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Many municipal plants often times have problems with ammonia reduction and nitrification. Some times this can be due to solids handling reduction and the recycle of ammonia in the returning supernatant. Many plants used digestors to reduce the amount of solids they need to process. What they often do though is to return the supernatant to the front of the plant and thereby increase the ammonia loading. This continually recycles the ammonia in the system, and in the long run can sometimes cost more in electrical power to generate oxygen. Check out our training materials on solids handling, Total Nitrification Balance and ammonia problems. While this can be one cause of ammonia problems in a system, this newsletter is going to address another issue that is most often overlooked, Amines that may be present in the influent. Industrial plants such as chemical or refineries usually make it a standard practice to measuring amines present in the influent. They take these into account when performing a total nitrogen balance across a system in order to completely assess the efficiency of their nitrification removal process. Municipalities are not used to measuring amines. It is often overlooked and can sometimes be a contributing factor to problems with nitrification and violations of final effluent permits.
Well, where would these amines come from? Personal care products or household cleaning products may contain amine compounds. Restaurants, hospitals and hotels using cleaning and sanitizing agents. The food industry requires the use of disinfectants to sanitize food preparation areas, and serve preservative functions. Many institutional and fast food restaurants as well as many industrial plants, especially food plants need to use biocides in order to keep the working areas clean or sterile. This can be accomplished by addition of biocides; chemical compounds that are toxic to the present microorganisms. Biocides are used in an environment or a system to bring about rapid effective population reductions from which the microorganisms cannot easily recover. There are various different biocides, some of which have a wide range of effect on many different kinds of bacteria. They can be divided up into oxidizing agents and non-oxidizing agents. Oxidizing agents: Chlorine, Chlorine dioxide, Chloroisocyanurates, Hypochlorite, Ozone Non-oxidizing agents include: Acrolein, Amines, Chlorinated phenolics, Copper salts, Organo-sulphur compounds, Quaternary ammonium salts, Tertiary amines, amine oxides, Fatty Amines & Other Nitrogen Compounds Quaternary ammonium salts are surface-active chemicals that consist generally of one nitrogen atom, surrounded by substitutes containing eight to twenty-five carbon atoms on four sides of the nitrogen atom. Quaternary amines are soluble in both water and organic liquids and can greatly accelerate certain chemical reactions when added to a heterogeneous system. These amines are highly toxic and are as equally effective as chlorine dioxide disinfectants. This antibacterial activity is considered desirable for maintaining a sterile living environment. These compounds are generally most effective against bacteria in alkaline pH ranges. They are positively charged and will bond to the negatively charged sites on the bacterial cell wall. These electrostatic bonds will cause the bacteria to die due to stresses in the cell wall. They also cause the normal flow of life-sustaining compounds through the cell wall to stop, by declining its permeability. Use of quaternary ammonium salts is limited, due to their interaction with oil when present and the fact that they can cause foaming. Amines Amines are effective surfactants that can act as biocides due to their ability to kill microorganisms. They can enhance the biocidal effect of chlorinated phenolics when they are applied in water. Personal Care Products: Quaternary ammonium compounds are often used in contact lens solutions for cleaning and preservative purposes among other uses. Recently detergent manufacturers began to employ quaternary amines in order to increase the cleaning action of household detergents. Amines are often used as floor finish strippers, buffering agents in liquid laundry detergents and as fabric softeners. The antibacterial precursors of the quaternary ammonium compounds ("quats") are aliphatic long-chain ammonium salts. The direct counter part of soap may be considered as a primary ammonium salt. Both are surface-active substances. Primary long-chain ammonium salts are derived from the weakly basic aliphatic amines. Because quats are salt bases, they remain in solution in acidic as well as in basic media. Among the many quaternary ammonium salts available: benzalkonium chloride, alkylbenzyldimethylammonium chloride, methydimethyl ammonium chloride, methylbenzethonium chloride, hexadecylpyridinium chloride, and alkylisoquinolinium bromideBelow is a list of some of the compounds that your customers might be using that can impact your wastewater treatment plant- Amines are in more compounds than you might think Surfactant and Cleaning Chemicals and Their Functions ADMA® alkyldimethylamines and DAMA® dialkylmethylamines for amine oxides, quaternary ammonium compounds and betaines used in cleaning systems, biocides, fabric softeners and conditioners
Personal care products, although used in small amounts in each household, can add up in large population areas. Typical composition of a general-purpose cleaning agent can be provided from a Material Safety Data Sheet. Ask your customers to provide you with MSDS sheets for compounds that they might use in their facility. Composition of Typical General Purpose Cleaning Agent Tetrasodium ethylenediamine tetraacetate (chelating agent) Cleaning agents containing quaternary ammonium compounds such as alkylbenzyldimethyl ammonium chloride can be found in most grocery stores and supermarkets under a variety of brands. Some typical cleaning agents are listed below. (It should be noted that many detergents do not reveal their complete composition on the label.) Typical Enzyme Detergents Cleaning Agent pH Comments Pearl Plus (Flexo) 10 Active ingredient alkyl dimethyl benzylammonium chloride. Pine Scented 9 Corrosive to skin and eyes. Household Cleaner Use rubber gloves. Contains quaternary ammonium chlorides. Lysol 8 Corrosive. Contains alkyl dimethylbenzyl ammonium chloride. Use rubber gloves.
Ok, I am convinced, I believe there may be amines in my influent, so what do I do about it? The first thing you need to do if you are not already doing this is to check for the presence in your influent. The best way would be to check a composite sample (24-hour sample). This would make sure that you are catching any that might be present. In some plants, it might be that the only time they are present is for example at night when the restaurants close down and perform their routine clean up. It might be only in the morning when they start up, it might be when most households are home on the weekend and are doing clean-up around the house. At one plant, it might be that there is a small food or industrial plant and they are on a specific cleaning schedule bi-weekly. One way to find out is to ask all your industrial or restaurant customers. Talk to them and ask them if they recently changed cleaning compounds or what biocides and cleaners they use. Residential customer's usage will have to be judged by normal composite samples, since dilution factors will probably make their individual usage minimal as a contributing factor. The best way to avoid missing the amount of amines present in your influent that might be causing you problems is to take a composite sample every day for a week or extended period. If you do not have a composite sampler onsite, you can try to use a small polymer pump, a small hose and a bucket and set the pump speed to collect a small sample periodically. How do you measure amines? The old standard way is a TKN procedure- total Kjedahl nitrogen. Samples are digested in sulfuric acid in the presence of a mercuric oxide catalyst. The Kjeldahl nitrogen present is converted to ammonium cation. Potassium sulfate helps speed the conversion to ammonium.
Total Kjeldahl Nitrogen (TKN) a. TKN = ORG- N + NH3-N b. Digest sample in sulfuric acid and catalystOrg-N - ------ > NH4-Nc. Steam distillation to determine ammonia content Organic nitrogen (by difference) ORG-N = TKN - NH3-N TKN = ORG-N + NH3-N
There are now easier methods to measure Total Nitrogen- NH3, NO2 and NO3 A variety of test procedures and methods are now available for use by water and wastewater operators. They run the gamut from colorimetric, titrimetric, electrometric (meter & probe), turbimetric and nephlometric through demonstrative methods.
NH3, Nitrite and Nitrate nitrogen can easily be performed by Colorimetric procedure Normally nitrate and nitrite are found in very low to minimal concentrations in the influent. They should be measured in the final effluent if nitrification is required at a wastewater treatment plant. An increase in nitrates across a system will be a good measure to determine if nitrification is occurring. Total Nitrogen Total Nitrogen- For practical purposes in wastewater analysis,TN = ORG TN = ORG-N + NH3-N + NO2-N + NO3-NTKN = OR TKN = ORG- N + NH3-N TON = NO2TON = NO2-N + NO3-N
F AST, EFFICIENT ANALYSIS FOR 8 KEY WASTEWATER PARAMETERSNitrogen, Total Reagent Set, Test 'N Tube, 50/tests Product #: 2672245
Phosphorus 1. Total Phosphorus 2. Reactive Phosphorus 3. Acid Hydrolyzable Phosphorus Nitrogen 1. Total Nitrogen 2. Total Inorganic Nitrogen 3. Ammonia 4. Nitrate 5. Nitrite Wastewater analysts all overEfficient Testing Designed for maximum efficiency and minimal waste, Hach’s Test ‘N Tube™ Analysis Systems are the products of choice for wastewater treatment professionals all over the world. These innovative systems: • Feature accurately premeasured reagents—already in the vial or available in sealed, unitdose packages • Require minimal handling and less preparation time • Are less dependent on individual technique, producing precise and repeatable results • Minimize, and sometimes eliminate, the use of hazardous chemicals: — No cadmium is used in the TNT Nitrate method — No mercury is used in the TNT Ammonia method • Reduce laboratory waste and associated disposal problems Easy to Use 1. Simply add sample and reagents to the Test ‘N Tube™ vial and seal with the cap. 2. Digest up to 25 vials simultaneously in Hach’s COD Reactor. 3. Read results directly on a Hach spectrophotometer or colorimeter. 4. Dispose of reacted samples in the sealed vials both easily
Self-Filling Ampules Give Easy, Safe, Fast Analysis No mixing, measuring, calibrating or cleaning, just snap the ampule,
containing pre-measured unit dose of reagent, into the sample. You'll get
quantitative results in minutes with ±4% accuracy. VACUettes® Colorimetric Test Kits Designed for Highly Concentrated Samples Use a special auto-dilution feature that eliminates the need for a time-consuming and error-prone prelimin  ary
dilution. So, the entire test takes only two to three minutes. Specifications: Each 7mm ampule has a capillary pipet attached to its tip. It is calibrated to draw the correct volume of sample for one of four dilution factors: 25X, 50X, 100X and 1000X. Hold the ampule horizontally so the capillary tip contacts the sample. After the pipet fills, immerse in a diluent (usually tap water) and snap ampule tip. The sample and diluent are drawn into ampule where they are mixed with the reagent. Resulting color change can then be compared with liquid color standards to quantify results. Test Kits contain 30 ampules, comparator(s), sample cup, accessory solution (when necessary) and instructions. Refill Packs of 30 ampules and accessory solutions are also available. Comparators have a two-year shelf life.
Identify and Detect Ions and Compounds in Seconds A wide selection of strips allows rapid, easy analysis of a variety of technical processes and solutions. Specifications: Simply match test color to chart on strip container--no technical background or special skills required. Some strips are supplied with companion reagents in convenient dispenser bottles.
Titrets® Titrimetric Test Kits Conclusions: It does not matter which method you use, the only thing that matters is when you use it, how often you use it and how consistent you use your test methods. Where you pull the samples from also impact the calculations and your final test results. Make sure that if you are testing influent samples, that you are measuring total influent to the plant, including supernatant from sludge dewatering units or digestors. If they have a different feed point, test these streams separately if necessary, but be sure to include the final measurements in your calculations. These side streams are often overlooked and can also be a contributor to ammonia problems.
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Colorimetric
test methods offer on-the-spot results and can test for a variety of common
substances. 
FormacsTN
- Total Nitrogen Analyzer Skalar has a total nitrogen analyzer, the FormacsTN
Analyzer. Using a combustive catalytic procedure at 850°C followed by
chemiluminescence detection, this analytical technology shows excellent
correlation with established methodology. This new method of analysis is rapidly
becoming the alternative for cumbersome reference methods, such as Total
Kjeldahl Nitrogen (TKN). With this simple procedure reliable results are now
available in minutes without any waste production for a wide range of
water/environmental samples. 
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