Good Practice Guide for Improving

Accuracy of Dissolved Oxygen

Measurements
Teemu Näykki1
Lauri Jalukse2
Irja helm2
Ivo Leito2
1
Environmental Measurement and Testing Laboratory,
Finnish Environment Institute,
Hakuninmaantie 6, Helsinki 00430, Finland;
2
Institute of Chemistry,
University of Tartu,
Ravila 14a, Tartu 50411, Estonia;

Preparation of this guide was supported by the

European Metrology Research Programme
(EMRP), project ENV05 "Metrology for ocean
salinity and acidity".
 1

Good Practice Guide for Improving Accuracy of Dissolved

Oxygen Measurements
Teemu Näykki 1,, Lauri Jalukse 2, Irja Helm 2 and Ivo Leito 2
1
Environmental Measurement and Testing Laboratory, Finnish Environment Institute,
Hakuninmaantie 6, Helsinki 00430, Finland; e-mail: [email protected]
2
Institute of Chemistry, University of Tartu, Ravila 14a, Tartu 50411, Estonia;
E-Mails: [email protected] (L.J.); [email protected] (I.H.); [email protected] (I.L.)

Abstract: Dissolved oxygen concentration is a key parameter for characterizing natural and
wastewaters and for assessing the global state of the environment in general. The decrease of
dissolved oxygen levels in the world’s oceans, which is becoming increasingly obvious, is
expected to have an impact on the whole ecosystem of the Earth, including the carbon cycle,
the climate, etc. Dissolved oxygen measurements by sensors are often deemed easy
measurements by routine laboratories. In reality, the physical and chemical processes
underlying the measurements are complex and these measurements are not at all as robust as
often considered.

Based on the analysis of the results of the intercomparison a set of tools and
recommendations are given to the participants of how to improve the quality of their results.

Keywords: dissolved oxygen; interlaboratory comparison; sensors; quality control

Good Practice Guide… 2

Table of contents

1. Introduction .......................................................................................................................3

2. Aspects for Improving Quality of the Measurement Results ............................................4

2.1 Calibration ..................................................................................................................4

2.2 Temperature compensation.........................................................................................5

2.3 Salinity compensation ................................................................................................5

2.4 “In-House” Reference Material for DO Measurement ...............................................5

2.5 Setting up a Control Chart ..........................................................................................7

2.6 Sensor Lifetime ..........................................................................................................7

2.7 Checking the water flow dependency.........................................................................8

2.8 Using the proficiency test results for checking self-declared measurement uncertainty 8

2.9 Using the proficiency test results for measurement uncertainty estimation .............10

3. Example of using the “in-house” reference material .......................................................13

3.1 Experimental setup ...................................................................................................13

3.2 The Measurement Conditions...................................................................................14

4. Compilation of observations and recommendations .......................................................15

Acknowledgments ................................................................................................................15

References ............................................................................................................................16
Good Practice Guide… 3

1. Introduction
Dissolved oxygen (below DO) content in natural waters is an indispensable quantity whenever data are
collected for investigations of nature from a hydrobiological, ecological or environmental protection
viewpoint [1]. A sufficient concentration of DO is critical for the survival of most aquatic plants and
animals as well as for waste water treatment [2]. DO concentration is a key parameter for characterizing
natural and wastewaters and for assessing the global state of the environment in general [3]. The
decrease of DO levels in the world’s oceans, which is becoming increasingly obvious [3–6], is expected
to have an impact on the whole ecosystem of the Earth, including the carbon cycle [7], the climate [3,5],
etc. The current understanding of the dynamics of the processes and their interrelation is still far from
sufficient. Measurement and monitoring of dissolved oxygen concentration is essential for improving
that understanding.
The majority of dissolved oxygen measurements are made with the use of amperometric [8] and
optical sensors [9]. The performance of these sensors has dramatically improved over the years [10].
Nevertheless, accurate DO measurement with sensors is not easy because it is influenced by numerous
uncertainty sources [8,10,11]. Therefore, the agreement between the sensor-based DO data from
different laboratories has long been an issue and has caused a negative perception of the data using
sensors in the oceanography community. Because of this, the recent issue of the World Ocean Atlas [12]
was compiled taking into account only DO concentrations obtained with chemical titration methods
(first of all the Winkler titration method, WM) and rejecting all sensor-based data. A similar decision
was made in a recent study of DO decline rates in coastal oceans [6]. Yet, oceanographers need large
amounts of DO data, collected continuously around the clock during lengthy time periods (months),
often far away from any human settlement. Only sensor-based automatic measurements can satisfy this
need. It is thus important to make every effort to underpin the quality of sensor-based measurements.
DO concentration is a highly unstable parameter of water. Thus preparation of reference solutions
that are stable for extended periods of time is almost impossible. This complicates the standardization of
the measurements and preparation of certified reference materials (below CRM). This is as true for
Winkler titration as it is for sensor measurement of DO concentration. Also Nordtest TR 537 [13]
pointed out that there is a “long-term” uncertainty component from the variation in the calibration,
which is hard to measure, as no stable reference material or CRM is available for DO measurement. The
method suggested in Nordtest TR 537 for Winkler titration was to calibrate the same thiosulfate solution
several times during a few days and use the variation between the results for the uncertainty estimation.
Nevertheless, the highly important long-term variation component is only estimated by educated guess in
Nordtest TR 537, which cannot be considered fully satisfactory and the bias component of uncertainty is
not addressed at all.
However, in this guide we present a tool for laboratories: A robust method to prepare an in-house
reference material—water saturated with air—for DO measurement, which will help laboratories to
estimate their measurement bias. This will enable the use of the increasingly popular Nordtest
approach [13,14] and the MUkit software [15] for measurement uncertainty evaluation. In the Nordtest
approach, among other things, control sample and routine sample replicate results are utilized for
uncertainty evaluation. Also intercomparison measurement results may be exploited for uncertainty
estimation with the Nordtest approach.
Good Practice Guide… 4

Intercomparison measurements are also a viable means of underpinning measurement quality

with this unstable analyte. It is difficult to organize DO intercomparisons involving sending samples to
the participating laboratories as is usually done in the case of interlaboratory comparisons in other
chemical measurements. Given that most DO measurement instruments can be transported in situ,
interlaboratory comparisons are a good alternative. (The instrument, also called analyzer, generally
consists of an amperometric or optical sensor connected to a data processing and displaying unit). In situ
interlaboratory comparisons are intercomparison measurements, where all the participants (with their
own equipment and using their own competence) measure the same sample continuously at the same
time, at the same site [16]. This arrangement provides the best possibility for assessing participant
performance in determining DO content in water (Participant—laboratory participating in the
intercomparison and sending a worker and an instrument to the intercomparison).
Recently international in situ interlaboratory comparison measurements of dissolved oxygen
concentration have taken place at the University of Tartu [17] and on the research vessel R/V Aranda at
the Baltic sea [18]. The results revealed that the routine laboratories as a rule still do not fully master the
art of dissolved oxygen concentration measurement. The purpose of this communication is, based on the
results of the interlaboratory comparisons, to examine the performance of the laboratories in different
parts of the intercomparison, and based on these data, uncover the problems that the participants have
and to define a set of recommendations for the improvement of their performance. Also possible future
actions for improving competency of DO sensor measurement will be discussed.

2. Aspects for Improving Quality of the Measurement Results

2.1 Calibration
The commercial DO sensors use a linear calibration function, which calculates the dissolved oxygen
concentration from the actual measured signal (current or fluorescence signal). The function is defined
inside the sensor using two points—the zero oxygen concentration and the saturation concentration. The
zero point is usually fixed electronically. So, the calibration basically consists of recording the signal in
the reference medium, which in the case of the commercial DO sensors is usually air saturated with
water vapor. Together with calibration the instrument is also automatically adjusted to display the actual
concentration of dissolved oxygen.
It should be noted that there are small differences between sensor currents in water and in air.
Because of the sensor geometry, in water a so-called unmoved diffusion layer exists, which leads to a
signal depression of ~2%. However this is the problem only for amperometric sensors and, therefore, the
calibration target for them is 102% in water vapor-saturated air [19]. All commercial oxygen sensors are
equipped with manuals that, among other things, describe how to carry out calibration. According to
ISO 5814 the calibration should be checked daily and after relevant changes of ambient conditions (i.e.,
temperature or pressure) [19].
In the intercomparison, the elapsed time from the last calibration was very different from participant
to participant ranging from a few days to over one year. Calibration frequency around once a year is
unacceptably low, because the properties of the sensor change with time. This is also seen from the
Good Practice Guide… 5

results of this intercomparison. At the same time carrying out calibration is very easy, so that frequent
calibration is not a problem even at routine laboratory level.

2.2 Temperature compensation

If the measurements are carried out in the wider temperature range, the temperature compensation
(usually DO device perform it automatically) should be verified.

Using an in-house reference material/environment (as is presented in Chapter 2.4) the calibration
(usually 20 or 25 °C) is performed and then measurements in a wider temperature range (example ± 5,
±10 and ± 15 °C, in the range 1 - 40 °C, depending the sensor type) are also performed. All measured
values are compared to the saturation values (according to the Chapter 2.4 equations). If the
measurements are always carried out at low or high temperatures (example below or over 20 °C), also
the calibration should preferably be carried out at near or even at the same temperature.

2.3 Salinity compensation

If the measurements are carried out in the sea or ocean water and for calibration pure (deionised) water
was used, the automatic or manual salinity compensation should be verified. In this case, the
measurements may be carried out either two possible ways:

a) an artificially saline solution is prepared (for example using a KCl), which is saturated with air
and the oxygen content is measured with the sensor and the salinity is calculated or the measured
as conductivity/salinity. The measured DO value is compared with the theoretical value of the
saturation value (in that particular salinity).

b) the real sea water or ocean sample is measured with DO sensor and the results are compared
with the Winkler titration result.

2.4 “In-House” Reference Material for DO Measurement

Laboratories are encouraged to prepare their own “in-house” reference solution for dissolved oxygen
determinations as was prepared in this interlaboratory comparison (see Scheme 1). This solution could
be used for sensor calibrations as well as for controlling trueness of Winkler titration method in the
laboratory. The steps for preparing the solution are as follows:
1. Prepare deionized or distilled water. In ESTDO-2012 a MilliQ Advantage A 10 setup was used.
2. Place the deionized water into the vessel, which is in the thermostated water bath (for example
at 20 °C).
3. Pump clean air at a flow rate of 1 L/min through two consecutive saturation bottles half filled
with the same deionized water. This step is important to ensure that the air used is saturated with
water (air humidity is 100%).
4. Saturate water (Step 2) with the air (Step 3) until the dissolved oxygen reading is stable. Stability
criterion: DO reading should not change by more than 0.01 mg/L during 10 min. Usually this
kind of stability will be achieved in 2 h (the time also depends on the initial concentration) at
room temperature. Here the critical step besides the air flow velocity is the size of the air bubble.
The optimum diameter of the bubble is between 1 and 2 mm. A smaller bubble size will produce
supersaturation. Also, too high an air flow rate can produce supersaturation. We have carried out
Good Practice Guide… 6

tests and found that the equilibrium saturation concentration can change in the range of
±0.03 mg/L if the diameters of the bubbles change in the range of 1.3–10 mm (at a temperature of
20 °C this means a relative difference of 0.33%). The bubble diameter was estimated from
photographs of the bubbles taken against a ruler positioned in the water.
5. Measure the temperature of the water (Step 2) and the air pressure next to the water bath as
accurately as is possible for your laboratory.
6. Calculate the dissolved oxygen saturation concentration (CO2_saturation, in Table 1 and in the main
text this is equal to Cref) using Equations (6–8) or check the reference value from the ISO
5814:2012 Tables A.4 and A.5 in [19]. ISO 5814 gives the solubility of oxygen in water vs.
temperature and atmospheric pressure with 1 °C temperature interval and for air pressures such
as 967 hPa, 1000 hPa, 1013 hPa and 1033 hPa.
 A A A A 
C O2_saturation  exp  A1  2  32  43  54   W (6)
 T T  T  T  
where T is the temperature [K] of the water; A1, A2, A3, A4, A5 are constants and the values are
−1.393441 × 102, 1.575701 × 105, −6.642308 × 107, 1.2438 × 1010, −8.621949 × 1011,
respectively [20, 21]. W is the pressure correction factor [19]:
p  pH2O
W 
pn  pH2O_100% (7)

where p is the atmospheric pressure (Pa) at measurement conditions, pn is the atmospheric

pressure (Pa) at standard conditions (101,325 Pa), pH2O is the water vapor pressure (Pa) at
measurement conditions and pH2O_100% is the water vapor pressure (Pa) at 100% relative
humidity. This is calculated according to Equation 8 [21].
 B B 
pH2O_100%  pn  exp  B1  2  3 2  (8)
 T (T ) 

where B1, B2, B3 are constants and the values are 11.8571, −3840.7, −216961 respectively.
An example of Excel spreadsheet for the calculation of the DO concentration in saturation
conditions is given in Appendix Tables A1 and A2.
7. In order to achieve the DO concentration in the reference medium with a k = 2 expanded
uncertainty of 0.2 mg/L or lower, a measuring temperature with k = 2 expanded uncertainty in the
range of 0.1 to 0.2 °C is safe. Sufficient k = 2 uncertainty for air pressure measurement is 500 Pa.
Good Practice Guide… 7

Scheme 1. The experimental setup for the preparation of dissolved oxygen (DO) in-house
reference material.

DO sensors are placed

Janke & Kunkel Air is taken from
on the cell concentrically the ventilation inlet
RW20 mechanical
stirrer
Air pump
Chub-E4 two Pt100 Double air with
sensors water vapor
saturation tanks

Air saturated water

Second bath

Heating system

Cooling
5 cm
system

Modified thermostat CC2-K12

2.5 Setting up a Control Chart

A useful way to improve the quality of the measurement results is to maintain a control chart (Shewhart
X-chart) [22]. A control chart of the dissolved oxygen concentration measurement can be set up in two
ways: Either by measuring oxygen in moist air (saturated with water) or in water saturated with air as
was described, step by step, above. Ideally, a data point for the control chart should be recorded every
day on which the measurements are done. This enables observing trends in the sensor behavior and
taking action before things get out of hand. Detailed guidelines for setting up a control chart can be
obtained from the Nordtest Technical Report 569 Internal Quality Control—Handbook for Chemical
laboratories [22].

2.6 Sensor Lifetime

Sensor lifetime is strongly dependent on the sensor type, frequency of use and of maintenance, and the
properties of the samples that are measured. It is therefore almost impossible to give a universal estimate
of the lifetime. But the laboratories are encouraged to test their sensors (the zero value
test and response time test as described in reference [23]), maintain control charts and participate in
interlaboratory comparisons. Zero value test is carried out in oxygen-free environment. The oxygen-free
environment in water can be prepared using the sodium sulfite. It reacts with oxygen and forms the
sodium sulfate. Other possibility is to place the sensor in oxygen-free nitrogen in the gas phase, see the
details in reference [19], ISO 5814:2012.
Good Practice Guide… 8

2.7 Checking the water flow dependency

Based on the previous proficiency tests, the results of optical and electrochemical sensors generally
deviated from each other so that the results of electrochemical oxygen sensors were lower than the
results of optical oxygen sensors [18, 24]. Two possible reasons can be envisaged for the behavior of the
electrochemical sensors. Firstly, it is possible that the sensors’ parameters have drifted during the time
period from the last calibration to the intercomparison. Such drift almost always leads to lowering of the
values (not increasing), which is also observed here. Secondly, all electrochemical DO sensors have
some flow dependency because they consume oxygen at the membrane surface. Therefore the
electrochemical sensors need water movement and if this is not sufficient then lowered readings are
observed. In slow-moving water, mechanical stirring is necessary for most models.

In connection to Fieldoxy2014 proficiency test [18], tests were carried out for checking the flow
dependency of DO measurement results on water flow rate in the surface of the sensor (sensor type
SBE43; Seabird). It was noticed that flow velocities ca. 6-14 cm/s yielded DO results within 1.5% at 8.9
mg/l concentration level. If the flow rate of water was 0 cm/s, then the DO results were decreased
dramatically resulting DO concentration ca 65% lower than compared to flow speed of 14 cm/s.

Before DO measurements, the operator of electrochemical sensor should check that the movement of the
water is sufficient for the purpose.

2.8 Using the proficiency test results for checking self-declared measurement
uncertainty
If proficiency test provider reports z- and zeta-scores to the participants, this information is very useful,
when participant checks, if the self-declared measurement uncertainty is realistic or not.

z-score is calculated as follows:

z = ( x  X ) / s p , where
x = the result of the individual participant
X = the assigned value
sp= the target value of the standard deviation

zeta-score is calculated as follows:

zeta = ( x  X ) / ulab
2
 uc2 , where

x = the result of the individual participant

X = the assigned value
ulab = the standard uncertainty of the participant's result
uc = the standard uncertainty of the assigned value
Good Practice Guide… 9

How to interpret these results?

z score zeta score Action to take

Satisfactory Satisfactory No action; the result is good!
Satisfactory Not satisfactory The claimed uncertainty is too low, but the measured
values fills the requirement of the proficiency test.
Not satisfactory Satisfactory The result is within your claimed uncertainty, but not
within the limits of proficiency test. The uncertainty might
therefore be too high and should be checked against the
uncertainty requirement of your client.
Not satisfactory Not satisfactory The result deviates too much from the assigned value
and the reason should be clarified.
 10
2.9 Using the proficiency test results for measurement uncertainty estimation
Proficiency test results may be employed for estimation of bias of the DO measurement. According to
the Nordtest Handbook for measurement uncertainty estimation [13] and the standard ISO 11352 [14],
uncertainty is broken down into two main components: (1) within-laboratory reproducibility and (2)
method and laboratory bias. The within-laboratory reproducibility covers the random effects of
analytical results i.e. standard deviation of the measurement results. Sensor operator may for example
record at least 10 replicate measurement results of the same water sample under repeatability conditions
and repeat this during five different days with the instrument calibrated just before the measurements.
After that the (pooled) standard deviation (uRw) of the measurement results can be estimated (see
footnote 1).

The bias can be calculated using e.g. proficiency test results. The Nordtest handbook [13] suggests
having at least six different PT results. As the use of PT results for bias estimate is inferior to use of
certified reference material for same purpose, the participants should also consider setting up facility for
production of “in-house” reference material, water saturated with air, for dissolved oxygen
determination. This is described in detail in Sections 2.2 and 3 and references [17, 23].

Estimation of the random component (uRw):

Sensor measurements:
1. Record at least 10 replicate measurement results of same sample water in repeatability
conditions.
2. Repeat this during five different days with the instrument calibrated just before the
measurements. Calculate the (pooled) standard deviation (uRw) of the measurement
results.

Titration measurement:
1. Analyze at least 10 samples as duplicates.
2. Denoting the pairs of DO values measured in the natural water samples i with Ri,1 and
Ri,2, calculate their absolute difference Di (Equation 9).

| | (9)
3. Calculate the average difference, Dmean, of all individual Di values. (Equation 10)
∑
(10)
where M denotes the number of sample pairs.
4. Calculate the standard deviation as uRw = Dmean/1.128 (Equation 11), where the factor
1.128 accounts for converting the mean difference to the standard deviation when two
replicates are used for Di determination [13, 14].
Estimation of systematic component (ub):
Since several PT results are used for bias estimate,
1. Calculate Root Mean Square of bias (RMSb)
∑(𝑏 i )2
𝑀𝑆b =
𝑀 (12)
where bi is the bias estimate obtained from individual PTi measurement results, i=1, 2
and 3 (in this PT), M is the number of different PT results used.
2. Take also into account the average of the uncertainties of the assigned values. ( ̅ cref).
3. Calculate ub using Equation 13

1
This approach should be applied with caution, because it only gives the within-day variation (repeatability) for sampling
and measurement, and there will also be a “long-term” uncertainty component from the variation in the calibration. For DO
titration method Nordtest TR537 [13] suggests to calibrate the same thiosulphate solution several times during a few days
time, and use the variation between the results as additional component for reproducibility in calibration.
Good Practice Guide… 11

b = 𝑀𝑆b2 + ̅cref
2
(13)

Calculation of combined standard uncertainty (uc):

Combine standard uncertainties of random and systematic components as described in equation 14:
(14)

Calculation of expanded measurement uncertainty (U):

Apply coverage factor of “2” for calculating the expanded measurement uncertainty (Equation 15)

(15)
 12
Table 1. Example of Excel® spreadsheet for the calculation of measurement uncertainty of applying the
results of the proficiency test.
Good Practice Guide… 13

3. Example of using the “in-house” reference material

3.1 Experimental setup
Figure 1 presents the in-house reference material used during the 2012 interlaboratory comparison.

Figure 1. Photo of the experimental setup of creating the in-house reference material.

a
In the front of the photo: thermostat with the bath for the reference medium, the second saturation bottle and
the stirrer motor. The sensors are immersed concentrically through the lid (cover) of the reference medium
bath. The readout devices are on the right side of the thermostat. The temperature sensors are inside the foam
(shown by an arrow).

The saturation conditions were obtained as follows. Air-saturated MilliQ water was used as the
reference medium (equilibrium saturation medium). The pressure, humidity and temperature of the air
used for saturation were controlled and taken into account. The saturation medium was created in a
modified (a second bath and a mechanical stirrer were added) thermostat CC2-K12 (Peter Huber
Kältemaschinenbau GmbH, Germany) in MilliQ water with overall volume 3.9 L (Scheme 1). The obtained
temperature variability was lower than 0.01 C (expressed as standard deviation). The air used for
saturation of the reference medium was taken from the air inlet situated on the roof of the building. The
air used for saturation was first saturated with water to achieve relative humidity of 100% for the air. The
air flow velocity during calibration was around 1 dm3 min−1. The ordinary aquarium spray was used for
bubbling (at a depth of 13 cm). The estimated diameter of the bubbles was between 0.8 and 1.8 mm.
Good Practice Guide… 14

The measured environment was stirred using a four-bladed stirrer with constant speed (160 rpm).
Thus the DO probes of the participants were arranged concentrically in the bath and were immersed
approximately to the same depth for achieving the same velocity of water movement in the location of
each sensor. According to our experience over the years [16], this setup permits achieving the best
possible uniformity of the measurement conditions between the participants, and the differences
between the DO concentrations in the vicinity of different sensors are negligible. Stirrer dimensions and
its location in the reference medium are also given in Scheme 1.

3.2 The Measurement Conditions

As reference values (assigned values) for DO, the theoretical DO saturation concentrations were used
and they were calculated as described in the standard ISO 5814:2012 [19]. The experimental setup for
creating the water saturated with air under carefully controlled conditions and the calculation method for
obtaining the reference values and their uncertainties have been verified using the gravimetric Winkler
titration method [25]. The uncertainty of the reference value was estimated according to the ISO GUM.
All the major uncertainty sources, such as temperature measurement, temperature instability, air
pressure, air humidity, oxygen concentration in air, the mathematical model itself, possible over- or
undersaturation, etc., were taken into account. The two most important uncertainty sources are possible
over- or undersaturation and the uncertainty of the mathematical model itself [25]. The uncertainties of
the reference DO concentrations used in this intercomparison were conservatively estimated as
±0.15 mg/L (k = 2). The temperature of the MilliQ water was measured by calibrated digital
thermometer Chub-E4 (Model No. 1529, Serial No. A44623, manufacturer Hart Scientific) with two
Pt100 sensors (Serial No. 0818 and 0855). The last calibration was made in May 2011 (by the Estonian
NMI, AS Metrosert). The uncertainties of all temperature measurements (including the bath instability
uncertainty source) are ±0.05 C (k = 2). The atmospheric pressure was measured by digital barometer
PTB330 (Serial No. G37300007, manufactured by Vaisala Oyj, Finland, calibrated by manufacturer 19
September 2011) with uncertainty 10 Pa (k = 2). The level of air humidity after the second saturation
vessel was measured using digital hygrometer Almemo 2290–8 with sensor ALMEMO FH A646 E1C
(manufacturer AHLBORN Mess- und Regelungstechnik GmbH). The humidity of the air bubbled
through the water in the second bath was around 100% RH. The uncertainties of all relative humidity
measurements are ±5% RH (k = 2).
Good Practice Guide… 15

4. Compilation of observations and recommendations

 Optical sensors are in general more robust and require less skill in usage than the amperometric
sensors. The latter need more maintenance (replacement of the membrane and electrolyte
solution) and are more sensitive to stirring of the solution and temperature.
 The sensors should be regularly calibrated.
 The zero current of the sensors should periodically be checked.
 Use of “in-house” reference material and routine sample replicate results together with control
charts enable laboratories to estimate measurement uncertainty of the DO measurement with the
Nordtest approach [13] more easily and more reliably than before. Näykki et al. recently
published a paper presenting software support for the measurement of uncertainty evaluation
based on the Nordtest approach [15].
 Control charts should be set up for daily quality control
 Participation in interlaboratory comparisons or proficiency tests may be exploited to check if the
self-declared uncertainty estimate is realistic [26].
 Participation in interlaboratory comparisons or proficiency tests may be exploited in estimation of
measurement uncertainty.

Acknowledgments

This work was supported by the European Metrology

Research Programme (EMRP), project ENV05 “Metrology for
ocean salinity and acidity”. The EMRP is jointly funded by the
EMRP participating countries within EURAMET and the
European Union.
The work has also been partially supported by the grant No. 9105 from the Estonian Science
Foundation and by the joint graduate school “Functional materials and technologies” of Tartu University
and Tallinn Technical University receiving funding from the European Social Fund under project
1.2.0401.09-0079 in Estonia.
Good Practice Guide… 16

References

1. Nagy, S.A.; Dévai, G.Y.; Grigorszky, I.; Schitchen, C.S.; Tóth, A.; Balogh, E.; Andrikovics, S. The
measurement of dissolved oxygen today—Tradition and topicality. Acta Zool. Acad. Sci. Hung.
2008, 54, 13–21.
2. Hobbs, J.P.A.; McDonald, C.A. Increased seawater temperature and decreased dissolved oxygen
triggers fish kill at the Cocos (Keeling) Islands, Indian Ocean. J. Fish Biol. 2010, 77, 1219–1229.
3. Keeling, R.F.; Garcia, H.E. The change in oceanic O2 inventory associated with recent global
warming. Proc. Natl. Acad. Sci. USA 2002, 99, 7848–7853.
4. Shaffer, G.; Olsen, S.M.; Pedersen, J.O.P. Long-term ocean oxygen depletion in response to carbon
dioxide emissions from fossil fuels. Nat. Geosci. 2009, 2, 105–109.
5. Keeling, R.F.; Körtzinger, A.; Gruber, N. Ocean Deoxygenation in a Warming World. Annu. Rev.
Marter. Sci. 2010, 2, 199–229.
6. Gilbert, D.; Rabalais, N.N.; Diaz, R.J.; Zhang, J. Evidence for greater oxygen decline rates in the
coastal ocean than in the open ocean. Biogeosci. Discuss. 2009, 6, 9127–9160.
7. Joos, F.; Plattner, G.-K.; Stocker, T.F.; Körtzinger, A.; Wallace, D.W.R. Trends in marine
dissolved oxygen: Implications for ocean circulation changes and the carbon budget. EOS Trans.
AGU 2003, 84, 197–204.
8. Helm, I.; Jalukse, L.; Leito, I. Measurement uncertainty estimation in amperometric sensors: A
tutorial review. Sensors 2010, 10, 4430–4455.
9. McDonagh, C.; Burke, C.S.; MacCraith, B.D. Optical chemical sensors. Chem. Rev. 2008, 108,
400–422.
10. Johnson, K.S.; Needoba, J.A.; Riser, S.C.; Showers, W.J. Chemical sensor networks for the aquatic
environment. Chemical sensor networks for the aquatic environment. Chem. Rev. 2007, 107, 623–
640.
11. Jalukse, L.; Leito, I. Model-Based measurement uncertainty estimation in amperometric dissolved
oxygen concentration measurement. Meas. Sci. Technol. 2007, 18, 1877–1886.
12. Garcia, H.E.; Locarnini, R.A.; Boyer, T.P.; Antonov, J.I. World Ocean Atlas 2005, Volume 3:
Dissolved Oxygen, Apparent Oxygen Utilization, and Oxygen Saturation; Levitus, S., Ed.; NOAA
Atlas NESDIS 63; US Government Printing Office: Washington, DC, USA, 2006.
13. Magnusson, B.; Näykki, T.; Hovind, H.; Krysell, M. Handbook for Calculation of Measurement
Uncertainty in Environmental Laboratories, 3.1 ed.; Nordtest TR 537; Nordic Innovation: Oslo,
Norway, 2012.
14. International Standard Organization (ISO). Water Quality—Estimation of Measurement
Uncertainty based on Validation and Quality Control Data; ISO 11352:2012; ISO: Geneva,
Switzerland, 2012.
15. Näykki, T.; Virtanen, A.; Leito, I. Software support for the Nordtest method of measurement
uncertainty evaluation. Accred. Qual. Assur. 2012, 6, 603–612.
16. Jalukse, L.; Vabson, V.; Leito, I. In situ interlaboratory comparisons for dissolved oxygen
concentration and pH. Accred. Qual. Assur. 2006, 10, 562–564.
Good Practice Guide… 17

17. Jalukse, L.; Helm, I.; Leito, I. Dissolved Oxygen Concentration Interlaboratory Comparison
Measurement; ESTDO-2012 Final Report; Available online: http://www.ut.ee/katsekoda/ILC/
O2_2012/ESTDO-2012_final_report.pdf (accessed on 8 April 2013).
18. Leivuori, M.; Näykki, T.; Leito I.; Helm I.; Jalukse L.; Kaukonen L.; Hänninen P.; Ilmakunnas M.,
Field measurement intercomparison, Field measurements of dissolved oxygen concentration,
Reports of Finnish environment institute 24/2014, Finnish environment institute, Helsinki, Finland,
2014
19. International Standard Organization (ISO). Water Quality—Determination of Dissolved
Oxygen—Electrochemical Probe Method; ISO 5814:2012; ISO: Geneva, Switzerland, 2012.
20. Benson, B.B.; Krause, D., Jr. The concentration and isotopic fractionation of gases dissolved in
freshwater in equilibrium with the atmosphere. 1. Oxygen. Limnol. Oceanogr. 1980, 25, 662–671.
21. Mortimer, C.H. The oxygen content of air-saturated freshwaters over ranges of temperature and
atmospheric pressure of limnological interest. Mitt. Int. Ver. Theor. Angew. Limnol. 1981, 22, 1–23.
22. Hovind, H.; Magnusson, B.; Krysell, M.; Lund, U.; Mäkinen, I. Internal Quality Control, 4th ed.;
Nordtest Technical Report 569; Nordic Innovation: Oslo, Norway, 2011. ‘
23. Näykki T,; Jalukse L,; Helm I,; Leito I,; Dissolved oxygen concentration interlaboratory
comparison: What can we learn?, Water, 2013, 5:420–442.
24. Leivuori, M.; Björklöf, K.; Näykki, T.; Väisänen, R.; Laboratorioiden välinen pätevyyskoe 5/2013,
proficiency test for field measurements of oxygen, temperature, pH and electrical conductivity (In
Finnish) Suomen ympäristökeskuksen raportteja 30/2013, Finnish environment institute, Helsinki,
Finland, 2013
25. Helm, I.; Jalukse, L.; Leito, I. A highly accurate method for determination of dissolved oxygen:
Gravimetric Winkler method. Anal. Chim. Acta 2012, 741, 21–31.
26. Analytical Method Committee. Is My Uncertainty Estimate Realistic? AMC Technical Brief No. 15;
Available online: http://www.rsc.org/images/realistic-estimate-technical-brief-15_tcm18-214874.pdf
(accessed on 8 April 2013).