IBP1141_19

THE USE OF OPTICAL SENSOR TO

INVESTIGATE DISSOLVED OXYGEN
IN CRUDE
Jefferson Rodrigues de Oliveira1

Copyright 2019, Brazilian Petroleum, Gas and Biofuels Institute - IBP

This Technical Paper was prepared for presentation at the Rio Pipeline Conference and Exhibition 2019, held
between 03 and 05 of September, in Rio de Janeiro. This Technical Paper was selected for presentation by the
Technical Committee of the event according to the information contained in the final paper submitted by the
author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is
presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute’ opinion, or that of its
Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Pipeline
Conference and Exhibition 2019.

Abstract

This paper deals with the evaluation of dissolved oxygen probes used in crude oil environment
through tests that simulate the variation of oxygen concentration. The objective of this work is
to show the possibility of dissolved oxygen monitoring evaluation in the integrity of pipelines
related to internal corrosion, in order to define an adequate measurement technique in function
of efficiency, effectiveness and cost/benefit. The scenario evaluation consisted on laboratory
tests with different optical probes simulating field equivalent conditions – used on pipeline
inspection process. Besides that, some in situ tests with more aggressive environments showed
the possibility of using this technique to monitor the dissolved oxygen in crude oil.

Keywords: Corrosion, Dissolved Oxygen, Crude Oil.

1. Introduction

Internal corrosion of equipment is one of the main problems affecting the integrity of
oil and gas production facilities. The corrosive nature of the flowing fluids, which may be
subject to contaminants such as free water, CO2, microorganisms, H2S, temperature, salts and
dissolved oxygen (DO), can considerably increase the corrosivity of fluids to the most used
material in pipelines and equipment - carbon steel.
For these reasons, some corrosion control methods are used such as protective coatings,
corrosion inhibitor injection, PIGs, as well as physicochemical analyzes to better understand
the fluid characteristics such as pH, temperature, DO, between others. In this way, the internal
corrosion monitoring becomes an extreme important tool for the control method application,
sensitive to the corrosivity potential of the fluids.
Since it is not possible to monitor all parameters that indicate changes in the fluid
corrosivity, the focused attention is on specific parameters measured in the field and which may
indicate an increase or decrease of this corrosivity. As an example the monitoring of dissolved
oxygen content, pH, electrical conductivity and temperature.

______________________________
Master, Mechanical Engineer – Petrobras
 Rio Pipeline Conference and Exhibition 2019

The dissolved oxygen monitoring fluids finds wide application in the activities of the
oil and gas industry, with the mainly focus on corrosion phenomena. In practice, the monitoring
of the amount of dissolved oxygen is already routinely used in the beverage and food industry,
in agriculture (aquaculture), in sewage treatment plants and as a clinical tool for blood analysis
[4]. In addition, dissolved oxygen is the main element in the metabolism of aerobic
microorganisms that inhabit, in concomitance with anaerobic bacteria, in oil distribution
terminals.
Among the current methods available for determination of dissolved oxygen, the
method employing a polarographic dissolved oxygen sensor, also known as a membrane or
electrometric electrode, represents the standard method for determination of this parameter,
with possibility of use in real time monitoring of according to section 4500-O Oxygen
Dissolved [2]. This is the Clark cell based method [18] where an oxygen permeable membrane
separates the internal electrolyte and the electrodes (cathode and anode) from the external
medium. In the polarization condition of the electrodes, the oxygen concentration of the
medium will be proportional to the current between the electrodes.
Sensors constructed commercially available have a bulb design. The bibliographical
research of this theme revealed numerous articles describing its construction also in the planar
form. The electrodes were constructed using screen-printing, sputtering (ion impact) or
photocorrosion techniques on a flat substrate. The sensors construction in planar form has as
immediate impact the reduction of the cost of production, because it allows a scale production,
rational use of noble materials and the obtaining of miniaturized sensors.
In addition to the membrane electrode, other known techniques for dissolved oxygen
measurements are manometric, chemical, electrochemical and optical methods. The
manometric method based on a pressure or volume measurement is performed in an appropriate
chamber. It is an appropriate method presented in some situations; however, it requires complex
and expensive apparatus. Among chemical methods, the best-known and most widely used
method is WINKLER [33] apud BROENKOW; CLINE [6]. Samples with concentration values
lower than 10% of saturation are imprecise by the WINKLER method, which has undergone
many modifications until become a standard method for water samples.
Faster and more automated, electrochemical methods are the most widespread in DO
analysis in the laboratory and in the field, including polarography, voltammetry and
amperometry among the most commonly used techniques.
Optical methods, including spectrophotometers, are widely used to quantify dissolved
oxygen by reagents that are sensitive specifically to the O2 in the sample, causing some change
in the medium (color, absorbance, fluorescence). The spectrophotometric method can be
combined with the WINKLER (modified) method for analyzes at low DO concentrations.
With the advent of fiber optics, oxygen sensors have come to be called "oxygen optodes"
or oxygen fiber optic sensors. The spectrophotometry or fluorometry method, or
spectrophotometry, depending on whether the substances used are fluorescence or absorption
indicators, respectively [30]. In this method, the oxygen interacts with the reactants,
immobilized on the optical fiber, altering some characteristic of the optical signal (fluorescence,
absorbance, phase change).
The DO measurement technique using luminescence was incorporated as the C method
of ASTM D888-05 [3], according to the APHA [2]. This method is also incorporated in the
Standard Methods for Examination of Water and Waste Water, a publication with standardized
methods for measuring the parameters adopted by various agencies. Through an online
consultation, section 4500-O Oxygen (Dissolved), ed. 22, 2012, presents the luminescent
method 5210 B for DO measurement [2].

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Recently, the literature indicates an increase of papers that describe the development of
this type of sensor for dissolved oxygen. They report the development of optical DO sensors
through the immobilization of luminescent indicators, mainly of ruthenium complexes, in
planar substrates. Following the ASTM normalization methodology, the leading manufacturers
of analytical devices have begun an intense campaign to sell their new devices, which adopt the
luminescent technique. In common, manufacturers mention valuable characteristics for DO
measurement, such as not affected by interferers, long service intervals, and no need to stir the
sample differently from membrane-based sensors.
The luminescent sensors were able to solve some of the difficulties encountered in the
manufacture of planar sensors based on electrochemical electrodes. It allowed their application
in monitoring conditions that were not possible in the experimental tests with electrodes
covered by membrane. The tests also helped to question the strong projection of the luminescent
technique, since the conventional technique (electrochemical) that has been in existence for
more than 40 years presents satisfactory results, considering the materials, electronics and
processing required.
The development of this study aims at the evaluation of optical DO sensors with specific
characteristics to provide measurements on crude oil. Most of these sort of probes are compact
construction/design, low cost and adequate period (greater than three months) between
maintenance, high performance, and technical characteristics that distingue them to the
polarographics probes.
Laboratory tests performed on two probes to better understand the construction and
design characterization for the probes performance, accuracy, speed of response, stability,
reproducibility and durability, identifying possible degradation mechanisms. In addition, some
field testes with the approved model showed good correlation. All laboratory work performed
in the dependencies of Petrobras Research and Development Center – Laboratory of Autoclaves
of PDISO/TMC.

1.1 Dissolved Oxygen Sensor – Electrochemical Sensor

The polarographic sensor used to measure dissolved oxygen – electrometric method or electrode covered
by membrane – is the most common and commercial sensor for water-based fluids. Such an electrochemical
method has the following operating principle: the oxygen flow crosses a gas-permeable membrane, reaching the
surface of a negatively polarized electrode in relation to the anode, both electrodes immersed in an electrolyte. The
current generated by the reduction of oxygen over the cathode is proportional to the absolute pressure of the oxygen
outside the membrane. Figure 1.1 illustrates such a measurement system featuring a commercial sensor, composed
of two electrodes, and a membrane. The membrane separates the electrodes and the electrolyte from the test
solution, while maintaining a thin layer of electrolyte in contact with the cathode.
The polarographic sensor is based on the CLARK CELL, developed in 1959, which has been the basis of
virtually all subsequent oxygen detectors through membrane-coated electrodes. The electrochemical method of
determining the DO is well known and widespread today was designed by Leland CLARK, where it started by
testing sealing a platinum cathode with glass, and covering first with cellophane and polyethylene. In 1954,
CLARK conceived and built the first membrane-coated electrode, which had the anode and cathode behind a non-
conductive polyethylene membrane [11].

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Figure 1.1 – Polarographic Sensor principles [21].

Since the publication of the CLARK patent in 1959, a number of devices have been described, and by
convention the name for the electrochemical technique for detecting dissolved oxygen based on membrane-
covered electrodes is thus established: if an external source detection is called polarographic (or commonly
polarographic OD sensor). When a current arises spontaneously between the electrodes of the cell, the sensor is
called a galvanic. The need for an external source or the spontaneity of the current is related to the constitution of
the materials used in the construction of the electrodes [13-18].
Cathodes used as noble metals: Pt, Au or Ag. For the anode, when using metals such as Zn, Cd, Al and
Pb, the potential difference will arise spontaneously (galvanic probe). In sensors where requires external
polarization, the reference electrodes Ag/AgCl and Ag/Ag+ are the most used, therefore they need to be always
connected to an external power source to avoid loss of calibration.

1.2 Dissolved Oxygen Sensor – Luminescence (Optical)

The detection of oxygen through luminescence has been studied since the publication of KAUTSKY
(1939) apud VARNEY [31], who described the principle of the suppressive effect of luminescence by oxygen.
However, only from BERGMAN (1968) apud LEINER [18], the first fluorosensor oxygen sensor was obtained.
Advances in electronics, optical devices and signal processing techniques have contributed to the development of
luminescence-based oxygen sensors.
Clark's electrodes perform well in most situations, but it also has some limitations including oxygen
consumption, relatively long response time, and the tendency of contaminants attack the electrode such as proteins,
hydrogen sulfide, and organic compounds. Consequently, great efforts carried out the development of the optical
sensors for DO measurements, or "optrodos" analogous to the electrodes. Advantages of these sensors: no oxygen
consumption in the process; requires no reference electrode; insensitive to flow rates or sample velocity, immune
to the external electric field [8], precision similar to the titration method WINKLER and low sensitivity to the
presence of H2S [29]. For some applications, luminescence-based oxygen sensors have an alternative technic
propose, and highly recommended in the miniaturization of the sensor tip [16-26]. Optical sensors are more
attractive than conventional polarographic sensors because of their high selectivity, which is not parallel to most
of the chemical sensors [20]. They are immune to chemical interferes such as Cl2, SO2 and H2O2 at low
concentrations [29]. However, a limitation of these sensors is the strong influence of temperature on the
luminescence reduction/degradation process.
The construction of optical oxygen sensors consist of a luminescent indicator and an optical system. The
oxygen sensitive luminescent indicator impregnated with a membrane or a sol-gel (sol - stable dispersion of
colloidal particles – size 1 to 100 nm – in a fluid; gel - system formed by the rigid structure of colloidal particles
– colloidal gel – or strands – polymeric gel – that immobilizes the liquid phase in its interstices. The advantages
of using the sol-gel (linear aggregation of primary particles) process in immobilizing species include: (1) ambient
processing conditions; (2) adjustable film porosity; (3) good thermal stability; (4) optical transparency and (5)
simple procedures to capture dopants [32].
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The optical system includes the excitation source (LEDs or laser), optical filters to select the desired
length, waveguides (optical fiber), photodetectors such as photodiode or photomultiplier tube, as well as the signal
processing and control system [34]. Thus, DO measurement is based on the ability of certain substances to undergo
the action of oxygen as a dynamic suppressor of fluorescence. For example, if a ruthenium complex is illuminated
with a blue light emitting diode, it will be excited and emit a red luminescent light with intensity (or life time)
directly dependent on the oxygen concentration present, as shown in figure 1.2 [29].

Figure 1.2 - Principle of operation of the optical oxygen sensor where (excitation spectrum) 1λ < 2λ (emission
spectrum), (intensity of luminescence with absence O2) I0 > I (intensity of luminescence with presence O2), with
absence O2) 0 τ > τ (life time with presence O2) [31-29].

The main difficulties associated with the construction of the optical sensors are the immobilizations of
species that respond to DO and the relatively high cost of the excitation and detection system. Recently, many
authors describe optical DO sensors that use light-emitting diodes (LEDs) and sol-gel films deposited on the
surface of an optical fiber [9]. The study of optical oxygen sensors can be considered interdisciplinary, since it
involves varied areas such as inorganic chemistry, organic synthesis, chemical polymers, modeling, optics and
electronics.
Most of the published work based on optical DO sensors describe suppression of fluorescence, but this
technique of transductance presents some drawbacks for its measurement. The main ones are the susceptibility to
external light source, sensor movement, changes in the optical path, degradation or leaching of the indicator. To
reduce these effects, or even minimize, it is better operate the sensor in the time domain instead of intensity [19].
The increase on temperature reduces the intensity of fluorescence. The degree of temperature dependence depends
on the compound. Its effect is related to collision suppression. The increase in temperature suggests an increase in
molecular motion and collisions, which steal energy from molecules [12]. In order to avoid additional fluctuations
originating from the optoelectronic devices affecting the sensitivity of the photodetector, recommends temperature
control for photodetectors and amplifiers [17].
Avoid other issues at the tip of the sensor: trapped air, biological growth, and system pressure variation.
Gas bubbles with higher oxygen partial pressure (pO2) than liquid can cause higher rates of DO penetration through
the membrane present in the environment. This occurrence is more common in sensors installed vertically in
pressure vessel lids (small reactor) with dispersion systems. Ensure the disperser is not near the sensor installation
to do not affect proper functionality. Therefore, the tip sensors installation should be far from the gas bubbles
direct exposure for better operation. Biological growth on sensor membranes can occur in some facilities. The
biological growth will react to cover the membrane and consume DO, preventing its entry. Symptoms of biological
growth appear with gradual declines in the readings (Figure 1.3). The sensors must be mounted at an angle or even
upside down in applications where biological growth is expected by coating the membranes. In extreme cases,
operators should consider mounting the sensors in the headspace and relying on Henry's law for the dissolved
oxygen content calculation [21]. Figure 1.4 present some examples of in-situ problems.

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Figure 1.3 – Air bubbles Impact and biological growth. Gas bubbles with higher pO 2 than in the media
result in too high (false) reading. Membrane cells consume oxygen, which can result in low reading [21].

1 2

3 4 5

Figure 1.4 – Some examples of in-situ problems: 1- Faulty / unstable signal - possible cause: mechanical damage
to sensor or membrane. 2- Signal peak - possible cause: air bubbles present in the membrane media. 3- Gradual
decline of the signal - possible causes: membrane coating or bacteria growth. 4- Gradual increase of the signal -
possible causes: increased system pressure without compensation or degraded membrane. 5- Signal Peaks with
Posed - possible causes: floating system pressures between several processes [21].

2. EXPERIMENTAL PART

The two optical DO sensors (InPro 6970i – Mettler Toledo; HIOX_NEOFOX – Ocean Optics)
were mounted and tested simultaneously in a glass cell with a useful volume of 1 liter and teflon
lid. In addition to the two sensors, a bubbler for the nitrogen gas (N2 – 5.0 purity) and another
one for compressed atmospheric air were set up to purge the system, deaerating and aerating,
respectively.

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Figure 2.1 – Test cell.

Sensor Tmax. (ºC) Pmax.(bar) DO (ppb)

HIROX_NEOFOX 100 1 4 - 8000
InPro 6970i 40 12 2 - 2000

Figure 2.2 – Tested electrodes and some characteristics.

2.1 EXPERIMENTAL PROCEDURE

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The experimental procedure followed the sequence below, at room temperature:

1. Preparation and cleaning of the cell and filling it with oil;

2. Carry out two-point calibration of the NEOFOX and InPro 6970i system: high O 2 concentration (ambient air
with approximately 20% of O2) and low O2 concentration (N2 saturated environment);
3. Measure the dissolved oxygen in a cell with distilled water and note the value with the two electrodes. Repeat
this procedure for the two electrodes, every time the electrode is removed from the cell being measured DO in the
oil, to read the DO in distilled water, after the electrode is sanitized with soap and water;
4. Insert the electrodes into the cell with oil and perform the alignment for the purge of compressed air;
5. Start the bubbling of compressed air in high flow (600 ml/min aprox.), minimum of four bubbles per second.
After 2 hours register the dissolved oxygen concentration value measured in the oil;
6. Stop the bubbling of compressed air and start the bubbling of N 2. After 2 hours register the dissolved oxygen
concentration value measured in the oil;
7. Repeatedly alternating the bubbling of compressed air and nitrogen gases every two hours in order to verify the
variation of DO in the oil with the two electrodes during the same period.
8. At the end of each test day and on weekends, leave the bubble of compressed air in the cell aligned.
9. At the end of 24 days, stop the test.

The crude oil used was collected from Pre-Salt formation. The characteristics of API residual oil of 28.55 refer to
dead oil (no gas) and laboratory temperature tested.

3. RESULTS

The presented results show graphs on Figure 3.1 where the measured values of dissolved
oxygen in the crude oil are visualized over the test time.

Figure 3.1 - Oxygen concentration dissolved in oil and the ambient temperature of 22 ° C ± 2.

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It is possible to notice that the optical electrode InPro 6970i presents behavior
proportional to the type of gas being purged in the cell, oscillating differently compared to the
NEOFOX electrode, throughout the test time, again, as regards the variation of bubble gases.
No further calibration or adjustment was required on the InPro 6970i electrode. The Ocean
Optics NEOFOX electrode required several system calibration adjustments. Even so, the
measures were not proportional to the gases purged in crude oil.
The calibration requirement showed large variation in the measured value of the
dissolved oxygen concentration in the distilled water used as standard to verify the electrode
condition. Before the start of the crude oil tests, DO measurement in distilled water ranged from
9 to 10 ppm.
The InPro 6970i electrode presented repeatability in all measurements in the distilled
water throughout the test - reversal of bubbling N2 / compressed air.

4. DISCUSSION

The proposed test is not standardized. There is no standard for crude oil DO
measurements, so the above study only confirm the feasibility or otherwise of optical meters
being used for DO measurements in crude oil for the test condition itself. For a better
understanding of the petroleum technique, it would be important to study more
comprehensively other systems, adapt existing standards for measurements in aqueous
solutions, and test other electrodes of different brands and methods.
The Mettler Toledo optical sensor met the requirements proposed in the test, where there
is no standard that references DO measurement in petroleum. Concurrent oscillation with the
bubble gas in crude oil was verified for a preliminary and expedited response as requested by
the requesting management. However, a more comprehensive and comprehensive test is
recommended. The sensitivity to the presence of oxygen was measured through the luminescent
intensity with real-time monitoring with various bubbles of N2 and compressed air.
The results obtained confirmed the promising use of the luminescent technique, being
an option to the difficulties encountered in the continuous use of electrochemical sensors,
especially in petroleum environment.
Both equipment tested have the limit of detection near, according to characteristics and
technical specifications of the suppliers. Field reports indicated the low sensitivity and precision
of polarographic electrodes, compared to the luminescence technique.
A better response was obtained for the bubble gas for the luminescence method of the
Mettler Toledo equipment, since the electrode reading area is approximately 5 times larger than
the NEOFOX electrode area. As indicated in the literature, the reading area influences the
reliability of the result as a function of the medium to be measured. As there is no standard that
regulates this type of study, possibly this would be one of the limitations of the electrodes of
dimensions smaller or equal to the one of NEOFOX.
Something to be encouraged would be the salinity variation of the sample which may
impair the sensor response time. These tests were not performed. Only crude oil, as it was
withdrawn from the reservoir, was used without chemicals. As the crude oil may have high
salinity (reaching 200,000 mg / L in NaCl), when collected in presal reservoirs for example, the
Mettler Toledo electrode response provided better reproducibility.
Optical detection was recently regulated by ASTM. This study served to evaluate the
possibility of measuring OD in petroleum, something not yet regulated by the norms. However,
it is known from field reports that the polarographic electrode lasts approximately two days of
measurement. Then cleaning and replacement of the membrane and the electrolyte is required.
It was not the scope of this paper to compare electrochemical and optical methods, but rather
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to demonstrate the feasibility of scheduling oil OD measurements with luminescence

electrodes. However, some observations regarding the development of miniaturized sensors
(Ocean Optics) and their operation may be mentioned. In general, the miniaturization and
production of the sensor is facilitated in the optical system, except for its detection and
excitation system (photodiode and LEDs). The cost and complexity of the electronics involved
are likely to be similar in both methods as long as the optical system is measured through the
intensity.

5. CONCLUSIONS

The Mettler Toledo electrode behaved with better reproducibility of response, as a

function of the bubble gas (N2 / compressed air), when compared to the electrode of Ocean
Optics regarding the study presented related to the inversions of gases used to vary the
concentration of OD. The tip of the sensor, called the CAP by the company, was intact
throughout the test.
Field tests with the same sensor must be performed to verify the operation of the system,
mainly considering its temperature limitation. The Ocean Optics probe is not suitable for oil
OD measurement, possibly depending on the area, approximately 5 times smaller than the
Mettler Toledo electrode area. This issue is discussed in the literature.
Regarding cost-benefit, in terms of the need for two-day exchange of the polarographic
electrode membranes and the possible discrediting of the measurements, the luminescence
system becomes a good option for oil DO measurements. However, there is a need for a greater
approach to investigations in order to be sure of the studies.

6. RECOMMENDATIONS

The results obtained in this paper confirm the feasibility of the proposed DO
measurement in petroleum. It is essential that the temperature limitation of the equipment is
respected, for longer sensor life and accuracy of measurements. In addition to strictly follow
the procedures and protocols of the company, that supplies the equipment.
Complementarily, it would be important for the continuity of this paper the possibility
of longer tests and with more equipment available on the market. In addition to comparisons
with existing standards, even if only for tests with aqueous fluids.
Measuring the dissolved oxygen in the lifetime of the luminescence of the electrode
indicators, cited as a technique used in most commercial sensors, would indicate better reading
stability for the optical system in the medium of interest (petroleum).

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