Introduction
It’s all about hydrogen ions and water. Hydrogen, you remember, the most abundant molecule on earth, is in the upper right-hand corner of the periodic table of elements. It is just one proton and one electron. Two hydrogen molecules combine with one oxygen molecule to form water. The hydrogen ion (H+) in water has a positive charge; the mirror image chemical is the hydroxyl ion (OH-) that has a negative charge. These two ions are like a teeter-totter. When one is up, the other is down. An acid has a high concentration of hydrogen ions and a low concentration of hydroxyl ions. A base is just the opposite. Put an acid and a base together carefully because they react with vigor to make water and release a lot of energy.
To understand pH, buffers, total alkalinity, and chlorine in any body of water like a pool, spa, pond or drinking water, you have to understand hydrogen ions. [Read more…]
We have all walked into a swimming pool facility, health club, or small motel and immediately recognized that “chlorine” smell emanating from the pool. We have grown to accept the odor and the other side effects of chlorine disinfection as the price paid to have a sanitary swimming pool. The odor and many of these side effects are not actually caused by the chlorine, but are the by-products of chlorine disinfection. Chlorine and bromine are common aquatic system disinfectants and are very effective at killing bacteria. They, and their halogen brothers fluorine and iodine, are all effective sanitizers because they are strong oxidizers (oxidation is the way bacteria is killed). Halogens, like chlorine, are all one electron short of filling their outer electron shell. They are always looking for another compound from which to steal an electron (oxidize). However, their oxidative power is not limited to just attacking bacteria.
Disinfection by-products (DBP) are formed when chlorine oxidizes organic compounds. These organic compounds are found in bacteria and many are critical for the bacteria to live and thrive. However, a lot of organic compounds are naturally present in our water, and putting people into the water introduces even more of these materials (dead skin cells, sweat, urine, etc). When chlorine interacts and oxidizes these organic compounds, it results in a tremendous amount of newly created compounds…but, these now contain chlorine (DBP). We generally classify some of these as combined chlorine or chloramines. It has now been established that many of these DBP are toxic, and while most remain in the water, some are quite volatile and released from the water into the air (i.e. chloroform). These DBP are what we recognize as that “chlorine” smell.
In short, chlorine is going to cause a reaction with anything in its path, and some of these reactions are going be toxic. So, that funky “pool smell” isn’t the chlorine. It’s the dark side of chlorine’s work.
Research at Embro Corporation (Creative Water Solutions’ sister company) is actively investigating the process by which DBP are formed, and the levels of DBP in swimming pools and spas. Our early results have demonstrated that Sphagnum moss leads to a reduction in DBP levels within the first few months of use in a swimming pool. Pointing to the importance of this research are the increasing numbers of scientific articles documenting production of toxic DBP in aquatic systems. They illustrate increased health problems for those experiencing high exposure to these compounds, including competitive and avid recreational swimmers. Stay tuned to our newsletter and website for the newest results of our research in this area.
The publication of a recent article in the February, 2012 issue of the Journal of Allergy and Clinical Immunology adds to the evidence, and increasing concern, of the unhealthy effects of exposure to disinfection by-products (DBP) in swimming pools. The article, entitled “Airway remodeling and inflammation in competitive swimmers training in indoor chlorinated swimming pools” by Bougault et al provides evidence that intense, long term training in indoor chlorinated swimming pools leads to airway changes similar to those seen in asthma.
The study examined 23 competitive swimmers, age 17 and up. The swimmers were evaluated during a period of rest, at least 3 days after their last competition or strenuous training workout. The evaluation tests included standard lung capacity testing, allergy testing, and bronchoscopy with biopsy collection for pathological evaluation.
The findings of the study demonstrated inflammatory and airway remodeling changes in bronchial biopsies of competing swimmers similar to non-athletes with mild asthma. In fact, some of the measured inflammatory parameters were greater than that seen in asthmatic subjects. A majority of the swimmers had atopy (allergic hyperresponsiveness), an important point according to the authors, “as a recent hypothesis stated that atopy may develop in swimmers because of an increasing exposure to chlorination products.”
Whether recreational swimmers and children will develop these changes remains to be determined. However, according to the authors, “reduction of chloramine exposure in pool environments should be considered.”
Reference:
Airway remodeling and inflammation in competitive swimmers training in indoor chlorinated swimming pools. Bougault, V, Loubaki L, Joubert, P et al. J Allergy Clin Immunol 2012; Vol. 129(2):351-358
During our test this last summer at the St. Paul, MN outdoor aquatic park we surveyed the swimmers twice a week. One of the most striking findings was that swimmers with asthma did not need to use their inhalers when swimming in the pools that were conditioned with PoolNaturally® Plus. We then treated the indoor aquatic park in St. Paul and had similar results.
Able to Swim AgainWatch movie online The Transporter Refueled (2015)
In fact one lady wrote to me about her inability to swim indoors due to her asthma. She was a competitive swimmer in her younger years and had to stop swimming because of severe breathing problems from asthma caused by the air in the pool. She heard about the sphagnum moss treated pools and how people could swim without using their inhalers so she tried swimming again. She reported that she could do a full workout without breathing problems and thanked me for “giving her back her favorite sport”.
With a little research the relationship between recreational and home water, chlorine and asthma became clear.
The Chemical Reactions
Here is what happens when we use chlorine to sanitize water in a pool or in our municipal water supply. As it turns out chlorine is not the problem. A byproduct of chlorine and biological molecules that contain nitrogen is the formation chloramines. These chloramines come in many different forms such as mono, di, and trichloramines. One of these compounds, a molecule called trinitrochlorine, has been implicated in causing airway irritation.
Trinitrochlorine is a volatile molecule that is extremely irritating to tissues such as your eyes, skin and airways. Because the molecule is volatile, it rises to the surface of water and is easily inhaled. In fact, in a pool, the levels of trichloronitrate are highest in the air right on top of the water. So every time a swimmer takes a breath, they inhale an irritant that causes airway constriction called reactive airway disease. The smell we all associate with a chlorine pool is actually the smell of the multiple species of chloamines, not chlorine. The problem is that chlorine is so reactive, it immediately finds and combines with nitrogen containing compounds to create chloramines.
Correlation between Pools and Asthma
A recent study reported in the pediatric literature, showed that children who are repeatedly exposed to swimming pools have a significantly higher incidence of reactive airway disease or asthma, than those who aren’t exposed to pools.
In our research laboratory, we are currently studying why the pools treated with PoolNaturally® Plus don’t cause this reactive airway response, skin irritation, or burning eyes and don’t smell. We know that for chlorine to become trichloronitrate you need chlorine, nitrogen containing biological molecules and a low pH. It could be that the amount of organic contamination in the pool correlates with the amount of trichloronitrate because organic contamination contains and produces huge amounts of nitrogen containing molecules and it creates a local microenvironment that has a very low pH. It could therefore be the “engine” that drives the formation of these toxic molecules. In the laboratory we know that the moss in PoolNaturally® Plus inhibits the formation of organic contamination and if our hypothesis is correct it could greatly reduce the formation of chlorine to trichloronitrate by removing the primary nitrogen source, the organic contamination.
This last summer we added our Sphagnum moss pool product to the Highland Park Aquatic Center in St. Paul. We treated two pools. One was a 430,000 gallon Olympic pool and the other was a 22,500 gallon children’s activity pool. You can read about the results on our website.
One lesson we learned involved cyanuric acid, outdoor pools, and chlorine. The accepted dogma is that cyanuric acid is required for outdoor pools and spas to stabilize the chlorine against UV degradation. In fact, most granular or solid chlorine sold in stores is stabilized with cyanuric acid. Dichlor and Trichlor have cyanuric acid in the formula.
When cyanuric acid interferes with chlorine
We started to try and understand the chemistry and science of cyanuric acid because of its side effects. Cyanuric acid above a certain concentration (which is dependent on pH) inhibits chlorine’s (hypochlorous acid to be precise) ability to oxidize bacteria. Failure to oxidize means no killing.
We also found that cyanuric acid is denser than water so it sinks to the bottom of a body of water. Therefore, the level of cyanuric acid on the surface of the pool or spa is the lowest level in the pool and it increases from there to the bottom. It will be the highest in the deepest part of the pool.
We tested this at the Olympic-sized pool. We sampled water at the bottom, middle and top of the pool. The cyanuric acid was set for 40 ppm. At the surface the level was 30-40 ppm, in the middle it was 60-70 ppm and at the bottom it was 100 ppm. From the middle of the pool to the bottom hypochlorous acid was essentially ineffective.
The other fact about cyanuric is that it is nonvolatile. That means as you add more and more to your pool or spa the concentration continues to increase. The only way to decrease the concentration is to empty some water and replace it with fresh water without cyanuric acid so you dilute out the chemical. In places where the spa or pool is full all year long, the concentration of cyanuric acid can increase to the point where the pool has no effective chlorine. I think this is why most pools have algae outbreaks starting in the bottom of the pool. The high cyanuric acid levels inhibit hypochlorous acid so no killing of algae occurs.
The experiment
So, after we learned this, I decided to decrease the cyanuric acid level in the pools gradually to see if it is really needed. The pool engineers told me “if you do that there will be no free chlorine in this pool in the morning.” We agreed to decrease cyanuric acid by 10 ppm each week and monitor the results. The free chlorine levels never decreased and the combined chlorine remained at 0. We decreased the cyanuric acid to zero and never added any more for the rest of the summer. The levels slowly decreased to zero as makeup water diluted out the cyanuric acid. The children’s activity pool behaved exactly the same.
In another pool we treated we were able to manage the large pool all summer without any cyanuric acid and maintained free chlorine levels from 1-3 ppm with no combined chlorine all summer.
Water treated with moss doesn’t need cyanuric acid
The bottom line is that with moss treated water, cyanuric acid is not needed. The mechanism for this probably centers around organic contamination. I don’t think that cyanuric acid prevents chlorine from UV degradation or the free chlorine levels would have decreased in the outdoor pools we treated. We know the moss inhibits organic contamination formation in the laboratory and know that organic contamination absorbs chlorine. We know that free chlorine levels skyrocket when moss is added to the pool and to maintain a level of 1-3 ppm free chlorine, the chlorine added to the pool decreases by over half. So a pool with moss doesn’t need cyanuric acid. That allows the chlorine added to the pool to remain active providing effective microbial control.