SOP of TOC Analyzer

Standard Operation Procedure of

Total Organic Carbon Analyzer

In Prof. Wyman’s Laboratory 701

This is a simplified instruction of the operation when the catalyst and others work well. More detailed instruction and troubleshooting could be found in the User’s Manual.

** The liquid sample TOC ranges from 0-400ppm; solid sample (dry weight) 0-100 mg with TOC 40-60% currently. To quantify samples out of this range, further equilibrium of the catalyst and new calibration will be needed.

0. The check list for both liquid and solid samples analysis before you start:

a. To fill the Cooler Drain Container with Water. (Do not bend drain tubing, as this may prevent drain discharge.)

b. To fill the Humidifier with Water c. To prepare Dilution Water and needle rinsing waterd. To prepare Hydrochloric acid (2N for NPOC and TC)e. To empty waste containerf. To check Oxygen pressure (at least 100 psi)

Figure 1. Humidifier, Dilution Water and needle rinsing water, and waste container from left to right

Prepared by Taiying Zhang in August 2010 Page 1

1. Liquid sample analysis

I. Standard and Sample preparation

a. Make the standard glucose solution with TOC 400 ppm. This could be prepared with 0.1% glucose standard solution by dilution number 10.

b. Estimate the carbon content in the liquid solution based on the amount of biomass dissolved in the solution and determine the dilution number.

c. Use DI water to dilute the solution with pipet and balance into the dry and clean sample vials with the volume of 40 ml.

d. Load the samples into the autosampler as shown in middle of Figure 1.

II. Sample Analysis

a. Start. Start TOC-Control V from the Windows Start menu, and click the Sample Table Editor button. (The Sample Table Editor can also be started directly from the Windows Start menu and from the shortcut icon created on the desktop.)

The Sample Table Editor application starts up.


b. Creating a Sample Table.1. Click in the Sample Table tab of the file viewer, or click on the toolbar.

The Select H/W Settings window is displayed.

2. Select the System to be used and enter a comment if necessary.3. Click OK. A new Sample Table is created, and opened in the Sample

Table Editor.

c. Creating a Calibration Curve File.A calibration curve file is created to set the analysis parameters for measuring known standard solutions and generating a calibration curve.

1 Click New in the Calibration Curve tab of the file viewer. (The Calibration Curve Wizard (Page 1) System Information page can


also be displayed by selecting File – New – Calibration Curve.The Calibration Curve Wizard (Page 1) System Information page is displayed.

2 Select the system configuration to be used.

3 Click Next. The Calibration Curve Wizard (Page 2) Calibration Curve Type page is displayed.


4 Enter the type of calibration curve. Note: Dilution cannot be performed for IC measurement with the TOCVCPN. Since Div. Standard Solutions / Fixed Dilution and Div.Standard Solutions (auto correction of dilution factor) are not enabled, select Dilution from Standard Solution.

5 Click Next. The Calibration Curve Wizard (Page 3) Analysis Information page is displayed. Analysis type shall be the same as that of the samples to be


analyzed.

6 Enter the basic analysis parameters.

7 Click Next. The Calibration Curve Wizard (Page 4) Calibration Measurement Parameters page is displayed (default settings).Suggested No. of injection is 3/5 for higher accuracy. The unit shall be the same as


that of the samples to be analyzed. Suggested unit is ppm.

8 Enter the advanced parameters. Depending on the Analysis type, some items may not be displayed. Note: Refer to the following table to ensure that the concentration does not exceed the maximum concentration specified for the respective analysis type. If the concentration exceeds the maximum value, the instrument performance may be adversely affected.



9 Click Next. The Calibration Curve Wizard (Page 5) Calibration Points List page is displayed.

10 Enter the advanced parameters for each calibration point. Depending on the settings, some items may not be displayed.

11 Change the calibration point parameters as necessary using the Edit Calibration Point Parameters dialog box. Depending on the settings in the Calibration Curve Wizard (Page 2) Calibration Curve Type page, the contents of the Edit Calibration Point Parameters dialog box may differ. Dilution from Standard Solution is the suggested method.


The Edit Calibration Point Parameters dialog box is displayed as follows if the dilution setting is Div. Standard Solutions (auto correction of dilution factor).

12 Click OK. The Calibration Curve Wizard (Page 5) Calibration Points List page is displayed.

13 Click Next


14 Enter the remaining parameters. Suggest to use the default settings.

15 Click Finish. The calibration curve file is saved.

d. Creating a Method.1 Click New in the Method tab of the file viewer. The Method Wizard (Page 1)

System Information page is displayed. The Method Wizard (Page 1) System Information page can also be displayed by selecting File – New – Method.


2 Select the system to be used.

3 Click Next.The Method Wizard (Page 2) Analysis Information page is displayed.

4 Enter the basic method information.


5 Click Next. The Method Wizard (Page 3) Calibration Curves page is displayed.

6 Select the calibration curve files that will be incorporated into the method. Up to 3 calibration curve files can be selected. If multiple calibration curve files are selected, the software selects the most suitable calibration curve during the analysis. For information on this function, refer to the following page.

7 Click Next.


8 Set the advanced analysis parameters. Depending on the Analysis type setting, some items may not be displayed.


9 Click Next. The Method Wizard (Page 5) Peak Time Parameters page is displayed.

10 Enter the peak detection parameters.

11 If there is a Next button at the bottom of the page, click it and repeat this procedure from step 6. Note: If the Analysis type is one of the following TC, IC, NPOC, POC or TN, a Finish button will be displayed at the bottom of the page. In this case, proceed to step 12. The other analysis types consist of combinations of the above five types. For example, TOC is a combination of TC and IC. If there are any analysis types for which the parameters have not been set, the parameters pages are displayed so the items can be set. When all of the parameters are entered for all of the analysis types, the Finish button is displayed at the bottom of the page.

12 Click Finish. The method file is saved.


e. Editing the Sample Table.

1. Insert the calibration curve (standard solutions) into the Sample Table. Drag the calibration curve file from the Calibration Curve tab of the file viewer.

2. Insert the unknown samples into the Sample Table. Drag the method file from the Method tab of the file viewer.

When analyzing multiple samples using the same conditions, the inserted sample can be reproduced by copying and pasting. Select the inserted sample, right-click in the cell at the left end of the row, and click Copy.

Select the rows in the Sample Table corresponding to the number of samples to


set, right-click in the cell at the left end of the row, and click Paste.


3. Click Vial number in the Sample Table.

4. Enter the vial numbers. Enter a number in a Vial column cell, click on the lower right part of the cell, and drag downward to enter a series of sample vial numbers all at once.

5. Click OK to close the window and automatically set all of the vial numbers in the Sample Table.

f. Run the Samples Analysis1 Open the Sample Table, and connect to the Instrument by clicking

Connect. Turn on carrier gas (oxygen 40 psi)

The ready state of the instrument is shown at the right end of the toolbar. Approximately 30 - 40 minutes are required for the temperature of the furnace to rise and the baseline to stabilize.


2 Check the background. 3 Run the analysis by clicking Start.

Select the procedure to be performed when the analysis sequence is complete.• Keep running: The instrument remains in the Ready state at the completion of the analysis sequence even after analysis is completed.• Shut down instrument: The instrument automatically turns off at the completion of the analysis sequence.• Sleep: The instrument enters the sleep state, and restarts at a specified date and time.Suggest to keep running.

4 Click Start to begin the analysis sequence. 5 View and Output the Analysis Results: after a peak appears, click to open the

Sample window.


The sample window is displayed. Each of the sample analyses can be reviewed.

6 Output to a File. Click File – Ascii Export – ASCII Export Norm(Meas Data Only) to output the contents of the Sample Table in text format. The file that is output can be opened in a text editor or Microsoft Excel to view the content

7 Ending AnalysisClick Shutdown.


Select the appropriate shutdown process.• Shut down instrument: The instrument power turns off after about 30 minutes.• Sleep: The instrument enters a sleep state, and restarts automatically at a specified date and time.Suggested to leave it on unless it will be idle for longer than two weeks or power outage.


1I. Solid sample analysis** Solid sample analysis includes two modules: TC and IC, which require different treatments of sample boats and Quartz-glass filter paper.Note: Due to the potential loss of crystal solid during the combustion, recommend to use the standard solution other than solid, especially without Quartz-glass filter paper. The stand used to hold sample boats during analysis should be made of an inorganic material, such as ceramic, glass, or metal, with a surface free from contamination.

a. Sample Boats, Measurement Tools, and Quartz-glass Filter Paper Heat the sample boats in a furnace to oxidize any carbon content. Use an electric furnace of the type normally used in a laboratory. Note: Tweezers are supplied to handle sample boats. Heat the tip of the tweezers that contacts the sample boat to red hot in the furnace or with gas burner to oxidize any attached carbon

Procedure for TC Analysis1. Heat the sample boat in the furnace at approximately 900°C for 20 minutes. Heatthe quartz-glass filter paper in the furnace at approximately 600°C for 20 minutes.2. Store the heat-treated sample boat, quartz glass filter paper and tweezers in aclean container or case.a. Sample Preparation Using a new sample boat for each sample is recommended. However, a sample boat may be reused if the sample analyzed does not contaminate, modify, or degrade the sample boat material. Do not reuse the quartz-glass filter paper.

Sample Boat Cleaning Procedure (TC)1. Remove as much of the sample remaining in the used sample boat as possible.2. Use a brush or the tip of a scraper to scrape off pieces adhering to the bottom of the

sample boat.3. Soak the boat in approximately 2M sulfuric acid or hydrochloric acid for about 10

minutes.4. Wash under running tap water for several minutes.5. Rinse the tap water off the boat with de-ionized or distilled water. Dry the boat.6. Bake the dried sample boat in a furnace at approximately 900°C for 20 minutes.

Note: • Evaluate whether a sample boat can be reused by running a blank test (an analysis with no sample in the boat) to determine the amount of residual carbon.• For some samples, it may not be possible to reuse the sample boat even after performing the above treatment procedure. In these cases, use a more appropriate method to remove the residual material from the sample boat or use a new sample boat.

Ceramic FiberCeramic fiber can be reused in cases where a pure product, such as glucose, is measured as the standard.Although ceramic fiber can be treated according to the above method to remove any contamination, the use of new ceramic fiber is recommended because it is relatively

The combustion-oxidation reaction (TC analysis) and the carbonate acidification reaction (IC analysis) are more efficient when the sample particles are smaller in size.


Drying the SampleSolid samples may be weighed and measured directly after sampling or they can be dried before they are weighed and measured.The following three methods are used to dry samples before weighing.1) heating with an electric isothermal dryer2) air-drying over a spread-out sample3) freeze dryingSelect the appropriate method for the analytical objectives.

Note: Volatile organic components contained in a sample may be lost during drying.

Solid SamplesWeighing accuracy is directly reflected in the accuracy of the analysis results. To reduce errors associated with weighing, use an analytical balance or microbalance to carefully weigh the sample directly into a tared heat-treated sample boat.Note: • Reduce the effects of poor distribution, which commonly occur with solid samples.

• Reduce the weighing error.• Reduce the impact of external contamination, by choosing a sample amount that will produce a result close to the upper limit of the instrument (about 30mg C).

Note: Consider the combustion characteristics of each individual sample when determining the amount of sample. Due to a lack of oxygen during combustion, samples that burn extremely rapidly tend to burn less completely with increasing sample size.

Analyzing Crystalline Samples Such as Oxalic Acid or GlucoseCover the sample boat because these samples may scatter during combustion. If part of the sample scatters out of the sample boat during combustion, artificially low and inaccurate results will be obtained.Use the supplied ceramic fiber to cover the sample. Ceramic fiber allows good ventilation and is unaffected by heat and oxygen. Fashion a long, thin cover from ceramic fiber to roughly cover the opening of the sample boat, and place it over the sample.Do not cover the sample boat for IC analyses.

Liquid SamplesThe following two sampling methods are available for liquid samples:1) Weighing the sample with a balance2) Measuring the volume of the sample with a microsyringe or pipetteNote • The maximum measurable mass of a liquid sample is 0.5g for TC and 0.3g for IC.


b. Sample table and analysisTo edit the sample table is the same as the liquid sample with ASL except the test is with SSM other than ASL and there is no vial number involved.

With SSM, the sample could be loaded one by one manually as shown in the following figures.

Note • The O-ring is easy to pull out when the lid is pushed too closely, so the nut shall be loosen enough before sliding the lid.

Figure 2.Solid sample module close (left) and open (right)The injection number and sample amount are not shown in the sample table, which was input as selecting repeat or next sample during the test.


The review and output of the results could be performed in the same way as the ASL.

IC process need be developed later since we have not tested it yet.

Procedure for IC Analysis.1. Soak the sample boat in 2 or 3M hydrochloric acid for about 10 minutes.2. Rinse well with purified water and dry in an oven.

Preparing the Ceramic FiberWhen analyzing a sample that may scatter during combustion, cut off a suitable amount of supplied ceramic fiber and cover the sample with it. Heat the ceramic fiber in the furnace, as described for the sample boat.

Heat the Ceramic Fiber1. Cut off a suitable amount of ceramic fiber for a single analysis (approx. 40 to60mg).2. Shape the ceramic fiber to about 35mm long x 10mm wide.3. Heat the ceramic fiber, as described for the sample boat.4. Use the heat-treated tweezers to insert the heat-treated ceramic fiber into aclean container or case for storage.


IC Analysis of CarbonatesAdding phosphoric acid to a carbonate during IC analysis will cause a violent reaction that may allow part of the sample to scatter outside the sample boat. Pre-moisten this type of sample with a small amount of water.


List of Authorized Users of TOC

If you name is not on this list, please contact responsible user to set up a training.

ID User name (please type) Signature Date authorized Note

1 Taiying Zhang 8-23-2010 responsible user

2 Hongjia Li 8-23-2010 responsible user

3 Deepti Tanjore(?) 8-23-2010

4 Qing Qing 8-23-2010

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Responsible users:

Taiying Zhang, 951-781-5780(o), 319-541-3484(cell), [email protected]

Hongjia Li,

To book any spot to use the TOC, please do it by google calender. If you have no access to it, please email Taiying.


mailto:[email protected]

Documents

SOP of TOC Analyzer