determination of seawater carbonate system parameters: co2
TRANSCRIPT
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KONGSBERG PROPRIETARY: This document contains KONGSBERG information which is proprietary and confidential. Any disclosure, copying, distribution or use is prohibited if not otherwise explicitly agreed with KONGSBERG in writing. Any authorised reproduction in whole or in part, must include this legend. © 2015 KONGSBERG – All rights reserved.
7th FerryBox Workshop in Heraklion, Crete
April 7, 2016
Determination of Seawater Carbonate System
Parameters: CO2, TA, pH
Steffen Aßmann, Peer Fietzek
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Outline
• Background
• Determination of the Carbonate Parameters
– Dissolved CO2
– Total Alkalinity
– pH value
• Application Examples
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KONGSBERG PROPRIETARY: This document contains KONGSBERG information which is proprietary and confidential. Any disclosure, copying, distribution or use is prohibited if not otherwise explicitly agreed with KONGSBERG in writing. Any authorised reproduction in whole or in part, must include this legend. © 2015 KONGSBERG – All rights reserved.
Kongsberg Maritime Contros GmbH
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Kongsberg Maritime Contros GmbH
Facts
– Founded in 2006 as CONTROS Systems & Solutions GmbH
– Based in Kiel, Germany
– 100% purchased by
Kongsberg Maritime
in March 2015
Team
– KMCON
approx. 16 employees
– Devision
approx. 40 employees
Business fields
– Science:
Environmental Monitoring
– Industry:
Offshore Oil & Gas
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Kongsberg Maritime Contros GmbH
Product Portfolio
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Kongsberg Maritime Contros GmbH
New Portfolio – Systems
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Integrated environmental measuring solutions:
• Modular Subsea Monitoring-Network
(MSM)
• K-Lander / K-Observer
System backbone DPU:
• Versatile data
communication and
logging device
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KONGSBERG PROPRIETARY: This document contains KONGSBERG information which is proprietary and confidential. Any disclosure, copying, distribution or use is prohibited if not otherwise explicitly agreed with KONGSBERG in writing. Any authorised reproduction in whole or in part, must include this legend. © 2015 KONGSBERG – All rights reserved.
CONTROS HydroC CO2
Sensor for Dissolved CO2 in Water
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CONTROS HydroC®CO2
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• Very robust and versatile; can be
used in water depths up to 6000 m
• Easy integration with almost every
oceanographic measurement
system and platform
Use it wherever you want
• Fast response time; first signal
derived in under 7 seconds
No worries about loosing a
signal
• Long-term quality tracing of the
measured signal
Built in quality control
CO2 – Carbon Dioxide
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CO2
H2O
CONTROS HydroC®CO2
Measurement Intervals and Principle
Zero Flush Measure
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Warmup Zero
• Warmup
Stable measuring conditions
• Zero
Baseline determination for drift
correction
• Flush
Flagged response data / in-
situ response time test
• Measure
Measuring data
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CONTROS HydroC®CO2
Principle
• Dissolved gasses and water vapour equilibrate through the membrane
• Gas concentration is measured by NDIR within a gas circuit; Zeroing included
• Internal data logger saves NDIR signals along with 𝑇, 𝑝 and 𝑟𝐻
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Application Example Shipborne Measurements at Gas Release Site
• CO2-release experiment in Ardmucknish Bay, Scotland, 2012:
• Release started with 90 kg CO2/day; later 150 kg/day
• Two weeks in total
• Sensor used in a CTD frame from a boat:
• Vertical profiling and horizontal towing
• At the release and at reference sites
08.04.2016 WORLD CLASS - through people, technology and dedication Page 11Atamanchuk, et al., 2015
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Application Example Shipborne Measurements at Gas Release Site
Horizontal towing through active area Profiling after CO2 release
• Gas bubble detection
• Event detection on a sub-minute scale and profiling capability through
response time correction
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Atamanchuk, et al., 2015
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KONGSBERG PROPRIETARY: This document contains KONGSBERG information which is proprietary and confidential. Any disclosure, copying, distribution or use is prohibited if not otherwise explicitly agreed with KONGSBERG in writing. Any authorised reproduction in whole or in part, must include this legend. © 2015 KONGSBERG – All rights reserved.
CONTROS HydroFIA TAAnalyzer for Total Alkalinity in Seawater
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CONTROS HydroFIA®TA
• Worlds first commercially
available autonomous TA
analyzer
• Autonomous deployment longer
than one month possible
No more bottled samples
Save time and money
• Low sample / chemicals
consumption
Decreased cost per meas.
• Easy setup
Replacing the sophisticated
lab setup
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TA – Total Alkalinity
FIA – Flow Injection Analyses
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CONTROS HydroFIA®TAMeasurement Principle
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• Sample is aspirated through
the feed inlet
• Titration with hydrochloric acid
(HCl) to a pH range of 3.0 to
4.5
• Addition of the acid-base
indicator dye bromocresol
green for spectrometric pH
detection
• Calculation of TA using
temperature and salinity of the
sample water
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CONTROS HydroFIA®TAMeasurement Intervals
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Flush BlankAcid +
IndicatorMixing +
DegassingMeasure
• Flush
Full replacement of the sample solution; water intake closed and
subsequent sample treatment.
• Blank
Recording the blank spectrum of the sample.
• Indicator / Acid Injection
Injection of the hydrochloric acid and indicator dye into the sample loop.
• Degassing / Mixing
Full removal of the CO2; Looping of acidified, indicator-added sample until
complete removal of DIC.
• Measure
Spectrophotometric pH detection.
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CONTROS HydroFIA®TA Development Activities
Project TAACT
• Tracking Ocean Alkalinity Using
New Carbon Measurement
Technologies
• NOAA funding for 4 analyzers over
3 years (2015 – 2018)
• Establishing baseline data and
autonomous techniques (i.a.
CONTROS HydroFIA TA) for OA
data collection that support
offshore fisheries and climate
applications
Project
• A large scale EU Horizon 2020
research and innovation project
contributing to the Trans-Atlantic
Research Alliance and GEO.
• Budget: € 20.65m for 4 years
(April 2015 – June 2019)
• Development of a Atlantic
Observing Network
• Optimization of the HydroFIA TA
for usage on VOS lines
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Application Example
Mediterranean Sea
• Measurements in the Mediterranean Sea: Transit Panarea-Malaga
• Measurement Cycle: 5 minutes
• Period: 5 days
• ≈1500 values
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HydroFIA TA vs Reference Samples
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HydroFIA TA vs Reference Samples
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2400 2420 2440 2460 2480 2500 2520 2540 2560 2580 2600 26202400
2420
2440
2460
2480
2500
2520
2540
2560
2580
2600
2620
TA
cont. n
ew
TA ref
Linear (04.06.2015 13:43:38)
Equation: y = Intercept + Slope*x
Weighting: No Weighting
Value Error
Intercept 12.8563 137.77795
Slope 1.01407 0.05587
Reduced Chi-Sqr 82.81913
R-Square 0.95368
Pearson's r 0.97657
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KONGSBERG PROPRIETARY: This document contains KONGSBERG information which is proprietary and confidential. Any disclosure, copying, distribution or use is prohibited if not otherwise explicitly agreed with KONGSBERG in writing. Any authorised reproduction in whole or in part, must include this legend. © 2015 KONGSBERG – All rights reserved.
CONTROS HydroFIA pH
Analyzer for pH in Seawater
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CONTROS HydroFIA®pH
• High quality continuous pH
measurements
Carbonate chemistry
applicable
• Autonomous deployment longer
than one month possible
No more bottled samples
Save time and money
• Low sample / chemicals
consumption
Decreased cost per meas.
• Easy setup
Replacing the sophisticated
lab setup
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pH – Proton Concentration
FIA – Flow Injection Analyses
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CONTROS HydroFIA®pHPrinciple
• FIA system using an indicator
dye m-Cresol purple
• Determination of the
concentration of the indicator
acid (HI-) / base (I2-) due to
different absorption spectra
using a CCD spectrometer
• Calculation of the pH value
using Henderson–Hasselbach
equation
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Wavelength (nm)
Ab
so
rba
nce
HI−
I2−
pH = p𝐾𝑎 + log10I2−
HI−
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CONTROS HydroFIA®pHMeasurement Intervals
• Sample
Continuous sample stream.
• Indicator
Injection of the indicator.
• Temp. Control
Steadily controlled sample stream.
• Measure
Spectrophotometric pH detection
in the cuvette.
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Sample IndicatorTemp. Control
Measure
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CONTROS HydroFIA®pH Development Activities
Project BONUS PINBAL
• Aiming at high accuracy pH
measurements
• Characterization of the used
indicator dye over a wide
salinity range
(approx. 0 – 40 psu)
• Evaluation of cross sensitivities
(DOM, H2S)
• Measurements at low pH
seawater
(wide pH working range)
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Application ExampleFinnmaid Ferry in the Baltic Sea
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Application ExampleFinnmaid Ferry in the Baltic Sea
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• Monitoring the spring in the Baltic Sea
• Measurements of pCO2 (HydroC CO2) and pH (HydroFIA pH prototype)
• At low salinities of approx. 7 psu
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KONGSBERG PROPRIETARY: This document contains KONGSBERG information which is proprietary and confidential. Any disclosure, copying, distribution or use is prohibited if not otherwise explicitly agreed with KONGSBERG in writing. Any authorised reproduction in whole or in part, must include this legend. © 2015 KONGSBERG – All rights reserved.
Overview
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Specification Sheet
CONTROS HydroC CO2 HydroFIA TA HydroFIA pH
Accuracy ± 1 %* ± 1 % ± 0.003^
Offset to
Reference± 0.6 µatm° N/A# ± 0.01+
Precision ± 1 % ± 0.2 % ± 0.001
Meas. Interval 1 s 6.5 min 1 min
Meas. Range 200 – 1000 µatm 1400 – 2400 µmol/kg 7 – 9
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* Applying pre- and post-deployment calibration
° Compared to a reference system from GO
# Calibrated with reference no initial offset
+ For impure indicator dye m-cresol purple
^ For the offset corrected pH of a standard