AssociationofZoosandAquariums(AZA)AnnualConference,KansasCity,MO,Sept712,2013

DISINFECTIONBYPRODUCTANDSECONDARYOXIDANTFORMATIONANDCONTROL DURINGCHLORINEANDOZONEDISINFECTIONOFSALTANDSEAWATERAQUARIA
CraigAdams1,HonglanShi2,ZhiminQiang3,RobertReed4
1

UtahStateUniversity,Dept.ofCivilandEnvironmentalEngineering,Logan,UT(craig.adams@usu.edu) 2 MissouriUniversityofScienceandTechnology,Dept.ofChemistry,Rolla,MO 3 StateKeyLabResearchCenterforEcoenvironmental Science,Beijing,PRC 4 UniversityofMissouri,Dept.ofCivilandEnvironmentalEngineering,Columbia,MO

Injecteddisinfectionbyproductsintobasins Disinfection byproducts and secondary oxidants are formed in treatment systems and injected in marine aquaria Recommendedoperationalapproachestolimithighconcentrationsofselected byproducts Discrete(ON/OFF)chlorineandozonedosing Itisrecommended thatdiscrete(ON/OFF)chlorinefeedpumps forchlorine addition NOTbeused.Insteadcontinuous proportional controllersinallofthe basinstreatmentsystemsforchlorineandozoneaddition shouldbeused. Aconstantaddition ofchlorinewillallowchlorinespeciestobemaintained at loweroverallconcentrations, andwillavoidspikesinconcentrations atthepoint ofapplication intreatment systems. Recommended operational approaches DPD and ORP control DPD control It is recommended that DPD control of chlorine dosing not be used. It is specifically recommended that chlorine dosing not be turned up in response to sunlight driven decay of total chlorine during the daylight hours. This change should reduce the increased concentrations of disinfection byproduct irritants in treated water being injected into the basins. Operational procedures should include maximum dosing rates for ozone and chlorine. It is recommended that critical dosage rates for both free chlorine and ozone for which applied dosages should not exceed to prevent related health issues. DPD and ORP monitoring It is recommended that DPD and ORP monitoring of water in the treatment system be used only as a good measure of stability (with respect to total oxidants) of a system. Some key points Ozone rapidly converts to free chlorine in saline systems Free chlorine (HOCl) converts to free bromine (HOBr) in sea water and high bromide salt water Free chlorine and free bromine react with ammonia to form haloamines (chloramines (e.g., NCl3) and bromamines) Free chlorine and bromine react with natural organic matter, fecal matter, food, etc. to form a suite of organic and inorganic disinfection byproducts (DBP) This soup of DBPs is thought to be responsible for potential health issues or irritation (that is, it is likely that a variety of different DBPs) The goal is to minimize concentrations of DBPs locally and generally This can be achieved through appropriate treatment approaches including how oxidants are dosed, and choice of biological and filtration treatment processes Selected references
Shi, H., Qiang, Z., Adams, C. (2013) Formation of haloacetic acids, halonitromethanes, bromate and iodate during chlorination and ozonation of seawater and saltwater of marine aquaria systems, Chemosphere. (Available via ePub; In press) Qiang, Z., Jiang, Y., Ben, W., Adams, C., Dong, H. (2013) Monitoring free chlorine and free bromine in aquarium seawater treated by ozone, Analytical Methods, 4, 3646. Shi, H., Adams, C. (2012) Occurrence and Formation of Trihalomethanes in Marine Aquaria Studied Using Solid Phase Microextraction Gas ChromatographyMass Spectrometry, Water Environment Research, 84, 202208. Shi, H. Adams, C., (2009) Rapid ICICP/MS Method for Simultaneous Analysis of Iodoacetic Acids, Bromoacetic Acids, Bromate, and other Related Halogenated Compounds in Water, Talanta, 79, 523527. Reed, R., and Adams, C. (2002) Ozonation of Artificial Saltwater Aquaria: Reaction Kinetics and Byproducts, International Ozone Association PanAmerican Group Conference, RaleighDurham, NC, USA (May 21, 2002). Reed, R., Adams, C., Cole, S. (2001) Ozonation of Artificial Saltwater Aquaria Systems, Ozone World Congress (International Ozone Association), 1:379389, London, UK (September 12, 2001).

Key objectives: Develop and/or validate analytical methods for measurement of water quality parameters and constituents in salt water and seawater. Determine possible chemical cause(s) of chemical irritants formed in salt water and natural seawater aquaria. Provide solutions to the disinfection byproduct problems through treatment system design and operations. Major challenges of this project Complex aqueous matrixThe methods generally used for water analysis do not work for seawater samples. Potential irritant chemicals and DBPs can be volatile, unstable (light sensitive, temperature sensitive), and/or toxic. Some of the potential irritants are newly discovered compounds; their properties are not well studied; the analytical methods are (were) not yet available. Experimentalwaters NaturalSeaWater=NSW HighBromideSaltWater=HBSW LowBromideSaltWater=LBSW Oxidant chemistry (ozone, chlorine, bromine) Oxidant chemistry in saltwater is very different than in drinking water due to presence of high chloride concentrations (and other constituents). Analytical methods (e.g., ion chromatography, total organic carbon, etc.) highly problematic due to high total dissolved solids (TDS). Chemical kinetic modeling used to elucidate fundamental oxidant chemistry occurring.
Chloridereactions(Hoigne etal.1985;HaagandHoigne,1983):
O3 +Cl O2+OCl k1c =0.003M1s1 O3 +OCl 2O2+Cl k2c =110M1s1 2O3 +OCl 2O2+Cl O3 k3c =30M1s1

Potentially lower DBPs in bulk basin

INLET STREAM FROM WATER TREATMENT

BASIN
Potentially higher DBPs in injector stream

Haloamines bySPME/GC/MS
Ingeneral, monobromamine anddibromamine appeartobethe mostprevalent haloamines inhigher bromidewaters

Septumlined cap SPME fiber in headspac e Sample in vial

SPMEGC/MSmethodfortrihalomethanes (THM)
In general, significant THM formation is observed in chlorinated and ozonated sea and salt waters. Chromatograms of four chlorinated water samples analyzed using the SPME GCMS method and the HP5ms column for separation are shown.

ReactionofOCl/Br
Br +OCl OBr +Cl k=6.77(103) M1s1
(Grguric etal.,1994; Bousher etal.,1986)

Haloacetic acidmethodbyICICPMS
Haloacetic acids are formed during ozonation and chlorination of salt and seawaters. A sample chromatogram of bromo and iodoacetic acids, and bromate and iodate, and bromide and iodide is shown.

Bromidereactions(HaagandHoigne (1983):
O3 +Br O2+OBr k1B =160M1s1 O3 +OBr 2O2+Br k2B =330M1s1 2O3 +OBr 2O2+BrO3 k3B =100M1s1

d[OCl]/dt =d[Br]/dt =k1B[Br][OCl] =160M1s1[0.0000125][6(106)]= =1.2(108)Ms1

@1ppmBr and[OCl]=6(106)M

Genericrateexpression d[X]/dt =kx[X][O3]

k1c[Cl]=0.003M1s1[0.7]=0.002s1 @25,000ppmCl k1B[Br]=160M1s1[0.0000125]=0.002s1 @1ppmBr k1B[Br]=160M1s1[0.00000125]=0.0002s1 @0.1ppmBr

Modelingresults
1.00E-04 1.00E-05 Conc (M)

Caseshowninplotsbelow:O3 (0.5mg/L)withCl (25,000mg/L)andBr (varied)(Noammonia)

0.1 ppm Br10 ppm Br-

1.00E-04 1.00E-05 Conc (M) 0 50 100 150 Seconds 200 250 300 1.00E-06 1.00E-07 1.00E-08 1.00E-09

1.00E-06 1.00E-07 1.00E-08 1.00E-09 1.00E-10

O3 OBrBrO3OClClO3-

50

100

150 Seconds

200

250

300

1 ppm Br-

50 ppm Br-

1.00E-04 1.00E-05

1.00E-04 1.00E-05 Conc (M) 1.00E-06 1.00E-07 1.00E-08 1.00E-09

0 50 100 150 Seconds 200 250 300

Conc (M)

1.00E-06 1.00E-07 1.00E-08 1.00E-09

Halonitromethane byliquidliquidextraction(LLE)GC/MS
Sample
0 50 100 150 Seconds 200 250 300

HNMsconcentration(g/L) CNM DCNM TCNM BNM BCNM DBNM Total HNM

NSW

Solving large set of differential equations (one for each species) simultaneously in addition to equilibrium equations provide model results for concentrations of ozone, free bromine (hypobromate), bromate, free chlorine (hypochlorate) and chlorate with time. The results show that as bromide concentration increase from 0.1 to 1 to 10 to 50 mg/L (as Br): ozone is rapidly converted to free chlorine species free chlorine is converted to free bromine (hypobromate).

Inlet(Jan,2008) Mainbasin(Jan,2008) HBSW Inlet(Jan,2008) Mainbasin(Jan,2008) LBSW Inlet(Jan,2008) Mainbasin(Jan,2008)

3.99 0.52

<0.09 <0.09 <0.09 0.45 <0.09 <0.09 2.14 3.15 10.22

<0.10 0.52 <0.10 <0.10 <0.10 <0.10 36.2 47.7 46.55

0.81 0.21 4.98 0.41 0.56 <0.06 2.31 2.82 4.87

0.28 0.17 <0.10 0.27 0.63 6.00 2.65 5.08 6.59

1.00 1.04 9.00 3.51 3.16 7.10 5.23 10.9 6.93

6.08 2.46 13.98 5.64 5.10 13.10 48.5 69.7 75.16

Mainbasin(May,2008) <0.07 1.00 0.75

Acknowledgements
Undergraduate research assistants: Alex Winters and Kristine Brown Graduate research assistants: Y. Jiang, W. Ben., H.. Dong, S. Cole Many other individuals have participated and contributed in significant ways including engineers, aquaria operators, and specialists of many types. The authors gratefully acknowledge the support of the Environmental Research Center at MS&T for instrumental support.

Notes:
1. Similar disinfection byproducts are, hence, formed during ozonation as seen with chlorination. 2. With ammonia present, free chlorine and free bromine are converted to chloramines and bromamines (as well as other disinfection byproducts).

Mainbasin(May,2008) <0.07 <0.07 <0.07

Mainbasin(May,2008) <0.07