, and signal processing (for General Electric’s jet engine together DCU and University College Dublin and whose goal is “to capture
manufacturing); computer graphics (with Rensselaer’s Center for Interactive the world digitally in a comprehendible way.” As such, the AIC is integrating
Computer Graphics); artificial intelligence and parallel symbolic computation leading-edge research in wireless sensing, content extraction from video and
(for DEC’s OPS5, XCON and RuleWorks); radioastronomy and SETI (with audio media, collaborative reasoning, and personalization. He has published
Harvard University, Cambridge); transplant immunology (for the American over 100 peer-reviewed papers in international science journals and is a
Red Cross); virtual and augmented reality, real-time physical and chemical coauthor and editor of two books, which were both published by Wiley.
sensing, and ubiquitous computing (with Mitsubishi Electric); and real-time His research interests include molecular recognition; host–guest chemistry;
statistical categorization of texts (for the CRM114 Discriminator anti-spam ligand design and synthesis; electrochemical and optical chemical sensors and
system). He has appeared on numerous educational television shows and holds biosensors; lab-on-a-chip; sensor applications in environmental, clinical, food
26 U.S. patents. quality and process monitoring; development of fully autonomous sensing
devices; wireless sensors; and sensor networking.

King Tong Lau received the Ph.D. degree in electrochemical biosensor devel-
opment from University of London, London, U.K., in 2001.
He is currently a Senior Research Chemist with the National Centre for Sen-
sor Research, Dublin City University, Dublin, Northern Ireland. His research
interests include molecular recognition and development of low-cost deploy-
able sensor devices for chemical, environmental, and food quality monitoring.

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