Cyanuric Acid in Commercial Swimming Pools and its Effects on Chlorine’s “Staying Power” And Oxidation Reduction Potentials By Aaron Askins Submitted to the Graduate Faculty of North Carolina State University in partial fulfillment of the requirements for the Degree of Master of Environmental Assessment Raleigh, North Carolina 2013 Approved by advisory committee: Committee Chair: Linda R. Taylor, PE Abstract Cyanuric acid levels in commercial swimming pools has been a controversial topic in the swimming pool industry in the past few years. This chemical is known for its stabilizing abilities by protecting chlorine from the ultraviolet rays of the sun which cause photolysis. Cyanuric acid has received recognition for this ability, but has also received blame for over stabilization which reduces the effectiveness of sanitization and oxidation reduction potential (ORP) of chlorine. This loss in effectiveness could possibly result in recreational water illnesses arising due to water quality standards being compromised. Local and state regulations can make it unclear on what parameters cyanuric acid levels should be in commercial swimming pools due to its inconsistencies across the United States. These variances are wide and could possibly lead to confusion amongst pool professionals to exactly where they should be when applying this chemical. In this project a look at the “staying power” of chlorine and its oxidation reduction potential at various levels of cyanuric acid will hopefully develop an understanding on where the ideal range of this chemical should be kept. This along with surveys from North Carolina professional pool companies and an interview with a local official who oversees commercial pool inspections in Wake County will develop a foundation on the perception of how pool professionals view this chemical and its capabilities along with testing for its levels. An overall ideal range on cyanuric acid levels for swimming pools that require stabilized chlorine will be reached through the information gathered on this project. This will help the pool professional understand its use and keep higher water quality standards in commercial swimming pools. i Biography Aaron Askins began his career in the swimming pool industry during his sophomore year at Indiana University while in pursuit of his Bachelor’s Degree in Business Administration. Upon completion of his degree, he continued to stay within the trade and has worked in many facets of the industry including service, construction, and distribution. During this time, he has not only helped in the construction of hundreds of pools, but has also spent an abundant amount of time in chemistry and technical training. In the past he has felt that the industry has always been somewhat antiquated and has lagged in technological development, as well as, a lack of growth in professional individuals to help promote advancement in the industry. He would like to continue to see an influx of educated individuals enter the industry, as well as, help the people that are currently within the trade achieve the necessary training that will benefit them in the industry. Aaron’s aspiration to have a career in the environmental field has pushed him to look at issues in the swimming pool industry that have impacted the environment and the people that are within it. He entered the Masters of Environmental Assessment Program at North Carolina State University due to the desire to be within this field, as well as, his passion for studying science and natural resources. Aaron hopes to further develop himself within the environmental arena so that he can cultivate a career that will ultimately help individuals and businesses improve themselves so that today’s environmental issues will diminish. ii Acknowledgements I would like to thank all the professional pool companies who took time to speak with me on the questions I had about cyanuric acid levels in commercial swimming pools. This allowed me to form a foundation on what the first-hand perception was of this chemical within the North Carolina swimming pool industry. I would also like to thank the Section Chief of the Wake County Plan Review and Sanitation Program, Terry Chappell, for his time in providing what is expected by local officials when regulating and maintaining commercial swimming pools. His information on regulations and testing provided me with what the pool professional faces while maintaining their commercial swimming pools. iii Table of Contents I. Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i II. Biography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii III. Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii 1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 1.1 Physical Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 1.2 Testing and Regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 2. Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 2.1 Cyanuric Acid and UV Effect on Free Chlorine Readings (Methods). . 19 3. Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .22 4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .26 IV. Works Cited . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .28 iv 1 Introduction Cyanuric acid (C H N O ) in chlorinated swimming pools reduces the rate of decomposition of 3 3 3 3 free available chlorine by ultraviolet rays in sunlight. This odorless white granular substance, which also goes by the names of stabilizer or conditioner, has been used in public and private swimming pools since 1958 to increase the stability of chlorine (O'Connell, 2003). The desire to have stabilized chlorine is derived from a need to properly sanitize water that will be used by humans for recreational use. Since many pools rely on chlorine compounds to kill bacteria and viruses that can be introduced to a swimming pool, it is important that free chlorine levels are not compromised. A compromised chlorine level could lead to recreational water illnesses that could be resultant from viruses, germs, and bacteria that include culprits such as cryptosporidium, giardia, legionella, and MRSA. The swimming pool industry is an expansive industry that involves over 10.5 million swimming pools in the United States (APSP, 2013). According to the Center for Disease Control and Prevention (CDC) approximately 301 million swimming visits were made to swimming pools by persons over the age of six in 2009 making it the fourth most popular recreational activity in the United States (Centers for Disease Control and Prevention, 2013). Going deeper into this data, thirty-six percent of children the age of 7-17 years and fifteen percent of adults swim at least six times a year. For the ages of 7-17 years, this means swimming is the most popular recreational activity in the United States. Due to the incredible vastness of the people involved with this recreational activity, regulations are put forth for the commercial part of the industry to control how these bodies of water are chemically maintained. Some research shows that these 5 regulations are inconsistent and can vary state to state, county to county, and even sometimes inspector to inspector. The question could be asked if this inconsistency within regulations could create confusion amongst pool professionals that may lead to poorly maintained pools and therefore an increased risk of recreational water illnesses. The CDC stated that in 2008 almost 1 in 8 (12% or 13,532 of 111,487) routine pool inspections conducted identified serious violations that threatened public health and safety and resulted in immediate closure. Also the CDC specified that more than 1 in 10 (10.7% or 12,917 of 120,975) routine pool inspections recognized pool disinfectant level violations (Centers for Disease Control and Prevention, 2013). The CDC recommends chlorine be continuously at 1-3 parts per million. These type of violations in 2007-2008 resulted in nearly 14,000 cases of recreational water illnesses being reported to the CDC. Cryptosporidium is a highly chlorine resistant parasite that infects the small intestine (Kraft, 2010) and was a major culprit for these illnesses. Chlorine, in one form or another, is the most used barrier to the spread of germs in the water that people swim. Swimming pool chlorines come in six forms and can be classified as an unstabilized or stabilized form. Unstabilized chlorines include chlorine gas (Cl ), sodium 2 hypochlorite (NaOCl), calcium hypochlorite (Ca(OCl) ), and lithium hypochlorite (LiOCl). An 2 additional alternative to unstabilized chlorine use are salt systems that use electrolysis to produce a sodium chloride solution. Stabilized chlorines, which contain cyanuric acid and are also known as chlorinated isocyanurates, include Trichloro-s-triazinetrione (Trichlor) and Sodium Dichloro-s-triazinetrion (Dichlor). Dichlor is usually marketed for the residential swimming pool market whereas Trichlor is often used for small commercial pools, such as those 6 at hotels and motels (Lincoln, 2008). These different types of chlorines can also vary by ease of use or handling, cost, active ingredients, and inert ingredients. Regardless of the form, they all have two similar functions. These functions include killing or inactivating microorganisms that are present within the water and to oxidize any organic contaminants introduced to the water by the bathers. Studies have shown that only 10% of chlorine is needed for sanitization while 90% of chorine is used for oxidation (Taylor Technologies, Inc., 2011). The oxidation-reduction potential (ORP) is a value that can be taken to evaluate a chlorines work value. These chlorines all have their advantages and disadvantages, but all produce a similar product, hypochlorous acid (HOCl) (Figure 1). Figure 1. Comparison of chlorine sanitizers Chlorine Gas CHLORINE GAS + WATER  HYPOCHLOROUS ACID + MURIATIC ACID [Cl ] [H O] [HOCl] [HCl] 2 2 Advantages Disadvantages  least expensive chlorine sanitizer  high capital costs required; feasible when pool is greater than 200,000 gallons  dangerous to handle; complex regulations and associated costs  lowers pH dramatically; destroys total alkalinity; high base demand Sodium Hypochlorite SODIUM HYPOCHLORITE + WATER  HYPOCHLOROUS ACID + SODIUM ION [NaOCl] [H O] [HOCl] [Na+] 2 Advantages Disadvantages  completely soluble in water  contains 90% water; bulky and heavy to  when sold as a bulk liquid, least costly source handle; readily bleaches clothes/carpets of chlorine outside of chlorine gas  most alkaline chlorine sanitizer; significant acid  clean product; no residue in pool water demand  significant decomposition in storage 7 Figure 1. (continued) Calcium Hypochlorite CALCIUM HYPOCHLORITE + WATER  HYPOCHLOROUS ACID + CALCIUM ION (HARDNESS) [Ca(OCl )] [H O] [HOCl] [Ca+2] 2 2 Advantages Disadvantages  easily handled; compact source of chlorine  increases pH; high acid demand  no significant storage decomposition  for hard water; significantly raises calcium  for soft water; significantly increases calcium hardness hardness  creates some turbidity due to inert insolubles Lithium Hypochlorite LITHIUM HYPOCHLORITE + WATER  HYPOCHLOROUS ACID + LITHIUM ION [LiOCl] [H O] [HOCl] [Li+] 2 Advantages Disadvantages  safest chlorine chemical to handle  highest cost chlorine sanitizer  completely soluble in water  high TDS chemical due to significant inert  dissolves quickly at normal pool temperatures content (71%)  no premixing required; will not bleach vinyl liners at normal pool temperatures Trichloro-s-triazinetrione [trichloroisocyanuric acid (TCCA)] TCCA TABLETS + WATER  HYPOCHLOROUS ACID + STABILIZER [TRICHLOR] [H O] [HOCl] [CYANURIC ACID] 2 Advantages Disadvantages  slow dissolving; good for chlorinators  reduces total alkalinity  convenient to use  high base demand; requires addition of sodium bicarbonate  high-strength chlorine; readily supports combustion on contact with paper, rags, paint, oil, etc.  overstabilization possible 8 Figure 1. (continued) Sodium Dichloro-s-triazinetrion [sodium dichloroisocyanurate (NaDCCA)] NaDCCA GRANULES + WATER  HYPOCHLOROUS ACID + STABILIZER [DICHLOR] [H O] [HOCl] [CYANURIC ACID] 2 Advantages Disadvantages  easily handled  most expensive stabilized chlorine  little effect on pH; no acid or base demand  overstabilization possible *Information from Figure 1 is based off information from the Taylor Technologies Pool & Spa Water Chemistry booklet. When adding any one of these chlorines to water, they produce the product of hypochlorous acid (HOCl). This is the vital chemical that inactivates the microorganisms and oxidizes the organics within the body of water. This is the free chlorine measurement that is taken (along with the much weaker OCl-) to determine the effective level of chlorine residual that is in the body of water. HOCl is a weak acid that has four main reactions it can go through that will negatively affect swimming pool sanitization (Taylor Technologies, Inc., 2011). The first reaction is the dissociation of HOCl. This reaction is highly dependent upon pH. As pH increases the HOCl can dissociate into the hydrogen ion (H+) and the hypochlorite ion (OCl-) as seen below. HOCl  OCl- + H+ Although OCl- is considered an active sanitizer, it is much weaker than HOCl and has only 1% of its killing abilities. The second reaction that HOCl faces is its reaction with microorganisms and organics. After HOCl does its job of killing microorganisms or oxidizing organics, it will become an inactive chloride ion (Cl-) and no longer effective in sanitizing. Thirdly, its reaction with 9