Comparative validation of amperometric and optical analyzers of dissolved oxygen: a case study  

I. Helm, G. Karina, L. Jalukse, T. Pagano, I. Leito, Environmental Monitoring and Assessment 2018, 190, 313

Irja Helm,1 Gerli Karina,1,2 Lauri Jalukse,1,2 Todd Pagano,3 Ivo Leito1,*

1
University of Tartu, Institute of Chemistry, Ravila 14a, Tartu 50411, Estonia
2
Current address: Estonian Veterinary and Food Laboratory, Kreutzwaldi 30, 51006 Tartu, Estonia
3
Department of Science & Mathematics, Rochester Institute of Technology, Rochester, New York 14623, United States

* Corresponding author: Tel: +372-5 184 176, e-mail: [email protected]

Table S1 Characteristics  of the sensors as provided by manufacturers.

Characteristic WTW HACH

Measuring range (linear range) 0 – 50 mg/L 0.1 – 20 mg/L
10% (flow rate) > 3 cm/s)
Influence of flow rate 5% (flow rate) > 10 cm/s) Not specified
1% (flow rate) > 18 cm/s)
Parameters related to precision and ±0.1 mg/L for 0 to 8 mg/L
±0,5% (in the range 5-30°C)
accuracy ±0.2 mg/L for greater than 8 mg/L
Accuracy of temperature
±0.1 °C ±0.3 °C
measurement
t90 < 10 s
Stabilization time T90% at 10
Stabilization time t95 < 16 s
seconds (when stirred)
t99 < 60 s
Zero signal < 0,1% Not specified
Drift (in one month) 3% -
Pressure measurement accuracy - ±0,8%
min. 6 months with one electrolyte
Working life without maintenance 1 year
fill
Oxygen own consumption at 20 °C 0.008 μg/h-1 (mg/L)-1 No own consumption
Source of data Ref 1 Ref 2
Table S2. Measurement uncertainty using the ISO GUM method with Kragten approach
Data from River Emajõgi
Cread_meas  Cstir  CΔt  Cdrift  Clinearity b0 Cread_cal_0  Ccal  Ccal_0  Cread_cal Cread_cal  Cread_cal_0
Cresult   b0  b1 
  b1 b1 Ccal  Ccal_0
Ccal  Ccal_0

HACH
Experimental data for calculating different uncertainty contributions:
u(Ccal_rep) 0.0039 mg/L Pooled standard deviation of the readings at stirring rate 120 rpm
u(Ccal_0_rep) 0.0049 mg/L The largest pooled standard deviation of the readings
u(Cmeas_Rep) 0.0686 mg/L Reproducibility: pooled standard deviation of differences between reading and reference value
u(Ccal) 0.031 mg/L From Ref 3
b1stir -0.00094 %/% The slope of stirring graph (% of the reading vs % of the stirring rate from calibration stirring rate)
b1Δt 0.024 %/°C The slope of temperature compensation graph (temperature °C vs relative difference from reference temperature in %)
b1drift -0.0079 mg/L The slope of the drift graph ( number of days passed from calibration vs reading difference from the reference value mg/L )
s(b1drift) 0.0008 mg/L Standard deviation of the slope of the drift graph
b1linearity 0.0277 - The slope of the linearity graph starting at 11 mg/L (electrochemical reading mg/L vs readings difference mg/L)

Input quantities
Value Unit Comment
Calibration
Cread_cal_0 0 mg/L Sensor reading right after calibration/checking zero value
Cread_cal 8.95 mg/L Sensor reading right after calibration Constants for salinity calculation (Ref 6):
Ccal_0 0 mg/L Calibration environment DO concentration at oxygen-free conditions, here always 0 a0 0.008
Ccal 8.891 mg/L Calibration envirnment DO concentration at saturation, calculated by the Ref 4 a1 -0.1692 C(KCl at 25°C) *
tcal_ref 19.929 °C Temperature of calibration solution measured with reference thermometer a2 25.3851 53.903805 mS/cm
Pcal_ref 98991 Pa Air pressure at the time of calibration measured with reference barometer a3 14.0941 *
Notes:
tcal_sensor 20.1 °C Temperature of calibration solution measured with DO-meter a4 -7.0261 Ref 5: conductivity of SSW at SP=35, t_68=15, p=0; 42.9140 mS/cm
Pcal_sensor 100100 Pa Air pressure at the time of calibration measured with DO-meter a5 2.7081 Ref 7: factor for calculating the conductivity from 15 °C to the 25 °C is found as 1.25608904610271
b0 0.0005
Measurement b1 -0.0056
Cread_meas 9.85 mg/L Reading of the measured sample b2 -0.0066
k 0.34 mS/cm conductivity of the sample, used for calculating the activity coefficient b3 -0.0375
Salinity 0.159 PSU Salinity, calculated from measured conductivity (recalculated to 25 C), using Refs 5, 6 and 7 b4 0.0636
tsample 9.6 °C Sample temperature, measured with DO-meter b5 -0.0144
Δvstir 50 % estimated flow rate compared to the flow rate of calibration X 400 *Rt
Δdays 3 The number of days passed from the last calibration Y 100 *Rt

Model components Uncertainty components

Denotion Value Unit uc Relative u1 u2
Cread_cal_0 0 mg/L 0.0056984 0.0028867513 u(C cal_res) ±half of the last 0.0049
digit u(Ccal_rep) repeatabilty of the reading
Cread_cal 8.95 mg/L 0.0048542 0.0542% 0.0028867513 u(Ccal_0_res) ±half of the last 0.0039
digit u(Ccal_0_rep) repeatabilty of the reading
Ccal_0 0 mg/L 0.0057735 0.0057735027 u(Ccal_0) estimation
Ccal 8.89 mg/L 0.031 0.3487% 0.031 u(Ccal) Estimated as in Ref 3
Cread_meas 9.85 mg/L 0.0687046 0.6975% 0.0028867513 u(Cmeas_res) ±half of the last 0.0686
digit u(Cmeas_Rep) Reproducibility of the reading
γ 1.0010 - 0.0002944 0.0294% 0.0002944011 ± half of the activity coefficient difference from 1
ΔCstir 0 mg/L 0.0026798 0.0026797984 ±Δvstir *b1stir*Cread_meas/100%
ΔCΔt 0 mg/L 0.0145512 0.0145511781 ±Δt*b1Δt/100%*Cread_meas
ΔCdrift 0 mg/L 0.0151534 0.0151533934 ±Δdays*(b1drift+s(b1drift))
ΔClinearity 0 mg/L 0 0 ±ΔC from 11 mg/L*b1linearity (if Cread_meas>11)

Denotion Value Unit uc Cread_cal_0 Cread_cal Ccal_0 Ccal Cread_meas γ ΔCstir ΔCΔt ΔCdrift ΔClinearity
Cread_cal_0 0 mg/L 0.0056984 0.0056983563 0 0 0 0 0 0 0 0 0
Cread_cal 8.95 mg/L 0.0048542 8.95 8.9548542 8.95 8.95 8.95 8.95 8.95 8.95 8.95 8.95
Ccal_0 0 mg/L 0.0057735 0 0 0.0057735 0 0 0 0 0 0 0
Ccal 8.89068375987 mg/L 0.031 8.8906837599 8.8906838 8.8906838 8.9216838 8.8906838 8.8906838 8.8906838 8.8906838 8.8906838 8.8906838
Cread_meas 9.85 mg/L 0.0687046 9.85 9.85 9.85 9.85 9.9187046 9.85 9.85 9.85 9.85 9.85
γ 1.00101983533 - 0.0002944 1.0010198353 1.0010198 1.0010198 1.0010198 1.0010198 1.0013142 1.0010198 1.0010198 1.0010198 1.0010198
ΔCstir 0 mg/L 0.0026798 0 0 0 0 0 0 0.0026798 0 0 0
ΔCΔt 0 mg/L 0.0145512 0 0 0 0 0 0 0 0.0145512 0 0
ΔCdrift 0 mg/L 0.0151534 0 0 0 0 0 0 0 0 0.0151534 0
ΔClinearity 0 mg/L 0 0 0 0 0 0 0 0 0 0 0

Cresult 9.77 mg/L 9.7753135956 9.7694517 9.7741763 9.8088329 9.8429301 9.7718764 9.7774097 9.7891904 9.789788 9.7747504
uCresult 0.079 mg/L 0.0005632331 -0.005299 -0.000574 0.0340826 0.0681798 -0.002874 0.0026593 0.01444 0.0150376 0
UCresult 0.16 mg/L, k=2 3.172315E-07 2.808E-05 3.296E-07 0.0011616 0.0046485 8.259E-06 7.072E-06 0.0002085 0.0002261 0
UCresult rel 1.62 %, k=2 0.0062888
En (vs WTW) = -0.76396 0.0% 0.4% 0.0% 18.5% 73.9% 0.1% 0.1% 3.3% 3.6% 0.0%
100.0%
Table S3. Measurement uncertainty using the ISO GUM method with Kragten approach
Data from River Emajõgi
Cread_meas  Cstir  CΔt  Cdrift  Clinearity b0 Cread_ cal_0  Ccal  Ccal_ 0  Cread_cal Cread _cal  Cread_cal_0
Cresult   b1 
b0  Ccal  Ccal_0
  b1 b1 Ccal  Ccal_ 0

WTW
Experimental data for calculating different uncertainty contributions:
u(Ccal_rep) 0.020 mg/L Pooled standard deviation of the readings at stirring rate 120 rpm
u(Ccal_0_rep) 0.020 mg/L The largest pooled standard deviation of the readings
u(Cmeas_Rep) 0.051 mg/L Reproducibility: pooled standard deviation of differences between reading and reference value
u(Ccal) 0.031 mg/L From Ref 3
b1stir 0.0146 %/% The slope of stirring graph (% of the reading vs % of the stirring rate from calibration stirring rate)
b1Δt -0.078 %/°C The slope of temperature compensation graph (temperature °C vs relative difference from reference temperature in %)
b1drift 0.0038 mg/L The largest slope of the drift graph (number of days passed from calibration vs reading difference from the reference value mg/L)
s(b1drift) 0.0009 mg/L Standard deviation of the slope of the drift graph

Input quantities
Value Unit Comment
Calibration
Cread_cal_0 0 mg/L Sensor reading right after calibration/checking zero value Constants for salinity calculation (Ref 6):
Cread_cal 8.89 mg/L Sensor reading right after calibration a0 0.008
Ccal_0 0 mg/L Calibration environment DO concentration at oxygen-free conditions, here always 0 a1 -0.1692
Ccal 8.891 mg/L Calibration envirnment DO concentration at saturation, calculated by the Ref 4 a2 25.3851 C(KCl at 25°C) *
tcal_ref 19.929 °C Temperature of calibration solution measured with reference thermometer a3 14.0941 53.903805 mS/cm
Pcal_ref 98991 Pa Air pressure at the time of calibration measured with reference barometer a4 -7.0261 Notes:
*

tcal_sensor 19.9 °C Temperature of calibration solution measured with DO-meter a5 2.7081 Ref 5: conductivity of SSW at SP=35, t_68=15, p=0; 42.9140 mS/cm
Pcal_sensor 99200 Pa Air pressure at the time of calibration measured with DO-meter b0 0.0005 Ref 7: factor for calculating the conductivity from 15 °C to the 25 °C is found as 1.25608904610271
b1 -0.0056
Measurement b2 -0.0066
Cread_meas 9.97 mg/L Reading of the measured sample b3 -0.0375
k 0.34 mS/cm conductivity of the sample, used for calculating the activity coefficient b4 0.0636
Salinity 0.159 PSU Salinity, calculated from measured conductivity (recalculated to 25 C), using Refs 5, 6 and 7 b5 -0.0144
tsample 9.1 °C Sample temperature, measured with DO-meter X 400 *Rt
Δvstir 50 % estimated flow rate compared to the flow rate of calibration Y 100 *Rt
Δdays 3 The number of days passed from the last calibration

Model components Uncertainty components

Denotion Value Unit uc Relative u1 u2
Cread_cal_0 0 mg/L 0.0200416 0.0028867513 u(Ccal_res)
±half of the last digit 0.0198 u(Ccal_rep) repeatabilty of the reading
Cread_cal 8.89 mg/L 0.0200416 0.2254% 0.0028867513 u(Ccal_0_res)
±half of the last digit 0.0198 u(Ccal_0_rep) repeatabilty of the reading
Ccal_0 0 mg/L 0.0057735 0.0057735027 u(Ccal_0)
estimation
Ccal 8.89 mg/L 0.031 0.3487% 0.031 u(Ccal)Estimated as in Ref 3
Cread_meas 9.97 mg/L 0.0512693 0.5142% 0.0028867513 u(Cmeas_res)
±half of the last digit 0.0512 u(Cmeas_Rep) reproducibility of the reading
γ 1.0010 - 0.0002957 0.0295% 0.0002956669 ± half of the activity coefficient difference from 1
ΔCstir 0 mg/L 0.0420612 0.042061173 ±Δvstir *b1stir*Cread_meas/100%
ΔCΔt 0 mg/L 0.0482473 0.0482472623 ±Δt*b1Δt/100%*Cread_meas
ΔCdrift 0 mg/L 0.0080672 0.0080672109 ±Δdays*(b1drift+s(b1drift))

Denotion Value Unit uc Cread_cal_0 Cread_cal Ccal_0 Ccal Cread_meas γ ΔCstir ΔCΔt ΔCdrift
Cread_cal_0 0 mg/L 0.0200416 0.0200416234 0 0 0 0 0 0 0 0
Cread_cal 8.89 mg/L 0.0200416 8.89 8.91004162335408 8.89 8.89 8.89 8.89 8.89 8.89 8.89
Ccal_0 0 mg/L 0.0057735 0 0 0.00577 0 0 0 0 0 0
Ccal 8.89068375987 mg/L 0.031 8.8906837599 8.89068375986826 8.89068 8.92168376 8.8906838 8.8906838 8.8906838 8.8906838 8.8906838
Cread_meas 9.97 mg/L 0.0512693 9.97 9.97 9.97 9.97 10.021269 9.97 9.97 9.97 9.97
γ 1.00102422029 - 0.0002957 1.0010242203 1.00102422029154 1.00102 1.00102422 1.0010242 1.0013199 1.0010242 1.0010242 1.0010242
ΔCstir 0 mg/L 0.0420612 0 0 0 0 0 0 0.0420612 0 0
ΔCΔt 0 mg/L 0.0482473 0 0 0 0 0 0 0 0.0482473 0
ΔCdrift 0 mg/L 0.0080672 0 0 0 0 0 0 0 0 0.0080672

Cresult 9.96 mg/L 9.96 9.94 9.96 10.00 10.01 9.96 10.00 10.01 9.97
uCresult 0.092 mg/L 0.002417391 -0.022404597063975 -0.0007 0.03473046 0.0512208 -0.002941 0.0420214 0.0482016 0.0080596
UCresult 0.18 mg/L, k=2 5.843779E-06 0.000501965969599 5E-07 0.0012062 0.0026236 8.65E-06 0.0017658 0.0023234 6.496E-05
UCresult rel 1.851 %, k=2 0.0085009
0.1% 5.9% 0.0% 14.2% 30.9% 0.1% 20.8% 27.3% 0.8%
100.0%
Table S4. Measurement uncertainty using the ISO GUM method with Kragten approach
Data from Lake Ilmatsalu 1
Cread_meas  Cstir  CΔt  Cdrift  Clinearity b0 Cread_ cal_ 0  Ccal  Ccal_0  Cread_ cal Cread_ cal  Cread_cal_0
Cresult   b1 
b0  Ccal  Ccal_0
  b1 b1 Ccal  Ccal_0

HACH
Experimental data for calculating different uncertainty contributions:
u(Ccal_rep) 0.0039 mg/L Pooled standard deviation of the readings at stirring rate 120 rpm
u(Ccal_0_rep) 0.0049 mg/L The largest pooled standard deviation of the readings
u(Cmeas_Rep) 0.0686 mg/L Reproducibility: pooled standard deviation of differences between reading and reference value
u(Ccal) 0.031 mg/L From Ref 3
b1stir -0.00094 %/% The slope of stirring graph (% of the reading vs % of the stirring rate from calibration stirring rate)
b1Δt 0.024 %/°C The slope of temperature compensation graph (temperature °C vs relative difference from reference temperature in %)
b1drift -0.0079 mg/L The slope of the drift graph (number of days passed from calibration vs reading difference from the reference value mg/L )
s(b1drift) 0.0008 mg/L Standard deviation of the slope of the drift graph
b1linearity 0.0277 - The slope of the linearity graph starting at 11 mg/L (electrochemical reading mg/L vs readings difference mg/L)

Input quantities
Value Unit Comment
Calibration
Cread_cal_0 0 mg/L Sensor reading right after calibration/checking zero value
Cread_cal 8.95 mg/L Sensor reading right after calibration Constants for salinity calculation (Ref 6):
Ccal_0 0 mg/L Calibration environment DO concentration at oxygen-free conditions, here always 0 a0 0.008
Ccal 8.891 mg/L Calibration envirnment DO concentration at saturation, calculated by the Ref 4 a1 -0.1692 C(KCl at 25°C) *
tcal_ref 19.929 °C Temperature of calibration solution measured with reference thermometer a2 25.3851 53.903805 mS/cm
Pcal_ref 98991 Pa Air pressure at the time of calibration measured with reference barometer a3 14.0941 Notes:
*

tcal_sensor 20.1 °C Temperature of calibration solution measured with DO-meter a4 -7.0261 Ref 5: conductivity of SSW at SP=35, t_68=15, p=0; 42.9140 mS/cm
Pcal_sensor 100100 Pa Air pressure at the time of calibration measured with DO-meter a5 2.7081 Ref 7: factor for calculating the conductivity from 15 °C to the 25 °C is found as 1.25608904610271
b0 0.0005
Measurement b1 -0.0056
Cread_meas 10.94 mg/L Reading of the measured sample b2 -0.0066
k 0.578 mS/cm conductivity of the sample, used for calculating the activity coefficient b3 -0.0375
Salinity 0.274 PSU Salinity, calculated from measured conductivity (recalculated to 25 C), using Refs 5, 6 and 7 b4 0.0636
tsample 16 °C Sample temperature, measured with DO-meter b5 -0.0144
Δvstir 50 % estimated flow rate compared to the flow rate of calibration X 400 *Rt
Δdays 24 The number of days passed from the last calibration Y 100 *Rt

Model components Uncertainty components

Denotion Value Unit uc Relative u1 u2
Cread_cal_0 0 mg/L 0.0056984 0.0028867513 u(Ccal_res) ±half of the last 0.0049
digit u(Ccal_rep) repeatabilty of the reading
Cread_cal 8.95 mg/L 0.0048542 0.0542% 0.0028867513 u(Ccal_0_res) ±half of the last 0.0039
digit u(Ccal_0_rep) repeatabilty of the reading
Ccal_0 0 mg/L 0.0057735 0.0057735027 u(Ccal_0) estimation
Ccal 8.89 mg/L 0.031 0.3487% 0.031 u(Ccal) Estimated as in Ref 3
Cread_meas 10.94 mg/L 0.0687046 0.6280% 0.0028867513 u(Cmeas_res) ±half of the last 0.0686
digit u(Cmeas_Rep) Reproducibility of the reading
γ 1.0017 - 0.0004823 0.0482% 0.0004823072 ± half of the activity coefficient difference from 1
ΔCstir 0 mg/L 0.0029763 0.0029763446 ±Δvstir *b1stir*Cread_meas/100%
ΔCΔt 0 mg/L 0.0063106 0.0063106458 ±Δt*b1Δt/100%*Cread_meas
ΔCdrift 0 mg/L 0.1212271 0.121227147 ±Δdays*(b1drift+s(b1drift))
ΔClinearity 0 mg/L 0 0 ±ΔC from 11 mg/L*b1linearity (if Cread_meas>11)

Denotion Value Unit uc Cread_cal_0 Cread_cal Ccal_0 Ccal Cread_meas γ ΔCstir ΔCΔt ΔCdrift ΔClinearity
Cread_cal_0 0 mg/L 0.0056984 0.0056983563 0 0 0 0 0 0 0 0 0
Cread_cal 8.95 mg/L 0.0048542 8.95 8.9548542 8.95 8.95 8.95 8.95 8.95 8.95 8.95 8.95
Ccal_0 0 mg/L 0.0057735 0 0 0.0057735 0 0 0 0 0 0 0
Ccal 8.89068375987 mg/L 0.031 8.8906837599 8.8906838 8.8906838 8.9216838 8.8906838 8.8906838 8.8906838 8.8906838 8.8906838 8.8906838
Cread_meas 10.94 mg/L 0.0687046 10.94 10.94 10.94 10.94 11.008705 10.94 10.94 10.94 10.94 10.94
γ 1.00167076125 - 0.0004823 1.0016707612 1.0016708 1.0016708 1.0016708 1.0016708 1.0021531 1.0016708 1.0016708 1.0016708 1.0016708
ΔCstir 0 mg/L 0.0029763 0 0 0 0 0 0 0.0029763 0 0 0
ΔCΔt 0 mg/L 0.0063106 0 0 0 0 0 0 0 0.0063106 0 0
ΔCdrift 0 mg/L 0.1212271 0 0 0 0 0 0 0 0 0.1212271 0
ΔClinearity 0 mg/L 0 0 0 0 0 0 0 0 0 0 0

Cresult 10.85 mg/L 10.85061617 10.843487 10.848096 10.887198 10.917504 10.844147 10.85232 10.855627 10.969591 10.849368
uCresult 0.144 mg/L 0.0012478652 -0.005881 -0.001272 0.0378295 0.0681354 -0.005221 0.0029517 0.0062584 0.1202228 0
UCresult 0.29 mg/L, k=2 1.557167E-06 3.459E-05 1.618E-06 0.0014311 0.0046424 2.726E-05 8.712E-06 3.917E-05 0.0144535 0
UCresult rel 2.6 %, k=2 0.02064
En (vs WTW) = -2.173484 0% 0% 0% 7% 22% 0% 0% 0% 70% 0%
100.0%
Table S5. Measurement uncertainty using the ISO GUM method with Kragten approach
Data from Lake Ilmatsalu 1
Cread_meas  Cstir  CΔt  Cdrift  Clinearity Cread_cal  Cread_cal_0
b0 Cread_ cal_0  Ccal  Ccal_0  Cread _cal b1 
Cresult   b0  Ccal  Ccal_0
  b1 b1 Ccal  Ccal_ 0

WTW
Experimental data for calculating different uncertainty contributions:
u(Ccal_rep) 0.020 mg/L Pooled standard deviation of the readings at stirring rate 120 rpm
u(Ccal_0_rep) 0.020 mg/L The largest pooled standard deviation of the readings
u(Cmeas_Rep) 0.051 mg/L Reproducibility: pooled standard deviation of differences between reading and reference value
u(Ccal) 0.031 mg/L From Ref 3
b1stir 0.0146 %/% The slope of stirring graph (% of the reading vs % of the stirring rate from calibration stirring rate)
b1Δt -0.078 %/°C The slope of temperature compensation graph (temperature °C vs relative difference from reference temperature in %)
b1drift 0.0038 mg/L The largest slope of the drift graph (number of days passed from calibration vs reading difference from the reference value mg/L)
s(b1drift) 0.0009 mg/L Standard deviation of the slope of the drift graph

Input quantities
Value Unit Comment
Calibration
Cread_cal_0 0 mg/L Sensor reading right after calibration/checking zero value Constants for salinity calculation (Ref 6):
Cread_cal 8.89 mg/L Sensor reading right after calibration a0 0.008
Ccal_0 0 mg/L Calibration environment DO concentration at oxygen-free conditions, here always 0 a1 -0.1692
Ccal 8.891 mg/L Calibration envirnment DO concentration at saturation, calculated by the Ref 4 a2 25.3851 C(KCl at 25°C) *
tcal_ref 19.929 °C Temperature of calibration solution measured with reference thermometer a3 14.0941 53.903805 mS/cm
Pcal_ref 98991 Pa Air pressure at the time of calibration measured with reference barometer a4 -7.0261 *
Notes:
tcal_sensor 19.9 °C Temperature of calibration solution measured with DO-meter a5 2.7081 Ref 5: conductivity of SSW at SP=35, t_68=15, p=0; 42.9140 mS/cm
Pcal_sensor 99200 Pa Air pressure at the time of calibration measured with DO-meter b0 0.0005 Ref 7: factor for calculating the conductivity from 15 °C to the 25 °C is found as 1.25608904610271
b1 -0.0056
Measurement b2 -0.0066
Cread_meas 11.655 mg/L Reading of the measured sample b3 -0.0375
k 0.578 mS/cm conductivity of the sample, used for calculating the activity coefficient b4 0.0636
Salinity 0.274 PSU Salinity, calculated from measured conductivity (recalculated to 25 C), using Refs 5, 6 and 7 b5 -0.0144
tsample 15.4 °C Sample temperature, measured with DO-meter X 400 *Rt
Δvstir 50 % estimated flow rate compared to the flow rate of calibration Y 100 *Rt
Δdays 24 The number of days passed from the last calibration

Model components Uncertainty components

Denotion Value Unit uc Relative u1 u2
Cread_cal_0 0 mg/L 0.0200416 0.00288675135 u(Ccal_res)
±half of the last digit 0.0198 u(Ccal_rep) repeatabilty of the reading
Cread_cal 8.89 mg/L 0.0200416 0.2254% 0.00288675135 u(Ccal_0_res)
±half of the last digit 0.0198 u(Ccal_0_rep) repeatabilty of the reading
Ccal_0 0 mg/L 0.0057735 0.00577350269 u(Ccal_0)
estimation
Ccal 8.89 mg/L 0.031 0.3487% 0.031 u(Ccal)Estimated as in Ref 3
Cread_meas 11.66 mg/L 0.0512693 0.4399% 0.00288675135 u(Cmeas_res)
±half of the last digit 0.0512 u(Cmeas_Rep) reproducibility of the reading
γ 1.0017 - 0.0004846 0.0484% 0.00048462754 ± half of the activity coefficient difference from 1
ΔCstir 0 mg/L 0.0491698 0.04916980658 ±Δvstir *b1stir*Cread_meas/100%
ΔCΔt 0 mg/L 0.0235006 0.02350057849 ±Δt*b1Δt/100%*Cread_meas
ΔCdrift 0 mg/L 0.0645377 0.06453768743 ±Δdays*(b1drift+s(b1drift))

Denotion Value Unit uc Cread_cal_0 Cread_cal Ccal_0 Ccal Cread_meas γ ΔCstir ΔCΔt ΔCdrift
Cread_cal_0 0 mg/L 0.0200416 0.0200416234 0 0 0 0 0 0 0 0
Cread_cal 8.89 mg/L 0.0200416 8.89 8.91004162335408 8.89 8.89 8.89 8.89 8.89 8.89 8.89
Ccal_0 0 mg/L 0.0057735 0 0 0.00577 0 0 0 0 0 0
Ccal 8.89068375987 mg/L 0.031 8.8906837599 8.89068375986826 8.89068 8.92168376 8.8906838 8.8906838 8.8906838 8.8906838 8.8906838
Cread_meas 11.655 mg/L 0.0512693 11.655 11.655 11.655 11.655 11.706269 11.655 11.655 11.655 11.655
γ 1.00167879905 - 0.0004846 1.001678799 1.00167879904551 1.00168 1.0016788 1.0016788 1.0021634 1.0016788 1.0016788 1.0016788
ΔCstir 0 mg/L 0.0491698 0 0 0 0 0 0 0.0491698 0 0
ΔCΔt 0 mg/L 0.0235006 0 0 0 0 0 0 0 0.0235006 0
ΔCdrift 0 mg/L 0.0645377 0 0 0 0 0 0 0 0 0.0645377

Cresult 11.64 mg/L 11.64 11.61 11.63 11.68 11.69 11.63 11.69 11.66 11.70
uCresult 0.110 mg/L 0.0062038437 -0.026174015847165 -0.0018 0.04057362 0.0511873 -0.005627 0.0490912 0.023463 0.0644345
UCresult 0.22 mg/L, k=2 3.848768E-05 0.000685079105568 3E-06 0.00164622 0.0026201 3.166E-05 0.0024099 0.0005505 0.0041518
UCresult rel 1.9 %, k=2 0.012137
0% 6% 0% 14% 22% 0% 20% 5% 34%
100.0%
Table S6. Measurement uncertainty using the ISO GUM method with Kragten approach
Data from Lake Ilmatsalu 2
Cread_meas  Cstir  CΔt  Cdrift  Clinearity b0 Cread_ cal_ 0  Ccal  Ccal_0  Cread_ cal Cread_ cal  Cread_cal_0
Cresult   b1 
b0  Ccal  Ccal_0
  b1 b1 Ccal  Ccal_0

HACH
Experimental data for calculating different uncertainty contributions:
u(Ccal_rep) 0.0039 mg/L Pooled standard deviation of the readings at stirring rate 120 rpm
u(Ccal_0_rep) 0.0049 mg/L The largest pooled standard deviation of the readings
u(Cmeas_Rep) 0.0686 mg/L Reproducibility: pooled standard deviation of differences between reading and reference value
u(Ccal) 0.031 mg/L From Ref 3
b1stir -0.00094 %/% The slope of stirring graph (% of the reading vs % of the stirring rate from calibration stirring rate)
b1Δt 0.024 %/°C The slope of temperature compensation graph (temperature °C vs relative difference from reference temperature in %)
b1drift -0.0079 mg/L The slope of the drift graph (number of days passed from calibration vs reading difference from the reference value mg/L )
s(b1drift) 0.0008 mg/L Standard deviation of the slope of the drift graph
b1linearity 0.0277 - The slope of the linearity graph starting at 11 mg/L (electrochemical reading mg/L vs readings difference mg/L)

Input quantities
Value Unit Comment
Calibration
Cread_cal_0 0 mg/L Sensor reading right after calibration/checking zero value
Cread_cal 9.03 mg/L Sensor reading right after calibration Constants for salinity calculation (Ref 6):
Ccal_0 0 mg/L Calibration environment DO concentration at oxygen-free conditions, here always 0 a0 0.008
Ccal 8.979 mg/L Calibration envirnment DO concentration at saturation, calculated by the Ref 4 a1 -0.1692 C(KCl at 25°C) *
tcal_ref 19.909 °C Temperature of calibration solution measured with reference thermometer a2 25.3851 53.903805 mS/cm
Pcal_ref 99915 Pa Air pressure at the time of calibration measured with reference barometer a3 14.0941 Notes:
*

tcal_sensor 20.1 °C Temperature of calibration solution measured with DO-meter a4 -7.0261 Ref 5: conductivity of SSW at SP=35, t_68=15, p=0; 42.9140 mS/cm
Pcal_sensor 100100 Pa Air pressure at the time of calibration measured with DO-meter a5 2.7081 Ref 7: factor for calculating the conductivity from 15 °C to the 25 °C is found as 1.25608904610271
b0 0.0005
Measurement b1 -0.0056
Cread_meas 11.95 mg/L Reading of the measured sample b2 -0.0066
k 0.558 mS/cm conductivity of the sample, used for calculating the activity coefficient b3 -0.0375
Salinity 0.264 PSU Salinity, calculated from measured conductivity (recalculated to 25 C), using Refs 5, 6 and 7 b4 0.0636
tsample 19.2 °C Sample temperature, measured with DO-meter b5 -0.0144
Δvstir 50 % estimated flow rate compared to the flow rate of calibration X 400 *Rt
Δdays 0 The number of days passed from the last calibration Y 100 *Rt

Model components Uncertainty components

Denotion Value Unit uc Relative u1 u2
Cread_cal_0 0 mg/L 0.0056984 0.0028867513 u(Ccal_res) ±half of the last 0.0049
digit u(Ccal_rep) repeatabilty of the reading
Cread_cal 9.03 mg/L 0.0048542 0.0538% 0.0028867513 u(Ccal_0_res) ±half of the last 0.0039
digit u(Ccal_0_rep) repeatabilty of the reading
Ccal_0 0 mg/L 0.0057735 0.0057735027 u(Ccal_0) estimation
Ccal 8.98 mg/L 0.031 0.3452% 0.031 u(Ccal) Estimated as in Ref 3
Cread_meas 11.95 mg/L 0.0687046 0.5749% 0.0028867513 u(Cmeas_res) ±half of the last 0.0686
digit u(Cmeas_Rep) Reproducibility of the reading
γ 1.0016 - 0.0004536 0.0453% 0.0004535706 ± half of the activity coefficient difference from 1
ΔCstir 0 mg/L 0.0032511 0.003251126 ±Δvstir *b1stir*Cread_meas/100%
ΔCΔt 0 mg/L 0.0015132 0.0015131537 ±Δt*b1Δt/100%*Cread_meas
ΔCdrift 0 mg/L 0 0 ±Δdays*(b1drift+s(b1drift))
ΔClinearity 0 mg/L 0.0151737 0.0151736987 ±ΔC from 11 mg/L*b1linearity (if Cread_meas>11)

Denotion Value Unit uc Cread_cal_0 Cread_cal Ccal_0 Ccal Cread_meas γ ΔCstir ΔCΔt ΔCdrift ΔClinearity
Cread_cal_0 0 mg/L 0.0056984 0.0056983563 0 0 0 0 0 0 0 0 0
Cread_cal 9.03 mg/L 0.0048542 9.03 9.0348542 9.03 9.03 9.03 9.03 9.03 9.03 9.03 9.03
Ccal_0 0 mg/L 0.0057735 0 0 0.0057735 0 0 0 0 0 0 0
Ccal 8.97924395507 mg/L 0.031 8.9792439551 8.979244 8.979244 9.010244 8.979244 8.979244 8.979244 8.979244 8.979244 8.979244
Cread_meas 11.95 mg/L 0.0687046 11.95 11.95 11.95 11.95 12.018705 11.95 11.95 11.95 11.95 11.95
γ 1.00157121453 - 0.0004536 1.0015712145 1.0015712 1.0015712 1.0015712 1.0015712 1.0020248 1.0015712 1.0015712 1.0015712 1.0015712
ΔCstir 0 mg/L 0.0032511 0 0 0 0 0 0 0.0032511 0 0 0
ΔCΔt 0 mg/L 0.0015132 0 0 0 0 0 0 0 0.0015132 0 0
ΔCdrift 0 mg/L 0 0 0 0 0 0 0 0 0 0 0
ΔClinearity 0 mg/L 0.0151737 0 0 0 0 0 0 0 0 0 0.0151737

Cresult 11.86 mg/L 11.866011647 11.857816 11.862335 11.90515 11.932401 11.85882 11.867418 11.865692 11.86419 11.879255
uCresult 0.082 mg/L 0.0018216867 -0.006374 -0.001855 0.04096 0.0682113 -0.00537 0.0032278 0.0015023 0 0.0150647
UCresult 0.16 mg/L, k=2 3.318542E-06 4.063E-05 3.441E-06 0.0016777 0.0046528 2.884E-05 1.042E-05 2.257E-06 0 0.0002269
UCresult rel 1.4 %, k=2 0.0066464
En (vs WTW) = -0.150899 0% 1% 0% 25% 70% 0% 0% 0% 0% 3%
100.0%
Table S7. Measurement uncertainty using the ISO GUM method with Kragten approach
Data from Lake Ilmatsalu 2
Cread_meas  Cstir  CΔt  Cdrift  Clinearity b0 Cread_ cal_0  Ccal  Ccal_ 0  Cread_cal Cread _cal  Cread_cal_0
Cresult   b1 
b0  Ccal  Ccal_0
  b1 b1 Ccal  Ccal_ 0

WTW
Experimental data for calculating different uncertainty contributions:
u(Ccal_rep) 0.020 mg/L Pooled standard deviation of the readings at stirring rate 120 rpm
u(Ccal_0_rep) 0.020 mg/L The largest pooled standard deviation of the readings
u(Cmeas_Rep) 0.051 mg/L Reproducibility: pooled standard deviation of differences between reading and reference value
u(Ccal) 0.031 mg/L From Ref 3
b1stir 0.0146 %/% The slope of stirring graph (% of the reading vs % of the stirring rate from calibration stirring rate)
b1Δt -0.078 %/°C The slope of temperature compensation graph (temperature °C vs relative difference from reference temperature in %)
b1drift 0.0038 mg/L The largest slope of the drift graph (number of days passed from calibration vs reading difference from the reference value mg/L)
s(b1drift) 0.0009 mg/L Standard deviation of the slope of the drift graph

Input quantities
Value Unit Comment
Calibration
Cread_cal_0 0 mg/L Sensor reading right after calibration/checking zero value Constants for salinity calculation (Ref 6):
Cread_cal 8.98 mg/L Sensor reading right after calibration a0 0.008
Ccal_0 0 mg/L Calibration environment DO concentration at oxygen-free conditions, here always 0 a1 -0.1692
Ccal 8.979 mg/L Calibration envirnment DO concentration at saturation, calculated by the Ref 4 a2 25.3851 C(KCl at 25°C) *
tcal_ref 19.909 °C Temperature of calibration solution measured with reference thermometer a3 14.0941 53.903805 mS/cm
Pcal_ref 99915 Pa Air pressure at the time of calibration measured with reference barometer a4 -7.0261 Notes:
*

tcal_sensor 19.9 °C Temperature of calibration solution measured with DO-meter a5 2.7081 Ref 5: conductivity of SSW at SP=35, t_68=15, p=0; 42.9140 mS/cm
Pcal_sensor 100100 Pa Air pressure at the time of calibration measured with DO-meter b0 0.0005 Ref 7: factor for calculating the conductivity from 15 °C to the 25 °C is found as 1.25608904610271
b1 -0.0056
Measurement b2 -0.0066
Cread_meas 11.92 mg/L Reading of the measured sample b3 -0.0375
k 0.558 mS/cm conductivity of the sample, used for calculating the activity coefficient b4 0.0636
Salinity 0.264 PSU Salinity, calculated from measured conductivity (recalculated to 25 C), using Refs 5,6 and 7 b5 -0.0144
tsample 18.9 °C Sample temperature, measured with DO-meter X 400 *Rt
Δvstir 50 % estimated flow rate compared to the flow rate of calibration Y 100 *Rt
Δdays 0 The number of days passed from the last calibration

Model components Uncertainty components

Denotion Value Unit uc Relative u1 u2
Cread_cal_0 0 mg/L 0.0200416 0.0028867513 u(Ccal_res)
±half of the last digit 0.0198 u(Ccal_rep) repeatabilty of the reading
Cread_cal 8.98 mg/L 0.0200416 0.2232% 0.0028867513 u(Ccal_0_res)
±half of the last digit 0.0198 u(Ccal_0_rep) repeatabilty of the reading
Ccal_0 0 mg/L 0.0057735 0.0057735027 u(Ccal_0)
estimation
Ccal 8.98 mg/L 0.031 0.3452% 0.031 u(Ccal)Estimated as in Ref 3
Cread_meas 11.92 mg/L 0.0512693 0.4301% 0.0028867513 u(Cmeas_res)
±half of the last digit 0.0512 u(Cmeas_Rep) reproducibility of the reading
γ 1.0016 - 0.0004546 0.0454% 0.000454618 ± half of the activity coefficient difference from 1
ΔCstir 0 mg/L 0.0502878 0.0502877816 ±Δvstir *b1stir*Cread_meas/100%
ΔCΔt 0 mg/L 0.0053411 0.0053410915 ±Δt*b1Δt/100%*Cread_meas
ΔCdrift 0 mg/L 0 0 ±Δdays*(b1drift+s(b1drift))

Denotion Value Unit uc Cread_cal_0 Cread_cal Ccal_0 Ccal Cread_meas γ ΔCstir ΔCΔt ΔCdrift
Cread_cal_0 0 mg/L 0.0200416 0.0200416234 0 0 0 0 0 0 0 0
Cread_cal 8.98 mg/L 0.0200416 8.98 9.00004162335408 8.98 8.98 8.98 8.98 8.98 8.98 8.98
Ccal_0 0 mg/L 0.0057735 0 0 0.00577 0 0 0 0 0 0
Ccal 8.97924395507 mg/L 0.031 8.9792439551 8.97924395507017 8.97924 9.01024396 8.979244 8.979244 8.979244 8.979244 8.979244
Cread_meas 11.92 mg/L 0.0512693 11.92 11.92 11.92 11.92 11.971269 11.92 11.92 11.92 11.92
γ 1.00157484298 - 0.0004546 1.001574843 1.00157484298099 1.00157 1.00157484 1.0015748 1.0020295 1.0015748 1.0015748 1.0015748
ΔCstir 0 mg/L 0.0502878 0 0 0 0 0 0 0.0502878 0 0
ΔCΔt 0 mg/L 0.0053411 0 0 0 0 0 0 0 0.0053411 0
ΔCdrift 0 mg/L 0 0 0 0 0 0 0 0 0 0

Cresult 11.90 mg/L 11.91 11.87 11.90 11.94 11.95 11.89 11.95 11.91 11.90
uCresult 0.087 mg/L 0.0065337146 -0.02649992594014 -0.0019 0.04108452 0.0511844 -0.005399 0.0502045 0.0053322 0
UCresult 0.17 mg/L, k=2 4.268943E-05 0.000702246074833 4E-06 0.00168794 0.0026198 2.915E-05 0.0025205 2.843E-05 0
UCresult rel 1.468 %, k=2 0.0076343
1% 9% 0% 22% 34% 0% 33% 0% 0%
100.0%
Table S8. Measurement uncertainty using the ISO GUM method with Kragten approach
Data from Jordan spring
Cread_meas  Cstir  CΔt  Cdrift  Clinearity b0 Cread_ cal_ 0  Ccal  Ccal_0  Cread_ cal Cread_ cal  Cread_cal_0
Cresult   b1 
b0  Ccal  Ccal_0
  b1 b1 Ccal  Ccal_0

HACH
Experimental data for calculating different uncertainty contributions:
u(Ccal_rep) 0.0039 mg/L Pooled standard deviation of the readings at stirring rate 120 rpm
u(Ccal_0_rep) 0.0049 mg/L The largest pooled standard deviation of the readings
u(Cmeas_Rep) 0.0686 mg/L Reproducibility: pooled standard deviation of differences between reading and reference value
u(Ccal) 0.031 mg/L From Ref 3
b1stir -0.00094 %/% The slope of stirring graph (% of the reading vs % of the stirring rate from calibration stirring rate)
b1Δt 0.024 %/°C The slope of temperature compensation graph (temperature °C vs relative difference from reference temperature in %)
b1drift -0.0079 mg/L The slope of the drift graph (number of days passed from calibration vs reading difference from the reference value mg/L )
s(b1drift) 0.0008 mg/L Standard deviation of the slope of the drift graph
b1linearity 0.0277 - The slope of the linearity graph starting at 11 mg/L (electrochemical reading mg/L vs readings difference mg/L)

Input quantities
Value Unit Comment
Calibration
Cread_cal_0 0 mg/L Sensor reading right after calibration/checking zero value
Cread_cal 9.03 mg/L Sensor reading right after calibration Constants for salinity calculation (Ref 6):
Ccal_0 0 mg/L Calibration environment DO concentration at oxygen-free conditions, here always 0 a0 0.008
Ccal 8.979 mg/L Calibration envirnment DO concentration at saturation, calculated by the Ref 4 a1 -0.1692 C(KCl at 25°C) *
tcal_ref 19.909 °C Temperature of calibration solution measured with reference thermometer a2 25.3851 53.903805 mS/cm
Pcal_ref 99915 Pa Air pressure at the time of calibration measured with reference barometer a3 14.0941 Notes:
*

tcal_sensor 20.1 °C Temperature of calibration solution measured with DO-meter a4 -7.0261 Ref 5: conductivity of SSW at SP=35, t_68=15, p=0; 42.9140 mS/cm
Pcal_sensor 100100 Pa Air pressure at the time of calibration measured with DO-meter a5 2.7081 Ref 7: factor for calculating the conductivity from 15 °C to the 25 °C is found as 1.25608904610271
b0 0.0005
Measurement b1 -0.0056
Cread_meas 7.71 mg/L Reading of the measured sample b2 -0.0066
k 0.896 mS/cm conductivity of the sample, used for calculating the activity coefficient b3 -0.0375
Salinity 0.432 PSU Salinity, calculated from measured conductivity (recalculated to 25 C), using Refs 5, 6 and 7 b4 0.0636
tsample 7.1 °C Sample temperature, measured with DO-meter b5 -0.0144
Δvstir 50 % estimated flow rate compared to the flow rate of calibration X 400 *Rt
Δdays 2 The number of days passed from the last calibration Y 100 *Rt

Model components Uncertainty components

Denotion Value Unit uc Relative u1 u2
Cread_cal_0 0 mg/L 0.0056984 0.0028867513 u(Ccal_res) ±half of the last 0.0049
digit u(Ccal_rep) repeatabilty of the reading
Cread_cal 9.03 mg/L 0.0048542 0.0538% 0.0028867513 u(Ccal_0_res) ±half of the last 0.0039
digit u(Ccal_0_rep) repeatabilty of the reading
Ccal_0 0 mg/L 0.0057735 0.0057735027 u(Ccal_0) estimation
Ccal 8.98 mg/L 0.031 0.3452% 0.031 u(Ccal) Estimated as in Ref 3
Cread_meas 7.71 mg/L 0.0687046 0.8911% 0.0028867513 u(Cmeas_res) ±half of the last 0.0686
digit u(Cmeas_Rep) Reproducibility of the reading
γ 1.0028 - 0.0008189 0.0817% 0.0008188753 ± half of the activity coefficient difference from 1
ΔCstir 0 mg/L 0.0020976 0.0020975884 ±Δvstir *b1stir*Cread_meas/100%
ΔCΔt 0 mg/L 0.0141017 0.0141016638 ±Δt*b1Δt/100%*Cread_meas
ΔCdrift 0 mg/L 0.0101023 0.0101022622 ±Δdays*(b1drift+s(b1drift))
ΔClinearity 0 mg/L 0 0 ±ΔC from 11 mg/L*b1linearity (if Cread_meas>11)

Denotion Value Unit uc Cread_cal_0 Cread_cal Ccal_0 Ccal Cread_meas γ ΔCstir ΔCΔt ΔCdrift ΔClinearity
Cread_cal_0 0 mg/L 0.0056984 0.0056983563 0 0 0 0 0 0 0 0 0
Cread_cal 9.03 mg/L 0.0048542 9.03 9.0348542 9.03 9.03 9.03 9.03 9.03 9.03 9.03 9.03
Ccal_0 0 mg/L 0.0057735 0 0 0.0057735 0 0 0 0 0 0 0
Ccal 8.97924395507 mg/L 0.031 8.9792439551 8.979244 8.979244 9.010244 8.979244 8.979244 8.979244 8.979244 8.979244 8.979244
Cread_meas 7.71 mg/L 0.0687046 7.71 7.71 7.71 7.71 7.7787046 7.71 7.71 7.71 7.71 7.71
γ 1.00283666728 - 0.0008189 1.0028366673 1.0028367 1.0028367 1.0028367 1.0028367 1.0036555 1.0028367 1.0028367 1.0028367 1.0028367
ΔCstir 0 mg/L 0.0020976 0 0 0 0 0 0 0.0020976 0 0 0
ΔCΔt 0 mg/L 0.0141017 0 0 0 0 0 0 0 0.0141017 0 0
ΔCdrift 0 mg/L 0.0101023 0 0 0 0 0 0 0 0 0.0101023 0
ΔClinearity 0 mg/L 0 0 0 0 0 0 0 0 0 0 0

Cresult 7.64 mg/L 7.6441346697 7.6408697 7.6458351 7.6713708 7.7131024 7.6387397 7.6470571 7.6589599 7.6549943 7.6449772
uCresult 0.075 mg/L -0.000842517 -0.004107 0.0008579 0.0263936 0.0681252 -0.006237 0.0020799 0.0139827 0.0100171 0
UCresult 0.15 mg/L, k=2 7.098349E-07 1.687E-05 7.36E-07 0.0006966 0.004641 3.891E-05 4.326E-06 0.0001955 0.0001003 0
UCresult rel 2.0 %, k=2 0.0056951
En (vs WTW) = -0.36882 0% 0% 0% 12% 81% 1% 0% 3% 2% 0%
100.0%
Table S9. Measurement uncertainty using the ISO GUM method with Kragten approach
Data from Jordan spring
Cread_meas  Cstir  CΔt  Cdrift  Clinearity b0 Cread_ cal_0  Ccal  Ccal_ 0  Cread_cal Cread _cal  Cread_cal_0
Cresult   b1 
b0  Ccal  Ccal_0
  b1 b1 Ccal  Ccal_ 0

WTW
Experimental data for calculating different uncertainty contributions:
u(Ccal_rep) 0.020 mg/L Pooled standard deviation of the readings at stirring rate 120 rpm
u(Ccal_0_rep) 0.020 mg/L The largest pooled standard deviation of the readings
u(Cmeas_Rep) 0.051 mg/L Reproducibility: pooled standard deviation of differences between reading and reference value
u(Ccal) 0.031 mg/L From Ref 3
b1stir 0.0146 %/% The slope of stirring graph (% of the reading vs % of the stirring rate from calibration stirring rate)
b1Δt -0.078 %/°C The slope of temperature compensation graph (temperature °C vs relative difference from reference temperature in %)
b1drift 0.0038 mg/L The largest slope of the drift graph (number of days passed from calibration vs reading difference from the reference value mg/L)
s(b1drift) 0.0009 mg/L Standard deviation of the slope of the drift graph

Input quantities
Value Unit Comment
Calibration
Cread_cal_0 0 mg/L Sensor reading right after calibration/checking zero value Constants for salinity calculation (Ref 6):
Cread_cal 8.98 mg/L Sensor reading right after calibration a0 0.008
Ccal_0 0 mg/L Calibration environment DO concentration at oxygen-free conditions, here always 0 a1 -0.1692
Ccal 8.979 mg/L Calibration envirnment DO concentration at saturation, calculated by the Ref 4 a2 25.3851 C(KCl at 25°C) *
tcal_ref 19.909 °C Temperature of calibration solution measured with reference thermometer a3 14.0941 53.903805 mS/cm
Pcal_ref 99915 Pa Air pressure at the time of calibration measured with reference barometer a4 -7.0261 Notes:
*

tcal_sensor 19.9 °C Temperature of calibration solution measured with DO-meter a5 2.7081 Ref 5: conductivity of SSW at SP=35, t_68=15, p=0; 42.9140 mS/cm
Pcal_sensor 100100 Pa Air pressure at the time of calibration measured with DO-meter b0 0.0005 Ref 7: factor for calculating the conductivity from 15 °C to the 25 °C is found as 1.25608904610271
b1 -0.0056
Measurement b2 -0.0066
Cread_meas 7.75 mg/L Reading of the measured sample b3 -0.0375
k 0.896 mS/cm conductivity of the sample, used for calculating the activity coefficient b4 0.0636
Salinity 0.432 PSU Salinity, calculated from measured conductivity (recalculated to 25 C), using Refs 5, 6 and 7 b5 -0.0144
tsample 6.9 °C Sample temperature, measured with DO-meter X 400 *Rt
Δvstir 50 % estimated flow rate compared to the flow rate of calibration Y 100 *Rt
Δdays 2 The number of days passed from the last calibration

Model components Uncertainty components

Denotion Value Unit uc Relative u1 u2
Cread_cal_0 0 mg/L 0.0200416 0.0028867513 u(Ccal_res)
±half of the last digit 0.0198 u(Ccal_rep) repeatabilty of the reading
Cread_cal 8.98 mg/L 0.0200416 0.2232% 0.0028867513 u(Ccal_0_res)
±half of the last digit 0.0198 u(Ccal_0_rep) repeatabilty of the reading
Ccal_0 0 mg/L 0.0057735 0.0057735027 u(Ccal_0)
estimation
Ccal 8.98 mg/L 0.031 0.3452% 0.031 u(Ccal)Estimated as in Ref 3
Cread_meas 7.75 mg/L 0.0512693 0.6615% 0.0028867513 u(Cmeas_res)
±half of the last digit 0.0512 u(Cmeas_Rep) reproducibility of the reading
γ 1.0028 - 0.0008203 0.0818% 0.0008203185 ± half of the activity coefficient difference from 1
ΔCstir 0 mg/L 0.0326955 0.0326954956 ±Δvstir *b1stir*Cread_meas/100%
ΔCΔt 0 mg/L 0.0451439 0.0451438731 ±Δt*b1Δt/100%*Cread_meas
ΔCdrift 0 mg/L 0.0053781 0.0053781406 ±Δdays*(b1drift+s(b1drift))

Denotion Value Unit uc Cread_cal_0 Cread_cal Ccal_0 Ccal Cread_meas γ ΔCstir ΔCΔt ΔCdrift
Cread_cal_0 0 mg/L 0.0200416 0.0200416234 0 0 0 0 0 0 0 0
Cread_cal 8.98 mg/L 0.0200416 8.98 9.00004162335408 8.98 8.98 8.98 8.98 8.98 8.98 8.98
Ccal_0 0 mg/L 0.0057735 0 0 0.00577 0 0 0 0 0 0
Ccal 8.97924395507 mg/L 0.031 8.9792439551 8.97924395507017 8.97924 9.01024396 8.979244 8.979244 8.979244 8.979244 8.979244
Cread_meas 7.75 mg/L 0.0512693 7.75 7.75 7.75 7.75 7.8012693 7.75 7.75 7.75 7.75
γ 1.00284166656 - 0.0008203 1.0028416666 1.00284166656109 1.00284 1.00284167 1.0028417 1.003662 1.0028417 1.0028417 1.0028417
ΔCstir 0 mg/L 0.0326955 0 0 0 0 0 0 0.0326955 0 0
ΔCΔt 0 mg/L 0.0451439 0 0 0 0 0 0 0 0.0451439 0
ΔCdrift 0 mg/L 0.0053781 0 0 0 0 0 0 0 0 0.0053781

Cresult 7.73 mg/L 7.72 7.71 7.73 7.75 7.78 7.72 7.76 7.77 7.73
uCresult 0.082 mg/L -0.002800148 -0.017207633397724 0.0008 0.02667809 0.0511197 -0.006316 0.0326001 0.0450122 0.0053624
UCresult 0.16 mg/L, k=2 7.840828E-06 0.00029610264715 6E-07 0.00071172 0.0026132 3.989E-05 0.0010628 0.0020261 2.876E-05
UCresult rel 2.132 %, k=2 0.006787
0% 4% 0% 10% 39% 1% 16% 30% 0%
100.0%
Table S10. Measurement uncertainty using the ISO GUM method with Kragten approach
Data from Pärnu coast
Cread_meas  Cstir  CΔt  Cdrift  Clinearity b0 Cread_ cal_ 0  Ccal  Ccal_0  Cread_ cal Cread_ cal  Cread_cal_0
Cresult   b1 
b0  Ccal  Ccal_0
  b1 b1 Ccal  Ccal_0

HACH
Experimental data for calculating different uncertainty contributions:
u(Ccal_rep) 0.0039 mg/L Pooled standard deviation of the readings at stirring rate 120 rpm
u(Ccal_0_rep) 0.0049 mg/L The largest pooled standard deviation of the readings
u(Cmeas_Rep) 0.0686 mg/L Reproducibility: pooled standard deviation of differences between reading and reference value
u(Ccal) 0.031 mg/L From Ref 3
b1stir -0.00094 %/% The slope of stirring graph (% of the reading vs % of the stirring rate from calibration stirring rate)
b1Δt 0.024 %/°C The slope of temperature compensation graph (temperature °C vs relative difference from reference temperature in %)
b1drift -0.0079 mg/L The slope of the drift graph (number of days passed from calibration vs reading difference from the reference value mg/L )
s(b1drift) 0.0008 mg/L Standard deviation of the slope of the drift graph
b1linearity 0.0277 - The slope of the linearity graph starting at 11 mg/L (electrochemical reading mg/L vs readings difference mg/L)

Input quantities
Value Unit Comment
Calibration
Cread_cal_0 0 mg/L Sensor reading right after calibration/checking zero value
Cread_cal 9.03 mg/L Sensor reading right after calibration Constants for salinity calculation (Ref 6):
Ccal_0 0 mg/L Calibration environment DO concentration at oxygen-free conditions, here always 0 a0 0.008
Ccal 8.979 mg/L Calibration envirnment DO concentration at saturation, calculated by the Ref 4 a1 -0.1692 C(KCl at 25°C) *
tcal_ref 19.909 °C Temperature of calibration solution measured with reference thermometer a2 25.3851 53.903805 mS/cm
Pcal_ref 99915 Pa Air pressure at the time of calibration measured with reference barometer a3 14.0941 Notes:
*

tcal_sensor 20.1 °C Temperature of calibration solution measured with DO-meter a4 -7.0261 Ref 5: conductivity of SSW at SP=35, t_68=15, p=0; 42.9140 mS/cm
Pcal_sensor 100100 Pa Air pressure at the time of calibration measured with DO-meter a5 2.7081 Ref 7: factor for calculating the conductivity from 15 °C to the 25 °C is found as 1.25608904610271
b0 0.0005
Measurement b1 -0.0056
Cread_meas 11.12 mg/L Reading of the measured sample b2 -0.0066
k 3.1 mS/cm conductivity of the sample, used for calculating the activity coefficient b3 -0.0375
Salinity 1.587 PSU Salinity, calculated from measured conductivity (recalculated to 25 C), using Refs 5, 6 and 7 b4 0.0636
tsample 18.4 °C Sample temperature, measured with DO-meter b5 -0.0144
Δvstir 50 % estimated flow rate compared to the flow rate of calibration X 400 *Rt
Δdays 3 The number of days passed from the last calibration Y 100 *Rt

Model components Uncertainty components

Denotion Value Unit uc Relative u1 u2
Cread_cal_0 0 mg/L 0.0056984 0.0028867513 u(Ccal_res) ±half of the last 0.0049
digit u(Ccal_rep) repeatabilty of the reading
Cread_cal 9.03 mg/L 0.0048542 0.0538% 0.0028867513 u(Ccal_0_res) ±half of the last 0.0039
digit u(Ccal_0_rep) repeatabilty of the reading
Ccal_0 0 mg/L 0.0057735 0.0057735027 u(Ccal_0) estimation
Ccal 8.98 mg/L 0.031 0.3452% 0.031 u(Ccal) Estimated as in Ref 3
Cread_meas 11.12 mg/L 0.0687046 0.6178% 0.0028867513 u(Cmeas_res) ±half of the last 0.0686
digit u(Cmeas_Rep) Reproducibility of the reading
γ 1.0095 - 0.0027494 0.2723% 0.002749401 ± half of the activity coefficient difference from 1
ΔCstir 0 mg/L 0.0030253 0.0030253156 ±Δvstir *b1stir*Cread_meas/100%
ΔCΔt 0 mg/L 0.0026597 0.0026596613 ±Δt*b1Δt/100%*Cread_meas
ΔCdrift 0 mg/L 0.0151534 0.0151533934 ±Δdays*(b1drift+s(b1drift))
ΔClinearity 0 mg/L 0.0019167 0.0019166777 ±ΔC from 11 mg/L*b1linearity (if Cread_meas>11)

Denotion Value Unit uc Cread_cal_0 Cread_cal Ccal_0 Ccal Cread_meas γ ΔCstir ΔCΔt ΔCdrift ΔClinearity
Cread_cal_0 0 mg/L 0.0056984 0.0056983563 0 0 0 0 0 0 0 0 0
Cread_cal 9.03 mg/L 0.0048542 9.03 9.0348542 9.03 9.03 9.03 9.03 9.03 9.03 9.03 9.03
Ccal_0 0 mg/L 0.0057735 0 0 0.0057735 0 0 0 0 0 0 0
Ccal 8.97924395507 mg/L 0.031 8.9792439551 8.979244 8.979244 9.010244 8.979244 8.979244 8.979244 8.979244 8.979244 8.979244
Cread_meas 11.12 mg/L 0.0687046 11.12 11.12 11.12 11.12 11.188705 11.12 11.12 11.12 11.12 11.12
γ 1.00952420438 - 0.0027494 1.0095242044 1.0095242 1.0095242 1.0095242 1.0095242 1.0122736 1.0095242 1.0095242 1.0095242 1.0095242
ΔCstir 0 mg/L 0.0030253 0 0 0 0 0 0 0.0030253 0 0 0
ΔCΔt 0 mg/L 0.0026597 0 0 0 0 0 0 0 0.0026597 0 0
ΔCdrift 0 mg/L 0.0151534 0 0 0 0 0 0 0 0 0.0151534 0
ΔClinearity 0 mg/L 0.0019167 0 0 0 0 0 0 0 0 0 0.0019167

Cresult 10.95 mg/L 10.954422575 10.947291 10.951907 10.990991 11.02085 10.923427 10.956156 10.955796 10.968102 10.955064
uCresult 0.085 mg/L 0.001246431 -0.005885 -0.001269 0.0378148 0.0676739 -0.02975 0.0029799 0.0026198 0.0149261 0.0018879
UCresult 0.17 mg/L, k=2 1.55359E-06 3.463E-05 1.611E-06 0.00143 0.0045798 0.000885 8.88E-06 6.863E-06 0.0002228 3.564E-06
UCresult rel 1.5 %, k=2 0.0071746
En (vs WTW) = -0.408879 0% 0% 0% 20% 64% 12% 0% 0% 3% 0%
100.0%
Table S11. Measurement uncertainty using the ISO GUM method with Kragten approach
Data from Pärnu coast
Cread_meas  Cstir  CΔt  Cdrift  Clinearity b0 Cread_ cal_0  Ccal  Ccal_ 0  Cread_cal Cread _cal  Cread_cal_0
Cresult   b1 
b0  Ccal  Ccal_0
  b1 b1 Ccal  Ccal_ 0

WTW
Experimental data for calculating different uncertainty contributions:
u(Ccal_rep) 0.020 mg/L Pooled standard deviation of the readings at stirring rate 120 rpm
u(Ccal_0_rep) 0.020 mg/L The largest pooled standard deviation of the readings
u(Cmeas_Rep) 0.051 mg/L Reproducibility: pooled standard deviation of differences between reading and reference value
u(Ccal) 0.031 mg/L From Ref 3
b1stir 0.0146 %/% The slope of stirring graph (% of the reading vs % of the stirring rate from calibration stirring rate)
b1Δt -0.078 %/°C The slope of temperature compensation graph (temperature °C vs relative difference from reference temperature in %)
b1drift 0.0038 mg/L The largest slope of the drift graph (number of days passed from calibration vs reading difference from the reference value mg/L)
s(b1drift) 0.0009 mg/L Standard deviation of the slope of the drift graph

Input quantities
Value Unit Comment
Calibration
Cread_cal_0 0 mg/L Sensor reading right after calibration/checking zero value Constants for salinity calculation (Ref 6):
Cread_cal 8.98 mg/L Sensor reading right after calibration a0 0.008
Ccal_0 0 mg/L Calibration environment DO concentration at oxygen-free conditions, here always 0 a1 -0.1692
Ccal 8.979 mg/L Calibration envirnment DO concentration at saturation, calculated by the Ref 4 a2 25.3851 C(KCl at 25°C) *
tcal_ref 19.909 °C Temperature of calibration solution measured with reference thermometer a3 14.0941 53.903805 mS/cm
Pcal_ref 99915 Pa Air pressure at the time of calibration measured with reference barometer a4 -7.0261 Notes:
*

tcal_sensor 19.9 °C Temperature of calibration solution measured with DO-meter a5 2.7081 Ref 5: conductivity of SSW at SP=35, t_68=15, p=0; 42.9140 mS/cm
Pcal_sensor 100100 Pa Air pressure at the time of calibration measured with DO-meter b0 0.0005 Ref 7: factor for calculating the conductivity from 15 °C to the 25 °C is found as 1.25608904610271
b1 -0.0056
Measurement b2 -0.0066
Cread_meas 11.16 mg/L Reading of the measured sample b3 -0.0375
k 3.1 mS/cm conductivity of the sample, used for calculating the activity coefficient b4 0.0636
Salinity 1.587 PSU Salinity, calculated from measured conductivity (recalculated to 25 C), using Refs 5, 6 and 7 b5 -0.0144
tsample 18.1 °C Sample temperature, measured with DO-meter X 400 *Rt
Δvstir 50 % estimated flow rate compared to the flow rate of calibration Y 100 *Rt
Δdays 3 The number of days passed from the last calibration

Model components Uncertainty components

Denotion Value Unit uc Relative u1 u2
Cread_cal_0 0 mg/L 0.0200416 0.0028867513 u(Ccal_res)
±half of the last digit 0.0198 u(Ccal_rep) repeatabilty of the reading
Cread_cal 8.98 mg/L 0.0200416 0.2232% 0.0028867513 u(Ccal_0_res)
±half of the last digit 0.0198 u(Ccal_0_rep) repeatabilty of the reading
Ccal_0 0 mg/L 0.0057735 0.0057735027 u(Ccal_0)
estimation
Ccal 8.98 mg/L 0.031 0.3452% 0.031 u(Ccal)Estimated as in Ref 3
Cread_meas 11.16 mg/L 0.0512693 0.4594% 0.0028867513 u(Cmeas_res)
±half of the last digit 0.0512 u(Cmeas_Rep) reproducibility of the reading
γ 1.0095 - 0.0027558 0.2730% 0.0027558368 ± half of the activity coefficient difference from 1
ΔCstir 0 mg/L 0.0470815 0.0470815136 ±Δvstir *b1stir*Cread_meas/100%
ΔCΔt 0 mg/L 0.009001 0.0090009938 ±Δt*b1Δt/100%*Cread_meas
ΔCdrift 0 mg/L 0.0080672 0.0080672109 ±Δdays*(b1drift+s(b1drift))

Denotion Value Unit uc Cread_cal_0 Cread_cal Ccal_0 Ccal Cread_meas γ ΔCstir ΔCΔt ΔCdrift
Cread_cal_0 0 mg/L 0.0200416 0.0200416234 0 0 0 0 0 0 0 0
Cread_cal 8.98 mg/L 0.0200416 8.98 9.00004162335408 8.98 8.98 8.98 8.98 8.98 8.98 8.98
Ccal_0 0 mg/L 0.0057735 0 0 0.00577 0 0 0 0 0 0
Ccal 8.97924395507 mg/L 0.031 8.9792439551 8.97924395507017 8.97924 9.01024396 8.979244 8.979244 8.979244 8.979244 8.979244
Cread_meas 11.16 mg/L 0.0512693 11.16 11.16 11.16 11.16 11.211269 11.16 11.16 11.16 11.16
γ 1.00954649882 - 0.0027558 1.0095464988 1.00954649882446 1.00955 1.0095465 1.0095465 1.0123023 1.0095465 1.0095465 1.0095465
ΔCstir 0 mg/L 0.0470815 0 0 0 0 0 0 0.0470815 0 0
ΔCΔt 0 mg/L 0.009001 0 0 0 0 0 0 0 0.009001 0
ΔCdrift 0 mg/L 0.0080672 0 0 0 0 0 0 0 0 0.0080672

Cresult 11.05 mg/L 11.06 11.03 11.05 11.09 11.10 11.02 11.10 11.06 11.06
uCresult 0.089 mg/L 0.0046397779 -0.024614424154711 -0.0013 0.03816131 0.0507802 -0.030092 0.0466324 0.0089151 0.0079903
UCresult 0.18 mg/L, k=2 2.152754E-05 0.000605869876468 2E-06 0.00145629 0.0025786 0.0009055 0.0021746 7.948E-05 6.384E-05
UCresult rel 1.607 %, k=2 0.0078875
0% 8% 0% 18% 33% 11% 28% 1% 1%
100.0%
Table S12. Measurement uncertainty using the Nordtest approach. Optical analyzer.
Cresult-Cref (%) Stirring test
HACH drift1 drift 2 temp_komp act sr n
Possible bias: 0.3% 0.7% 0.18% 1.1% 0.11% 30.00
Estimated by the data of drift estimation, temperature compensation tests and measurements in water with higher salinity. 1.3% 0.6% 0.12% 1.0% 0.10% 30.00
Drift is measured two times during one month, alltogether 33 individual results. 1.4% 0.4% -0.25% 1.5% 0.08% 30.00
Temperature compensation tests include measurements in one day, alltogether 5 individual bias determinations. 1.4% 0.1% -0.24% 1.8% 0.09% 210
Measurements in KCl solution were made in one day and include 4 individual results. 0.7% -1.2% -0.41%
1.4% -1.1%
RMSbias_rel 1.31% RMS bias 
 (biasi ) 2 2 1.1% -2.1%
n u (bias)  RMS bias  u (Cref ) 2
u(Cref)rel 0.40% 1.0% -2.1%
u (Cref ) 
 u (Cref )i
2
u(bias)= 1.37% 1.6% -2.1%
Intermediate precision: n 0.5% -2.2%
Estimated by the drift measurement data. 1.0% -2.0%
Intermediate precision has been estimated as the pooled standard deviation of the relative differences of results from the reference value. 1.6% -1.7%
Measurements were done with two different sensor calibration values whereby on calibration was used during one month. 1.1% -2.3%
u(Rw)rel= 0.26% 0.8% -2.2%
0.9% -1.8%
uc  u ( Rw ) 2  u (bias) 2 0.3% -1.1%
uc= 1.40% 0.8%
So for the sample 10 mg/L the standard uncertainty is 0.14 mg/L
Table S13. Measurement uncertainty using the Nordtest approach. Amperometric analyzer.
Cresult-Cref (%) Stirring test
WTW drift1 drift 2 temp_komp act sr n
Possible bias: 0.0% 0.0% -0.90% -0.3% 1.06% 30.00
Estimated by the data of drift estimation, temperature compensation tests and measurements in water with higher salinity. -0.6% 0.1% -0.56% -0.4% 1.11% 30.00
Drift is measured two times during one month, alltogether 30 individual results. -0.4% -0.6% 0.41% 0.0% 1.10% 30.00
Temperature compensation tests include measurements in one day, alltogether 5 individual bias determinations. -0.7% 0.1% 0.71% -2.4%
Measurements in KCl solution were made in one day and include 4 individual results. -0.8% 0.4% 0.98%
-0.9% 0.8%
RMSbias_rel 0.97% RMS bias 
 (biasi ) 2 u(bias)= 1.05% 0.4% 0.0%
u(Cref)rel 0.40% n 2 -0.7% 0.5%
 u(Cref )i
2 u (bias)  RMS bias  u (Cref ) 2 -1.6% 0.5%
u (Cref ) 
Intermediate precision: n -0.3% 0.6%
Estimated by the drift measurement data. -0.5% 0.9%
Intermediate precision has been estimated as the pooled standard deviation of the relative differences of results from the reference value. -0.4% 2.1%
Measurements were done with two different sensor calibration values whereby on calibration was used during one month. -1.7% 2.6%
u(Rw)rel= 1.00% -0.6%
-1.1%
uc  u ( Rw ) 2  u (bias) 2 -1.3%
uc= 1.45% -1.3%
So for the sample 10 mg/L the standard uncertainty is 0.15 mg/L
References to the Electronic Supplementary Material:
1. HACH Company (2006). HQ Series Portable Meters, USER MANUAL, edition 5.
2. Weilheim 2002, WTW GmbH & Co. KG Operating Manual, CellOx 325 Dissolved oxygen sensor. Available at:
http://www.globalw.com/downloads/WQ/cellox325.pdf
3. Helm, I., Jalukse, L., and Leito, I. (2012). A highly accurate method for determination of dissolved oxygen:
Gravimetric Winkler method. Anal. Chim. Acta 741, 21–31. doi:10.1016/j.aca.2012.06.049.
4. Benson, B. B., and Krause, D. (1984). The concentration and isotopic fractionation of oxygen dissolved in
freshwater and seawater in equilibrium with the atmosphere. Limnol. Oceanogr. 29, 620–632.
doi:10.4319/lo.1984.29.3.0620.
5. McDougall, T.J. and P.M. Barker. Getting started with TEOS-10 and the Gibbs Seawater (GSW) Oceanographic
Toolbox, 2011, 28pp., SCOR/IAPSO WG127, ISBN 978-0-646-55621-5.
6. Clesceri, L. S., American Public Health Association, American Water Works Association, and Water Pollution
Control Federation eds. (1998). Standard methods: for the examination of water and wastewater. 20. ed.
Washington: American Public Health Ass.
7. ISO 7888, Water quality - Determination of electrical conductivity, 1985.