INSTRUMENTATIONFACILTIES Carbonate Overview of instrumentationfor Techniques & Sensors for Studies of TRAINING COURSE ONBEST PRACTICES Cape Town, South Africa Ocean AcidificationOcean -

systemmeasurements: OA RESEARCH Lisa RobbinsLisa

INSTRUMENTATIONFACILTIES • • • • application Parameters and sensorsthat are right for your Resources Sensors/Techniques for carbonate parameters Introduction – – – – – 5 4 3 2 1 . CO . Alkalinity . . DIC . pH p CO

3

- 2 2

- discussion

-

TA

Outline

INSTRUMENTATIONFACILTIES Disclaimer: describing equipment implicit or explicitimplicit or in endorsements and chemicals We make no

SENSORSFACILTIES • • • • http://www.ioccp.org International Ocean Carbon Coordination Project (IOCCP http://dx.doi.org/ Science and Technology technology for a new era of ocean chemistry. Environmental Byrne, RH, Alliance for Coastal Technologies(ACT, Science, Needs and Availability, Emerging Themes in Ocean Acidification Martz et al. Oceanography 2014 2015 Some ReferencesSome , Measuring acidification:ocean New Technology for Ocean Acidification Research 10.1021 )

, 48 vol /es : 5

28 , 405819 352 , n 2 - 5 , , 40 360 p . -

http://www.act 47 .

- us.info -

SENSORSFACILTIES http://www.ioccp.org

FACILTIES INSTRUMENTATIONFACILTIES • • Discrete Sampling • • • Challenges ininstruments sensors and equipment Compatibility Response maintenance Ease and of use assessment/quality control Routines for quality Accuracy/precision time

with other

• • • • • • • • • • • • Autonomous equipment Compatibility Response time Ruggedness consumption Power requirementsand Frequency of Sensitivity Ease Size/weight Long maintenance Costs for installation and assessment/qualitycontrol Routines for quality Accuracy/precision of use and maintenance termdrift to

biofouling measurements with other

INSTRUMENTATIONFACILTIES Summary of Techniquesof Summary &Sensors

INSTRUMENTATIONFACILTIES ( • usually Buffers with Certified • eg Spectrophotometric using indicators Potentiometric determination ., m absorbance pH Differenceof electricalpotential across glass use a glass electrode/ glass a use reference electrodepair sensitive indicatortodye seawater isadded sample -

Cresol Purpleor is measured on a spectrophotometermeasured on Tris Benchtop

or seawater thymol

pH Sensors blue)

membrane

then then -

a multi

- wavelength

INSTRUMENTATIONFACILTIES • reference electrode Potentiometric pH of seawater usingglass – – – – – – – – Precision of Need to frequently calibrate Calibration time can be lengthy calibrate Must use Certified Tris seawateror buffers to Electrodes have varying degrees of reliability Temperature control of solutions Must minimize Available for pH Measurements

~ less than 0.02 gas exchange when handling -

0.002

$ 1 , pH units 000 -

USD drift of system

samples

INSTRUMENTATIONFACILTIES • Spectrophotometric – – – – – – – – Can Can be automated Limited amounts referenceof pH materials available Run time less than reproducibility) measurement uncertainty (about mCP of time to use theright indicator dye perturbation test Dyes have specific pH range Temperature must be controlled for solutions andcells Must minimize Some set ups allow continuous measurement

impurity impurity (Yao & Byrne, pH Measurements gas exchange when handling

-

need toneed ~know ofthe pH water ahead 20 pH min (sample to data)

- 2007

need toneed also run ) will cause the 10

times its

samples

INSTRUMENTATIONFACILTIES Precision/ Accuracy Stds Hardware/Chemical/ Disadvantages Advantages When toWhen use

pH Measurements

monitoring rapid changesspatially system changes; flow goodthru for monitoring andin situ laboratory samples; High accuracyand precision for Discrete andsemi < indicator, software ( holder ( ~> Spectrophotometer( areCells expensive;T= ~ needto perform perturbationtest Dyes have narrow range;pH Need time to warm upspec for stability Indicatorimpurity; More precision Procedure canbe somewhat automated;hi Calibrationis straightforward; Spectrophotometric 0.003 7.5

- expensive 12.5 - 400 . 0008

K+) ); glass/optical); cells( , /

tempcontrol ( ±

0.002 - discreteflow

1 3 K); K/

pH 7.5 3 std - 20

-

12.5 2

min

- 4 - through 200 K),cell K(spec

carbon

ea ); changes* suitedfor monitoring rapid pH where precisionnecessary; isn’t andstat,pH for smaller samples, Monitoring 0.001 control device pH electrode,mV meter, temp judiciously( Electrodesmust be chosen strength;Less precise (< recalibrate;Sensitive to ionic Drift of calibration calibrated Run Timeis short Electrodes Potentiometric pH

/ ± 0.002

-

are cheaperspecthan Convenient - eg

for tank experiments , buffer, standards ., ., Ross pH units - - once electrode

needto

Orion)

0.001

);

INSTRUMENTATIONFACILTIES Will see in lab this afternoonthis inlab see Will DIY: Components of oneof the cheapest pH

Spec V • • • • • • • • •

~ $ jacket Water bath/cell Indicator dye Cell holder Cell Computer/software Fiber optics Light source Spec (Ocean optics)

4

, 500

USD

pH

FACILTIES • • Commercially available pHsystems Benchtop Spectrophotometers, Potentiometric:Orion,

-

discrete samples

ie pH Metrohm ., ., Agilent,

Sensors

Satlantic SeaFET Sunburst AFT - pH SP pH

Underway SensorLab 200

- SM

2015 From:Modified Martzet al , Oceanography, Sensorlab SP Sunburst SAMI 101 - pH pH - Autonomous LB

Satlantic SeaFET

INSTRUMENTATIONFACILTIES INSTRUMENTATIONFACILTIES SeaFET Honeywell estuary in McMurdo Sound (GretchenHofmann) Deep water(Ken Johnson) intertidalapplications (F Chavez MBARI) upper PopularCommercially autonomous -

can be used autonomous or flow thru 100 DuraFET m of the ® being is used asautonomous ocean ocean (Martz) referenced spectrophotometricdetermination pH of Precision:better than TypicalStability: InitialAccuracy: Measurement Range:

SeaFET Sensors toTRISbuffer certified

Ocean pH sensor Ocean pH 0.05 0.005 (estimated

2 0.0011 / month (estimated/ month - - 9

precision . pH

systemsoperating in the Calibration:

)

001

)

pH INSTRUMENTATIONFACILTIES • • Infrared GasAnalyzer Coulometric 2 . Dissolved

inorganic inorganic

carbon

INSTRUMENTATIONFACILTIES DIC

Marianda APOLLO SCITECHMarianda AS AIRICA Marianda VINDTA 2 . Dissolved 3 D/

Benchtop 3 C

- C 3

inorganic inorganic Marianda underway) VINDTA

3 Underway D (discreteD and

carbon Autonomous

INSTRUMENTATIONFACILTIES • • BENCHTOPANALYZERSDIC • Popular Total Analyzers Carbon Apollo Marianda NIHON – – – Airica VINDTA titrationAlkalinity) determinationof Total inorganiccarbonand VINDTA Scitech Ans : discrete: sampling (Versatile Instrumentfor the 3

Co Co D: discreteD: underway and

DIC AnalyzerAS

3 C : discrete: sampling

- C 3

INSTRUMENTATIONFACILTIES • • • • • • potentiometry absolute interferences ( scrubber reaction products through a post carbon facilitates inorganic carbon to be intodispenser the causing sample flask, dioxide. gas to CO Built added Aliquot of acid thru System Sample deliveredinto Resulting CO 2 - free - eliminate atmospheric carbon in in

is purged is a with coulometric heater and magnetic stirrer the fast to remove carrier gas transports the )

, or infraredspectroscopy 2

is measured is Principles of Principles expulsion inorganic potential

titration, evolved. the sample the sample CO the acid the acid 2 using using -

free

- carrier flask

DIC Operation

SENSORSFACILTIES available Commercially toWhen use Precision/Accuracy / Hardware/Chemical Disadvantages Advantages Std

DIC Measurements

samples/hour biologist; Cost:~ May be “over kill” for the Expensive> Not as precise stability;good precision proven long term Small samples( Coulometric 3 UIC, VINDTAMarianda, T P and samplematrix; Discrete;sensitiveless ± loops/carbonate/ CRM chamber, carrier gas, extraction Coulometer, chemicals, D (SOMMA),

0.05 %/

1 gas um/kg 50

as NDIR K 5 indep

50

DIC ml);

K;

4

of

to

DIC, Apollo matrix; less sensitive Discrete, Semi 0.1 extractionchamber, CRM IR Analyzer, carrier gas, exchange; protectfrom gas calibrate tempdependent); of calibrationcurve, Calibrationissue (shape samples( on Good small sensitivity Less hazardouswaste; Coulom Faster NDIR DIC % ( Airica

±

persample than SciTech, moored 2 indep

(

6 often; 0.75 µ

- Cost: mol 10

/hour); to sample mls) of of andT P - /kg) discrete;

must ~ 50

K;

commercially avail.) MICA, SEAS flow through Discreteand semi Custom Opticalcellused achieve Uses spec setup yourself other techniques(~ Couldbe cheaperthan Spec DIC

stability -

needs timeneeds to

-

(not

- discrete 20

K) if if K) INSTRUMENTATIONFACILTIES with LI with Airica InorganicAnalyzer) Carbon UIC Coulometer

(AutomatedInfra Red - COR 7000 Apollo

Scitech

INSTRUMENTATIONFACILTIES • 1 . Discrete measuring measuring pH, AT or DIC taking water samples and “flow thru” system involves CO 3 2 . p measurements without - CO

calculated 2

sensors & equilibration

• 2 . Autonomous glider with On autonomous buoy or pCO

2 sensor

INSTRUMENTATIONFACILTIES 3 . Flow through General Oceanics

Inc

-

underway systemsunderway Guard CutterHealy Lamont -

built pCO built 2

Analyzer aboardthe Coast

INSTRUMENTATIONFACILTIES Thin Bubbler Rain Spectrophotometricmeasurements Non waysMultiple analyzing ofCO straightforward running. to once use levels. streamflowing seawater of iscalibrated and using Equipmentfor this measurement is p(CO - - • film: • measurements Advantage: systemsthese Disadvantage: mayup Set take some time, dispersive infra 2 type ): Calibrationagainst standardCO Air

type: - : showerhead + headspace air showerhead+ headspace : (CO waterCO 2 (bubble seawater(bubble carrier with gas) gasmembrane) permeable 2 -

red(NDIR) equilibration pCO are analyzer e.g mechanism ( mechanism designed designed

~ $ ~

2 2 10

gases Sensors , 000

. to runautonomously LiCOR

- 50 flowing SWflowing equilibrates gas/airwith 2

but can be relatively canbut be , 000 tanks fromseawater:

CO +USD. 2 /H of air with knownwithCOof air

2 O It usually requiresa analyzer CO .

2

gas 2

) INSTRUMENTATIONFACILTIES Commercially available When to use Precision/accuracy Hardware/Chemical/ Disadvantages Advantages p CO

2

/ Std f

(CO

Sundans air Kimoto GeneralOceanus, Batelle In situ . gases equilibrator, NDIR, standard regularcalibrationNeeds Chemicals No required in situ systems) NDIR 01 ppm/ 2

-

monitoring based (flowbased thru

Seaology ) Measurements

1 ( Marianda ppm - marine CO

,

Pro

Oceanics

)

- 2

,

and , ** Sunburst (AFT), In situ monitoring equilibration membrane indicatorSpec, dyesolution biofouling May moresusceptible tobe alkalinity dyeof solution, Must prepare and calibrate during measurements require not calibrationsDoes (flow thru and in situ) Spectrophotometric ±

2 Picarro - 3 uatm

(ring

- downcavity)

p

CO , 2

FACILTIES INSTRUMENTATIONFACILTIES • • Bench top • • • • • • • • SUNDANS (Surface Underway carbon dioxide pressurepartial Batelle Pro CO Oceanus: General Apollo Sunburst: AFT system Kimoto portable CO Contros SubCTech near touses IR laser measurespectral signal of CO Picarro PCO

Sci

G

Hydroc Oceanics 1200

-

Ocean PackOcean Tech Underway 2 - CO CO

CO sensors 2

2 2 - Pro CV, Mini Pro, CO /H 2 and and SAMI CO 2 flow through 20 analyzer and Air

(wavelength scanned cavity ring down spectrometer 2 -

; Super CO

lots of optionslots - Marine COMarine 2 Pro

2

2 2 autonomous monitoring molec

Analyser

)

-

FACILTIES • • Immersible • • • • 600 Turner Designs Batelle 300 Pro Oceanus: 110 Pro Oceanus:CO 600 Pro Oceanus:CO to Contros 6000 m) m m) m) pCO )

m

Hydroc

2 sensors more limitedif you want Mini ProCO -

CO C 2 2 - Sense (toSense Pro (to Pro CV(to 2 flow thru immersible 2 (to -

• • Moorings/Gliders / AUVs Sunburst SAMI Picarro

-

surface -

CO 2

INSTRUMENTATIONFACILTIES • •

42 Battelle CO Pro - -

Mini ProMini CO K 2 -

Oceanus SystemsOceanus - Pro 2 - Pro:$ Seaology

Some pCOSome CO 18.4 2 :$ : $ 15.4 K+ 31

K+ -

2

• Sensors $ SunburstSensors – – – AFT SUPERCO SAMI - CO - CO 2 : 2 2

system - $ 14 K

INSTRUMENTATIONFACILTIES Temperature range Calibrationrange Gas stream pressure Gas stream humidity CO Precision: Gas stream pressure Gas stream humidity CO Accuracy: calibrated detectorto the interfaceto provide PSICOThe 2 2 concentration concentration

from 2 Pro - Pro™fitted is an with . The . The 0 - – 0 600 Oceanus Systems Inc. CO – 0.01 ± - 600 an equilibratedan gas stream PSICO 2

1 ± ~ 1 ± to 2 1 1 ppm mb mb mb ppm ppm mb ppm ( ppm 35

2 *

˚C

-

Pro™ isfactory

alternateranges available byspecialorder) IR detector

and and

2 - PRO™

INSTRUMENTATIONFACILTIES Autonomous pCOAutonomous MAPCO

Pro Oceanus 2

Sensors

SAMI - CO

2

INSTRUMENTATIONFACILTIES Autonomous pCOAutonomous Scripps Ocean Real Acidification MONITORING PORTFOLIO (CROAMP) THECORALREEFOCEANACIDIFICATION (SOAR) Monitoring (SOAR) Program 2

Sensor Platforms Sensor - time

INSTRUMENTATIONFACILTIES • • of apH change in seawater sample and analyze the Determined by adding acid Spectrophotometric & closedcell Potentiometric titration: Open electrode electromagnetic field titrimeter 4

. Total Alkalinity

to

INSTRUMENTATIONFACILTIES Available When to Use Precision/accuracy Standard Hardware/ Disadvantages Advantages

instruments Chem

/

Total Alkalinity Marianda (mostly cell) nutrients and org characterization; avoid ocean carbOpen + + dispenser; CRM & acid sample acid, electrode, pH meter, Titration setup: Simple complexapparatus weigh sample, Piston sticks, Very bubble sensitive, time; Can giveDIC at same titration Closed - -

1 5 umol umol

-

cell cell, /kgaccuracy /kgprecision

cannot cannot

acids

potentiometric Open Metrohm Dickson Marianda VINDTA Apollo Kimoto organic acids) (avoid hi nuts and calcification studies ocean; Open titration more than point one precision up goes with uM + dispenser, CRM ,and sample acid, acid Electrode, pH good needs electrode up; Can be automated; 10 potential run so time stabilization of the Run - 0.1 - 12 ;

time includes includes time 1.5 1.5 %( min; Easymin; toset - Sci

cell prec

uM

Tech

titration/ prec : lab : lab

meter,

at sea); 0.7 0.7

3 S

Spectrophotometric TA and and organic acids) Calcification studies (avoid hi nutrients ~ ~ CRM dye,and acid, acid sample dispenser, titration Spec spectrophotometer,cell, sensitive bubbles; dispensing should be v. accurate); Indicator, Calibrate CRM with Uses 1 spec; measure same pH w Shortest run 2 1 uM umol accuracyumol precisionumol

20 prec - 100

one point point one titration (acid ; 2

uM time: ~ time: ml sample; ml acc

7 -

8

min; can min;

FACILTIES TA

• • • ~ Combined Repeatability~ Sample volume~ Marianda APOLLO SCITECHMarianda VINDTA Scripps TotalScripps AT KimotoTotal AT 1.5 3 µ S/ mol 3 Total Alkalinity Systems C AS C Benchtop /kg std - ALK

2

uncertainty

0.5 125 µ

mol mL Contros HydroFIA /kg

Underway

Autonomous

INSTRUMENTATIONSENSORSFACILTIES DIY Alkalinity Set up • • • • • • • • • Nitrogen gas plateStir Indicator dye Cell holder Square cell Computer/software Fiber optics Light source Spec (Ocean optics)

-

Helma

-

GCB

Glass

INSTRUMENTATIONFACILTIES techniques Carbonate ion systemusing spectrophotometric PbCO 5

Corrected . Measuring Carbonate. Measuring Ion 3 0

Spectra

FACILTIES Parameter now being used When toWhen use Standard Hardware/Chemical/ Disadvantages Advantages

Calculatingsaturation state pb controlled,opticalcells,indicator Spectrophotometer,temp carbonparameters forincludedon’t calculationof programs (CO carbon ofthe New;some ion Directmeasurement carbonateof Spec CO -

carbonate 3 - 2

2 sys,

CO

2 calc,

etc ) pCO pH TA DIC

FACILTIES 2

Marianda APOLLO SCITECHMarianda VINDTA APOLLO SCITECHMarianda AS AIRICA Marianda VINDTA 3 3 S/ D/

3 3 C AS C Benchtop C

- C - ALK 3

2

Marianda SUNDANS Sunburst AFT Sunburst SuperCO Gen GO Sunburst AFT Contros HydroFIA - 8050 - pCO SP pH oceanics

2 2 2 2

Underway

APOLLOSCITECH SensorLab 200 SubCTech OceanPack MOG AS Kimoto - - SM P

2 701

SubCTech OceanPack Contros HydroC Batelle Seaology Sensorlab SP Sunburst SAMI 101 - pH pH - Autonomous LB

Pro Satlantic Turner Des SAMI CO Sunburst SeaFET C - 2 - Oceanus Sense - PRO - CO

2

SENSORSFACILTIES pCO DIC TA pH p p Willyou co t Whatequipmentyoudo have? youspatial Do need and youparameters?didthe How choose youDo have at least two parameters? emporalresolution data?of the

recisionyoudo need? hysical,biologicalchemical,and processes?Whatof kind

2

Parameters Sensorsand that are right for your Open Open Ocean - locate instrumentsto capture variabilitythe of

Estuary/ Coastal

application

Lab

Exp

SENSORSFACILTIES • First parameter : DIC is good andhas advantages So what parameters should you measure? • – appropriate not: or Second parameter: depends on your situation what is cell density Independent of matrix, temperature, pressure, and • • • right indicator dye; good notpair a and with pCO is goodpH variableSpec totomeasure: need choose but experiments measure youIf are monitoring pCO casehigh the nutrients of organicor acids) Calcification ordeepwaters -

exceptvolumewhen islimited lab as such

2 thenthat’s bestthe variable to -

TAgood parameter(but in not

2

SENSORSFACILTIES Finally, don’t forget the Certified Material (CRM)!

Reference