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TweetBalancing your pool water will keep your family and pool safe. It’s important to regularly check your pool to ensure your pool water has the proper alkalinity levels. Why lower the pool water alkalinity level? How-to-lower-total-alkalinity Although high total alkalinity does not cause severe damage to your pool equipment and surfaces as low alkalinity, alkalinity […]
Balancing your pool water will keep your family and pool safe. It’s important to regularly check your pool to ensure your pool water has the proper alkalinity levels.
Why lower the pool water alkalinity level?
Although high total alkalinity does not cause severe damage to your pool equipment and surfaces as low alkalinity, alkalinity levels need to remain balanced so as to reduce any unexpected maintenance costs that occur due to wear and tear of pool equipment, for instance reducing the pool pump efficiency because of plugged filters and decreased pipe flow from scale build up.
When swimming in a pool that has high alkalinity levels, you will often get skin irritations. The skin and hair will become sticky and your eyes may burn to some degree.
Controlling the pH level in a pool that has high alkalinity is difficult, as the cushioning properties of the water to withstand alterations in acidity increases. This means that if you want to adjust the pH levels in the water, you will have to use higher amounts of chemicals.
Maintaining well balanced total alkalinity levels in your pool is a crucial step in ensuring your pool water is healthy. Balancing the total alkalinity is one of the three different adjustments you need to also do so that you can balance your swimming pool water. The rest are calcium hardness and pH. Always adjust the total alkalinity first, except in situations where the pH is way below 7.0. If it’s below 7.0, get it to that level and then adjust the total alkalinity.
How To Lower Alkalinity In Pool Water
First things first….
Ensure you get the right pool size, more so the volume, as this is necessary in establishing the amount of chemical you need to add to your swimming pool. You want it to be in the mid range of about 80-120ppm (parts per million) for the total alkalinity off your pool.
There are two main chemicals that are available in lowering pool alkalinity. They are Muriatic acid and sodium bisulfate or dry acid.
How to lower total alkalinity with Muriatic Acid
NOTE: Muriatic acid is hydrochloric acid that’s slightly diluted. This acid burns the skin and eyes so you will need to wear protective clothing such as rubber gloves, goggles and an apron that’s long sleeved when working with this chemical.
1. Begin by testing your swimming pool water alkalinity level. You need to establish if the level is high and by what percentage
2. Switch off your swimming pool pump. Give your pool an hour so that the water stops circulating. You want your water to be totally still.
3. Carefully read the product label f you had not done that before. Establish how much you need to add according to the amount your level is over (in ppm) and the total volume of your swimming pool.
4. For Muriatic acid, you can either dilute it or pour it directly into the water. If you have a diving pool, do it at the deep end. Alternatively, you can pour portions in different sports especially if you have an above ground pool or a shallow pool. Ensure the stream is tight so that the acid flows deep into the water. You want it to get to the floor of your swimming pool.
5. Allow the swimming pool to sit for an hour and then turn your pool pump back on again.
6. Test your total alkalinity levels after about 6 hours or before 24 hours are over after adding the Muriatic acid to give the pool time to adjust to the chemical you have added.
7. If you check after two to three days and you realize your alkalinity levels have not dropped to the required levels, you can repeat the entire process. Sometimes, it may take several days for the total alkalinity to re-balance.
8. Ensure you also test your pH levels and adjust it if necessary. Sometimes it may drop.
How to lower total alkalinity using sodium bisulfate or dry acid
1. Start by first testing the pool water total alkalinity levels. By all means avoid strips as they may not give you accurate results. Instead use Taylor Lamotte drops based Total Alkalinity test if it’s possible. You may get this at your local home depot.
2. Switch off the swimming pool pump and give it about an hour so that the pool circulation stops.
3. After an hour get back to work. I hope by now you have read carefully the products label. If you have not, then you had better do so before you get started. If your level is more than 120ppm, then you will have to decrease the level to approximately 100ppm. Carefully read the label at the back of the product to establish how much of the product you need to add. In most cases, sodium bilsufate is usually 93.2% pure, so watch out for that percentage on the package you buy.
4. In a bucket of water, dilute the dry acid. Ensure the substance completely dissolves.
5. Go to the deep end of the pool and pour the dilute acid into the water ensuring the stream is as narrow as possible. A narrow stream penetrates both the upper part of the water and gets as deep as possible. This will help in preventing any disruptions of the pH level in the water.
6. Allow the pool to sit still for about an hour. Switch the pool pump on again after one hour.
7. After 6 hours, you can test again the total alkalinity level.
8. If you realize you need to bring down the level of alkalinity, dilute and add more dry acid. However, you should wait for about two to three days before doing this as the total alkalinity may decrease on its own somehow.
Maintaining the right levels of total alkalinity in your pool is one of the vital three water balancing procedures. As a pool owner, you should be able to test your total alkalinity and know how to decrease the level if it’s on the higher side. You should also know what chemicals are available to lower total alkalinity and how much to add into your pool depending on your pool size and the alkaline levels in the pool.
Reprinted with the kind permission of PoolUniversity.org, a good source of information on proper swimming pool care.
The TOP Pool Professionals use the Myron L PS9, which measures 9 Parameters: Conductivity, Mineral/Salts, TDS, Alkalinity, Hardness, LSI, pH, ORP/Free Chlorine, Temperature.
TweetAnyone and everyone who is responsible for operating and maintaining a swimming pool or spa has to test, monitor, and control complex, interdependent chemical factors that affect the quality of water bathers are immersed in. Additionally, aquatic facilities operators must be familiar with all laws, regulations, and guidelines governing what these parameters should be. Why? […]
Anyone and everyone who is responsible for operating and maintaining a swimming pool or spa has to test, monitor, and control complex, interdependent chemical factors that affect the quality of water bathers are immersed in. Additionally, aquatic facilities operators must be familiar with all laws, regulations, and guidelines governing what these parameters should be.
Why? Because the worst breeding ground for any kind of microorganism is a warm (enough) stagnant pool of water. People plus stagnant water equals morbid illness. That’s why pools have to be circulated, filtered, and sanitized – with any number of chemicals or methods, but most frequently with chlorine compounds. However, adding chemicals that kill the bad microorganisms can also make the water uncomfortable, and in some cases unsafe, for swimmers. Additionally, if all the chemical factors of the water are not controlled, the very structures and equipment that hold the water and keep it clean are ruined.
So the pool professional must perform a delicate balancing act with all the factors that affect both the health and comfort of bathers and the equipment and structures that support this. Both water balance – or mineral saturation control – and sanitizer levels must constantly be maintained. This is achieved by measuring pertinent water quality factors and adding chemicals or water to keep the factors within acceptable parameters.
Water is constantly changing. Anything and everything directly and indirectly affects the relationship of its chemical parameters to each other: sunlight, wind, rain, oil, dirt, cosmetics, other bodily wastes, and any chemicals you add to it. Balanced water not only keeps swimmers comfortable, but also protects the pool shell, plumbing, and all other related equipment from damage by etching or build-up and stains.
The pool professional is already well acquainted with pH, Total Alkalinity (TA), and Calcium Hardness (CH); along with Total Dissolved Solids (TDS) and Temperature, these are the factors that influence water balance. Water that is in balance is neither aggressive nor oversaturated.
Aggressive water lacks sufficient calcium to saturate the water, so it is hungry for more. It will eat anything it comes into contact with to fill its need, including the walls of your pool or spa or the equipment it touches. Over-saturated water cannot hold any more minerals, so dissolved minerals come out of solution and form scale on pool and equipment surfaces.
The pH of pool water is critical to the effectiveness of the sanitizer as well as the water balance. pH is determined by the concentration of Hydrogen ions in a specific volume of water. It is measured on a scale of 0-14, 0-7 being acidic and 7-14 being basic.
You must maintain the pH of the water at a level that assures the sanitizer works effectively and at the same time protects the pool shell and equipment from corrosion or scaling and the bathers from discomfort or irritation. If the pH is too high, the water is out of balance, and the sanitizer’s ability to work decreases. More and more sanitizer is then needed to maintain the proper level to kill off germs. Additionally, pH profoundly affects what and how much chemical must be added to control the balance. A pH of between *7.2 – 7.6 is desirable in most cases.
*As one of the most important pool water balance and sanitation factors, pH should be checked hourly in most commercial pools. Even if you have an automatic chemical monitor/controller on your system, you need to double-check its readings with an independent pH test. With saltwater pools, pH level goes up fast, so you need to check it more often. Tests are available that require reagents and subjective evaluation of color depth and hue to judge their pH. But different users interpret these tests differently, and results can vary wildly.
Myron L’s POOLPRO™ gives instant lab-accurate, precise, easy-to-use, objective pH measurements, invaluable in correctly determining what and how much chemical to add to maintain water balance and effective sanitizer residuals.
Total Alkalinity (TA) is the sum of all the alkaline minerals in the water, primarily in bicarbonate form in swimming pools, but also as sodium, calcium, magnesium, and potassium carbonates and hydroxides, and affects pH directly through buffering. The greater the Total Alkalinity, the more stable the pH. *In general, TA should be maintained at 80 – 120 parts per million (ppm) for concrete pools to keep the pH stable. Maintaining a low TA not only causes pH bounce, but also corrosion and staining of pool walls and eye irritation. Maintaining a high TA causes over-stabilization of the water, creating high acid demands, formation of bicarbonate scale, and may result in the formation of white carbonate particles (suspended solids), which clouds the water. Reducing TA requires huge amounts of effort. So the best solution to TA problems is prevention through close monitoring and controlling. Myron L’s Alkalinity Test Kit comes with sodium hydrogen sulphate tablets and a mixing/measuring vial to determine alkalinity in parts per million.
The other water balance parameter pool professionals are most familiar with is Calcium Hardness (CH). CH is the calcium content of the water and is measured in parts per million. Low CH combined with a low pH and low TA significantly increases corrosivity of water. As the water becomes more aggressive, the solubility of calcium carbonate also increases. This means that plaster and marcite pool finishes will deteriorate quickly because calcium carbonate is a major component of both plaster and marcite. Low CH also leads to corrosion of metal components in the pool plant, particularly in heat exchangers. Calcium carbonate usually provides a protective film on the surface of copper heat exchangers and heat sinks. This thin layer prevents much water-to-metal interaction but does not adversely affect the heating process. Without this protective layer caused by low CH, heat exchangers and associated parts can be destroyed prematurely. Strangely enough, as water temperature increases, solubility of calcium carbonate decreases. *The recommended range for most pools is 200 – 400 ppm. Calcium hardness should be tested at least monthly and has the least significant effect on the water balance when compared to pH and TA.
Total Dissolved Solids (TDS) is the sum of all solids dissolved in water. If all the water in a swimming pool was allowed to evaporate, TDS would be what was left on the bottom of the pool – like the white deposits left in a boiling pot after all the water has evaporated. Some of this dissolved material includes hardness, alkalinity, cyanuric acid, chlorides, bromides, and algaecides. TDS also includes bather wastes, such as perspiration, urine, and others.
TDS is often confused with Total Suspended Solids (TSS). But TDS has no bearing on the turbidity, or cloudiness, of the water, as all the solids are truly in solution. It is TSS, or undissolved, suspended solids, present in or that precipitate out of the water that make the water cloudy.
High TDS levels do affect chlorine efficiency, algae growth, and aggressive water, but only minimally. TDS levels have the greatest bearing on bather comfort and water taste – a critical concern for commercial pool operators. At levels of over 5,000ppm, people can taste it. At over 10,000ppm bather towels are scratchy and mineral salts accumulate around the pool and equipment. Still some seawater pools comfortably operate with TDS levels of 32,000ppm or more.
As methods of sanitization have changed, high TDS levels have become more and more of a problem. *The best course of action is to monitor and control TDS by measuring levels and periodically draining and replacing some of your mature water with new, lower TDS tap water. This is a better option than waiting until you must drain and refill your pool, which is not allowed in some areas where water conservation is required by law. However, you can also decrease TDS with desalinization equipment as long as you compensate with Calcium Hardness. (Do not adjust water balance by moving pH beyond 7.8.)
Regardless, you do need to measure and compensate for TDS to get the most precise saturation index and adjust your pH and Calcium Hardness levels accordingly. *It is generally recommended that you adjust for TDS levels by subtracting one tenth of a saturation index unit (.1) for every 1,000ppm TDS over 1,000 to keep your water properly balanced. When TDS levels exceed 5,000ppm, it is recommended that you subtract half of a tenth, or one twentieth of unit (.05) per 1,000ppm. And as the TDS approaches that of seawater, the effect is negligible.
Hot tubs and spas have a more significant problem with TDS levels than pools. Because the swimmer load is relatively higher, more chemicals are added for super-chlorination and sudsing along with a higher concentration of bather wastes. The increased electrical conductance that high TDS water promotes can also result in electrolysis or galvanic corrosion. Every hot water pool operator should consider a TDS analyzer as a standard piece of equipment.
A TDS analyzer is required to balance the water of any pool or spa in the most precise way. Myron L’s POOLPRO and POOLMETER™ immediately display TDS levels to correctly calculate your water’s saturation index and to ensure you take corrective action before TDS gets out of hand.
Temperature is the last and least significant factor in maintaining water balance. As temperature increases, the water balance tends to become more basic and scale producing. Calcium carbonate becomes less soluble, causing it to precipitate out of solution. As temperature drops, water becomes more corrosive.
In addition to helping determine water balance, temperature also affects bather comfort, evaporation, chlorination, and algae growth (warmer temperatures encourage growth). Myron L’s POOLPRO also precisely measures temperature to one tenth of a degree at the same time any other parameter is measured.
The formula for determining water balance is called the Langlier Index, or Saturation Index. It is determined by the following formula:
SI= (pH + TF + CF + AF ) – 12.1
Where TF is the temperature, CF is Calcium Hardness, and AF is Total Alkalinity adjusted for temperature. 12.1 is the Total Dissolved Solids constant. Consult appropriate conversion charts to obtain the correct values for each variable.
– An index between -0.5 and +0.5 is acceptable pool water.
– An index of more than +0.5 is scale-forming.
– An index below -0.5 is corrosive.
pH, Total Alkalinity, and Calcium Hardness are the big three contributors to water balance. *Pool water will often be balanced if these factors are kept within the recommended ranges.
The most immediate concern of anyone monitoring and maintaining a pool is the effectiveness of the sanitizer – the germ-killer. There are many types of sanitizers, the most common being chlorine in swimming pools and bromine in hot tubs and spas. The effectiveness of the sanitizer is directly related to the pH and, to a lesser degree, the other factors influencing water balance.
To have true chemical control, you need to monitor both the sanitizer residual and the pH and use that information to chemically treat the water – that’s where ORP comes in. ORP indicates the ability of oxidizers to burn up organic matter in the water, which means your water is clean and sanitary. There are colorimetric tests used to determine the amount of effective sanitizer for chlorine and other elements, but none is as objective and precise in determining the total killing power of all sanitizers as ORP.
ORP stands for Oxidation Reduction Potential (or REDOX) of the water and is measured in millivolts (mV). The higher the ORP, the greater the killing power of all sanitizers, not just free chlorine, in the water. ORP is the only practical method available to monitor sanitizer effectiveness. Thus, every true system of automatic chemical control depends on ORP to work.
The required ORP for disinfection will vary slightly between disinfecting systems and is also dependent on the basic water supply potential, which must be assessed and taken into account when the control system is initialized. *650mV to 700 – 750mV is generally considered appropriate.
Electronic controllers can be inaccurate and inconsistent when confronted with certain unique water qualities, so it is critical to perform manual testing with separate instrumentation. *For automatic control dosing, it is generally recommended that you manually test pH and ORP prior to opening and then once during the day to confirm automatic readings.
*Samples for confirming automatic control dosing should be taken from a sample tap strategically located on the return line as close as possible to the probes in accordance with the manufacturer’s instructions. If manual and automatic readings consistently move further apart or closer together, you should investigate the reason for the difference.
ORP readings can only be obtained with an electronic instrument. Myron L’s POOLPRO provides the fastest, most precise, easy-to-use method of obtaining ORP readings to check the effectiveness of the sanitizer in any pool or spa. This is the best way to determine how safe your water is at any given moment.
A relatively new development, saltwater pools use regular salt, sodium chloride, to form chlorine with an electrical current much in the same way liquid bleach is made. As chlorine – the sanitizer – is made from the salt in the water, it is critical to maintain the salt concentration at the appropriate levels to produce an adequate level of sanitizer. It is even more important to test water parameters frequently in these types of pools and a spa, as saltwater does not have the ability to respond adequately to shock loadings (super-chlorination treatments).
Most saltwater chlorinators require a *2,500 – 3,000ppm salt concentration in the water (though some may require as high as 5,000-7,000ppm). This can barely be tasted, but provides enough salt for the system to produce the chlorine needed to sanitize the water.
(It is important to have a good stabilizer level – *30 – 50 ppm – in the pool, or the sunlight will burn up the chlorine. Without it, the saltwater system may not be able to keep up with the demand regardless of salt concentration.)
Taste and salt shortages are of little concern to seawater systems that maintain an average of 32,000ppm. In these high-salt environments, you need to beware of corrosion to system components that can distort salt level and other parameter readings.
Additionally, incorrect salt concentration readings can occur in any saltwater system. The monitoring/controlling components can and do fail or become scaled — sometimes giving a false low salt reading. Thus, you must test manually for salt concentration with separate instrumentation before adding salt.
You must also test salt concentration manually with separate instrumentation to re-calibrate your system. This is critical to system functioning and production of required chlorine. Myron L’s POOLPRO conveniently tests for salt concentration at the press of the button as a check against automatic controller systems that may have disabled equipment or need to be re-calibrated.
As you can see, there are many factors affecting the comfort and sanitation of pool and spa water and the functioning of the equipment and structures that hold it, and no one instrument or method can be used to determine ALL of them, but Myron L’s POOLPRO gives you the most precise and comprehensive water testing instrument in one easy-to-use, handheld waterproof unit. Where precision counts, we’ve got you covered.
RECORD KEEPING – What to do with all those measurements …
Now that you have the data, you have to correctly transcribe, evaluate, and report it to the proper government agencies, or at least archive it as permanent record of proper compliance to whatever regulations apply to your pool or spa. (As if sanitizing and balancing the chemistry of the water wasn’t enough.)
*It is recommended (by the World Health Organization and other entities) that data handling be done objectively and that data be recorded in a common format and in the most accurate way. Also, data should be stored in more than one permanent location and made available for future analysis. *Most municipalities require commercial aquatic facilities to keep permanent records onsite and available for inspection at any time.
*Myron L’s POOLPRO makes it easy to comply with data record requirements. The POOLPRO is an objective means to test ORP, pH, TDS, temperature and the mineral/salt content of any pool or spa. You just rinse and fill the cell cup by submerging the waterproof unit and press the button of the parameter you wish to measure. You immediately get a standard, numerical digital readout – no interpretation required – eliminating all subjectivity. Up to 100 date-time-stamped readings can be stored in memory and then later transferred directly to a computer using our BluDock™ accessory package. You just set the unit on the Bludock and download the data to the computer. The user never touches or tampers with the data, reducing the potential for human error in transcription. The data can then be imported into any program necessary for record-keeping and analysis. *The Bludock is the fastest, easiest, best way to keep records that comply with governing standards.
Myron L Company’s POOLPRO is SIMPLY the best.
*Consult your governing bodies for specific testing, chemical concentrations, and all other guidelines and requirements. The ranges suggested here are meant as general examples.
Myron L Company assumes no responsibility for lack of compliance to specific regulations governing the testing and control of parameters in your pool and/or spa.
TweetStay up-to-date with an ever-changing world of water treatment regulations, industry events, news, and science with the Water Industry Resources page at MyronLMeters.com. We believe that a strong, well-informed water industry network is essential. We’ve put together a user-friendly page for water treatment professionals with science updates, networking, news, government resources, associations, and publications for […]
Stay up-to-date with an ever-changing world of water treatment regulations, industry events, news, and science with the Water Industry Resources page at MyronLMeters.com. We believe that a strong, well-informed water industry network is essential. We’ve put together a user-friendly page for water treatment professionals with science updates, networking, news, government resources, associations, and publications for both North American and International water industry professionals. If you have suggestions or events you’d like to see on this page, please let us know.
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TweetYears ago, high purity water was used only in limited applications. Today, deionized (Dl) water has become an essential ingredient in hundreds of applications including: medical, laboratory, pharmaceutical, cosmetics, electronics manufacturing, food processing, plating, countless industrial processes, and even the final rinse at the local car wash. THE DEIONIZATION PROCESS The vast majority of dissolved […]
Years ago, high purity water was used only in limited applications. Today, deionized (Dl) water has become an essential ingredient in hundreds of applications including: medical, laboratory, pharmaceutical, cosmetics, electronics manufacturing, food processing, plating, countless industrial processes, and even the final rinse at the local car wash.
THE DEIONIZATION PROCESS
The vast majority of dissolved impurities in modern water supplies are ions such as calcium, sodium, chlorides, etc. The deionization process removes ions from water via ion exchange. Positively charged ions (cations) and negatively charged ions (anions) are exchanged for hydrogen (H+) and hydroxyl (OH-) ions, respectively, due to the resin’s greater affinity for other ions. The ion exchange process occurs on the binding sites of the resin beads. Once depleted of exchange capacity, the resin bed is regenerated with concentrated acid and caustic which strips away accumulated ions through physical displacement, leaving hydrogen or hydroxyl ions in their place.
Deionizers exist in four basic forms: disposable cartridges, portable exchange tanks, automatic units, and continuous units. A two-bed system employs separate cation and anion resin beds. Mixed-bed deionizers utilize both resins in the same vessel. The highest quality water is produced by mixed-bed deionizers, while two-bed deionizers have a larger capacity. Continuous deionizers, mainly used in labs for polishing, do not require regeneration.
TESTING Dl WATER QUALITY
Water quality from deionizers varies with the type of resins used, feed water quality, flow, efficiency of regeneration, remaining capacity, etc. Because of these variables, it is critical in many Dl water applications to know the precise quality. Resistivity/ conductivity is the most convenient method for testing Dl water quality. Deionized pure water is a poor electrical conductor, having a resistivity of 18.2 million ohm-cm (18.2 megohm) and conductivity of 0.055 microsiemens. It is the amount of ionized substances (or salts) dissolved in the water which determines water’s ability to conduct electricity. Therefore, resistivity and its inverse, conductivity, are good general purpose quality parameters.
Because temperature dramatically affects the conductivity of water, conductivity measurements are internationally referenced to 25°C to allow for comparisons of different samples. With typical water supplies, temperature changes the conductivity an average of 2%/°C, which is relatively easy to compensate. Deionized water, however, is much more challenging to accurately measure since temperature effects can approach 10%/°C! Accurate automatic temperature compensation, therefore, is the “heart’ of any respectable instrument.
RECOMMENDED MYRON L METERS
Portable instruments are typically used to measure Dl water quality at points of use, pinpoint problems in a Dl system confirm monitor readings, and test the feed water to the system. The handheld Myron L meters have been the first choice of Dl water professionals for many years. For two-bed Dl systems, there are several usable models with displays in either microsiemens or ppm (parts per million) of total dissolved solids. The most versatile instruments for Dl water is the 4P or 6PFCE Ultrameter II™, which can measure both ultrapure mixedbed quality water and unpurified water. It should be noted that once Dl water leaves the piping, its resistivity will drop because the water absorbs dissolved carbon dioxide from the air. Measuring of ultrapure water with a hand-held instrument requires not only the right instrument, but the right technique to obtain accurate, repeatable readings. Myron L meters offer the accuracy and precision necessary for ultrapure water measurements.
Inline Monitor/controllers are generally used in the more demanding Dl water applications. Increased accuracy is realized since the degrading effect of carbon dioxide on high purity water is avoided by use of an in-line sensor (cell). This same degradation of ultrapure water is the reason there are no resistivity calibration standard solutions (as with conductivity instruments). Electronic sensor substitutes are normally used to calibrate resistivity Monitor/controllers.
Myron L Meters carries a variety of inline instruments, including resistivity Monitor/controllers designed specifically for Dl water. Seven resistivity ranges are available to suit any Dl water application: 0-20 megohm, 0-10 megohm, 0-5 megohm, 0-2 megohm, 0-1 megohm, 0-500 kilohm, and 0-200 kilohm. Temperature compensation is automatic and achieved via a dual thermistor circuit. Monitor/controller models contain an internal adjustable set point, piezo alarm connectors and a heavy-duty 10 amp relay circuit which can be used to control an alarm, valves, pump, etc. Available options include 4-20 milliamp output, 3 sensor input, 3 range capability and temperature. Internal electronic sensor substitutes are standard on all Monitor/controllers.
Sensors are available constructed in either 316 stainless steel or titanium. All sensors are provided with a 3/4″ MNPT polypropylene bushing and 10 ft./3 meters of cable. Optional PVDF or stainless steel bushings can be ordered, as well as longer cable lengths up to 100 ft./30 meters.
The following table briefly covers recommended Myron L meters for Dl water applications.
Tweet Reverse Osmosis RO Meter – RO-1: 0-1250 ppm with color band RO Meters The choice of professionals for years, this compact instrument has been designed specifically to demonstrate and test Point of Use (POU) reverse osmosis or distillation systems. By measuring electrical conductivity, it will quickly determine the parts per million/Total Dissolved Solids […]
TweetINTRODUCTION AND OVERVIEW The most popular germicide used in water treatment is chlorine, which kills bacteria by way of its power as an oxidizing agent. Chlorine is used not only as a primary disinfectant at the beginning of the treatment process, but also at the end to establish a residual level of disinfection during distribution […]
INTRODUCTION AND OVERVIEW
The most popular germicide used in water treatment is chlorine, which kills bacteria by way of its power as an oxidizing agent. Chlorine is used not only as a primary disinfectant at the beginning of the treatment process, but also at the end to establish a residual level of disinfection during distribution as a guard against future contamination.
The most popular field test instruments and test systems for judging the level of residual chlorine, also called Free Available Chlorine (FAC), are based on colorimetric methods whereby dyeing agents are added to the sample being tested. These additives react to FAC causing a color change in the test sample. While they may detect the presence of FAC, they do not directly measure the electrochemical characteristic of FAC responsible for its disinfecting power: Oxidation-Reduction Potential (ORP). They give an incomplete and sometimes misleading picture of sanitizing strength. These methods have gained industry-wide acceptance. Unfortunately, so have the weaknesses and inaccuracies inherent to them.
The Free Chlorine Equivalent (FCE) feature avoids these pitfalls by directly measuring ORP, the germ-killing property of chlorine and other oxidizing germicides. It displays both the ORP reading (in millivolts DC) for the sample being tested as well as an equivalent free chlorine concentration in familiar ppm (parts per million). It accounts for the very significant effect of changing pH on chlorine sanitizing power; can be used for other types of oxidizing germicides and; will track the effect of additives, such as cyanuric acid, that degrade chlorine effectivity without changing the actual concentration of free available chlorine present.
NaOCl, common household bleach (5.3% NaOCl by weight) is the most popular chlorinating agent in use today. When added to water it hydrolyzes as:
NaOCl + H2O HOCl + Na+ + OH-
Sodium hypochlorite Water Hypochlorous acid Sodium ion Hydroxide
Additionally, some of the HOCl dissociates into H+ and OCl-:
HOCl H+ + OCl-
Hypochlorous acid hydrogen ion hypochlorite ion
Both HOCl and OCl- are oxidants and effective germicides, particularly against bacteria and viruses, with some effectivity against protozoa and endospores. HOCl is the stronger and more effective of the two species.
When chlorine is added to water, not all of it is available to act against future contaminates. Some is deactivated by sunlight. Some is consumed by reactions with other chemicals in the water or by out-gassing as Cl2. More commonly, it is used up directly by disinfection of the pathogens already
present in the water or by combining with ammonia (NH3) and ammonium (NH4+) (byproducts of living bacteria) to form various chloramine compounds.
Chlorine Demand is the amount of chlorine in solution that is used up or inactivated after a period of time and therefore not available as a germicide.
Free Available Chlorine
Free Available Chlorine (FAC) is any residual chlorine that is available, after the chlorine demand is met, to react with new sources of bacteria or other contaminants. According to White’s Handbook of Chlorination and Alternative Disinfectants, 5th edition, this is the sum of the all of the chemical species that contain a chlorine atom in the 0 or +1 oxidation state and are not combined with ammonia or other organic nitrogen. Some species of FAC that might be present are:
• Molecular chlorine: Cl2
• Hypochlorous acid: HOCl
• Hypochlorite: OCl-
• Trichoride: Cl3- a complex formed by molecular chlorine and the chloride ions (Cl-)
In most applications the two most common species of free chlorine will be HOCl and OCl-. Much of the Cl2 will hydrolyze into HOCl that, depending on pH, will stay in the form of HOCl or partially dissociate into OCl-. Cl3- is very unstable and only trace amounts will be present. In fact, in most of the literature describing chlorination and the monitoring of chlorine residuals, free chlorine is considered to be the sum of HOCl and OCl-.
Chlorine dioxide, ClO2, is another chlorine derivative used in some public water supplies as a disinfectant. It is 10 times more soluble in water than chlorine and doesn’t hydrolyze into HOCl or dissociate into OCl-. In the absence of oxidizable substances and in the presence of hydroxyl ions, ClO2 will dissolve in water then decompose slowly forming chlorite ions (ClO2-) and chlorate ions (ClO3-), both of which are oxidants fitting White’s definition of free chlorine.
All other things being stable (temperature, pH, etc.), ORP values are related to FAC concentration levels. As the concentration of FAC in solution rises or falls, regardless of the species (HOCl, OCl-, ClO2-, ClO3- or Cl3-), the ORP value does, as well.
Combined and Total Chlorine
The term Combined Chlorine usually refers to residual chlorine that has combined with NH3 or NH4+ to form monochloramine (NH2Cl),
dichloramine (NHCl2) or trichloramine (NCl3). Combined chlorine is noteworthy here because chloramines are oxidizers and are used as germicides, though their reduction potential and therefore, disinfecting power is lower than other species of chlorine, such as HOCl, OCl- or ClO2.
Total chlorine is the sum of FAC and Combined Chlorine. An advantage of ORP-based systems is
that the aggregate ORP value of the water being tested includes the ORP levels contributed by all oxidizers, including chloramines. Therefore, ORP- based measurements automatically take into account Total Chlorine and can readily be used to judge total sanitizing strength.
Chlorine as an Oxidizing Germicide
Both HOCl and OCl- are oxidants and as such their effectivity as germicides can be determined using
ORP measurements. The cytoplasm and proteins in the cell walls of many harmful microbes are negatively charged (they have extra electrons). Any oxidant that comes into contact with the organism will gain electrons at the expense of the proteins, denaturing those proteins and killing the organism.
When enough chlorine is added to water to reach an ORP value of 650mV to 700mV, bacteria such as E. coli and Salmonella can be killed after only 30 seconds of exposure. Many yeast species and fungi can be killed with exposure of only a few minutes. Even ORP values of 350mV to 500mV indicate effective levels of chlorination with satisfactory microbe kill levels, although exposure times are required to be in the minutes rather than seconds.
The Importance of pH
pH significantly changes relative effectiveness of chlorine as a disinfectant. Different species of chlorine ions are more prevalent at different pH levels. Under typical water treatment conditions in the pH range 6–9, HOCl and OCl- are the main chlorine species. Depending on pH level, the ratio of these two free chlorine species changes.
Figure 1 – Distribution of Free Chlorine Species in Aqueous Solutions
Figure 1 shows that chlorine hydrolysis into HOCl is almost complete at pH ≤ 4. Dissociation of HOCl into OCl- begins around 5.5 pH and increases dramatically thereafter2. This is important because HOCl and OCl- do not have the same effectivity as disinfectants. HOCl can be 80-100% more effective as a disinfectant than OCl-. Optimum disinfection occurs at pH 5 to 6.5 where HOCl is the prevailing species of free chlorine present. As pH rises above that level, the ratio shifts towards being primarily OCl-. At pH 7.5 the ratio is about even. When the pH value rises to 8 or higher, OCl- is the dominant species. Therefore, assuming the concentration of Cl2 species is constant, the higher the pH of the solution rises above 5.5, the lower the oxidation capability and disinfecting power of the FAC.
The bottom line is knowing the concentration of FAC ions in a solution without taking pH into account can give an incomplete and sometimes incorrect picture of disinfecting power.
WHY A CHANGE IS NEEDED
The Problem with Colorimetric Testing
First and foremost, colorimetric tests only report how much chlorine is present, and as we saw in the previous section, knowing “how much” is not at all the same as knowing “how effective”.
Colorimeters and DPD kits add a reagent or several reagents to the water being tested that causes a color change representing the amount of FAC in water. In fact, they fundamentally change the chemistry of the water just to get an easy measurement.
The most obvious change is related to pH. The typical reagent/dye used in the process forces the pH of the sample to a specific level, usually 6.5 pH and thus radically alters the HOCl to OCl- ratio. If the original sample was at a pH of 7.4 to 7.6 (suggested levels for pools and spas) about 50% of the FAC present would be in the form of HOCl. At a pH of 6.5 this ratio rises to nearly 90%. While the actual concentration of FAC may be correct, a fact entirely overlooked is that the FAC in the source water includes about 40% of the much weaker sanitizing OCl-.
If that were the only change being made to the chemistry of the sample, it would be severe enough.
Figure 2 shows the result of a comparison test made using a UV spectrophotometer on two samples of water. Both were taken from a master water sample containing 5 ppm Cl2 prepared using a closed system that ensured no other oxidants or interferants were present. One was processed using a colorimeter reagent according to its operator’s manual instructions. The other was left untreated.
Figure 2: Chemical Alteration of Chlorinated Water by Colorimeter Additives
UV spectrophotometric analysis shows how dramatically the chemistry of the sample was changed by the addition of the colorimeter’s coloring reagent.
• The shift in the center of the spike indicates that the species of chlorine present has been altered. What was OCl- is now some other chemical species.
• The amplitude of the spike demonstrates how severely the amount of chlorine has been amplified.
• The absorption spectra where OCl- used to be is significantly depressed.
Because the area of UV absorption spectra where any OCl- would appear is so depressed, it is clear that a radical alteration is taking place above and
beyond simply changing the pH. The “ppm” value reported for the chlorine content of the water seems to be converted to a single species whose
concentration is significantly higher than the original OCl- content.
Even assuming a linear relationship between this altered chemistry and the original FAC content of the water that might be factored into the final colorimetric measurement, by completely divorcing the measurement from the pH of the source water, any direct correlation to the reduction potential of the FAC present and, therefore, real disinfecting power, is lost.
ORP = DISINFECTING POWER
What is ORP?
ORP is the acronym for Oxidation Reduction (REDOX) Potential. It is a differential measurement of the mV potentials built up between two electrodes exposed to solutions containing oxidants and/or reductants. ORP describes the net magnitude and direction of the flow of electrons between pairs of chemical species, called REDOX pairs. In REDOX reactions, one chemical of the pair loses electrons while the other chemical gains electrons. The chemicals that acquire electrons are called the oxidants (HOCl, OCl-, ClO2, bromine, hydrogen peroxide, etc.). The chemicals that give up electrons are called the reductants (Li, Mg2+, Fe2+, Cr, etc.).
Oxidants acquire electrons through the process of reduction, i.e., they are reduced. Reductants lose their electrons through the process of oxidation, i.e., they become oxidized.
How is ORP Measured?
ORP sensors are basically two electrochemical half- cells: A measurement electrode in contact with the solution being measured and a reference electrode in contact with an isolated reservoir of highly concentrated salt solution. When the solution being measured has a high concentration of oxidizers, it accepts more electrons than it looses and the measurement electrode develops a higher electrical potential than the stable potential of the reference electrode. A voltmeter in line with the two electrodes will display this difference in electrical potential (reported in mV). Once the entire system reaches equilibrium, the resulting net potential difference represents the Oxidation Reduction Potential (ORP). A positive reading indicates an oxidizing solution, and a negative reading indicates a reducing solution. More positive or negative values mean the oxidants or reductants present are stronger, they are present in higher concentrations or both.
What Does ORP Measure?
Measuring ORP is the most direct way to determine the efficacy of oxidizing disinfectants in aqueous solutions. It measures the actual chemical mechanism by which oxidizers, like chlorine, kill bacteria and viruses. The higher the ORP value, the stronger the aggregate residual oxidizing power of the solution, the more aggressively the oxidants in it will take electrons from the cells of microbes and, therefore, the more efficiently and effectively any source of new microbial contamination will be neutralized.
Also, because ORP measures the total reduction potential of a solution, ORP measures the total efficacy of all oxidizing sanitizers in solution: hypochlorous acid, hypochlorite, monochloramine, dichloramine, hypobromous acid, ozone, peracetic acid, bromochlorodimethylhydantoin, etc.
Can ORP Replace Free Chlorine Measurements?
When correlated with known disinfection control methods, measurements and bacterial plate counts, this type of measurement gives an accurate picture of the residual chlorine sanitizing activity reported as an empirical number that is not subject to visual interpretations. Solutions with certain ORP levels kill microbes at a certain rate. Period!
ORP was first studied at Harvard University in the 1930s as a method for measuring and monitoring microbial disinfection. It has been advocated as the best way to judge residual disinfecting power of chlorinated water by water quality experts since the 1960s. ORP has long been used in bathing waters as the only means for automatic chemical dosing. The World Health Organization (WHO) suggests an initial ORP value of between 680-720 mV for safe bathing water3 and ~800 mV for safe drinking water.
For the purpose of pretreatment screening to detect chlorine levels prior to contact with chlorine- sensitive RO membranes, some manufacturers of RO membranes and other water quality treatment equipment will also specify an ORP tolerance value for prescreening and influent control.
There are, however, applications where reporting residual disinfecting power in terms of FAC concentrations is preferred and sometimes required. While ORP measurements do not directly measure the concentration of FAC, they can be correlated to free chlorine levels in ppm. Variables such as pH and temperature must be accounted for or controlled. Interfering chemicals that might be present, such as other oxidants or reductants, must also be accounted for, or better yet, removed.
Once all these factors are known or controlled, ORP values can be linked to concentrations either by way of laboratory experimentation or via mathematical formulas like the Nernst Equation, an equation that describes the relationship between the electrode potential of a specific chemical in a solution and its concentration. In either case this is an often complex and laborious process … until now.
FCE = HANDHELD ORP ACCURACY
ORP Relevance in a Handheld Instrument
The Myron L Company has developed an innovative method for using ORP-based measurement to directly monitor the disinfecting power of free chlorine and report the result in both familiar ppm units as well as straight ORP mV values.
Myron L Company’s FCE function utilizes the accurate and reliable electronic design of Myron L Company’s instruments combined with simple one- button operation to make ORP-based chlorine measurement available in an easy-to-use, handheld field instrument. Other handheld instruments may measure ORP, but only a Myron L Company instrument equipped with FCE quickly correlates ORP and pH with FAC concentration. The FCE function also includes a predictive algorithm that extrapolates a final, stable ORP value of a solution without waiting out the long response time of the typical ORP sensor.
When the FCE function is active, the instrument display alternates between the Predicative ORP reading (mV) and the Free Chlorine Equivalent (FCE) concentration (ppm). Together these features combine to make ORP-based free chlorine measurement relevant in a handheld field instrument.
FCE – How and Why it Works
The Myron L Company FCE feature cross-references ORP values with pH levels to automatically arrive at a concentration value for FAC that reflects the effect of pH on the ratio of HOCl to OCl-. This correlation is derived from a series of experiments in which exact amounts of chlorine (in the form of laboratory grade bleach: 5% NaOCl; 95% H2O) were added to deionized water in a closed system, thus controlling and excluding possible interferants. By using both a pH measurement and an ORP measurement, FCE can determine the relative contributions of HOCl and OCl- to the final ORP value and factors them into a final concentration calculation.
Figure 3 – Sample Experimental Data Relating FAC ppm to ORP and pH
Similar experiments were performed using water to which precise amounts of calcium chloride (CaCl2) and sodium bicarbonate (NaHCO3) were added to slightly buffer the water. This allows the FC feature to correlate low ORP values to the typically low FAC concentrations of tap water after it has been in the municipal water system for several days.
FCE – pH Included, Not Ignored
Unlike other FAC test methods that ignore the effect of pH on sanitizing power by artificially forcing the pH of their test sample to a single value, Myron L Company’s FCE includes pH in its concentration calculation. This capability gives Myron L Company’s FCE the ability to compensate for the effect of the changing ratio of chlorine species as pH
changes, resulting in a FAC concentration value germane to the actual sanitizing power of the source water. OCl- is measured as OCl-, and HOCl is measured as HOCl. Those users who are primarily concerned with or who prefer free chlorine concentration levels have a reliable measurement that gives consistent and comparable results, reading to reading, without having to rigorously control or artificially manipulate the sample’s pH.
In addition, because the FCE function displays both the FAC concentration and a predicted, stable ORP value, the user can, by comparing these two values from successive measurements, track how ORP (and disinfecting power) falls as pH rises and how ORP rises as pH is lowered when concentration is constant.
FCE – Chemistry Measured, Not Altered
Both DPD kits and colorimeters may tell the user the FAC concentration of the sample in the test tube, but since the chemistry of that sample is quite different from the source water being analyzed, the results are imprecisely related to actual disinfection power.
DPD kits and colorimeters only imply true disinfecting power; they do not measure it, and that is, after all, the whole point of the exercise.
The Myron L Company FCE method avoids these pitfalls and inaccuracies. FCE measures the real, unaltered chemistry of source water, including moment-to-moment changes in that chemistry.
The following controlled study shows exactly how differently the two methods respond, particularly at the high end where the effects of changes in pH are the greatest. In this study measurements were made with a digital colorimeter and a Myron L Company Ultrameter II 6P equipped with FCE. The solutions tested were made with various known concentrations of NaOCl in deionized water. The water was heated to above 80°C to remove any CO2 and, therefore, avoid interference from REDOX reactions between HOCL, OCl- and carbonates (HCO3).
Table 1 – Comparison of FCE to Digital Colorimeter
In this study as the pH rises and the ratio of OCl- to HOCL rises dramatically, the FCE is able to accurately track the changing concentration of FAC. The colorimeter’s results do not.
FCE – Handheld ORP Accuracy Without the ORP Delay
One of the challenges in implementing an ORP- based free chlorine measurement in a handheld field instrument is the sometimes lengthy response time of ORP sensors. It is not uncommon for an ORP sensor to take 12 to 15 minutes to arrive at a valid stable reading. In extreme cases, such as an older sensor in poor condition and measuring a complex solution with a very low ionic strength, the ORP measurement can take up to an hour to fully stabilize. Obviously, for a handheld instrument these are unacceptably long times.
The Myron L Company FCE function includes a pioneering feature that dramatically reduces the wait for stable ORP readings. This unique feature determines an extrapolated, final, stabilized ORP reading within 1 to 2 minutes rather than the typical 15 minutes or hours for other ORP systems.
The Predictive ORP feature’s calculations are based on a model of sensor behavior developed through a series of experiments that measured the response time of a representative sample of ORP sensors over a range of controlled chlorine concentrations. The results of this set of experiments revealed that the shape of the curve is very similar for various ORP levels differing only in the initial starting point and the final stabilized reading.
Figure 4 – Example of ORP Sensor Response Study
Using a proprietary curve-matching algorithm, the Predictive ORP feature determines what point along the typical sensor response curve a measurement occurred and extrapolates an appropriate final reading. This extrapolated value is used to calculate the FCE ppm value without having to wait for the sensor to stabilize and is also reported directly to the instrument’s display.
FCE – FLEXIBILITY FOR THE REAL WORLD
Another advantage of an ORP-based measurement such as the Myron L Company FCE feature is that, within the limits of its range, it can be used to measure the disinfection effectivity of ANY oxidizing germicide. Myron L Company FCE measurement can be used with non-bleach oxidants, such as chloramines or even non-chlorine oxidants, such as peracetic acid, bromine or iodine.
The Predictive ORP value displayed when the FCE function is active is directly relevant for monitoring and controlling the sanitizing effectivity of oxidizing sanitizers besides HOCl and OCl-.
While the concentration values reported by the FCE function will not be absolutely correct for non-FAC oxidants, since they are based on a HOCl / OCl- model, FCE can still be an effective tool for monitoring relative changes in concentration levels. For absolute accuracy a correlative study should be performed to relate concentration levels of the oxidant in question to the ORP values displayed by the Predictive ORP feature and ppm values output by the FCE.
FCE = Effective Chloramine Control
A perfect example of the Myron L Company FCE ‘s flexibility is the use of chloramines as a germicide.
Chloramines are formed when chlorine (Cl2) and ammonia (NH3) come into contact, forming three different inorganic chemicals: monochloramine (NH2Cl), dichloramine (NHCl2) and trichloramine (NCl3). In some applications chloramines are considered an unavoidable side effect of the chlorination process; however, because they are also oxidants, there are other applications where they are used as the primary disinfectant in water treatment.
Chloramines are effective at killing bacteria and other microorganisms, but because their relative ORP levels are lower compared to HOCl or OCl- at the same concentrations, the disinfection process is slower.
Table 2 – Electrode Potentials of Chloramines vs. HOCl
On the plus side, chloramines last longer than HOCl and OCl- (as long as 23 days in some cases), impart a less strong flavor or smell and their sanitizing
strength is not appreciably affected by changing pH.
Most importantly, chloramine-based water treatment methods produce much fewer hazardous byproducts. The US EPA limits the total concentration of the four chief hazardous byproducts of chlorination (chloroform, bromoform, bromodichloromethane, and dibromochloromethane), referred to as total trihalomethanes (TTHM), to 80 parts per billion in treated water. To avoid exceeding theses standards, many municipal water districts prefer using chloramine rather than chlorine.
The following table shows typical ORP values for various concentrations of monochloramine (NH2Cl).
Table 3 – ORP Values for NH2Cl in Pure Water
When ORP levels of NH2Cl approach and exceed 500 mV, effective sanitization occurs with exposure times of 20 to 30 minutes. This is more than adequate for municipal water treatment.
Since Myron L Company FCE function bases its measurement on ORP, it presents an empirical, easy to interpret measurement, both in terms of the Predictive ORP display and the FAC equivalent concentration, allowing the user to monitor falling chloramine concentration as disinfection proceeds.
FCE and Cyanuric Acid (CYA) – Don’t Guess. Know!
Outdoor pool maintenance is a prime application where ORP-based chlorine measurement should be preferred. The use of chlorine to sanitize pools runs afoul of the fact that much of the chlorine added to an outdoor pool is deactivated by exposure to UV radiation in sunlight.
Cyanuric Acid (CYA) is often added to the pool water to “protect” FAC. In a typical pool at 7.6 pH about 50% of the FAC is OCl-, which reacts to UV radiation that passes through the Earth’s ozone layer (290nm). CYA combines with FAC to form N-chlorinated-cyanurates, which only react to UV radiation (215nm to 235nm) removed by the Earth’s ozone layer. Since N-chlorinated-cyanurates are also oxidizers, they also act as germicides. Unfortunately, they have much lower reduction potentials and, therefore, a much lower strength as a germicide.
Figure 5 – Effect of Cyanuric Acid on Chlorine ORP Values
Pool maintenance websites that advocate the use of cyanuric acid (not all of them do) often recommend levels of 40 to 80 ppm. Figure 5 shows how severely ORP and disinfecting power are affected by CYA.
The addition of only 20 ppm CYA decreases the pool water’s ORP 120 mV, reducing the effectivity of FAC from 1.5 ppm to an effectivity that is equivalent to only 0.3 ppm. Adding 40 ppm, or worse, 80 ppm, reduces sanitizing strength even more severely. This is definitely a case where more is not better.
A 1972 study on water chlorination showed that water treated with enough chlorine to kill 100% of the E. coli present in 3 minutes or less required almost 6 times as much chlorine be added for the same effect when 50 ppm of CYA was added.
Cyanuric acid beneficially affects pool chlorination by greatly reducing that portion of chlorine demand related to loss due to UV. Unfortunately, if you are using a colorimeter or DPD kit, it will tell you that your FAC concentration is unchanged and significantly misrepresent sanitizing strength
The Myron L Company FCE function’s ability to react to changes in ORP makes it an ideal tool for keeping track of how CYA affects residual sanitizing power when added to a chlorinated pool. The Predicative ORP display provides a direct and effective way to monitor changes in ORP values as CYA concentration increases. Because the FCE ppm
display reacts to changes in ORP and pH, it will reflect changes in the sanitizing strength as an “equivalent” or “effective” FAC concentration.
Judging the true effectivity of chlorine as an oxidizing germicide requires more than just knowing how much chlorine is present. Changing pH or the addition of additives like cyanuric acid can radically alter the effectivity of the chlorine present. To accurately measure the effects of these issues requires a test method based on the precise measurement of ORP (the chemical characteristic directly responsible for killing microbes like bacteria and viruses) and cross-referenced to pH.
The Myron L Company FCE is the first measurement function that allows handheld, field instruments to integrate ORP and pH measurements into a system for monitoring the residual disinfecting power of free available chlorine in aqueous solutions.
• It provides an empirical measurement that does not require interpretation.
• It is not affected by water color or turbidity.
• It measures the true chemistry of the water, unaltered.
• It accounts for changes in pH.
• It reports the effects of CYA on disinfecting power.
• It can be used to monitor non-chlorine oxidants.
Myron L Meters features the Myron L FCE function in several instruments that read free chlorine – the Ultrameter II 6P, the Ultrameter III 9P, the PoolPro PS9 and PS6 models, and the
new Ultrapen PT4, soon to be released.