Shimadzu TOC-L Analyzer with TNM-L and SSM-5000A
1 Purpose
This SOP describes the general operation, calibration, maintenance, and shutdown of the Shimadzu TOC-L total organic carbon analyzer and its companion modules: the TNM-L Total Nitrogen Module and the SSM-5000A Solid Sample Module. The TOC-L uses a 680 C combustion catalytic oxidation method, which is one of two principal approaches to TOC analysis (the other being wet chemical oxidation with persulfate); the high-temperature combustion method is preferred for environmental samples because it more completely oxidizes refractory organic matter such as humic substances (Sharp, 1993; Sugimura & Suzuki, 1988).
All instrument control is performed through the LabSolutions TOC software on the dedicated computer.
This SOP covers the instrument itself. For application-specific sample preparation, measurement modes, and calculations, refer to the relevant analytical SOPs:
- SOP-L311 Dissolved Organic Carbon in Water (NPOC)
- SOP-L407 Total Carbon (Soils) (SSM)
- SOP-L409 Microbial Biomass Carbon (CFE extracts)
- SOP-L418 Water-Extractable DOC (soil extracts)
2 Scope
- Applies to: All use of the Shimadzu TOC-L analyzer, TNM-L module, SSM-5000A module, and ASI-L autosampler in the EA Program laboratory, operated through LabSolutions TOC software
- Does not apply to: Manual or standalone operation without computer control; instruments at other institutions; application- specific sample preparation or data interpretation (see analytical method SOPs)
- Location: EA Program analytical laboratory, SGM 133
3 Responsibilities
| Role | Responsibility |
|---|---|
| Lab PI | Authorize instrument access, approve maintenance |
| Instrument Manager | Perform preventive maintenance, replace consumables, manage software updates |
| Trained Personnel | Operate the instrument per this SOP, log all runs |
| New Students | Complete training before independent use |
4 Definitions
- Catalytic combustion: Oxidation of organic carbon in the sample at 680 °C over a platinum catalyst in the presence of oxygen; the standard method used by the Shimadzu TOC-L for liquid samples.
- Dissolved organic carbon (DOC): Organic carbon in a water or soil extract sample that passes through a 0.45 µm filter; the NPOC method is the standard approach for DOC measurement.
- IC (inorganic carbon): Carbon present as carbonate, bicarbonate, and dissolved CO2; removed by acidification and sparging before NPOC measurement.
- NDIR detector (non-dispersive infrared detector): A detector that measures CO2 concentration by its absorption of infrared light at ~4.3 µm; the detection element in the Shimadzu TOC-L.
- NPOC (non-purgeable organic carbon): The organic carbon fraction remaining in a sample after acidification and sparging to remove inorganic carbon and purgeable volatile organic carbon; the operationally defined DOC measured by the Shimadzu TOC-L.
- SSM-5000A: The Shimadzu Solid Sample Module that combusts dried, ground solid materials (soils, sediments, plant tissue) directly in ceramic boats at up to 900 °C for total carbon analysis.
- TC (total carbon): The sum of all carbon forms (organic and inorganic) in a sample; measured by direct combustion without acidification.
- TOC (total organic carbon): TC minus IC; in practice, usually determined as NPOC for environmental samples.
- TON (total organic nitrogen): Total nitrogen minus inorganic nitrogen; measured simultaneously by the TNM-L module using chemiluminescence detection of NO produced during combustion.
5 Safety and Hazards
- Thermal: The combustion furnace operates at 680 C in liquid analysis mode and up to 900 C in SSM mode. Ceramic boats, combustion tubes, and furnace surfaces can cause severe burns.
- Chemical: Hydrochloric acid (2 M HCl) is used for acidification and inorganic carbon sparging. Phosphoric acid (25%) is used as the IC reagent. Avoid skin and eye contact with both.
- Compressed gas: The instrument requires high-purity carrier gas (air or oxygen) supplied from a pressurized cylinder at approximately 200 kPa. Follow all compressed gas safety procedures (National Research Council, 2011).
- Electrical: The instrument operates on high-voltage mains power. Do not open instrument panels or attempt internal repairs.
- Ozone: The TNM-L chemiluminescence detector uses an ozone generator. The instrument vents ozone through an internal decomposer, but ensure that the exhaust line is connected and unobstructed. If an ozone odor is detected, shut down the TNM-L and ventilate the area.
5.1 Required PPE
5.2 Emergency Procedures
For acid splashes, flush the affected area with water for at least 15 minutes. For burns from hot surfaces, apply cool running water and seek first aid. If ozone is detected, shut down the TNM-L, open windows, and leave the room until the odor dissipates. Refer to SOP-L002 Laboratory Safety and SOP-L003 Hazardous Materials Handling.
6 Instrument Description
6.1 System Overview
The Shimadzu TOC-L is a combustion catalytic oxidation analyzer that quantifies carbon (and, with the TNM-L, nitrogen) in liquid samples (Shimadzu Corporation, 2019b). The system in the EA Program laboratory consists of four main components:
- TOC-L analyzer: Combusts liquid samples at 680 C over a platinum catalyst. The resulting CO2 is measured by a non-dispersive infrared (NDIR) detector. The analyzer supports multiple measurement modes (TC, IC, TOC, NPOC, POC).
- TNM-L Total Nitrogen Module: Measures total nitrogen (TN) simultaneously with carbon analysis. Nitrogen compounds in the combustion gas are converted to nitric oxide (NO), which is detected by a chemiluminescence detector after reaction with ozone (Shimadzu Corporation, 2019a). The TNM-L operates in parallel with the NDIR carbon detector, so carbon and nitrogen data are acquired from the same injection.
- SSM-5000A Solid Sample Module: Accepts solid samples in ceramic boats for direct combustion at up to 900 C. Connects to the TOC-L for CO2 detection. The TNM-L is not used during SSM operation.
- ASI-L Autosampler: Holds up to 93 sample vials (8 mL or 40 mL) for unattended sequential analysis of liquid samples. Includes an automated rinse function between injections.
6.2 Measurement Modes (Liquid Samples)
| Mode | Full Name | What It Measures |
|---|---|---|
| TC | Total Carbon | All carbon (organic + inorganic) by direct combustion |
| IC | Inorganic Carbon | Carbonate/bicarbonate carbon by acidification and sparging only |
| TOC | Total Organic Carbon (by difference) | TOC = TC - IC; requires two sequential measurements |
| NPOC | Non-Purgeable Organic Carbon | Sample is acidified and sparged to remove IC, then combusted; the most common mode for routine analysis (APHA et al., 2012, Section 5310B) |
| POC | Purgeable Organic Carbon | Volatile organic carbon recovered during the sparging step; POC = TC - (NPOC + IC) |
| TN | Total Nitrogen (TNM-L) | All nitrogen species measured simultaneously with any carbon mode |
6.3 Detection Principles
The TOC-L and TNM-L rely on two detectors operating in series on the same combustion gas stream:
- NDIR detector (carbon): Infrared absorption by CO2 is proportional to the mass of carbon injected. The detector is selective for CO2 and insensitive to other combustion gases.
- Chemiluminescence detector (nitrogen, TNM-L only): NO in the combustion gas reacts with ozone (O3) to produce excited NO2*, which emits light as it returns to the ground state. The emitted light intensity is proportional to the mass of nitrogen injected (Walsh, 1989).
7 Required Materials
7.1 Instrument Components
| Component | Notes |
|---|---|
| Shimadzu TOC-L analyzer | With combustion furnace and NDIR detector |
| TNM-L Total Nitrogen Module | Chemiluminescence detector for TN |
| SSM-5000A Solid Sample Module | For direct combustion of solid samples |
| ASI-L Autosampler | 93-position; 8 mL or 40 mL vials |
| Dedicated computer | Running LabSolutions TOC software |
| Carrier gas (high-purity air) | Regulated to 200 kPa (or per manual) |
| Exhaust tubing | Connected to fume hood or building exhaust |
7.2 Consumables
| Item | Notes |
|---|---|
| TC catalyst (Pt on alumina beads) | Replace when blanks rise or sensitivity drops; typical life 3,000–5,000 injections |
| IC reagent (25% phosphoric acid) | For IC/NPOC acidification; check level weekly |
| Combustion tubes (quartz) | Inspect monthly; replace if cracked or discolored |
| Ceramic sample boats | For SSM; pre-combust at 900 C before first use |
| Halogen scrubber | Replace every 6–12 months or per manufacturer schedule |
| Dehumidifier / moisture trap | Drain weekly; more often in humid weather |
| Autosampler vials and septa | Acid-washed for trace-level work; use pre-combusted glass vials for NPOC |
| Syringe needle (instrument syringe) | Inspect for bends or clogs; replace as needed |
7.3 Calibration Standards
| Standard | Use | Preparation |
|---|---|---|
| Potassium hydrogen phthalate (KHP) | Primary TC/NPOC calibration | 2.125 g/L = 1,000 mg C/L stock (APHA et al., 2012) |
| Sodium bicarbonate / sodium carbonate | Primary IC calibration | See Shimadzu manual for concentrations |
| Potassium nitrate (KNO3) | Primary TN calibration (TNM-L) | 7.218 g/L = 1,000 mg N/L stock |
| Deionized water (18.2 MOhm) | Blanks, dilutions, and standard preparation | From Milli-Q; verify TOC less than 0.05 mg/L |
8 Procedure
All operations described below are performed through LabSolutions TOC. Do not adjust furnace temperature, gas flow, or other parameters using the instrument front panel unless directed by the instrument manager during troubleshooting.
8.1 Instrument Startup (Cold Start)
A cold start applies when the instrument has been fully powered down (furnace off, gas closed). Allow approximately 60 minutes from power-on to running samples.
- Open the carrier gas cylinder valve. Verify the regulator output pressure is set to 200 kPa at the instrument inlet. Check for leaks at all fittings (listen for hissing; apply leak-detection solution if uncertain).
- Verify that the exhaust line from the TNM-L ozone decomposer is connected and routed to the fume hood or building exhaust
- Check consumable levels:
- IC reagent bottle (25% phosphoric acid): refill if below the minimum line
- Dehumidifier / moisture trap: drain if water is visible
- Rinse water reservoir on the ASI-L: fill with fresh deionized water
- Power on the TOC-L main unit using the switch on the right side panel
- If the TNM-L is needed, power on the TNM-L using the switch on its rear panel
- Power on the ASI-L autosampler
- Turn on the dedicated computer and launch LabSolutions TOC
- In LabSolutions TOC, verify that communication with all modules is established. The status bar should show “Warming Up”
- Wait for the furnace to reach 680 C (approximately 20–30 minutes). The software status changes from “Warming Up” to “Ready”
- Wait for the TNM-L ozone generator and chemiluminescence detector to stabilize (approximately 30–45 minutes after power-on; the TNM-L status indicator changes to “Ready”)
- Run 3–5 injections of deionized water as system conditioning blanks to flush the injection port, syringe, and combustion tube. Discard these results.
- Run 3 additional deionized water blanks and verify baseline stability: TC blank values should be below 0.1 mg/L C; TN blank values should be below 0.1 mg/L N
8.2 Instrument Startup (From Standby/Sleep)
When the instrument is in standby mode (furnace at temperature, gas flowing, software idle), startup is faster:
- Launch LabSolutions TOC if not already open
- Verify that the status bar shows “Ready” for the TOC-L and (if applicable) the TNM-L
- Check the IC reagent level and drain the moisture trap
- Fill the ASI-L rinse reservoir with fresh deionized water
- Run 3 deionized water conditioning blanks. If blanks are below 0.1 mg/L C and 0.1 mg/L N, proceed to calibration.
8.3 Standby and Sleep Modes
Choose the appropriate idle mode based on how soon the instrument will be used again:
| Mode | Furnace | Carrier Gas | TNM-L | When to Use |
|---|---|---|---|---|
| Active standby | 680 C (on) | Flowing | On | Next run within 24 hours |
| Reduced standby | 680 C (on) | Flowing | Off | Next run within 2–3 days; no TN needed |
| Sleep | Off (cooling) | Closed | Off | No runs planned for 3+ days |
| Full shutdown | Off (cold) | Closed | Off | Extended break, maintenance, or relocation |
8.3.1 Entering Active Standby
- After the final sample, run 3–5 deionized water blanks to flush the system
- Leave the furnace at 680 C and the carrier gas flowing
- Leave the TNM-L powered on
- Empty the autosampler rack and cover with a dust cover
- The instrument manager may set the software to a low carrier gas flow rate overnight to conserve gas (consult the manual for the minimum flow that maintains a positive purge of the combustion tube)
8.3.2 Entering Reduced Standby
- Flush the system with deionized water blanks as above
- Power off the TNM-L (rear panel switch). This extends the ozone decomposer lifetime.
- Leave the TOC-L furnace at 680 C and gas flowing
- Cover the autosampler
8.3.3 Entering Sleep Mode
- Flush the system with deionized water blanks
- Power off the TNM-L
- In LabSolutions TOC, initiate a furnace cooldown (or simply power off the TOC-L)
- Once the furnace temperature drops below 200 C (approximately 90 minutes), close the carrier gas cylinder valve
- Power off the ASI-L
- Close LabSolutions TOC and shut down the computer
8.3.4 Full Shutdown
Follow the Sleep Mode steps, then:
- Allow the furnace to cool to room temperature
- Disconnect the carrier gas line if the instrument will be moved or serviced
- Empty the IC reagent bottle if the shutdown will exceed 30 days (phosphoric acid can corrode the reagent lines over long idle periods)
- Empty the ASI-L rinse reservoir to prevent microbial growth
- Cover the instrument with a dust cover
8.5 Calibration
Calibrate at the start of each analytical session or whenever the method, measurement mode, or concentration range changes. Carbon and nitrogen calibrations are built independently but can be run simultaneously if both detectors are active.
8.5.1 Carbon Calibration
- Prepare a multi-point calibration series from KHP dissolved in deionized water. Choose concentrations that bracket the expected sample range (e.g., 0, 1, 5, 10, 25, 50, 100 mg/L C). Prepare fresh daily or from a refrigerated stock per SOP-L020 (APHA et al., 2012).
- For IC calibration, prepare standards from sodium bicarbonate/sodium carbonate in deionized water
- In LabSolutions TOC, open the Method Editor and select the measurement mode (e.g., NPOC, TC, or TC-IC)
- Enter calibration standard concentrations in the Calibration window
- Load standards into the autosampler in order of increasing concentration
- Run the calibration sequence. The software will perform replicate injections (typically 3) of each standard and fit a regression
- Verify that r2 \(\geq\) 0.999 and that each standard back- calculates to within 10% of its nominal value (15% at the lowest standard is acceptable)
- Save the calibration curve
8.5.2 Nitrogen Calibration (TNM-L)
- Prepare a multi-point calibration series from KNO3 dissolved in deionized water (e.g., 0, 0.5, 1, 5, 10, 25, 50 mg/L N)
- In the Method Editor, confirm that TN measurement is enabled alongside the carbon mode
- Enter TN calibration concentrations in the Calibration window
- The TN calibration runs simultaneously with the carbon calibration if both are loaded in the same sample table; otherwise, run the TN standards as a separate sequence
- Verify that r2 \(\geq\) 0.999 for the nitrogen curve
- Save the calibration curve
8.6 Setting Up an Analytical Run (Liquid Samples)
- In the Method Editor, confirm the measurement mode, injection volume, number of replicate injections, and (for NPOC mode) sparge time and acid volume
- In the Sample Table, enter the run sequence:
- Calibration verification standard (mid-range) as the first sample
- Instrument blanks (deionized water) at the beginning, every 10–15 samples, and the end of the run
- Method blanks appropriate to the application (e.g., 0.5 M K2SO4 for soil extracts; consult the analytical method SOP)
- Sample vials in the order they are loaded in the autosampler
- A final calibration verification standard
- Set the dilution factor for each sample if applicable
- Verify that autosampler vial positions in the Sample Table match the physical rack positions
- Confirm that the rinse reservoir on the autosampler is filled with deionized water
- Click Start to begin the sequence
The software default is 3 replicate injections per sample. If the coefficient of variation (CV) among replicates exceeds 2%, the software can be configured to add up to 2 additional injections automatically (set in Method Editor under “Maximum Injections”). The outlier replicate is excluded from the reported mean.
8.7 Setting Up a Solid Sample Run (SSM-5000A)
- In LabSolutions TOC, switch to SSM mode
- Pre-combust ceramic boats at 900 C in a muffle furnace (SOP-L111) to remove residual carbon. Allow boats to cool in a desiccator.
- Weigh the solid sample into a clean ceramic boat. Record the mass to 0.01 mg.
- In the Sample Table, enter the sample ID, boat number, and sample mass
- Place the ceramic boat on the SSM sample port and push it into the furnace when prompted by the software
- The SSM combusts the sample; evolved CO2 flows to the TOC-L NDIR detector
- The software reports carbon content in mg C or as a percentage of sample mass
The TNM-L chemiluminescence detector is not used during SSM solid sample analysis. Total nitrogen in solid samples requires a separate instrument (e.g., the Flash EA; see SOP-L208).
8.8 Monitoring a Run in Progress
- Use the Instrument Monitor to watch real-time peak shapes and detector baselines
- If a peak appears saturated (flat top), the sample exceeds the calibration range. Pause the run, dilute the sample, and re-queue.
- If the CV among replicate injections exceeds 2%, investigate (air bubble, particulates, insufficient sample volume) and consider re-running.
- If the system blank rises above 0.5 mg/L C or 0.5 mg/L N during a run, the combustion tube or catalyst may need replacement. Complete the current run, note affected samples, and consult Section 9.
8.9 Data Export
- After the run, open the Data Browser and review all results
- Check that calibration verification standards recovered within 90–110% of their nominal values
- Export results to CSV: File > Export, including sample ID, mode, mean concentration, SD, CV, and number of valid injections
- Save the LabSolutions TOC run file (.toc) to the instrument computer and back up to the lab network drive
- Record the run date, analyst, method, and file name in the instrument logbook
9 Quality Control
QC procedures are tailored to each analytical method and are specified in the relevant method SOP. The following instrument-level QC applies to all runs (US Environmental Protection Agency, 2009):
- System blanks (deionized water) at the start of every session must read below 0.1 mg/L C and 0.1 mg/L N
- A calibration verification standard (mid-range) must be run at the beginning and end of every sample sequence, with recovery within 90–110%
- Replicate injection CV must be below 2% for liquid samples
- All QC results are recorded in the instrument logbook and in the exported data file
- For additional QC requirements (method blanks, duplicates, matrix spikes, continuing calibration verification frequency), refer to SOP-L802 Quality Control
10 Maintenance
10.1 Routine Maintenance Schedule
| Task | Frequency | Notes |
|---|---|---|
| System blank check | Before each analytical session | |
| Drain moisture trap / dehumidifier | Weekly (more often in humid conditions) | Prevents water from reaching the NDIR detector |
| Check IC reagent level | Weekly | Refill with fresh 25% H3PO4 when below the minimum line |
| Inspect injection syringe needle | Weekly | Replace if bent, corroded, or clogged |
| Check autosampler rinse reservoir | Before each session | Refill with fresh DI water |
| Inspect combustion tube | Monthly or every 500 injections | Look for discoloration, cracks, or catalyst settling |
| Replace TC catalyst | Every 3,000–5,000 injections or when blanks rise | Pt on alumina; record replacement date |
| Replace halogen scrubber | Every 6–12 months | Prevents halide damage to the NDIR detector |
| Replace TNM-L ozone decomposer | Annually | Degraded decomposer leaks ozone into the room |
| Replace SSM combustion tube | As needed | Inspect after each batch of solids |
| Carrier gas cylinder replacement | As needed | Monitor regulator pressure; order when below 500 psi |
| Software and firmware updates | As released by Shimadzu | Coordinate with instrument manager |
10.2 Catalyst Replacement Procedure
- Allow the furnace to cool to room temperature (power off the TOC-L and wait at least 3 hours, or use the forced-air cooling function if available)
- Wearing heat-resistant gloves and safety glasses, remove the combustion tube from the furnace per the manufacturer’s procedure
- Dispose of the spent catalyst (Pt on alumina) as hazardous waste (precious metal content; collect for EH&S pickup per SOP-L006)
- Fill the combustion tube with fresh catalyst to the manufacturer’s specified depth (approximately 12 cm)
- Add a thin layer of quartz wool above and below the catalyst bed
- Reinstall the combustion tube. Reconnect all tubing and fittings.
- Restart the furnace and allow it to reach 680 C
- Run 20–30 deionized water conditioning injections to stabilize the new catalyst. Blanks should decrease progressively to below 0.1 mg/L C.
- Run a calibration verification standard to confirm sensitivity before resuming sample analysis
- Record the replacement date, catalyst lot number, and conditioning results in the instrument logbook
10.3 Combustion Tube Inspection and Replacement
- Remove the combustion tube as described in Section 9.2, step 2
- Inspect for cracks, discoloration, or accumulation of non-volatile residue on the inner walls
- If the tube is damaged, replace with a new quartz combustion tube
- Repack with catalyst and condition as in Section 9.2
10.4 Syringe and Needle Maintenance
- Remove the syringe from the autosampler or manual injection port
- Inspect the needle for bends, burrs, or corrosion
- Flush the syringe barrel with deionized water, then with dilute HCl (0.1 M), then with deionized water again
- If the syringe plunger binds or the needle is damaged, replace the entire syringe assembly
- Reinstall and run 3 deionized water blanks to verify proper function
11 Troubleshooting
| Symptom | Probable Cause | Corrective Action |
|---|---|---|
| Blank values increasing over time | Catalyst degradation; contaminated combustion tube | Replace catalyst; inspect and replace combustion tube |
| Poor replicate precision (CV > 2%) | Air bubble in syringe; particulates in sample; insufficient volume | Check syringe for air leaks; re-filter sample; verify vial volume |
| NDIR signal saturated (flat-top peaks) | Sample exceeds calibration range | Dilute sample and re-run |
| TNM-L “Not Ready” status persists | Ozone generator not warmed up; decomposer exhausted; exhaust blocked | Allow more warm-up; replace decomposer; check exhaust tubing |
| No communication with instrument | Cable disconnected; software crash; instrument not powered on | Check cables; restart software; verify power |
| Autosampler skips vials | Position mismatch; septa not pierced | Verify positions; check that septa are intact |
| SSM signal noisy or irreproducible | Boat not fully inserted; sample mass too large; residual carbon on boat | Confirm position; reduce mass; pre-combust boats longer |
| Carrier gas pressure alarm | Cylinder empty or regulator set incorrectly | Replace cylinder; adjust regulator |
| Moisture trap fills rapidly | High humidity; furnace tube leak | Drain more frequently; inspect tube fittings for leaks |
| IC reagent not dispensing | Reagent bottle empty; tubing kinked or clogged | Refill bottle; inspect and replace tubing |
12 Waste Disposal
| Waste Type | Disposal Method |
|---|---|
| Acidified liquid waste (HCl/H3PO4) | Neutralize and dispose per SOP-L006 |
| Spent TC catalyst (Pt on alumina) | Collect for EH&S hazardous waste pickup (precious metal) |
| Used combustion tubes (quartz) | Standard glass waste (broken-glass box) if not contaminated |
| Used ceramic boats (SSM) | Clean and reuse, or standard trash |
| Autosampler rinse water | Drain |
| Calibration standard waste | Aqueous waste; drain if dilute |
13 References
15 Training Record
Before operating this instrument independently, personnel must:
- Read this SOP in full and the relevant sections of the Shimadzu TOC-L, TNM-L, and SSM-5000A user manuals
- Complete SOP-L002 Laboratory Safety and SOP-L003 Hazardous Materials Handling training
- Observe a trained operator perform a complete session: cold start, calibration (carbon and nitrogen), sample analysis, data export, and transition to standby
- Demonstrate competence preparing calibration standards (KHP and KNO3) per SOP-L020
- Perform a supervised analytical run with acceptable QC results (blanks below 0.1 mg/L, calibration verification recovery 90–110%, replicate CV below 2%)
- Demonstrate entering and exiting standby and sleep modes
- Be signed off by the instrument manager or PI