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Abstracts from the 1st Annual NSPI "Sanitizer Chemistry" Symposium

Sponsored by:
The National Spa and Pool Institute
with additional sponsorship by:
Amtrol
Aqua Biotechnologies
BioLab
Church and Dwight
Clearwater Tech
DEL Industries
DuPont
Eltech
Environmental Test Systems
Fountainhead Technologies
Hayward Pool Products
Journal of the Swimming Pool and Spa Industry
LaPorte Water Technologies
Muskin Leisure Products
N. Jonas and Co.
Pool Chlor
PPG
Teledyne Laars
Watkins Manufacturing
Abstracts:
S. D. Worley, Ph.D.
Auburn University
Novel NHalamine Water Biocides
The use of a class of organic compounds known as Nhalamines
for disinfection and stabilization of free chlorine and free bromine in
swimming pools and spa will be discussed. For those compounds soluble in
water, the discussion will focus on their longterm stabilities while
providing biocidal action in sunlight. For those compounds insoluble in
water, the use in a cartridge filter application for disinfecting spas will
be emphasized. Details about the novel compounds, for which the patent rights
are owned by Auburn University, will be presented to include physical properties,
synthesis methods, and biocidal and stability data. The most likely uses
of the compounds in commercial applications will also be addressed.
John A. Wojtowicz
Chemcon
The Langelier Saturation Index Overview and Update
It is a common misconception that the Langelier Saturation Index
applies only to closed systems because it was developed for water in distribution
lines. Since it based on calcium carbonate solubility equilibria, the Langelier
Saturation Index is applicable to both open and closed systems containing
dissolved calcium carbonate. The main difference is that in closed systems
the alkalinity can vary at a given pH whereas in open systems alkalinity
is fixed at a given pH. In addition, since alkalinities are much lower in
open systems at comparable pH values, saturation hardness is much higher.
Another common misconception is that swimming pools are open systems. Although
swimming pools are open in a physical sense, they are not open from a thermodynamic
(i.e., chemical equilibrium) standpoint. Periodic acid addition for pH control
replenishes lost carbon dioxide, preventing equilibration with the atmosphere.
Indeed, swimming pools exhibit the characteristics of closed systems, showing
the expected range and variability of alkalinity which is also typical of
many public water supplies. If swimming pools were open systems (i.e., in
equilibrium with atmospheric carbon dioxide), they would contain only 4
to 18 ppm alkalinity over the 7.2 to 7.8 pH range. At a given temperature,
swimming pool water chemistry must be balanced by adjusting pH, alkalinity,
and calcium hardness in order to maintain the proper saturation with respect
to calcium carbonate to avoid corrosion of metallic surfaces, etching of
tile grout and plaster, scaling, and cloudy water. Water balance is determined
by means of the Calcium Carbonate Saturation Index (SI), which
was originally devised (Langelier 1936) to provide corrosion control for
iron pipes in public water distribution systems by means of deposition of
thin films of CaCO3. This paper discusses revisions to the Saturation Index
equation due to more accurate values for the solubility product constant
of calcium carbonate as a function of temperature and more realistic ionic
strength corrections.
Roy D. Vore, Ph.D. and Michael J. Unhoch
Zeneca Biocides
The use of PHMB as a Sanitizer in Domestic Spas
The control of bacteria in spa water is much more demanding
than pool water. The heated water, higher concentrations of both organic
load and bacteria shed by bathers can result in unacceptable bacterial growth
developing in spa water within a few hours of heavy use. To prevent health
affecting bacterial outbreaks three approaches may be employed: continuous
feed of the sanitizer, daily monitoring and addition of the sanitizer, and
the use of a stable and nonload dependent sanitizer. Bromine and chlorine
require daily monitoring and adjustment. Polyhexamethylene biguanide (PHMB
or biguanide) is a nonoxidizing sanitizer that is minimally affected
by high bather use. Prior to registration for use in spas by the U.S. E.P.A.
the antibacterial performance of PHMB was measured in domestic spas with
simulated use levels of one person per 125 gallons for 30 minutes per day.
The spas were inoculated with high levels of bacteria implicated in spa
related skin rashes (Ps aeruginosa and Staphylococcus aureus) and those
shed in feces (Escherichia coli and Enterococcus faecalis) plus 2 pints
of synthetic bather load per day. Throughout the study period the PHMB treated
spa water had fewer bacteria than allowed by U.S. E.P.A. standards for recreational
water as well as fewer bacteria than allowed in drinking water. A calcium
hypochlorite spa exceeded E.P.A. standards for total coliforms on 13 of
14 days and had persistent levels of Ps aeruginosa. PHMB provided a significant
improvement in the control of spa associated bacteria when compared to calcium
hypochlorite.
Jacques M. Steininger, D. Eng. Sc.
Santa Barbara Control Systems
Comparison of Chlorine Testing Methods
Chlorinated water solutions were tested by amperometric titration
and colorimetric analysis and with two commercial test kits. The results
show good agreement between the first two methods and less accurate results
with the test kits. The response curves of ten (10) new ORP sensors show
that a minimum of 10 to 20 minutes of immersion time is required to obtain
stable readings. After stabilization, the standard deviation for ORP readings
is only 2 mV or about 0.2% of full scale value. The effects of Total Dissolved
Solids, pH and temperature on ORP readings were also analyzed under laboratory
conditions for varying chlorine concentration levels.
Tom Seechuk
LaMotte Company
MPS Interferences in the DPD Method
Monopotassium persulfate can appear as combined chlorine in
the DPD test. A new test method was developed, in cooperation with Dupont,
to not only eliminate the interference, but to allow the determination of
monopotassium persulfate concentration.
Bonnie B. Sandel, Ph.D.
Olin Chemicals Research
Chlorine Disinfection Chemistry
Chlorines unique properties have been exploited for water
disinfection for nearly 100 years, yet only recently, through comparisons
with alternative methods, have scientists begun to understand the multiple
features that make chlorination effective. This presentation deals with
three features of chlorine disinfection for pools and spas: rapidity of
action, persistence in the water and circulation system, and contributions
to biostability of the treated water. Starting with the evidence of microbial
risk and its relationship to the water circulation system, the discussion
will proceed to a comparison of laboratory and field experiment results
for a variety of chlorine and alternative sanitizer systems. Finally, guidelines
for optimizing chlorines use will be discussed.
Rip G. Rice, Ph.D.
Rice International Consulting Enterprises
Wolfram Hartwig, Ph.D.
Engineered Treatment Systems
Gordon R. Finch, Ph.D.
University of Alberta
Potentials for Ozone to Control Cryptosporidium Oocysts in Pools
Knowledge that ozone is the strongest disinfectant and oxidizing
agent available for controlling microorganisms in aqueous media is widespread
and well understood. As such, ozone is quite capable of assuring the inactivation
of cyst organisms, occasionally found in swimming pool waters, such as Giardia
lamblia and Cryptosporidium parvum. However to accomplish reliable
inactivation of C. parvum and G. lamblia cysts, ozone must be present in
sufficient concentrations in the waters containing these microorganisms
and for sufficient periods of time so that the product of C
(concentration of ozone in mg/L) times t (time of contact in
minutes) is at least equal to the Ct product specified by the
U.S. E.P.A. in the Surface Water Treatment Rule, promulgated in 1991 to
ensure disinfection of municipal drinking water supplies. These requirements
to meet a specified Ct value mean that ozone must be produced
in the gas phase in sufficient concentrations so that when applied to the
pool water, a sufficient level of ozone will be present to measure and monitor.
The higher the concentration of residual ozone in the water, the shorter
will be the reaction time necessary to assure attainment of the given Ct
value for the specific cyst organism at the temperature of the water. This
means that ozone generated by UV radiation cannot be effective for the inactivation
of C. parvum oocysts (Ct value of ca. 5 minmg/L) since
the levels of ozone in the gas phase are so low as to preclude developing
measurable ozone residuals in water for more than a few seconds in the immediate
area of contact. On the other hand, ozone generated by corona discharge
techniques (in concentrations above 12% using dried air as the feed
gas, and 35% using oxygenenriched air feed gas) can produce
significant levels of measurable residual ozone in water (several tenths
of a mg/L). If these levels of residual ozone are held for the several minutes,
an appropriate Ct value for C. parvum can be achieved readily.
The difficulties involved with the inactivation of C. parvum with ozone
and chlorine will be discussed, and recommendations will be developed.
Ed Lightcap
DuPont
Peroxygen Compounds as Oxidizers
Peroxygen compounds are fast becoming integral components of
many pool and spa water treatment programs. This presentation will review
the primary peroxygen compounds used and discuss their application and reactivity.
Robert J. Kulperger
Natural Chemistry, Inc.
Natural Enzyme Technology Applied to Pools and Spas
Enzymes are organic protein molecules that act as biological
catalysts to accelerate reactions in nature, such as the breakdown of organic
molecules. Used in pools and spas, enzymes biodegrade organic molecules
that traditionally require chemical oxidation to control. Natural enzymes
are a preferred enzymes source because of the range of enzymes required
in this application. Control of organics with natural enzymes reduces maintenance
by eliminating scum buildup and waterline ring, chloramines
cloudiness caused by organics, and rapid filter cycling due to organic fouling.
A reduction in chemical shock usage and cleaning compounds is also observed.
Ray Kramer
ELTECH Systems Corp.
Electrolytic Chlorine Generation
The basic electrochemical reactions for swimming pool chlorination
will be studied. Principal reactions at the anode and cathode will be discussed
with regard to the species present. Special attention will be paid to the
low level of salt present in pool water and the effects of low salinity
on electrode performance. Furthermore, the basic failure mechanism for anodes
involved with low salt chlorination will be discussed.
Robert A. Governal, Ph.D.
International Innovative Technologies
The Design of Advanced Pool and Spa Water Treatment Systems
Using Catalytic Filtration Technologies
The design and application of novel and patented catalytic filtration
technologies (CFT) will be presented towards the advancement of pool and
spa water treatment systems. System designs to be presented include loop
configurations as well as onepass recycle/reuse/reclaim systems. CFT
may become the next generation of water management and water treatment technologies,
since they are a new science that can improve the technical and economic
effectiveness of water treatment systems. A catalytic filter is a porous
separation device in which the filtration surface has been activated to
produce novel oxidation chemistries. Current filters available to end users
today are made from surfaces that are inert, or can break down in extreme
environments; these current filters are therefore designated as passive
filters. Since catalytic filters can be manufactured from pore size
ranges from reverse osmosis (molecular separations) through microfiltration
(bacterial, parasitic, and bulk colloidal separations) regimes, CFT can
be applied to a wide range of markets. CFT can be applied to pool and water
treatment systems in conjunction with current and future chemistries such
as muriatic acid, algicides, ozone, ultraviolet radiation, halogens and
chloramines, etc., to minimize pathogenic and organic contamination potentials.
CFT can increase the economic effectiveness of water treatment systems through
the minimizing of operational costs such as filter replacement, chemical
loading, and water replacement and disposal costs.
Carlos Enriquez, Ph.D.
Charles P. Gerba, Ph.D.
University of Arizona
Copper/Silver Ionization Disinfection
Proper disinfection of swimming pool water is essential to prevent
the transmission of pathogenic microorganisms. Several viral, bacterial,
and parasitic agents have been associated to outbreaks in poorly disinfected
recreational waters. Chlorine is the most commonly used disinfectant of
swimming pools. This chemical has proved to be a very efficient disinfectant
when used properly. However, its use may result in eye and skin irritation,
undesirable odor and, more importantly, in the formation of trihalomethane
compounds derived from the reaction of chlorine with organic matter. Alternative
disinfectants include the use of electrolytically generated copper and silver
ions. These metal ions are effective disinfectants against viruses and bacteria
of concern in swimming pools. Furthermore, enhanced microbial inactivation
is achieved when these metals are used in combination with low chlorine
levels. Use of copper and silver ions in water systems currently used in
swimming pools and spas may provide an alternative to high levels of chlorination.
Fernando del Corral, Ph.D.
Betty S. Johnson
Buckman Laboratories
Recreational Water Algaecides
The uncontrolled growth of algae in recreational water systems
can be aesthetically displeasing, and, if left unchecked, can be costly
and very labor intensive to clean up. In some cases, algae growth can even
provide a breeding ground for bacteria, creating unsanitary conditions.
The use of algaecides has customarily been utilized to aid the sanitizer
in preventing algal blooms. Currently, there are 152 registered, nonoxidizing
algaecide formulations for recreational water use in the United States (Pestbank
1996). Only 2 active classes account for most of the registered formulations.
Fortysix percent (46%) of all formulations are alkyl/diakyl/dioctyl
dimethyl ammonium chloride type (ADAC) formulations, 40% are polymeric quaternary
ammonium chloride formulations, and 12% are copperbased products.
Only a small fraction (2%) comprise combinationtype products (i.e.,
copper plus ADAC). There are other nonconventional, nonregistered
approaches for algal control such as ammonium sulfate and lanthanum carbonate.
Very little information has been recently generated and disseminated to
the industry as a whole regarding the efficacy of commercial algaecides.
Therefore, the objective of this study is to evaluate the effectiveness
(algaestatic and algaecidal properties) of nine commercial algaecides against
axenic cultures of Chlorella pyrenoidosa, Phormidium faveolarum and Eustigmatus
vischeri. In addition, the bacteriostatic properties of each product will
be evaluated impedimetrically against a common capsule forming coliform
bacteria, Enterobacter aerogenes and an unknown pigmented (pink) organism
isolated from a pool biofilm.
Mary Costanzo
Brian C. Bokowy
BioLab, Inc.
Bromine and Ozone: Chemistry and Operational Challenges Encountered
in the Treatment of Heavily Used Commercial Recreational Water Systems
Commercial recreational water systems such as large municipal
pools, aquatic centers, health clubs and interactive aquatic theme parks
are challenging water treatment environments. Organic and nitrogenous input
from heavy swimming loads can rapidly disable available oxidizer/disinfectant
levels necessitating constant chemical monitoring and the adoption of ancillary
processes to maintain premium water quality. This presentation will begin
with a brief, albeit detailed, assessment of truetolife bromine:ozone
chemistry encountered in commercial arenas followed by a review of the critical
ancillary processes necessary to satisfy water quality objectives.
Allen Clawson
DEL Industries
Side or Slipstream Application of Ozone and Ozone Dosing for
Commercial Swimming Pools The side or slipstream process of ozone application
to the main stream pool circulation water is reviewed, discussing economic,
safety and performance issues and advantages. Mass transfer efficiencies
and injectors are analyzed. Ozone dose parameters with details of chlorine/bromine
reduction are discussed, as determined by case studies and historical data.
Charles P. Gerba, Ph.D.
Peter Gerba
University of Arizona
Enteric Virus Outbreaks in Swimming Pools
Human enteric viruses cause a wide range of diseases including
gastroenteritis, fever, rash, hepatitis and meningitis, as well as nose,
eye, and respiratory infections. Enteric viruses originate from infected
individuals who excrete them in feces and nose and throat secretions. They
are more resistant to inactivation by chlorine than enteric diseasecausing
bacteria and have been sporadically isolated from community wading and swimming
pools. Outbreaks most commonly occur when there has been a failure to maintain
and adequate disinfection residual. Documented outbreaks have been most
commonly associated with adenovirus eye and throat infections, although
outbreaks of hepatitis A virus and enteroviral illnesses have been reported.
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