Introduction

Method overview

Alkalinity is the measure of how much acid it takes to lower the pH of a water sample enough to convert all bicarbonate (HCO₃^–) and carbonate (CO₃^2–) to carbonic acid (H₂CO₃). Although total alkalinity is equal to the stoichiometric sum of all bases in solution, not just carbonates, ~97% of alkalinity in typical seawater is due to carbonates.

Note that this method should only be used on interstitial water (IW) squeezed from the core material by the titanium squeezers. The RHIZON samplers alter the pH and alkalinity of the IW samples and should not be analyzed for alkalinity or pH.

Method theory

To measure alkalinity, a pore water sample is titrated with an acid to an endpoint at which carbonate is converted to bicarbonate and bicarbonate is converted to carbonic acid. In seawater, this endpoint occurs at about pH = 4.2.

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plays an important role in establishing the pH of the solution through a buffering effect. This change in slope, however, has no effect on the Gran extrapolation intercept with the y-axis and is not accurate enough to estimate sulfate concentrations.

Reagents

-         IAPSO standard seawater (alkalinity ~2.325 mM)

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-         Sodium carbonate (Na₂CO₃)

Reagent solutions

-         0.1 M HCl solution (premade from Fisher, AMS# CH5009)

-         0.7 M KCl solution (52 g KCl in 1 L reagent water)  - WHAT ABOUT 3 M KCl - DID WE USE 0.7 M IN THE PAST?

Stock standard solutions (1 L)

-         0.1 M borax solution (38.1 g borax in 1 L reagent water)

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-         0.5 M Na₂CO₃ (53.0 g sodium carbonate in 1 L reagent water)

Standard solutions (100 mL)

-         5 mM alkalinity (pipet 2.5 mL 0.1 M Na₂CO₃ into 97.5 mL 0.7 M KCl)

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-         100 mM alkalinity (pipet 10 mL 0.5 M Na₂CO₃ into 90 mL 0.7 M KCl)

Main instrument panel

Instrument calibration

To ensure accuracy of sample measurements, the titrator settings must be optimized. Calibration of the system includes calibrating the electrode, selecting a dispensing rate program and calculating a standard ratio.

Calibrating the electrode

Before the titrator an electrode can be used to measure samples, the electrode it must be calibrated against pH buffers in the range expected in samples. Generally, calibration at pH 4, 7 and 10 covers the necessary range.

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1. Make sure the water bath temperature is set to 25°C. Select Calibrate Electrodes from the main Alkalinity interface.
2. Enter your range of buffers (4, 7, 10).
3. Select your Drift Span. The default drift span is 30.
4. Place 3 mL of the first buffer solution in the vessel. Add stir bar. Remove the electrode from the storage solution, rinse with DI water, and blot dry with a Kimwipe. Do not rub the electrode, as this can cause a static charge. Insert the electrode tip into the titration vessel (not touching the bottom of the cup or the stir bar). Confirm that the frit is in the solution.
5. Select Cal 1 and then Start. Measure until the drift gets close to 0.0. Usually approximately 500 seconds will be adequate. Select Stop when satisfied with measurement.
6. When finished, clean vessel and the electrode.
7. Repeat steps 4–6 with each calibration buffer, selecting Cal2 and Cal3 when appropriate.
8. When all three buffers have been run, the slope value of the regression curve should be close to –59 pH/mV. Select OK-Save to save the calibration.

Dispensing rate

The rate at which the titrator dispenses the acid into the sample can be adjusted according to the expected alkalinity value. Higher alkalinities may require faster dispensing rates. The dispensing rate can be selected from a list of predetermined programs , or a new dispensing rate program can be created.

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1. Set your Stability Criteria for each step of the program: Measurement continues until Stability Criteria (mV/s) is satisfied.
2. Select your Increment for each mV level (initial to 150, 150 to 220 and 220 to 240): How much acid is added in each increment.
3. Set the Time Out for each step of the program: Seconds until rate program times out if Stability Criteria is not satisfied.
4. Save To File.

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Standard ratio

Calculating the standard ratio (estimated vs. actual alkalinity, “fudge factor”) for the anticipated range of alkalinity values accounts for measurement error in acid strength. Standard ratio can be calculated using borax solution, sodium bicarbonate solution , or IAPSO standard seawater, as necessary, to most closely match alkalinity values (within 5 mM, to preserve the first-order transfer function) of the unknown samples. Generally, IAPSO standard seawater is used to establish this ratio, and additional calibration standards are used if samples deviate >5 mM from the alkalinity of IAPSO (~2.325 mM). It is good practice to have IAPSO, 20 mM and 40 mM standard ratio corrections calculated before arriving at the first site. This prepares you for alkalinities up to 40 mM.

The measurement is repeated until at least 3 consistent measurements values are obtained within 5% of actual value for each standard:

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-         40 mM standard = 38–42 mM

Make sure to select a correct dispensing rate program for the standard in question. You can access the rates by selecting Edit Rates from the main alkalinity interface.

To start creating a standard ratio correction, select STANDARDS from the main alkalinity interface.

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1. Select the three measurements (or however many were done in the prior step) you want to average and click Average.
2. The window to the right shows the next step to in which you can save the new standard ratio to a new name correction or replace a prior namean old one. Usually we save as a new ratio (e.g. 371_13august). The window showing the name creation is not shown.
3. Click Done.
   
   

   To select a standard ratio for subsequent measurements go to Setup in the main alkalinity interface.

   
   
   

This window also shows where to set the electrode calibration values, the path to the datalog file, the default setting for the Drift Span, and where to select the standard ratio correction.

To select a saved standard ratio correction, double-click on a value in the listit.

Measuring samples

The system is now calibrated, dispensing rates selected (generally start with the slowest rate, assuming that alkalinity will be around the value of IAPSO) and standard ratio selected (again, generally start with the IAPSO standard ratio and adjust accordingly to what is measured in the samples).

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