BOD and COD Removal in Wastewater Using Hydrogen Peroxide

Hydrogen peroxide has been used to reduce the BOD and COD of industrial wastewaters for many years. While the cost of removing BOD / COD through chemical oxidation with hydrogen peroxide is typically greater than that through physical or biological means, there are nonetheless specific situations which justify the use of hydrogen peroxide. These include: Predigestion of wastewaters which contain moderate to high levels of compounds that are toxic, inhibitory, or recalcitrant to biological treatment (e.g., pesticides, plasticizers, resins, coolants, and dyestuffs); Pretreatment of high strength / low flow wastewaters where biotreatment may not be practical prior to discharge to a Publicly Owned Treatment Works (POTW); Enhanced separation of entrained organics by flotation and settling processes; and Supply of supplemental Dissolved Oxygen (DO) when biological treatment systems experience temporary overloads or equipment failure. As indicated by these examples, H2O2 can be used as a stand-alone treatment or as an enhancement to existing physical or biological treatment processes, depending on the situation.

Discussion of Applications and Mechanisms

Direct Chemical Oxidation Using Hydrogen Peroxide
Hydrogen peroxide can be used alone or with catalysts such as iron (Fe2+ or Fe3+), UV light, ozone (O3) and alkali to oxidize BOD/COD contributing compounds in wastewaters. The type of oxidation needed depends on the type of BOD/COD present. This relationship is present in the figure below. Chemical Oxygen Demand Oxidant Type A Type B Type C System (Sulfide, Thiosulfate, (Phenols, Cyanides, (BTEX, TOCl,
Sulfite) Amines) Paraffins)

Type A H2O2 Type B H2O2 / OHH2O2 / M+ H2O2 / H+ Type C H2O2 / Fe H2O2 / O3 H2O2 / UV

X X X X X X X X X X X X X X X X

Note: Whether an oxidant system will degrade a specific pollutant (i.e., affect its COD) will depend on the oxidant system and the pollutant. Type A oxidants react only with Type A pollutants; whereas, Type C

oxidants, being more reactive, react with most any pollutant. However, Type C oxidants generally react preferentially with Type A pollutants.

If a large fraction of the BOD/COD is contributed by inorganic reduced sulfur compounds such as sulfides, sulfides, or thiosulfate, then hydrogen peroxide alone is typically effective. Depending on the wastewater pH, the oxidation of these compounds by H2O2 yields sulfate or colloidal sulfur, neither which contribute to BOD/COD. If the primary contributors to BOD/COD are dissolved organics, then a more reactive oxidation system is needed. Moderate activation of hydrogen peroxide can be achieved by: 1) alkali (generating the perhydroxyl ion , OOH- the active agent in peroxide bleaching systems); 2) certain transition metals (e.g., tungstate, vanadate, molybdate) which form reactive peroxometal complexes in-situ; and 3) certain mineral acids (e.g., sulfuric) which form reactive peroxyacid derivatives such as peroxymonosulfuric acid (Caros Acid) exsitu. For the more recalcitrant organics such as chlorinated solvents, extremely reactive free radical systems (termed Advanced Oxidation Processes) are needed. A generalized reaction using Fentons Reagent for reducing BOD/COD can be expressed as follows: With Fe+2 Step-1:BOD/COD + H2O2 ---> partially oxidized species With Fe+2 Step-2:partially oxidized species + H2O2 ---> CO2 + H2O + inorganic salts The extent of oxidation (and therefore the degree of direct BOD/COD reduction) typically depends on the amount of hydrogen peroxide used. The theoretical hydrogen peroxide requirement is about 2.1 lbs (as 100%) per lb-BOD/COD oxidized. In many cases, however, complete digestion of the organic compounds to carbon dioxide and water is not needed. Partial oxidation to intermediate compounds minimizes chemical consumption and often results in substantial reductions in BOD/COD and toxicity.

Enhanced physical separation of BOD/COD with Hydrogen Peroxide

Enhanced physical separation of BOD/COD with hydrogen peroxide may occur is two ways. In the first case, partial oxidation of organic contaminants results in more polar (charged) substances which are more amenable to adsorption onto coagulants and flocculants. As illustrated in the example below, this allows BOD/COD removal efficiencies with less than stoichiometric hydrogen peroxide doses.

In the second case, enhanced physical separation (flotation) of fats, oils and greases (FOG) is provided by H2O2. This occurs by the natural decomposition of hydrogen peroxide to oxygen and water, i.e., hydrogen peroxide will supersaturate the wastewater with oxygen, which results in the formation of evenly dispersed microbubbles which scavenge FOG constitutents as they rise to the surface of the water. In some cases, this can increase BOD removal through dissolved air flotation cells from e.g., 50% to 9095%. Typical doses are 25-100 mg/L H2O2, the cost for which can often be offset against savings in coagulant use a polyelectrolyte polymer is generally still needed.

Hydrogen Peroxide as a supplemental oxygen source

The BOD removal efficiency of aerobic biological treatment processes depends on a number of factors including (but not limited to): influent BOD loading, F:M ratio, temperature, nutrient levels, and dissolved oxygen (DO) concentrations. Many biological treatment facilities use hydrogen peroxide to supplement DO levels when oxygen limited conditions in aeration basins or lagoons result in poor BOD removal. These conditions can be brought about by unexpected peaks in influent BOD loading; seasonal variations in BOD loading (e.g., fruit and vegetable processing); and hot weather which reduces the efficiency of oxygen transfer by mechanical aeration equipment (i.e., O2 solubility decreases as temperature increases). These conditions may or may not be accompanied by filamentous bulking (see Municipal Wastewater Applications : Filamentous Bulking Control). When hydrogen peroxide is used to supplement DO, it is metered directly into the aeration basin of a biological treatment system to provide an immediate source of DO. The conversion of hydrogen peroxide to DO in an activated sludge mixed liquor proceeds according to the following reaction: (Catalase enzyme) 2 H2O2 ---> O2 + 2 H2O Theoretical hydrogen peroxide requirement: 0.48 lbs H2O2 (100%) per mg/L DO Catalase enzyme is a natural decomposition catalyst for hydrogen peroxide, and is found in all activated sludge mixed liquors, being produced by most aerobic organisms. Because this enzymatic decomposition of hydrogen peroxide is very rapid, the oxygen

supplied by hydrogen peroxide is immediately available for uptake by the aerobic organisms. The above reaction shows that two parts of hydrogen peroxide will yield one part of DO. Therefore, the amount of hydrogen peroxide required to oxygenate the wastewater is surprisingly small. For example, the theoretical amount of hydrogen peroxide required to increase the DO by 1 mg/L in a treatment plant that averages 5 MGD flow is about 17 gpd-50%. In actual practice, the requirement may be higher due to inefficiencies in oxygen uptake and side reactions with oxidizable compounds.
Note: When measuring the BOD or COD of hydrogen peroxide treated wastewaters, it is important to determine the residual hydrogen peroxide concentration (if any) prior to analysis. This is because H2O2 will interfere with both of these analytical methods. In the standard BOD test, residual hydrogen peroxide in the sample will liberate oxygen over the test period, resulting in a "false low" BOD value (1 mg/L H2O2 = 0.5 mg/L DO). In the standard COD test, residual hydrogen peroxide will react with the potassium dichromate reagent, resulting in a "false high" COD value. For methods to remove residual hydrogen peroxide prior to BOD and COD analysis, or to mathematically account for the residual H2O2, see Interferences with Analytical Methods.

References

Cole, C.A., et.al., J.Water Pollut. Contr. Fed. 46:2579-2592 (1974). Cole, C.A., et.al., J.Water Pollut. Contr. Fed. 45:829-836 (1973). Houtmeyers, J. et.al. "Hydrogen Peroxide as a Supplemental Oxygen Source for Activated Sludge: Microbiological Investigations", European. J. Appl. Microbiol. 4:295-305 (1977). Steiner, Norbert, et.al. "Plant Experience using Hydrogen Peroxide for Enhanced Fat Flotation and BOD Removal", Environ. Progress 11(4):261-264 (Nov. 1992). Perley, William J., et.al. "Use of Hydrogen Peroxide to Control Upsets in the Treatment of Combined Sugar Refining and Sanitary Wastewater", presented at Calif. Water Pollut. Contr. Fed., 64th Annual Conf., Sacramento, Calif. (Apr. 9, 1992).

What is the difference between BOD, COD or TOC? Why do I have to measure them?
Almost all treatment plants are required to measure one of these three items as a measure of the pollution value in the water. COD should always measure higher than TOC and then BOD.

COD or Chemical Oxygen Demand is the total measurement of all chemicals in the water that can be oxidized. TOC or Total Organic Carbon is the measurement of organic

carbons. BOD- Biochemical Oxygen Demand is supposed to measure the amount of food (or organic carbons) that bacteria can oxidize.

For the purposes of this training, we are going to use the term Biological Oxygen Demand as well, the two terms have been interchanged, but if you are taking a wastewater operators test, stick to the Biochemical term. The purpose of this training is to get the basic understanding of what is going on across your system. You cannot have a biochemical oxygen demand or biochemical reaction without including biology! We are trying to get the concept across that one of these test methods is using biology, microbiology to be exact. The other two are using strictly chemical tests to measure pollution.

COD is usually a measurement of chemicals and the test is simple and easy to perform with the right equipment and can be done in 2 hours. BOD usually takes 5 days and TOC used to require large expensive pieces of equipment that could measure the sample in minutes, but was cost prohibitive. There are now test in tube kits that utilize COD digesters to run a test similar to a COD test method available to run a quick, simple and inexpensive TOC test. Below are more detailed specifics on each test.

Why do I have to measure them? The government came up with these test methods as a way to determine the amount of pollution in a water stream to try to control and limit the amount of chemicals that can pollute the lakes and rivers if left in a final effluent or discharge stream. Some municipalities want to measure the amount of chemicals in the incoming stream in order to asses surcharges as a way of measuring how much additional treatment their plant will have to do in order to get the incoming water clean.

It is not only important to know which test you are being measured on, but why, how the sample is pulled and the variations on how they perform the test method. Garbage in, garbage out, correct sampling procedures and methods are critical and can make the difference in violating a permit or not.

Just because a lab says they perform BOD does not necessarily mean they perform the procedures the exact same way. Check on the exact methods used.

Did you know some labs do not add bacterial seed cultures? If there are few or very little

bacteria in the sample, it will show that the BOD is low. It there are biocides present, it will show the result as low. If there are high levels of ammonia present in the sample or bits of algae present, a false high BOD reading will show up. If the sample sits for a few days and turns septic before the test is run, it will require more oxygen and if not set up properly, again a false reading will occur.

What is Chemical Oxygen Demand?

A COD test measures all organic carbon with the exception of certain aromatics (benzene, toluene, phenol, etc.) which are not completely oxidized in the reaction. COD is a chemically chelated/thermal oxidation reaction, and therefore, other reduced substances such as sulfides, sulfites, and ferrous iron will also be oxidized and reported as COD. NH3-N (ammonia) will NOT be oxidized as COD.

The use of COD results for wastewater compliance monitoring is increasing.

To measure oxygen demand, biochemical oxygen demand (BOD) relies on bacteria to oxidize readily available organic matter during a five-day incubation period. COD uses strong chemicals to oxidize organic matter. Generally, COD is preferred to BOD for process control measurements because results are more reproducible and are available in just two hours rather than five days. By the time you have the results from a five day test, the plant conditions are no longer the same, so real time monitor and control can not be relied upon by the use of BOD. COD is a quick and easy measurement to get a snap in time picture of what is going on in the system,

and with trending, long term predictions can be made and monitor and control of the process at the wastewater treatment plant can be optimized and controlled.

BOD simulates the actual treatment plant process by measuring the organic material microorganisms can oxidize. Although COD is comparable to BOD, it actually measures chemically oxidizable matter. The COD test is not a direct substitute for the BOD test; however, a ratio usually can be correlated between the two tests. This requires COD versus BOD testing over a specified period of time.

For industrial samples, COD may be the only feasible test because of the presence of bacterial inhibitors or other chemical interferences, which would interfere with a BOD determination. COD testing also gives the fast measurements required in many treatment systems for informed decisions regarding process control adjustments. Many industrial and municipal laboratories find that parallel COD and BOD testing is beneficial because the COD test can be used to target a specific BOD range. The need for multiple BOD dilutions is minimized or eliminated.

What is Total Organic Carbon?

Organic matter content is typically measured as total organic carbon and dissolved organic carbon, which are essential components of the carbon cycle. The Total Organic Carbon test measures all organic carbon as CO2. Therefore, all inorganic CO2, HCO3-, etc. Must be removed prior to the analysis.

TOC is often used when levels of organic matter (OM) are low. Total organic carbon is a good parameter to measure and actually a more accurate indication of some of the pollutants that cause the most problems than a BOD test. TOC doesn't differentiate between that portion of organic carbon, which can be metabolized (assimilated).

TOC used to be measured by expensive analyzers. Below are some of the older methods with analyzers. Typically TOC analyzers are composed of three primary categories: combustion oxidation, wet oxidation and photocatalytic oxidation. Some analyzers use a combination or mixture of technology.

(1)Combustion Oxidation/ NDIR Method (non-dispersive infrared gas analyzer) (2)WET OXIDATION- Persulfate oxidation / NDIR Method There are two types of this method, persulfate oxidation supported with UV (Ultraviolet) irradiation activation and heated persulfate oxidation. (3) CONDUCTIVITY- UV oxidation / Conductivity based TOC methods oxidize the TOC that is present to CO2 using UV radiation typically in the presence of a titanium oxide catalyst.

COMBUSTION OXIDATION The combustion method measures total carbon (TC). It requires samples injection by syringe into a high temperature furnace with a platinum or cobalt catalyst. This process oxidizes all of the carbon materials present to CO2.

For example, in one of these analyzers, TOC concentration is not directly measured; the Analyzer measures total carbon (TC) and total inorganic carbon (TIC) and subtracts TIC from TC to obtain TOC. An oxidizer and an acid are added to the sample. The acid reacts with bicarbonate and carbonate ions present in the sample to release carbon dioxide (CO2). The CO2 released from bicarbonate and carbonate ions represents the TIC in the sample. The sample is then subjected to ultra-violet (UV) radiation, which reacts with the oxidant and breaks down all

remaining carbon bonds in the sample to release CO2. The CO2 released from both the acid reaction and the UV radiation represents all the carbon (TC) released from the sample. TOC is then obtained by subtracting TIC from TC.

Newer methodology for TOC Analyses. One type of new methodology for TOC analyses is using closed-loop photocatalytic oxidation. The new TOC methodology includes a titanium dioxide slurry and a 400 nm light source for the oxidation process. The closed-loop TOC system incorporates a closed-loop design to eliminate the need for carrier gases and uses what is called dynamic endpoint detection, where all of carbon in the sample is oxidized to completion. The reaction is measured using a non-dispersive infrared (NDIR) detector. This new technology can directly measure TOC from a single sample eliminating the loss of purgable organics and results in comparable recoveries of various organic compounds when compared to the combustion TOC method. This new methodology can be used for the same applications where the traditional TOC methods have been employed.

There are now also Test N Tube reagents that can be used with COD digesters and Spectrophotometer analyzer. The test is performed in two hours, but the cost for capital equipment is nowhere in the same range. The method involves the oxidation of sample carbon to carbon dioxide by persulfate digestion. The carbon dioxide diffuses into a colored pH indicator solution where it is converted to carbonic acid. The resulting color change is directly proportional to the concentration of carbon present in the sample.

What is the meaning of C-BOD vs. BOD? There are too many terms and it is getting confusing to me. . . . . There are two completely different tests-a C-BOD test and a BOD test. Many times a C-BOD vs. BOD5 test is needed due to conditions at a plant. In some places where the nitrification of ammonia may not be complete (i.e., incomplete conversion of ammonia (NH3) to nitrate (NO3)) or where too high levels of amines or ammonia are present, false BOD readings may occur. This can occur in municipal lagoons,

chemical plants or refineries. For lagoon (pond) treatment systems or other situations where this may occur, it is recommended that a Carbonaceous Biochemical Oxygen Demand (CBOD or Inhibited BOD) should be reported and used in place of 5day Biochemical Oxygen Demand (BOD5). Nitrification is inhibited so that only the oxidation of COD occurs.

What is the difference between BOD vs. CBOD? BOD5 measures the oxidation of carbons and possibly nitrogenous compounds present in a water sample. CBOD only measures oxidation of carbons.

Where did BOD5 come from? The BOD test Originated in the United Kingdom due to pollution in the Thames River. Legend has it that the 5-day BOD (Biological or Biochemical Oxygen Demand) test was developed in England. Sewage was dumped in a river and it took five days for it to reach the ocean, hence the five-day incubation requirement in the BOD method.

It is rumored that a ferry tipped over and that many of the people who fell in the river got sick or died. This was not due to drowning, but due to the effects of the pollution in the river. The Royal Commission on Sewage Disposal recommended and adopted the BOD5 test in 1908. The duration of the test is normally 5 days. The Average temperature is = 20 degrees C. 300 ml are usually used. Dark Incubation is needed to restrict the growth of algae. The final measurement is usually expressed as O2 mg/l. BOD measures all biodegradable organic carbons, and under certain conditions, oxidizable nitrogen present in the waste.

The biochemical oxygen demand (BOD) test tries to closely model an aerobic wastewater treatment system and the natural aquatic ecosystem. It measures oxygen taken up by the bacteria during the oxidation of organic matter. The test usually runs for a five-day period, but can run 7 or 10 days as well, depending on specific sample circumstances.

BOD uses and limitations: BOD testing has its widest application in measuring waste loadings of treatment plants, and in evaluating the efficiency of treatment processes. It is of limited use in industrial wastewaters containing heavy metal ions, cyanides, and other substances that may be toxic to the microorganisms.

Unfortunately, the test has flaws. It is usually seeded with the type of bacteria found in municipal plants. The types of bacteria needed in papermills or refineries usually differ in species from the standard procedures method. The hard to degrade organics found in some of these systems also may take longer than 5 days to break down, so a BOD test will give an inaccurate measurement of the amount of pollution that may be present in a waste stream.

The test is a 5 day test, during that time if the pH drops, or if there are insufficient nutrients for the bacteria to consume the organics, the bacteria will be limited.

Well, I guess it is really important to know these terms, how and where I sample my system as well as who runs the tests. .. .

More Troubleshooting

What is the difference between C-BOD, Total BOD and N-BOD? Now I am really

confused?

Toxicity vs. High BOD loading

BOD and COD Definitions faq161-1159 Posted: 20 Sep 05 (Edited 20 Dec 05) . Any oxidizable material present in a natural waterway or in an industrial wastewater will be oxidized both by biochemical (bacterial) or chemical processes. The result is that the oxygen content of the water will be decreased. Basically, the reaction for biochemical oxidation may be written as: Oxidizable material + bacteria + nutrient + O2 => CO2 + H2O + oxidized inorganics such as NO3, SO4, etc. Oxygen consumption by reducing chemicals such as sulfides and nitrites is typified as follows: S-- + 2 O2 => SO4-NO2- + 0.5 O2 => NO3Since all natural waterways contain bacteria and nutrient, almost any waste compounds introduced into such waterways will initiate biochemical reactions (such as shown above). Those biochemical reactions create what is measured in the laboratory as the Biochemical or Biological Oxygen Demand (BOD). Oxidizable chemicals (such as reducing chemicals) introduced into a natuaral water will will similarly initiate chemical reactions (such as shown above). Those chemical reactions create what is measured in the laboratory as the Chemical Oxygen Demand (COD). Both the BOD and COD tests are a measure of the relative oxygen-depletion effect of a waste contaminant. Both have been widely adopted as a measure of pollution effect. The BOD test measures the oxygen demand of biodegradable pollutants whereas the COD test measures the oxygen demand of biogradable pollutants plus the oxygen demand of nonbiodegradable oxidizable pollutants. The so-called 5-day BOD measures the amount of oxygen consumed by biochemical oxidation of waste contaminants in a 5-day period. The total amount of oxygen consumed when the biochemical reaction is allowed to proceed to completion is called the Ultimate BOD. The Ultimate BOD is too time consuming, so the 5-day BOD has almost universally been adopted as a measure of relative pollution effect. There are also many different COD tests. Perhaps, the most common is the 4-hour COD.