Biodegradation of Melamine and Cyanuric Acid by a Newly-Isolated
Cyanuric Acid Stabilizer What is all the fuss about?...©2017 Lonza CT Values (MAHC A 5.7.3.1.1.2)...
Transcript of Cyanuric Acid Stabilizer What is all the fuss about?...©2017 Lonza CT Values (MAHC A 5.7.3.1.1.2)...
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Cyanuric Acid Stabilizer What is all the fuss about? Ellen Meyer, Arch Chemicals February 9, 2017 NPC Conference New Orleans LA
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Overview
Chemistry of cyanuric acid (CYA) Impact on build up of CYA Impact on water balance Chlorine stabilization with cyanuric acid
The effect of cyanuric acid on chlorine kill rates In the lab In the pool
Recent Crypto data Implications for pool maintenance
Sanitizer residuals Remediation procedures Measurement issues CYA control
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Cyanuric Acid Double headed arrow (↔) means reaction can go back and forth
Cyanuric Acid Enol tautomer
Isocyanuric Acid Keto tautomer
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Chlorination of Cyanuric Acid
Isocyanuric Acid
Trichloroisocyanuric Acid
+ 3 HOCl + H2O
Hypochlorous Acid
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Cyanuric Acid Equilibria (O’Brien)
Cy3-
ClCy2-
Cl2Cy- HCl2Cy
H2ClCy HClCy-
H3Cy H2Cy- HCy2-
Cl3Cy
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Cyanuric Acid Equilibria with H+ (Using O’Brien measurements)
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0 2 4 6 8 10 12 14
% S
pe
cie
s
pH
H3Cy pKa 6.88
H2Cy-
pKa 11.40
HCy-2
pKa 13.5
Cy-3
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Cyanuric Acid Equilibria with Cl (Using O’Brien values)
1 ppm AvCl, 20 ppm CYA, pH 7.5, 800 ppm TDS, 85 °F
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
0 2 4 6 8 10 12 14
%Sp
eci
es
pH
[H2ClCy]
[HClCy–]
[ClCy2–]
[HCl2Cy]
[Cl2Cy–]
[Cl3Cy]
[HOCl]
[OCl-]
AvCl = Available Chlorine, TDS = Total Dissolved Solids
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Cyanuric Acid Equilibria with Cl (O’Brien)
1 ppm AvCl, 20 ppm CYA, pH 7.5, 800 ppm TDS, 85 °F
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
6.4 6.6 6.8 7.0 7.2 7.4 7.6 7.8 8.0 8.2 8.4 8.6
%Sp
eci
es
pH
[H2ClCy]
[HClCy–]
[ClCy2–]
[HCl2Cy]
[Cl2Cy–]
[Cl3Cy]
[HOCl]
[OCl-]
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So how does this impact pool operation?
• How much does CYA build up over time?
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Trichloroisocyanuric acid
Atom Number of atoms
Molecular weight, g/mole
Weight %
Carbon (C) 3 3 x 12.01 15.5%
Nitrogen (N) 3 3 x 14.01 18.1%
Oxygen (O) 3 3 x 16.00 20.7%
Total 3C+3N+3O = CYA 9 126.06 54.2%
Chlorine (Cl) 3 3 x 35.45 45.8%
Molecular weight = 232.41
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CYA Products
• Add cyanuric acid independent of sanitizer
– 95-100% granular cyanuric acid
• Add chlorinated cyanuric acid as sanitizer/shock
– Trichloroisocyanuric acid • 54% CYA, so for every 100 lb of trichlor added to a pool, 54 lb of CYA is
added
– Dichloroisocyanuric acid • Hydrated (49% CYA)
• Anhydrous (57% CYA)
– Rough rule of thumb • For every pound of trichlor or dichlor added, you are adding ~½ pound of
CYA
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Cyanuric Acid Accumulation Rate Model When using Trichloroisocyanuric acid as Primary Sanitizer
0
100
200
300
400
500
0 7 14 21 28 35 42 49 56 63 70 77 84
CYA
(p
pm
)
Days
5 ppm/day 10 ppm/day
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How does CYA impact water balance?
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Water Balance- pH
pH = -log [H+]
H2O ↔ H+ + OH-
Minimum pH 7.2, Maximum pH 7.8
MAHC 5.7.3.4.1, APSP-11 7.1
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pH
pH 7 = neutral [H+] = [OH-]
pH <7.2
Corrosion of plaster, grout and metal
Eye irritation
pH >7.8
Scale, mineral precipitation
Eye irritation
Chlorine less effective
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Adjusting pH
pH = -log [H+]
To lower pH Acids contribute H+ to lower pH
Muriatic acid = hydrochloric acid HCl (aq) ↔ H+ + Cl-)
Dry acid = sodium bisulfate NaHSO4 ↔ H+ + Na+ + SO4
2-
Carbon dioxide (CO2) CO2 + H2O ↔ HCO3
- + H+
To raise pH Bases take away H+ to raise pH
Soda ash = sodium carbonate (Na2CO3) Na2CO3 + H+ ↔ 2Na+ + HCO3
-
HCO3- = bicarbonate
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pH
Lowering pH by adding CO2
CO2 + H2O => HCO3- + H+
Raising pH by losing CO2 to the air
HCO3- + H+ => CO2 + H2O
pH will drift up when carbonate alkalinity is present
Faster in spas
High temperatures
Aeration of the water
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Alkalinity
What is Alkalinity ?
Measure of pH buffering capacity
Buffer = something that keeps the pH from going up and down quickly
Something that absorbs H+ when an acid is added
Something the contributes H+ when a base is added
Carbonate
HCO3- + H+ ↔ H2CO3
When acid is added HCO3- + H+ → H2CO3
When base is added H2CO3 → HCO3- + H+
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Carbonate Alkalinity
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0 2 4 6 8 10 12 14
% S
pe
cie
s
pH
Carbonic Acid H2CO3
Bicarbonate HCO3
- Carbonate CO3
2-
Buffers best at pH where two lines cross
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Cyanurate Alkalinity
Cyanuric acid (stabilizer) does provide buffer capacity
Cyanuric acid does not gas off and make pH drift like carbonate buffers
Cyanuric acid is measured in alkalinity test
Cyanuric acid does not provide corrosion protection for plaster
You must have carbonate alkalinity to protect plaster
+ H+ ↔
-
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Cyanurate Alkalinity
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% S
pe
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pH
Cyanuric acid H3Cy
Cyanurate H2Cy-
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Alkalinity
For water balance need carbonate alkalinity
Example :
Total Alkalinity (TA, measured value) = 90
Stabilizer (measured value) = 120
(high, but common near season’s end)
Carbonate Alkalinity
= 90 - 1/3 (120)
= 90 - 40
= 50 (low)
pH Replace 1/3 with
7.9 1/ 2.7
7.7 1/ 2.9
7.5 1/ 3.2
7.3 1/ 3.6
7.1 1/ 4.2
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Alkalinity
Low Carbonate Alkalinity
pH changes abruptly and frequently with small chemical additions
Water may be corrosive in one area of pool and scaling in another
Overall- water will be more corrosive
pH of water drifts with the pH of the sanitizer
High Carbonate Alkalinity
pH changes slowly - stays around 8.0 to 8.4 and returns even after adjustment with acid
pH of water drifts up
Water will cause scaling and may appear cloudy or dull
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Alkalinity
Adjusting Alkalinity
To lower carbonate alkalinity
Muriatic acid (hydrochloric acid, HCl(aq))
Dry acid (sodium bisulfate, NaHSO4)
HCO3- + H+ → CO2 + H2O
Other acidic pool chemicals (trichlor, chlorine gas)
To raise carbonate alkalinity
Sodium bicarbonate (NaHCO3)
Soda ash (sodium carbonate, Na2CO3)
Will raise pH too
Other pool chemicals (calcium hypochlorite)
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How does CYA impact chlorine chemistry?
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Cyanuric Acid vs. Percentage Free Chlorine Remaining After One Hour
Stabiliser (Cyanurate) Use in Outdoor Swimming Pools http://www.health.nsw.gov.au/environment/factsheets/Pages/stabiliser-cyanurate.aspx
CYA, ppm
%Loss
0 35%
10 12%
20 5%
30 3%
40 2%
mg/L = ppm
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HOCl as a function of pH HOCl ↔ OCl- + H+
HOCl is the primary active sanitizer in chlorine pools
Dissociation constant from G. C. White, Handbook of Chlorination, Second Edition, Van Nostrand Reinhold Company, New York, 1986
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20
40
60
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5 6 7 8 9 10 11
Perc
en
t H
OC
l
pH
pH %HOCl
5.0 99.7%
7.0 77.5%
7.5 52.2%
8.0 25.7%
9.5 1.1%
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Cyanuric Acid Equilibria with Cl (O’Brien)
1 ppm AvCl, 20 ppm CYA, pH 7.5, 800 ppm TDS, 85 °F
0%
10%
20%
30%
40%
50%
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70%
80%
90%
100%
6.4 6.6 6.8 7.0 7.2 7.4 7.6 7.8 8.0 8.2 8.4 8.6
%Sp
eci
es
pH
[H2ClCy]
[HClCy–]
[ClCy2–]
[HCl2Cy]
[Cl2Cy–]
[Cl3Cy]
[HOCl]
[OCl-]
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HOCl- Varying Free Chlorine (FC) and CYA pH 7.5, 85 °F, 800 ppm TDS
Equilibrium constants from O’Brien 1972
CYA, ppm
%HOCl for 1 ppm FC
0 47%
5 13%
10 7%
20 3%
50 1%
0%
5%
10%
15%
20%
25%
30%
35%
40%
45%
50%
0 10 20 30 40 50
%H
OC
l
CYA, ppm
1 ppm FC
2 ppm FC
3 ppm FC
4 ppm FC
10 ppm FC
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How does CYA impact chlorine activity?
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Disinfection Efficacy CT Values
Concentration x Time = CT
Usually 3 log (99.9%) reduction in ppm∙minutes
Will vary with pathogen strain, temperature, pH, etc.
Assumed to be linear
If CT = 100 ppm minutes Then
It will take 100 minutes to kill the organism with 1 ppm
Or It will take 1 minute to kill the organism with 100 ppm
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CT Values (MAHC A 5.7.3.1.1.2)
Tests conducted with chlorine demand free water with 1 ppm chlorine at pH 7.5, 77° F, no CYA
These values will be higher in the presence of CYA
Organism Time
E. coli O157:H7 Bacterium <1 minute
Hepatitis A Virus About 16 minutes
Giardia Protozoan About 45 minutes
Cryptosporidium Protozoan About 15,300 minutes (10.6 days)
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Effect of CYA on Chlorine Kill Rates
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0 50 100 150 200 250 300 350 400
CT,
pp
m m
in
CYA, ppm
Anderson 1965 S. faecalis
Fitzgerald 1967 S. faecalis
Golaszewski 1994 P. aeruginosa
Robinton 1967 E. coli
Robinton 1967 S. faecalis
Robinton 1967 Staph. aureus
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Effect of CYA on Chlorine Kill CT with CYA / CT without CYA
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10
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0 50 100 150 200 250 300 350 400
CT
wit
h C
YA /
CT
wit
ho
ut
CYA
CYA, ppm
Anderson 1965 S. faecalis
Fitzgerald 1967 S. faecalis
Golaszewski 1994 P. aeruginosa
Robinton 1967 E. coli
Robinton 1967 S. faecalis
Robinton 1967 Staph. aureus
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Chloramine Comparison Values from EPA LT1ESWTR Disinfection Profiling and Benchmarking, 2003 EPA 816-R-03-004, pH 7-9, 25 °C, 3-log
Pathogen CT Free Chlorine (FC), ppm min
CT Chloramine (CC), ppm min
CT CC / CT FC
Giardia 45 750 17
Viruses 2 497 249
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Effect of CYA on Chlorine Kill Rates • Fitzgerald 1967
──●── No CYA
−−○−− With CYA
– 0.5 ppm AvCl used
– 1:1 molar AvCl:N = 5:1 ppm (by weight)
– Cyanuric acid does not appear to hinder the activity of combined chlorine
With 0.1 ppm NH3-N, there is enough nitrogen for all of the chlorine to be present as combined chlorine.
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Study Total Pools (stabilized)
Results
Yamashita 1988 19(9) Time (minutes) required for inactivation of poliovirus, ~1 ppm AvCl Unstabilized Stabilized Polio 40 sec >3 min
Yamashita 1990 6(3) Time (minutes) required for inactivation of poliovirus, 1 ppm AvCl Unstabilized Stabilized Polio <1 min >2-5 min
Effect of CYA on Chlorine Kill Rates- In Pool Water
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Effect of CYA on Bacterial Counts in Pools Study Total Pools (stabilized) Results- Percent of Pools that Passed the Criteria
Kowalski 1966 15 (7) 1960 138 (7) 1963
%Pass Unstabilized Stabilized ‘60 Total 82 88 ‘63 Total 90 98 ‘60 e coli 96 98 ‘63 e coli 89 96
Rakestraw 1994 (Pinellas 1992 study)
486(396) %Pass Unstabilized Stabilized <500 HPC 86 91 No T Colif 84 92 No F Colif 90 95 No non Colif 41 32
Favero 1964 12 (3) Low bather load 6 (3)
More Pseudomonas in stabilized pools %Pass Unstabilized Stabilized e. Coli 83 72 Staph 97 80 Total count 64 47
LeGuyader 1988 3749 (1055) %Pass Unstabilized Stabilized No Staph 50 40 No Pseud 97 86 No Colif 100 99
Black 1970 83(28) %Pass Unstabilized Stabilized No Colif 82 64
Yamashita 1990 6(3) %Pass Unstabilized Stabilized No Adenovirus 100 100 No Colif 100 92 Total plate counts 92 50
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Implications for Pool Maintenance- Continuous Treatment • Association of Pool and Spa Professionals (APSP)
– APSP-11 • CYA <100 ppm
• Model Aquatic Health Code (MAHC) – MAHC 5.7.3 Disinfection
• FAC – 1.0 ppm no CYA – 2.0 ppm with CYA
• CYA – <90 ppm, most venues – 0 ppm for spas and therapy pools
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Effect of CYA on Cryptosporidium (pH 7.5, 25°C) (Murphy et al. 2015)
Average FC
conc. (mg/L)
Average CYA
conc. (mg/L)
Average Time 3-log10
inactivation (hr)
Average Estimated 3-log10
CT value (mg·min/L)
21.6 0 8.2 10,500
21.1 8 14.1 17,800
19.1 16 27.5 31,500
40.6 0 5.1 12,400
40.9 9 6.2 15,300
38.3 15 8.4 19,400
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Effect of CYA on Cryptosporidium (pH 7.5, 25°C) (Murphy et al. 2015) Did not get 3-log removal with >16 ppm CYA
Average FC
conc. (mg/L)
Average CYA
conc. (mg/L)
Average time 1-log10
inactivation (hr)
Average Estimated 1-log10
CT value (mg·min/L)
21.6 0 2.7 3,500
21.2 48 61.9 76,500
40.6 0 3.7 4,100
38.5 46 17.2 40,000
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Effect of CYA on Cryptosporidium (pH 7.5, 25°C) (Murphy et al. 2015)
• 100 ppm CYA – 20 ppm AvCl
• 72 hours (3 days) 0.8-log10
• 144 hours (6 days) 1.6-log10
– 40 ppm AvCl • 24 hours 0.8-log10
• 72 hours 1.4-log10
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Implications for Pool Treatment- Remedial Treatment
• MAHC 6.5
– Close pool
– Remove fecal material (no vacuum)
– pH ≤7.5, temperature ≥77°F
– Operating filter while maintaining chlorine
– Test for chlorine multiple places
– Use only non-stabilized chlorine for remediation
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Remedial Treatment
• MAHC 6.5 Remedial treatment
– Use the following CT values for treatment
Contaminant Unstabilized Stabilized
Formed stool 50 ppm min (2 ppm 25 min)
100 ppm min (4 ppm 25 min)
Diarrheal stool 15,300 ppm min (20 ppm 12.75 hours)
Lower CYA to ≤15 ppm, and 20 ppm for 28 hours 30 ppm for 18 hours 40 ppm for 8.5 hours
Vomit 50 ppm min 100 ppm min
Blood 0 0
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MAHC 6.5 Remedial treatment
• Other options for diarrheal stool
– Unstabilized • Circulate through secondary disinfection system to achieve 1
oocyst/100 ml
– Stabilized • Circulate through secondary disinfection system to achieve 1
oocyst/100 ml, or
• Drain
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Measurement Issues
• Test Methods
– Melamine precipitation
– Test strips
– Most test methods have 100 ppm maximum • Need to dilute if reading is near maximum
• MAHC set 90 ppm maximum CYA limit due to testing issues >100 ppm
• Effect of CYA on ORP
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Cyanuric Acid Melamine Test
• This test is notoriously inaccurate • Melamine precipitation provides insoluble complex • Turbidity measurements prone to time dependence as
well as interference • Test is influenced by lighting conditions • Results can be operator dependent • If result is near top endpoint of method (i.e. >80 ppm),
the sample should be diluted and run again
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Cyanuric Acid
• Interference • Water temperature
• Effect • High temperatures, above 90 °F, can result in readings as
much as 15 ppm low • Low temperatures, below 60 °F, can result in readings that
are 15 ppm high • How you can tell
• Measure water temperature • What to do
• Warm sample to ideal temperature of 75 °F
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CYA precipitation?
• The previous slide would indicate that cold water reading will be higher than warm water readings
• Then why are winter time CYA readings often lower than summer?
• Temperature of water in the pool vs. temperature of sample when analyzed
– Previous slide has to do with testing interference from temperature of sample when analyzed
– Low CYA readings in winter may not be test interference, they may indicate CYA precipitation at low temperatures in the pool (anecdotal evidence)
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Cyanuric Acid Strips
• Interference • pH
• Effect • Inaccurate results
• How you can tell • Measure pH
• What to do • Adjust pH to the ideal
range of 7.4 to 7.6
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ORP Probes
• Nernst equation can be used to look at theoretical potential vs. CYA concentration
• These values should not be taken as absolute • Many factors will affect an ORP reading and the slope of this line • Nernst equation: E = Eo - (RT/nF) x ln ([Cl-]/[HOCl][H+])
1.12
1.13
1.14
1.15
1.16
1.17
1.18
1.19
0 20 40 60 80 100
Po
ten
tial
, V
CYA, ppm
Constants used: Eo = 1.49 V R = gas constant T = 85 °F n = 2 electrons F = Faraday constant [Cl-] = 100 ppm pH = 7.5 AvCl = 1 ppm TDS = 800 ppm
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ORP Probes
• Interference • Probe fouling from CYA
• Effect • Reading may be low or sluggish to respond
• How you can tell • Clean probe and see if the reading changes
• What to do • Clean probes according to manufacturer’s directions • To prevent contamination, store probes according to
manufacturer’s directions
Two effects from CYA 1. Lowering of ORP due to lowering of HOCl 2. Probe fouling with CYA
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CYA Control- Removal • Drain the pool
– Water restrictions
– Cost (water, treating fill water)
• Activated carbon – Efficiency is low
– Cost
– Possible disposal issues
• Melamine precipitation – Operational issues (staining, solids don’t settle, etc.)
• Unproven technologies
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CYA Removal Costs
Assume
100 ppm CYA in pool
1 lb Trichlor/10,000 gal/day used
Cleveland TN utility rates ($2.21/ft3, ~0.3¢/gal)
Pool size
Trichlor used (lbs/day)
AvCl used (lbs/day)
CYA added (lbs/day)
CYA residual added (ppm/day)
Daily water removal to maintain 100 ppm (gal)
Yearly cost in replacement water ($)
10,000 1.0 0.90 0.56 6.7 665 717
25,000 2.5 2.25 1.39 6.7 1663 1794
50,000 5.0 4.50 2.78 6.7 3326 3587
75,000 7.5 6.75 4.16 6.7 4990 5381
100,000 10.0 9.00 5.55 6.7 6653 7175
1,000,000 100.0 90.00 55.52 6.7 66529 71745
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CYA Control- Prevention
• Control additions of CYA
– Prudent use of CYA
– Prudent use of stabilized sanitizers
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Next Steps
• Enter the debate
• Conference for the Model Aquatic Health Code (CMAHC) for MAHC revisions
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References • Amburgey, J.E., and J.B. Anderson. (2011). Disposable Swim Diaper Retention of Cryptosporidium-sized Particles on
Human Subjects in a Recreational Water Setting. Journal of Water and Health. 9(4): 653-658.
• Amburgey, J.E., Walsh, K.J., Fielding, R.R., and M.J. Arrowood. (2012). Removal of Cryptosporidium and Polystyrene Microspheres from Swimming Pool Water with Sand, Cartridge, and Precoat Filters. Journal of Water and Health. 10(1): 31-42.
• Amburgey, James. E., Jonathan M. Goodman, Olufemi Aborisade, Ping Lu, Caleb L. Peeler, Will H. Shull, Roy R. Fielding, Michael J. Arrowood, Jennifer L. Murphy, and Vincent R. Hill, Are Swimming Pool Filters Really Removing Cryptosporidium?, available from pwtag.org.
• Anderson JR. A study of the influence of cyanuric acid on the bactericidal effectiveness of chlorine. Am J Public Health Nations Health. 1965 Oct;55(10):1629-37.
• Belosevic, FEMS Microbiol Lett. 2001, 204(1) 197-203.
• Black AP, Keirn MA, Smith JJ Jr, Dykes GM Jr, Harlan WE. The disinfection of swimming pool water. II. A field study of the disinfection of public swimming pools, Am J Public Health Nations Health. 1970 Apr; 60(4):740-50.
• Campbell, A.T. et al. 1995. Inactivation of oocysts of Cryptosporidium parvum by Ultraviolet radiation, Water Research, 29(11), 2583.
• Chappell CL, Okhuysen PC, Sterling CR, DuPont HL. Cryptosporidium parvum: intensity of infection and oocyst excretion patterns in healthy volunteers. J Infect Dis 1996;173:232--6.
• Clancy, J.L., Hargy, T. M., Marshall, M. M., Dyksen, J. E. 1997, Inactivation of Cryptosporidium parvum oocysts in water using ultraviolet light, Conference proceedings, AWWA International Symposium on Cryptosporidium and Cryptosporidiosis, Newport Beach, CA.
• Craik, Water Res. 2001, 35(6) 1387-98.
• DuPont HL, Chappell CL, Sterling CR, Okhuysen PC, Rose JB, Jakubowski W. The infectivity of Cryptosporidium parvum in healthy volunteers. N Engl J Med 1995;332:855--9.
• Favero, M. S., C. H. Drake, and G. B. Randall. 1964, Use of staphylococci as indicators of swimming pool pollution. U. S. Public Health Reports, 79:61-70.
• Fitzgerald GP, DerVartanian ME. Factors influencing the effectiveness of swimming pool bactericides. Appl Microbiol. 1967 May;15(3):504-9.
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References • Fitzgerald GP et al. Pseudomonas aeruginosa for the evaluation of swimming pool chlorination and algicides. Appl
Microbiol. 1969 Mar;17(3):415-21.
• Gerba, C.P. Assessment of enteric pathogen shedding by bathers during recreational activity and its impact on water quality, Quantitative Microbiology, 2000, 2, 55-68.
• Golaszewski G et al. The kinetics of the action of chloroisocyanurates on three bacteria: Pseudomonas aeruginosa, Streptococcus faecalis, and Staphylococcus aureus. Water Research 1994;28(1): 207-217.
• Goodgame RW et al. Intensity of infection in AIDS-associated cryptosporidiosis. J Infect Dis. 1993 Mar;167(3):704-9.
• Hijnen, Water Res. 2006, 40(1) 3-22.
• Hlavsa MC et al., 2014, MMWR 63(1), 6-10.
• Jokipii L, Jokipii AMM. Timing of symptoms and oocyst excretion in human cryptosporidiosis. N Engl J Med 1986;315:1643--7.
• Keuten, M.G.A., Schets, F.M., Schijven, J.F., Verberk, J.Q.J.C., Van Dijk, J.C., Definition and quantification of initial anthropogenic pollutant release in swimming pools, Water Research, 2012, 46, 3682-3692.
• Korich DG et al. Effects of ozone, chlorine dioxide, chlorine, and monochloramine on Cryptosporidium parvum oocyst viability. Appl Environ Microbiol. 1990 May;56(5):1423-8.
• Kowalski, X., Hilton, T. B., Comparison of chlorinated cyanurates with other chlorine disinfectants, Public Health Reports, 1966, 81(3), 282-288.
• LeGuyader, M., Grateloup, I., Relative importance of different bacteriological parameters in swimming pool water treated by hypochlorite or chloroisocyanurates, Journal Francais d’Hydrologie, 1988, 19, Fasc 2, 241-250.
• Linden, Water Sci. Tech. 2001, 43(12) 171-4.
• Lu, Ping. (2012). Enhanced removal of cryptosporidium parvum oocysts and cryptosporidium-sized microspheres from recreational water through filtration, Doctoral Dissertation. University of North Carolina at Charlotte.
• Murphy, J. L., Arrowood, M.J., Lu, X., Hlavsa, M.C., Beach, M.J., Hill, V.R., Effect of Cyanuric Acid on the Inactivation of Cryptosporidium parvum under Hyperchlorination Conditions, Environmental Science and Technology, 2015, 49(12), 7348-7355
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References • O’Brien, J. E., Hydrolytic and ionization equilibria of chlorinated isocyanurate in water, Ph.D. Dissertation, Cambridge, MA: Harvard
University, 1972.
• O’Brien, J.E., Morris, J.C., Butler, J.N., Equilibria in aqueous solutions of chlorinated isocyanurate, Chapter 14 in Chemistry of Water Supply, Treatment, and Distribution, Alan J. Rubin editor, Ann Arbor Science, Ann Arbor MI, 1974, ISBN 0-250-4036-7.
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