Online COD & BOD Analyzer – MO1000

There are several common methods to test wastewater and drinking water for organic pollutants, natural and chemical.  Chemical Oxygen Demand (COD), Biochemical Oxygen Demand (BOD) and, Total Organic Carbon (TOC) compromise the three main methods of testing water samples.  BOD and COD methods differ from TOC because they measure the amount of oxygen that is depleted by organic species in water.  Moreover, TOC is a measure of all carbon (both organic and inorganic), rather than the oxygen that is reduced by these species.  As written by a TOC manufacturer, “TOC on its own sheds no light on the oxidizability of the measured carbon or the amount of oxygen needed for its biodegradation.”  Specific to COD, it measures the reactive fraction of the TOC.  This is also known as oxidizability in the European Union.

View the full article: Comparison of COD, BOD and TOC Methods for organics, which summarizes the advantages and disadvantages of the COD, BOD and TOC methods, and compares them to the PeCOD method.

New PeCOD Analyzer orders typically include a slurry reagent starter kit providing the consumables to run the PeCOD analysis. These kits consist of Electrolyte, Calibrant, and Secondary Standard slurry reagents. Electrolyte is the reagent that is mixed with each sample, therefore it is typically the reagent to be used up first, requiring the user to purchase more from MANTECH. It is useful to know on average how many samples can be run with the electrolyte provided in the standard reagent starter kits, therefore we provide this information below.

You will need to know the color operating range of your PeCOD (Adv. Blue, Green, Yellow, or Red). If you plan to run a single analysis per sample, use the left column for 10mL total volume. If you require duplicate or triplicate analysis per sample, use the right column for 20mL total volume. Depending on how many samples are run per calibration, these numbers may vary.

The PeCOD Analyzer performs advanced oxidation on a small volume of sample. As the reaction proceeds, electrical charge is generated proportional to the oxygen being consumed. The PeCOD analyzer captures this generated charge, plotting the output current from the reaction over time as shown below. The area under the curve generated by plotting current over time is proportional to the COD of the sample. A blank charge is also determined for each sample, and subtracted from the total charge to ensure accuracy.

View the detailed overview of PeCOD technology and calculations here.

The primary driver of the peCOD method chemistry is advanced oxidation induced by photocatalysis with Titanium Dioxide (TiO2). Pure TiO2 is only photo-active at wavelengths below 380 nm. This is because a certain amount of light energy is required to bump the electrons around and cause the behaviors that we associate with photocatalysis. The UV LED in the PeCOD® COD Analyzer operates at a peak wavelength of 365 nm, with a minimum 360 nm and maximum 370 nm, ensuring that efficient photocatalysis is achieved.

pH Range: 4.0 – 10.0  (after mixing with electrolyte)

The peCOD method requires that the pH of a sample AFTER being mixed with electrolyte must be between 4 – 10. To determine if a sample must be pH-adjusted, mix the sample with peCOD electrolyte at the proper mixing ratio for your COD range, then test the pH of the mixture.

For example, the sample may have a pH of 3.0, but then after preparing with electrolyte, the pH is in the required range, therefore, it is acceptable for immediate peCOD measurement.

If samples have been preserved in acid, they should be neutralized using sodium hydroxide prior to analysis to avoid a low reading, as well as damage to the sensor. When the sample pH is below 4, the photocatalytic oxidation at the TiO2 sensor is affected, leading to poor reproducibility and charge values below theoretical expectation. Below a pH of 2, the TiO2 displays instability. When the pH is above 10, the charge measured for the reference and sample solution yield lower than expected values, again caused by interference at the TiO2 sensor. Sulphuric acid should be used to lower the pH of samples with a pH of 10 or more.

The PeCOD electrolyte solution is mainly composed of a low-concentration lithium nitrate solution. The PeCOD calibrant and check standard solutions supplied by MANTECH are composed of sorbitol.  These solutions contain a trade recipe preservative that allow for the longer shelf life, compared to solutions prepared manually. Calibrant and check standard solutions prepared manually, following the PeCOD Standard Recipe, can be used for up to two weeks.

View the PeCOD electrolyte slurry SDS here.

View the PeCOD calibrant slurry SDS here.

View the PeCOD QC check standard slurry SDS here.

View the PeCOD blank slurry SDS here.

There is a strong correlation between the PeCOD COD results and the dichromate COD results. To determine this, the two methods were compared vs. the theoretical oxygen demand (ThOD) for 34 organic species. See MANTECH’s technical bulletin for more information on the study.

Calibrations are comprised of 6 different stages. The first stage is called the “Normalization Phase” and lasts 100 seconds. During this time, the LED strength is adjusted to maintain a baseline electrical current of 20 mA. This is performed on the blank solution, containing range specific electrolyte and COD free deionized water. Once the LED is set, oxidation of the blank solution will occur. This is comprised of 3 stages, visualized by 3 distinct curves. The stages are known as the Burn-In, Pre-Burn, and Oxidation of port B. The blank acts as a zero reference for the calibration based on the charge generated from the DI and electrolyte mixture. The area under the curve is used to quantify charge. Once the Port B stages have completed, the Port A stages will begin. The calibrant and electrolyte mixture is introduced across the TiO2 sensor, where similar Pre-Burn and Oxidation curves are generated. The concentration of the calibrant is determined based on the sample COD/BOD range. Once the specified number of calibrations have completed, the calibrant solution can be run as a sample (referred to as a QC check). It is expected that the COD result will be + / – 5% of the standard COD/BOD value. To view an example of the stages of a PeCOD® calibration, view our video &list=PLLCp3SOh3VUis3EGUiMonY7KV28v4bwGM&index=7″>here.

On average, the cost per sample can range anywhere from $2.44-$3.00 per sample. The cost per sample varies depending on the COD/BOD range and the number of samples analyzed, as this affects consumable usage such as calibrant, electrolyte and sensors. In general, the cost per sample decreases with an increase in the number of samples. There are several reasons for this, one being that the sensor should be replace monthly, therefore running more samples per month will yield a better return on sensor usage. In addition, the PeCOD® requires a daily calibration; by running more samples per calibration users save on consumable costs associated with calibrant. There are no disposal costs for the PeCOD, whereas disposal costs accumulate via the traditional dichromate method with every sample vial.

*All prices in USD

The following tables summarize the impact of a range of common inorganic anions and cations on the determination of COD using the PeCOD® technique. You can download this FAQ as a pdf document at this link.

For each inorganic species, solutions containing 0, 20, 50, 100, 250, 500 ppm (by mass) of the anion or cation, 60ppm COD (as sorbitol) and 1M LiNO3 (containing 20ppm COD spike) were prepared and analyzed, unless otherwise stated. Therefore, the below ion concentrations represent the concentration IN THE CELL (i.e. if analyzed in a different range, the interference levels may vary due to different electrolyte dilution effects).