Article

An Intelligent Optical Dissolved Oxygen

Measurement Method Based on a Fluorescent
Quenching Mechanism
Fengmei Li, Yaoguang Wei *, Yingyi Chen, Daoliang Li and Xu Zhang
Received: 1 October 2015; Accepted: 1 December 2015; Published: 9 December 2015
Academic Editor: Frances S. Ligler

College of Information and Electrical Engineering, China Agricultural University, 17 Tsinghua East Road,
Beijing 100083, China; lifm@cau.edu.cn (F.L.); chyingyi@126.com (Y.C.); dliangl@cau.edu.cn (D.L.);
zhangxu_zx888@sina.com (X.Z.)
* Correspondence: weiyaoguang@gmail.com; Tel.: +86-10-6273-6764; Fax: +86-10-6273-7741

Abstract: Dissolved oxygen (DO) is a key factor that influences the healthy growth of fishes
in aquaculture. The DO content changes with the aquatic environment and should therefore
be monitored online. However, traditional measurement methods, such as iodometry and
other chemical analysis methods, are not suitable for online monitoring. The Clark method
is not stable enough for extended periods of monitoring. To solve these problems, this paper
proposes an intelligent DO measurement method based on the fluorescence quenching mechanism.
The measurement system is composed of fluorescent quenching detection, signal conditioning,
intelligent processing, and power supply modules. The optical probe adopts the fluorescent
quenching mechanism to detect the DO content and solves the problem, whereas traditional
chemical methods are easily influenced by the environment. The optical probe contains a
thermistor and dual excitation sources to isolate visible parasitic light and execute a compensation
strategy. The intelligent processing module adopts the IEEE 1451.2 standard and realizes intelligent
compensation. Experimental results show that the optical measurement method is stable, accurate,
and suitable for online DO monitoring in aquaculture applications.

Keywords: dissolved oxygen; fluorescent quenching; intelligent compensation

1. Introduction
Dissolved oxygen (DO) refers to the oxygen molecules dissolved in water and is essential to
maintain human and animal life. Oxygen is an important analyte because of its key role in the
life science, biotechnology, medicine, and aquaculture industries. The DO content in water is an
indication of water quality, and careful control of oxygen levels is important in the self-purification
processes of wastewater [1,2]. Water quality is closely related to the contaminants present in water,
such as H2 S, NO2 , NH4 + , and organic matter. Wastewater characteristics, including color, chemical
oxygen demand (COD), and biological oxygen demand (BOD), specifically indicate the level of
pollutants in industrial wastewater [3]. At the same time, DO plays a very important role in the
health and growth of aquatic organisms [4,5]. A DO content of less than 2 mg/L for a certain
number of hours causes the suffocation and death of aquatic organisms [6]. For humans, the DO
content of drinking water should not be less than 6 mg/L. Consequently, the determination of
oxygen concentrations is of high importance in the aquaculture industry and in daily life. However,
monitoring the DO content with all its external influencing factors, such as temperature, pressure,
and salinity, is difficult. To obtain an accurate DO content, the detection method should implement

Sensors 2015, 15, 30913–30926; doi:10.3390/s151229837 www.mdpi.com/journal/sensors

Sensors 2015, 15, 30913–30926

intelligent compensation. In general, three methods can be used to detect DO content: iodometric,
electrochemical, and optical methods [7,8].
The iodometric method [9,10] is a popular and precise method of detecting the DO content in
water. It is a fiducial method but has a complex detection process and cannot be used to detect the
water quality online. This method is mainly used as a benchmark in the laboratory environment
(off-line). The electrochemical method [11–14] uses electrodes to detect the current produced by
redox reactions at the electrodes. This method can be classified as polarographic type or galvanic
cell type based on the detection principle. The electrochemical method has a long history in the
detection of DO content; the first so-called Clark polarographic method was designed by Clark of
the YSI Company in 1956 [12]. In contrast to iodometry, the electrochemical method monitors DO
content by the oxidation-reduction reaction that occurs between the electrode and DO molecules
and consumes oxygen in the detection process. Given that instrumental drift is inevitable with the
large number of factors that are involved in determining the detection result, electrochemical sensors
require regular calibration and replacement. Optical DO sensors [15,16] are more attractive than the
iodometry and electrochemical methods because they have a fast response time, do not consume
oxygen, have a small drift over time, have the capability to withstand external disturbances, and
require marginal calibration. The detection principle of optical DO sensors is based on fluorescent
quenching, including fluorescent lifetime detection and fluorescent intensity detection. Intensity
detection can be achieved through the photodiode, unlike lifetime, which should be detected based
on the phase shift [17]. This study develops an intelligent optical measurement method based on the
fluorescent quenching mechanism.
The aforementioned methods have some advantages and disadvantages that make them
unsuitable to the aquaculture industry in China. First, the detection of DO content is difficult for
the aquarist who must deal with numerous factors which influence the aquaculture industry. A
comparison of the three methods shows that the electrochemical method is not a good choice because
of its weak anti-interference properties. Second, the DO content is not constant, and insufficient
concentration in natural water leads to the death of fishes. Thus, detecting DO content in real time
is very important. However, iodometry method water samples must be tested in the laboratory,
rendering this method unsuitable for monitoring organisms in actual production for this reason.
Finally, traditional optical sensors have several disadvantages, including susceptibility to changes
in external temperature, pressure, and salinity and attenuation of light source and drift because
of the degradation or leaching of the dye. The influence off all these factors can be decreased by
adding intelligent processing modules. The conventional optical DO sensor introduced from abroad
is expensive and does not have high accuracy when used in the aquaculture industry. Thus, designing
and developing an inexpensive and intelligent dedicated optical DO sensor is necessary.
This study proposes and develops an intelligent DO measurement method based on the
fluorescent quenching mechanism. The sensor contains four modules: fluorescent quenching
detection, signal conditioning, intelligent processing, and power supply modules. The sensor based
on fluorescent quenching has several advantageous aspects: lower power consumption, smaller size,
higher accuracy, and stronger anti-interference properties than iodometry or electrochemical sensors.

2. Materials and Methods

2.1. The Overall Design of Optical Dissolved Oxygen Sensor

Given the presence of unstable influencing factors, the sensor adopts an optical probe based
on the quenching of fluorescence. Compared with the traditional DO sensor, the intelligent optical
DO sensor proposed in this study has an enhanced probe structure and an additional intelligent
processing module. These calibration parameters are stored in the transducer electronic data sheet
(TEDS) memory. Figure 1 shows that the fluorescent quenching detection, signal conditioning,
intelligent processing, and power supply modules are included in the intelligent sensor.

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The fluorescent quenching detection module contains a temperature probe and a DO probe. The
temperature probe is responsible for collecting the water temperature signals, and the DO probe is
responsible for collecting the DO signals. The original input signal can be converted into 0–2.5 V
Sensors
voltage 2015, 15,
signal bypage–page
the signal conditioning circuits. The MSP430 microcontroller, which is the core of
the intelligent
Sensors
processing
2015, 15, page–page
module, is connected to the signal conditioning circuits, TEDS memory,
the intelligent processing module, is connected to the signal conditioning circuits, TEDS memory,
and serial interface [18]. The collected data are fused through multi-probe data fusion technology,
and serial interface [18]. The collected data are fused through multi-probe data fusion technology,
the
and the intelligent
DO
and the DOvalue processing
obtained
value obtained ismodule,
is is connected
transferred
transferred through
through tocompatible
the signal conditioning
compatible RS485
RS485 circuits,
interface
interface TEDS
after
after memory,
being
being processed
processed
and serial
and analyzed
and analyzed interface
by the [18]. The
microcontroller.
by the collected
microcontroller.The data
TheRS485are fused
RS485 interface through multi-probe
allowsthe
interface allows the data fusion
microcontroller
microcontroller technology,
to communicate
to communicate
and upper
with with
the the
the DO
uppervalue
PC. The
PC. obtained
sensor
The sensoris
is transferred
powered
is poweredbythrough
by an compatible
on-off
an on-off RS485
powersupply,
power supply,interface
which
which after being
is also
is also processed
controlled
controlled by the
by the
and
MSP430analyzed by the
microcontroller.microcontroller. The RS485 interface allows the microcontroller to communicate
MSP430 microcontroller.
with the upper PC. The sensor is powered by an on-off power supply, which is also controlled by the
MSP430 microcontroller.

Figure 1. Overall design of the optical DO sensor.

Figure 1. Overall design of the optical DO sensor.
Figure 1. Overall
2.2. Design of the Fluorescent Quenching design
Detection of the optical DO sensor.
Module
2.2. Design of the Fluorescent Quenching Detection Module
The schematic
2.2. Design of the fluorescent
of the Fluorescent Quenchingquenching detection module is shown in Figure 2. The probe
Detection Module
The schematic
has an approximateof the fluorescent
length quenching
of 16 cm and a diameter detection module
of 4 cm. The compactis shown in Figure 2. isThe
probe configuration usedprobe
has an The schematic
forapproximate of
length
compatibility with the fluorescent
theofrequirements quenching
16 cm and ofa the detection
diameter module
of 4 cm.
aquaculture is
The As
industry. shown
compact in Figure
probe
illustrated 2. The probe
configuration
in Figure 2, the is
has an approximate length of 16 cm and a blue
diameter ofsol-gel
4 cm. The compact probered
configuration is used
used DO
for probe contains dual
compatibility with high-brightness
the requirements ofLEDs, the aquaculturefilm, glass slide,
industry. optical filter,
As illustrated in blue
Figure 2,
for compatibility
optical filter with
paper, andthe requirements of theThis
aquaculture industry. As illustrated in resistance
Figure 2, the
the DO probe contains dualsilicon photodiode.
high-brightness modulesol-gel
blue LEDs, also includes a platinum
film, glass slide, red opticaltofilter,
DO probe
monitor contains
ambient dual high-brightness
temperature during blue LEDs,
measurements. sol-gel
The film,
fluorescentglass slide,
intensity red
and optical filter, blue
temperature are to
blue optical filter paper,
optical filter paper, and
andsilicon
siliconphotodiode.
photodiode. This
This module
module alsoalso includes
includes a platinum
a platinum resistance
resistance to
processed in the software for temperature calibration.
monitor ambient
monitor temperature
ambient temperature during
duringmeasurements.
measurements. The Thefluorescent
fluorescent intensity
intensity andand temperature
temperature are are
processed in the
processed in software
the softwareforfortemperature
temperaturecalibration.
calibration.

PCB OF1

PCB
Temperature Probe OF1 Reference
Blue
LED
Silicon Photodiode
Temperature Probe Blue Reference
LED
Blue Excitation
Silicon Photodiode
LED
OF3
Blue Excitation
LED
OF3 OF2
Metal Case

OF2
Metal Case
Glass Slide Sol-Gel Film

Glass Slide Sol-Gel Film

Figure 2. Schematic of the fluorescence quenching detection module.

Figure 2. Schematic
Figure
The dual high-brightness blue of
2. Schematic ofthe
LEDs fluorescence
the(LA470-02)
fluorescencearequenching
quenching
modulated detection
detection module.
module.
at the same frequency, so that
the reference LED can be used to compensate the excitation LED because the light intensity loss of
The dual high-brightness
the blue blue LEDs (LA470-02) are modulated at the same frequency, so that
The dualLEDs are exactly theblue
high-brightness same. At the
LEDs same frequency,
(LA470-02) the photodiode
are modulated at thecansame
reduce background
frequency, so that
the reference
radiation due LED
to can
the be
ambientused to
light compensate
in the the
measurement excitation LED
environment because
and the
avoid light
the intensity
excitation loss
of of
any
the reference LED can be used to compensate the excitation LED because the light intensity loss of
the blue LEDs
fluorescent are exactly
material. In thethe same.
addition, the At the
intensitysame frequency,
of frequency,
the LEDs arethe photodiode can reduce background
the blue LEDsdue
radiation are exactly
to the ambient same.
light Atthe
in themeasurement
same thereduced to a low
photodiodeavoid can
level at which
reduce the
background
photobleaching phenomenon of the dye has a smallenvironment
probability andof occurring the[19].
excitation of any
The central
radiation due tomaterial.
fluorescent the ambient light inthe
In excitation
addition, the measurement
intensity environment and aavoid the excitation of any
wavelength of the blue LED is aboutof465 thenm,
LEDs are reduced
which is filteredtoby low level
a blue at whichfilter
bandpass the
fluorescent material.phenomenon
photobleaching In addition, the intensity
dye has aofsmall the probability
LEDs are reduced to a[19].
low The
levelcentral
at which
paper to screen out the light of of
otherthewavelengths. The experimental of occurring
results show that the blue light
wavelength of the blue excitation LED is about 465 nm, which is filtered by a blue bandpass filter
paper to screen out the light of other wavelengths. The experimental results show that the blue light
30915
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Sensors 2015, 15, 30913–30926

the photobleaching phenomenon of the dye has a small probability of occurring [19]. The central
wavelength of the blue excitation LED is about 465 nm, which is filtered by a blue bandpass filter
paper to screen out the light of other wavelengths. The experimental results show that the blue light
can induce the sensitive membrane to emit fluorescence at 650 nm. To reduce the influence of parasitic
light, the probe is equipped with blue bandpass filter papers (OF1 and OF2) in front of the LEDs and
red high-pass filter (OF3) in front of the silicon photodiode. A silicon photodiode (OPT 301) is used
to receive the fluorescence emitted from the sol-gel film and blue light from the reference LED. The
blue excitation LED and blue reference LED are separated on different sides of the red high-pass
filter, which is beneficial in cutting off parasitic light and guaranteeing the accuracy of the optical
signal detection.
The fluorescent sensing film is the most important part of the DO sensor and its performance
significantly influences the accuracy, efficiency, and stability of the sensor. Researchers have
conducted several studies on fluorescence indicators [20–22] and found that the most common
fluorescent indicators contain metal porphyrin complexes, organic polycyclic aromatic hydrocarbons,
and transition metal complexes [23]. Ru(bpy)3 Cl2 has been chosen as the fluorescence indicator in this
study because of its highly emissive metal-to-ligand charge-transfer state, long lifetime, and strong
absorption in the blue-green region of the spectrum, which is compatible with the high-brightness
blue LED [20]. The dye is entrapped in a porous and hydrophobic sol-gel film that is approximately
0.04 mm. The sol-gel film is mounted on the glass slide surface, which should be transparent for the
excitation and luminescence to penetrate. The film should also be in the shape of an arc and maintain
a stable size; the arc surface is designed to increase the area of contact and avoid surface bubble. The
operating principle of the sensor is based on the fluorescent quenching mechanism. The fluorescent
quenching process is described by the Stern-Volmer equation [24–26]:

F0
“ 1 ` Ksv rQs (1)
F
where:

F0 denotes the fluorescence signal intensity of anaerobic water;

F denotes the fluorescence signal intensity of the water samples;
KSV denotes the Stern-Volmer constant; and
[Q] denotes the concentration of quencher.

As the equation shows, the degree of fluorescent quenching F0 /F has a straight-line relationship
with the concentration of the quencher [Q]. In this system, the quencher is the DO, so the DO content
can be determined by using Equation (1).

2.3. Design of the Signal Conditioning Module

The block diagram of the intensity measurement system is shown in Figure 3. The signal
conditioning module is responsible for collecting and processing the information. The dual LEDs
are modulated (MOD) into on-off at a frequency of 20 kHz. LED1 induces the sol-gel film to emit red
fluorescence. At the same time, LED2 emits blue light as a contrast. The luminescence signal from
the sensor dyes arrives time-delayed at the single photodiode (because of the luminescence lifetime
of the dye), so that the reference and luminescence signals are detected in different time windows
without interference. The fluorescence signal from the photodiode is converted to a voltage signal
via an I/V switching circuit. The signal is then amplified (AMP) to obtain a voltage signal of 0–2.5 V
and eliminate the higher harmonics of the signal. The voltage signal is filtered by a low pass (LP)
filter and provides a voltage signal proportional to the measured intensity shift. Finally, the output
voltage is divided by the voltage value based on the intensity in the anaerobic water to obtain F0 /F,
which has a linear correlation with the DO content. As presented in the Stern-Volmer equation, the
DO content can be determined.

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Sensors 2015, 15, page–page

Pt LED2

Sensors 2015, 15, page–page

RS485
OF1
MOD
Sensitive
MCU membrane PD
Pt LED2
LED1
TEDS
RS485 OF2
OF1 OF3
MOD
Sensitive
MCU membrane PD
LP amp LED1 I/V
TEDS
OF2
OF3
Figure
Figure 3. Schematic
3. Schematic of of
thethe signalconditioning
signal conditioning module.
module.
LP amp I/V
2.4. Design of the Intelligent Processing Module
2.4. Design of the Intelligent Processing Module
With the rapid development of computers, communications, and networks, the DO sensor
With theberapid Figure 3.of
Schematic of the signal conditioning module.
should more development computers,
intelligent, networked, communications,
and integrated [20]. To solveandthenetworks,
problems ofthetraditional
DO sensor
shouldoptical
be more intelligent,
sensors, networked,
the intelligent andsensor
optical DO integrated
proposed[20]. Tostudy
in this solveisthe problems
developed withof traditional
automatic
2.4. Design of the Intelligent Processing Module
opticalcompensations,
sensors, the intelligent
which are optical
suitable DO sensor
for the proposed
online detectioninof this study isover
aquaculture developed with automatic
long periods.
With the
compensations, rapidare
which development
suitable forofthecomputers, communications,
online detection and networks,
of aquaculture theperiods.
over long DO sensor
IEEE1451.2
should be moreStandard
intelligent, networked, and integrated [20]. To solve the problems of traditional
optical
IEEE1451.2The sensors,
Standard the intelligent optical DO sensor proposed in this study is developed with automatic
data transfer is implemented using the protocols described in IEEE 1451.2 [27,28]. The
compensations, which are suitable for the online detection of aquaculture over long periods.
intelligent
The sensor is
data transfer includes
implementeda smart using transducer interface module
the protocols described (STIM) in IEEE and 1451.2
network capableThe
[27,28].
application processor (NCAP), and the sensor provides a general interface standard and a TEDS
intelligent sensor
IEEE1451.2 includes a smart transducer interface module (STIM) and network capable
Standard
standard format for the intelligent sensor and the field bus. NCAP is connected to the STIM through
application processor
The data
(NCAP),
transfer
and the sensor
is implemented
provides a general interface standard and a TEDS
using the protocols described in IEEE 1451.2 [27,28]. The
an RS485 interface, as shown in Figure 4.
standard format
intelligent for theincludes
sensor
The calibration intelligent
parameters sensor
a smart and the
aretransducer
stored in field
interface
the bus. NCAP
TEDS module
as shown is(STIM)
connected
in Figure and to 4. the
network STIM
Through through
capable
these
an RS485 interface,
application as
processorshown (NCAP),in Figure
and 4.
the sensor provides
parameters, the original signals can been converted into corrected signals, including DO, a general interface standard and a TEDS
The calibration
standard format
temperature, forparameters
pressure,the intelligent
salinity, and aresensor stored
luminous and thein the
field
flux signals. TEDS
bus. NCAP as isshown
connected in toFigure
the STIM 4. through
Through
these an RS485 interface,
parameters, the as shown in
original Figure
signals D (1) can4.(2) been
D D( n) converted into corrected signals, including DO,
temperature,The pressure,
calibration Xparameters
f (salinity,
1 , X 2 ,...and 
X n ) luminous
are
i 0

stored
j 0
in C
...flux
p 0
the [ X1  Has1 ]i [shown
i , j ... pTEDS
signals. X 2  H 2in
] j ...[ X n  H4.
Figure p
n ] Through these (2)
parameters, the original signals can been converted into corrected signals, including DO,
temperature, pressure,Xsalinity,
In the equation, n denotes
Dÿpand Dÿ
1qthe pluminous
q Dÿ
2sensor q flux signals.
pnoutput variables; Hn denotes the revised output variables;
i j p
f pX
Dn denotes the X2 , ...X
1 , order q “ variables;
ofnoutput D (1) D (2) D ( n )C
... and i,j,…,prX
Ci,j...p 1 ´ H1the
denotes s rX 2 ´ H2 s ...rX
polynomial n ´ Hn s
coefficient. (2)
f ( X1 , X 2 ,... X n i)“0  j“0 p...“0 Ci , j ... p [ X 1  H1 ] [ X 2  H 2 ] ...[ X n  H n ]
i j p
(2)
i 0 j 0 p 0

In theInequation, Xn denotes
the equation, the
Xn denotes thesensor
sensoroutput variables; HHn ndenotes
output variables; denotesthethe revised
revised output
output variables;
variables;
Dn denotes the order
Dn denotes of output
the order variables;
of output andC
variables;and Ci,j,... denotes
denotes
i,j,…,p,p thethe polynomial
polynomial coefficient.
coefficient.

Figure 4. Model of data correction.

The calibration standard equation is shown in Figure 4. The relationship between the output
variables and revised output variables, such as DO, temperature, pressure, salinity, and luminous
Figure4.4.Model
Figure Model of
of5data
data correction.
correction.

The calibration standard equation is shown in Figure 4. The relationship between the output
variables and revised output variables, such as DO, temperature, pressure, salinity, and luminous
5
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Sensors 2015, 15, 30913–30926

The
Sensors calibration
2015, 15, page–pagestandard equation is shown in Figure 4. The relationship between the output
variables and revised output variables, such as DO, temperature, pressure, salinity, and luminous flux
flux signals
signals are converted
are converted into ainto a standard
standard form. form. The sensor
The sensor can directly
can directly determine
determine accurate
accurate valuesvalues
when
when
it uses it
theuses the calibration
calibration parameters
parameters stored instored in the
the TEDS, TEDS,
which not which not onlyautomatic
only facilitates facilitatesrecognition
automatic
recognition
but also solvesbut the
alsosensor
solvesautomatic
the sensorcorrection
automaticproblem.
correctionInproblem. In theoptical
the intelligent intelligent
DO optical
sensor, DOthe
sensor,
total, the total,
channel, andchannel, and TEDS
calibration calibration
must TEDS must In
be defined. bethis
defined.
study,Inthe
this study, the
definition of definition of total
total and channel
and channel
TEDS makes the TEDS makes the
intelligent intelligent
optical DO sensoroptical
moreDO sensor moreand
standardized, standardized, and that of
that of the calibration TEDSthe
calibration
may correctTEDS may correct
the original data the original
at any time.data at any
These time. These
functions havefunctions havefor
significance significance for the
the maintenance
maintenance
and diagnosisand diagnosis
of the sensorsof[29,30].
the sensors
Thus,[29,30]. Thus, theoptical
the intelligent intelligent
DO optical
sensor isDO sensor
called is called
a “plug anda
“plug device.
play” and play” device.

3. Experimentsand
3. Experiments andDiscussions
Discussions

3.1. Calibration and

3.1. Calibration and Validation
Validation
3.1.1. Temperature Compensation of the Optical DO Sensor
3.1.1. Temperature Compensation of the Optical DO Sensor
The temperature dependence of the oxygen sensor has a number of contributions, including the
The temperature dependence of the oxygen sensor has a number of contributions, including the
temperature dependence of the fluorescence sensing film, light source, and the diffusion coefficient
temperature dependence of the fluorescence sensing film, light source, and the diffusion coefficient
in the water. As discussed in Section 2.2, the light intensity related to temperature is measured by
in the water. As discussed in Section 2.2, the light intensity related to temperature is measured by the
the probe, and the temperature effect is measured by the sensor based on the thermistor [31]. This
probe, and the temperature effect is measured by the sensor based on the thermistor [31]. This study
study designs a correction model based on the temperature applicable to online DO monitoring. This
designs a correction model based on the temperature applicable to online DO monitoring. This
model can perform temperature compensation to reduce the influence of temperature through the
model can perform temperature compensation to reduce the influence of temperature through the
curve fitting algorithm.
curve fitting algorithm.
To eliminate the influence of temperature on sensitive film and light, anaerobic water and
To eliminate the influence of temperature on sensitive film and light, anaerobic water and
oxygen saturated solutions are prepared as standard solutions, which are heated with an integrated
oxygen saturated solutions are prepared as standard solutions, which are heated with an integrated
thermostatic magnetic blender (HWCL-1) from 0 ˝ C to 40 ˝ C in an off-light environment. The values
thermostatic magnetic blender (HWCL-1) from 0 °C to 40 °C in an off-light environment. The values
are measured by a commercial DO meter (YSI 6150) in steps of 5 ˝ C (0–40 ˝ C), and the data between
are measured by a commercial DO meter (YSI 6150) in steps of 5 °C (0–40 °C), and the data between
output signal and temperature obtained are displayed in the plot shown in Figure 5.
output signal and temperature obtained are displayed in the plot shown in Figure 5.

Figure
Figure 5. Line chart
5. Line chart of
of the
the DO
DO content
content and
and output
output voltage
voltage signal.
signal.

The relationship can

can be
be described
described by
by the
the following
following equations:
equations:

 DOt1  1   t1U
$
DO t1 “ β 1 ` β t1 U
DOt 2   2   t 2U
’
DO
’
’
 t2 “ β 2 ` β t2 U
’
(3)
&
 .. (3)
 DO  .   U
’
% DO tn “ βn ` βtn U
’
’
’
tn n tn
The slope is an important parameter to achieve the DO content, which changes with
temperature. The relationship between the slope and temperature can be obtained based on the
309186, the slope of the output voltage signal can be
curve fit method in this study. As shown in Figure
fitted by Equation (4):

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Sensors 2015, 15, 30913–30926

The slope is an important parameter to achieve the DO content, which changes with temperature.
The relationship between the slope and temperature can be obtained based on the curve fit method in
this study. As shown in Figure 6, the slope of the output voltage signal can be fitted by Equation (4):
Sensors 2015, 15, page–page

β t “ α0 ` α1 T ` α2 T 2 ` α3 T 3 ` α4 T 4 ` α5 T 5 (4)
t  0  1T   2T 2  3T 3   4T 4  5T 5 (4)
In the equation, α0 = 52.488, α1 = ´4.3436, α2 = 0.2157, α3 = ´0.0061, α4 = 0.00008,
In the equation,
α5 = ´0.0000004, α20 == 52.488,
and R α1 seen
0.9998, as = −4.3436, α2 =6,0.2157,
in Figure which αdenotes
3 = −0.0061, α4 = 0.00008, α5 = −0.0000004,
a very good linear fitting. The DO
and R 2 = 0.9998, as seen in Figure 6, which denotes a very good linear fitting. The DO content can be
content can be obtained at any temperature, taking Equation (4) into Equation (3), and Equation (5)
obtained
can then be atachieved.
any temperature, taking Equation (4) into Equation (3), and Equation (5) can then
be achieved.
2 3 4
DOt “DO
β `α0 U
 `0Uα1UT
1UT`α2 UT 2 ` α3 UT ` α4 UT ` α55 UT 5 (5)
2UT  3UT   4UT  5UT
3 4
t (5)

Figure 6.
Figure 6. Fitting
Fitting curve
curve of
of the
the slope.
slope.

The calibration standard Equation (2) in the TEDS calibration can be adapted as follows:
The calibration standard Equation (2) in the TEDS calibration can be adapted as follows:
1 5
DOt 1 
5 Cij [U  H1 ]  [T  H 2 ]
i j
(6)
ÿi ÿ 0 j 0
DOt “ Cij rU ´ H1 si ¨ rT ´ H2 s j (6)
If H1 = 0 and H2 = 0, then Equationi“
(6)
0 j“can
0 be presented by Equation (7):

 C00  C01T
DOt Equation
If H1 = 0 and H2 = 0, then (6)can
C02Tbepresented
C03T  C04by
2
T Equation
C05T 3
(7):
4 5

(7)
C10U  C11UT  C12UT 2 2 C13UT 3 3 C14UT 4 4 C15UT 5 5
DOt “ C00 ` C01 T ` C02 T ` C03 T ` C04 T ` C05 T
(7)
The calibration values `C10 Uare` Cconsistent
11 UT ` C12 UT 2the
with ` Cactual 3 ` C UT 4 ` C
13 UT temperature
14 and 5
output
15 UT voltage. The DO
value must be corrected according to the real-time temperature. Taking C00 = β, C00 − C05 = 0,C10 = α0,
C11 =Theα1, Ccalibration
12 = α2, C13 values
= α3, Care
14 = consistent
α4, and C15with = α5 the
intoactual
Equationtemperature and output
(7) and detecting the voltage.
temperatureThe and
DO
value
outputmust be corrected
voltage, the accurate according
DO value to can
the be
real-time temperature.
determined in the 0–40 Taking C00 =
°C range (i.e., C00range
β, the ´ C05of=the
0,
C =
sensor).
10 α , C = α ,
0The11temperature
1 C 12 = α
probe
2 , C = α , C
in this3 sensor
13 14 = αcan, and C
4 track 15 = α into
the temperature
5 Equation (7) and detecting
response of the DO sensor the
temperature
in real time,and outputachieving
thereby voltage, the accurate DO
temperature value can beindetermined
compensation in thewhere
an application 0–40 ˝frequent
C range
(i.e., the range of the sensor). The temperature probe in this sensor
short-term changes in temperature occur. The calibration curve based on intensity measurement can track the temperature
response of the DO
changes because ofsensor in real time,
the impactsof thereby
typical driftachieving temperature
sources, including thecompensation
leaching of the inindicator,
an application
LED
where
output,frequent
and ageingshort-term
of the changes in temperature
sol-gel matrix. Thus, the occur.
sensorTherequires
calibration curve based
recalibration on aintensity
after certain
measurement
period, but thechanges
frequency because
achievesof themuchimpactsof typical than
more progress drift the
sources, including the
electrochemical leaching
sensor. of the
In addition,
indicator, LED output, and ageing of the sol-gel matrix. Thus, the sensor
the temperature compensation should be processed in the shade to avoid the influence of daylight requires recalibration after
aand
certain period, but
background the frequency achieves much more progress than the electrochemical sensor. In
fluorescence.
addition, the temperature compensation should be processed in the shade to avoid the influence of
daylight and background
3.1.2. Pressure Compensation fluorescence.
of the Optical DO Sensor
Given that the DO value increases when the sol-gel film is moderately affected by pressure, the
pressure affects the accuracy of the measurement. Pressure compensation is needed in the
30919 [32] is as follows:
measurement of oxygen, and the correction formula
P
DO  CS * (8)
101.3
 Sensors 2015, 15, 30913–30926

3.1.2. Pressure Compensation of the Optical DO Sensor

Given that the DO value increases when the sol-gel film is moderately affected by pressure,
the pressure affects the accuracy of the measurement. Pressure compensation is needed in the
measurement of oxygen, and the correction formula [32] is as follows:

Sensors 2015, 15, page–page P

DO1 “ CS ˚ (8)
101.3
In the equation, DO’ denotes the DO in the pressure of P; CS denotes the normal atmospheric
In the equation, DO1 denotes the DO in the pressure of P; CS denotes the normal atmospheric
pressure value; and P denotes the actual atmospheric pressure value.
pressure value; and P denotes the actual atmospheric pressure value.
CS can
CS be
canobtained
be obtainedthrough
through the
thenational
national standard tableatatdifferent
standard table different temperatures.
temperatures. At different
At different
temperature,
temperature,the the
aqueous
aqueous solutions
solutionsare
aresubjected
subjected toto different
differentpressures.
pressures. AsAs mapped
mapped in Figure
in Figure 7, the7, the
experiment
experiment shows
showsthatthat
thetheoptical
opticalDODOsensor
sensor introduced
introduced in inthis
thisstudy
study cancan effectively
effectively eliminate
eliminate the the
effecteffect
of pressure andand
of pressure that the
that pressure
the pressurecompensation
compensation has hasa agood
good effect.
effect.

Figure
Figure7.7.Pressure
Pressure compensation test.
compensation test.

3.1.3.3.1.3.
Salinity Compensation
Salinity ofof
Compensation the
theOptical
OpticalDO
DO Sensor
Sensor
Given thatthat
Given thethe
solubility
solubility of oxygenininwater
of oxygen water decreases
decreases as theassalt
thecontent
salt content increases,
increases, the DO mustthe DO
be compensated according to the salinity. When the salinity (i.e., expressed as the total
must be compensated according to the salinity. When the salinity (i.e., expressed as the total salinity) salinity) is
below
is below 3535ppt,
ppt,the
thecorrection
correction formula
formula[32]
[32]is is
given by:by:
given
DO2 
DO “CCSS ´n∆C
nC
S S (9) (9)

In theInequation, DO”DO”
the equation, denotes the the
denotes DODO value at aatsalinity
value a salinityof n;
of C
n;S denotes
CS denotesthethe
DODO value in in
value pure water;
pure
n denotes
water;the salinitythe
n denotes value; andvalue;
salinity and ∆CSthe
ΔCS denotes reduction
denotes of DO according
the reduction to salinity
of DO according (1 ppt).(1 ppt).
to salinity
CS and ΔCS∆C
CS and can be obtained
S can be obtained through
throughthethenational standardtable
national standard tableat at different
different temperatures.
temperatures. The The
aqueous solution is measured using KCl, NH ++, and CO 2´ as ions in the experiment. The ion density
aqueous solution is measured using KCl, NH44 , and CO3 3 as ions in the experiment. The ion density
2−

of the
of the measurementsolutions
measurement solutions is
isbetween
between 0 and 40 ppt.
0 and 40 The
ppt.DO Thevalues
DO measured separatelyseparately
values measured are shown are
on the basis of the experimental data in Figure 8. The analysis of the data
shown on the basis of the experimental data in Figure 8. The analysis of the data shows that shows that the DO values
the DO
have certain effects when ionic strength regulators are added. The experiment shows that the optical
values have certain effects when ionic strength regulators are added. The experiment shows that the
sensor satisfies the salinity compensation in the aquatic environment. The salinity compensation
optical sensor satisfies the salinity compensation in the aquatic environment. The salinity
parameters are also stored in the calibration TEDS.
compensation parameters are also stored in the calibration TEDS.

30920
aqueous solution is measured using KCl, NH4+, and CO32− as ions in the experiment. The ion density
of the measurement solutions is between 0 and 40 ppt. The DO values measured separately are
shown on the basis of the experimental data in Figure 8. The analysis of the data shows that the DO
values have certain effects when ionic strength regulators are added. The experiment shows that the
optical2015,
Sensors sensor satisfies the salinity compensation in the aquatic environment. The salinity
15, 30913–30926
compensation parameters are also stored in the calibration TEDS.

Figure 8.
Figure 8. Salinity
Salinity compensation test.
compensation test.

3.1.4. Excitation
3.1.4. Excitation LED Compensation
LED Compensation
The experimental
The experimental results
results show
show that
that different
different intensities of the
intensities of the excitation
excitation LED
LED have
have aa large
large
influence on the fluorescence intensity of the sensitive film. The intelligent processing module
influence on the fluorescence intensity of the sensitive film. The intelligent processing module also also
allows for the adjustment of the calibration parameters to correct the excitation blue LED at the
allows for the adjustment of the calibration parameters to correct the excitation blue LED at the time time
of measurement (i.e., if this differs from the excitation at the time of calibration). The luminous flux
of measurement (i.e., if this differs from the excitation at the time of calibration). The luminous flux
attenuation curve of the blue LED shows a similar 8 exponential form at 100 ˝ C. When the service
time reaches about 10,000 h, the luminous flux of the blue LED (L470-02) drops to about 70% of
the original luminous flux. Thus, when the LEDs work beyond 10,000 h, the sensor probe must be
replaced. Before replacement, illuminant compensation is required to guarantee the accuracy of the
DO sensor. The experimental results show that this sensor can effectively compensate the effect of
the light source caused by the instability or aging of the light source. The compensation formula is
shown in the following equation, and the calibration parameters are also stored in the TEDS. When
the intensity of the reference blue LED changes, Equation (8) is used to correct the intensity value of
fluorescence quenched by oxygen:

eα eβ
Eδ “ Eγ ¨ p0.7 ď ď 1q (10)
eβ eα

In the equation, eα denotes the original intensity value of the reference LED; eβ denotes the
measured intensity value of the reference LED; Eγ denotes the measured intensity value of the
quenched fluorescence; and Eδ denotes the corrected intensity value of the quenched fluorescence.
The long-term stability of the sensor in aquaculture tank water has been continuously studied
for over 12 months. With the passage of time, the sol-gel matrix is prone to losing its original features,
which may cause drifts in calibration, leaching, and bleaching of the dye. As described above, if the
intensity of the fluorescence declines (i.e., after about 12 months), then the sensor probe should be
replaced rather than the whole sensor device with the separate structure.

3.2. Analysis of the Performance of the Sensor

To verify the performance of the sensor, the optical DO sensor is tested in terms of our
aspects: accuracy, stability, precision, repeatability, rapidity. Its superior performance proves that
the intelligent optical DO sensor can be used to monitor the DO content in the aquaculture industry.
The experimental processes are shown below.

3.2.1. Accuracy Test

In the laboratory, the room temperature is about 25 ˝ C, and three groups of standard aqueous
solutions are measured: 5.02, 9.98, and 18.03 mg/L. The defined oxygen contents are adjusted by
mixing the oxygen and nitrogen with mass flow controllers. The sample contents are checked using
a commercial DO meter. Compared with reference values, the experimental data in Table 1 show that

30921
 Sensors 2015, 15, 30913–30926

the relative error is less than ˘2%, the measurement error is less than 0.2 mg/L, and the resolution of
the optical DO sensor is 0.01 mg/L within the range of 0–20 mg/L, which conforms to the accuracy
requirements. At the same time, the temperature error is less than 0.5 ˝ C, which shows that the
temperature probe is accurate.

Table 1. Accuracy test.

Measurements Absolute Relative

Samples AVG
1 2 3 4 5 6 7 8 Error Error
5.02 4.86 4.79 4.89 4.93 4.89 4.91 5.09 4.98 4.92 0.1 1.99%
9.98 10.12 10.09 10.21 9.89 10.06 9.91 9.89 10.13 10.04 0.06 0.60%
18.03 17.85 17.83 17.91 17.87 17.96 17.87 17.93 18.03 17.91 0.12 0.67%

3.2.2. Stability Test

The response of the optical sensor appears to be stable within the measurement error, which
meets the specified stability requirement of 0.2 mg/L. In the laboratory, the DO content is measured
within 12 h15,inpage–page
Sensors 2015, steps of 1 h. The standard aqueous solution is adjusted by mixing the oxygen and
nitrogen with mass flow controllers. The experimental results are 2.51, 5.58, 7.22, 10.01, 14.56,
18.1218.12
and mg/L. As shown
mg/L. As shownin Figure 9, the
in Figure largest
9, the error
largest errorisisless
lessthan
than 0.02
0.02 mg/L,
mg/L, which
which meets the
meets the
requirements of the optical dissolved oxygen
requirements of the optical dissolved oxygen sensor. sensor.

9. Stability test.
Figure 9.

3.2.3. Precision
3.2.3. Precision Test
Test
Precision refers
Precision refers toto the
the discrete
discrete degree
degree ofof the
the values
values that
that are
are repeatedly
repeatedly measured
measured by by the
the same
same
method under the same experimental conditions for the same sample. Generally,
method under the same experimental conditions for the same sample. Generally, the relative standard the relative
standard deviation
deviation (RSD)
(RSD) is used to isexplain
used tothe
explain
sensorthe sensor precision.
precision. The RSD The RSD indicates
indicates that the
that the results areresults
more
are more concentrated. The standard solution contains Na SO , and this sample
concentrated. The standard solution contains Na2 SO3 , and this sample is continuously measured ten
2 3 is continuously
measured
times. The ten times. The results
measurement measurement
are shownresults are shown
in Table 2. Thein Table 2. The micro-controller
micro-controller calculates
calculates the RSD every
the measurements,
ten RSD every ten indicating
measurements, indicating
that the precisionthat the precision
of this of this
group of data group
is very of data
good when is the
veryRSDgood
is
when the RSD is less than 2%. The micro-controller inputs these data into the internal
less than 2%. The micro-controller inputs these data into the internal memory. As shown in Figure 10, memory. As
shown
the in Figure
results 10, the
show that theresults
sensorshowhas a that
highthe sensor has a high precision.
precision.

Table 2. Precision test.

AVG
Sample 1 2 3 4 5 6 7 8 9 10 Average RSD
average
A 5.56 5.62 5.60 5.44 5.49 5.51 5.50 5.82 5.71 5.60 5.59 1.97%

B 9.96 9.91 9.89 10.22 10.15 10.04 10.00 9.98 10.02 10.15 10.03 1.10%

C 18.90 18.85 18.86 18.74 18.69 30922

18.56 18.74 18.63 18.60 18.59 18.73 0.64%
 measured ten times. The measurement results are shown in Table 2. The micro-controller calculates
the RSD every ten measurements, indicating that the precision of this group of data is very good
when the RSD is less than 2%. The micro-controller inputs these data into the internal memory. As
shown in Figure 10, the results show that the sensor has a high precision.
Sensors 2015, 15, 30913–30926
Table 2. Precision test.

Table 2. Precision test. AVG

Sample 1 2 3 4 5 6 7 8 9 10 Average RSD
average
AVG Average
A Sample
5.56 1 5.62 2 3
5.60 45.44 5 5.49 6 7
5.51 85.50 9 5.8210 5.71 average
5.60 RSD
5.59 1.97%

B A9.96 5.56
9.91 5.62 9.89
5.60 5.44
10.22 5.4910.15
5.51 10.04
5.50 5.82
10.00 5.71 9.98
5.60 10.02 5.5910.15 1.97%
10.03 1.10%
B 9.96 9.91 9.89 10.22 10.15 10.04 10.00 9.98 10.02 10.15 10.03 1.10%
C 18.90
C 18.8518.8518.86
18.90 18.74 18.69
18.86 18.74 18.69
18.56 18.56 18.74 18.60
18.74 18.63 18.63
18.59 18.60 18.73
18.59 18.73
0.64% 0.64%

Figure 10.
Figure 10. Precision
Precision test.
test.

3.2.4. Repeatability Test

Na2 SO3 is added into the aqueous solutions 10
to achieve the sample solutions (i.e., 2.51, 9.24, and
12.57 mg/L). The sensor is used to measure the DO values of the sample solutions. The data are
recorded every hour and continuously measured ten times. Table 3 shows that the relative error is
less than 2%. The result of the data analysis indicate that the repeatability meets the requirements of
the optical DO sensor.

Table 3. Stability test.

Measurement Results
Samples Relative Error
1 2 3 4 5 6 7 8 9 10
2.51 2.54 2.5 2.44 2.56 2.62 2.48 2.63 2.55 2.59 2.63 1.59%
9.24 9.22 9.19 9.16 9.13 9.33 9.25 9.23 9.22 9.16 9.13 0.43%
12.51 12.49 12.44 12.45 12.44 12.67 12.71 12.58 12.55 12.49 12.51 0.16%

3.2.5. Speed Test

Two cups of water are prepared in laboratory. 5% Na2 SO3 and a suitable amount of CoCl2 are
added to one of them. They are placed in the air for two days to ensure that both temperatures
are same, which can eliminate the influence of temperature on the measurement results. Series A
indicates the change of DO content from tap water to anaerobic water, and the Series B line indicates
the change from anaerobic water to tap water. From Figure 11, we can see that the response time is less
than 3 min. After 1 min, the Series A is nearly 0 mg/L. However, the response time of Series B is about
3 min. The reason of this phenomenon is that the process of fluorescence quenching must achieve
dynamic balance. Series B should take some time to react, but it doesn’t need time in anaerobic water.
The data indicates that detection response speed meets the requirements of the optical DO sensor.

30923
indicates the change from anaerobic water to tap water. From Figure 11, we can see that the
response time is less than 3 min. After 1 min, the Series A is nearly 0 mg/L. However, the response
time of Series B is about 3 min. The reason of this phenomenon is that the process of fluorescence
quenching must achieve dynamic balance. Series B should take some time to react, but it doesn’t
need time
Sensors 2015,in anaerobic water. The data indicates that detection response speed meets the
15, 30913–30926
requirements of the optical DO sensor.

Figure 11. Speed Test.

Figure 11. Speed Test.

3.2.6. On-Site Verification Test

3.2.6. On-Site Verification Test
Figure 12 is the real-time graph of dissolved oxygen changes in aquaculture ponds. After
Figure 12 is the real-time graph of dissolved oxygen changes in aquaculture ponds. After sunrise,
sunrise, phytoplankton produces photosynthesis, which releases a large amount of oxygen. The
phytoplankton produces photosynthesis, which releases a large amount of oxygen. The increase of
increase of oxygen is more than the consumption, so the DO content gradually increases. Over a
oxygen is more than the consumption, so the DO content gradually increases. Over a period of time,
period of time, at the peak of photosynthesis, DO content is at a maximum. After sunset, the
at the peak of photosynthesis, DO content is at a maximum. After sunset, the phytoplankton undergo
phytoplankton undergo respiration which consumes oxygen instead of photosynthesis. In addition,
respiration which consumes oxygen instead of photosynthesis. In addition, with the respiration
with the respiration of aquatic animals, DO content decreases rapidly. After all night, the
of aquatic
Sensors animals, DO content decreases rapidly. After all night, the accumulation is reduced to
2015, 15, page–page
accumulation is reduced to a minimum at dawn. These changes perfectly accord with the test data,
a minimum at dawn. These changes perfectly accord with the test data, which proved that the
which proved that the developed DO sensor has a reliable performance. In contrast to change rates
of developed
oxygen consumedDO sensorbyhas
organisms,
a reliablethe temperature
performance. In has littletoinfluence
contrast on DO
change rates contentconsumed
of oxygen in the
on-site test.
by organisms, 11
the temperature has little influence on DO content in the on-site test.

Figure 12. 12.

Figure On-site Test.
On-site Test.

4. Conclusions
4. Conclusions
To detect the dissolved oxygen content exactly in aquaculture industry applications, an
To detect the dissolved oxygen content exactly in aquaculture industry applications, an
intelligent optical dissolved oxygen measurement method based on a fluorescent quenching
intelligent optical dissolved oxygen measurement method based on a fluorescent quenching
mechanism has been designed in this paper. The advantages of the unique sensor head based on
mechanism has been designed in this paper. The advantages of the unique sensor head based
fluorescent quenching have been highlighted and intensity measuring circuits and intelligent
on fluorescent quenching have been highlighted and intensity measuring circuits and intelligent
processing have been described. With the optical dissolved oxygen sensor probe in the paper, the
processing have been described. With the optical dissolved oxygen sensor probe in the paper, the
detection of dissolved oxygen became more accurate and interference-free. In view of the influence
detection of dissolved oxygen became more accurate and interference-free. In view of the influence
of temperature, pressure, salinity and blue excitation LED on measurement, this paper has designed
of temperature, pressure, salinity and blue excitation LED on measurement, this paper has designed
an intelligent processing module. The accurate DO content can be achieved by the intelligent optical
DO sensor with the correction coefficients stored in the calibration TEDS. The experiments have
shown that the sensor performance can meet the30924 specifications for the monitoring DO content in
aquaculture industry, such as low-power consumption, fast response, ability to detect online, high
accuracy and strong stability, which will enable reliable operation for periods of months at the very
Sensors 2015, 15, 30913–30926

an intelligent processing module. The accurate DO content can be achieved by the intelligent optical
DO sensor with the correction coefficients stored in the calibration TEDS. The experiments have
shown that the sensor performance can meet the specifications for the monitoring DO content in
aquaculture industry, such as low-power consumption, fast response, ability to detect online, high
accuracy and strong stability, which will enable reliable operation for periods of months at the very
least. In addition, the use of an optical measurement method and the intelligent calibration technique
could be applicable in other medical and environmental monitoring areas.

Acknowledgments: Funds for this research was supported by “Special Fund for Agro-scientific Research in the
Public Interest”, Modern Fishery Digitization and Integration & Demonstration of Internet of Things Technology
(201203017).
Author Contributions: Study concept and design: Yaoguang Wei, Daoliang Li and Yingyi Chen; data acquisition:
Fengmei Li and Xu Zhang; statistical analysis: Xu Zhang and Fengmei Li; writing of the manuscript: Fengmei Li
and Xu Zhang; study supervision: Daoliang Li, Yaoguang Wei and Yingyi Chen.
Conflicts of Interest: The authors declare no conflict of interest.

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