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Determination of Chemical
Mechanism for DBP +
Nicotinamide + Basic
Medium in Water
Disinfection Device
By: Samantha Espy
Overview
 How water is disinfected
 Relevant chemicals
 Purpose and goals
 Methods
 Conclusion
Process of Drinking-Water
Disinfection
 Microorganisms must be removed to prevent illness
 Disinfection removes organic matter
 Must have a residual effect
Disinfection By-Products
 Disinfectants: chlorine, ozone, chlorine dioxide, or
chloramines
 Naturally occurring organic matter: anthropogenic
contaminants, bromide, and iodide
Disinfection By-Products
 Specific article mentions 3 different categories
 Many many DBP’s
Health Risks
 Increased risk of bladder cancer with men
 Reproductive implications
 Respiratory symptoms
Haloacetic Acids
 Carboxylic acids (+) halogen atom (-) hydrogen atom in
acetic acid
 Electronegative halogen results in higher acidity by
stabilizing the negative charge of the conjugate base
 Most common: minichloroacetic acid, dichloroacetic acid,
trichloroacetic acid, monobromoacetic acid, dibromoacetic
acid
 Formed by chlorination, ozonation, or chloramination of
water + slightly acidic water +high organic content matter +
elevated temperature
HAA’s of Interest
 Chloroacetic Acid
 Dichloroacetic Acid
 Trichloroacetic Acid
 Bromoacetic Acid
 Dibromoacetic Acid
Trihalomethanes
 Three hydrogen atoms of methane are replaced by
halogen atoms
 Used in industry as solvents or refrigerants
 Environmental pollutants and may be carcinogenic
 Bigger threat in swimming pools than drinking water
THM’s of Interest
 Chloroform
 Bromoform
 Bromodichloromethane
 Dibromochloromethane
Nicotinamide
 Vitamin B group
 Great fluorescing agent
Specific Device
 DBP + Nicotinamide + Base = Fluorescence Detection
 Basic medium is used to detect fluorescence?
 Or Nicotinamide?
 Uses kinetics to determine rate law to create guidelines
Purpose
 Investigating the formation of complexes between
toxins in water, such as trihalomethanes and haloacetic
acids and nicotinamide in a basic medium
 To come up with a reasonable mechanism for the
reaction used in this device
Mechanism of Interest
Is the Fujiwara mechanism valid?
Progress
 Optimization of all THM’s, HAA’s, and any other
reactants needed
 First investigate the reaction of pyridine (and other
nitrogen containing molecules) with CCl2 so that we
may have a better understanding how nicotinamide
may react with chloroform, etc
 There is more literature on smaller nitrogen containing
molecules such as pyridine
Problems/Goals
 Run pyridine reaction using Gaussian software to
create a baseline for our unknown reaction with
nicotinamide
 Based on the previous mechanism, we can infer
possible binding sites for CCl2 to the nitrogen ring of
the nicotinamide
 Another problem to be investigated is the production of
CCl2 from CCl3- (after chloroform’s reaction with a
base)
Conclusion
 To find a final reaction pathway that is the most
optimized, and likely reaction mechanism of the water
filter product
 This equation can help further optimization of device
and offer repair options
References
 What is water disinfection. Lenntech.
http://www.lenntech.com/processes/disinfection/what-is-water-disinfection.htm Lenntech
BV. (date accessed 4/19/16)
 Water resources research center. University of the district of Columbia. Trihalomethane
Removal and Formation Mechanism in Water. R.C. Chawla; M.M. Varma; A. Balram;
M.M. Murali; and P. Natarajan.
 ScienceDirect. Elsevier. Trihalomethan hydrolysis in drinking water at elevated
temperatures. Xiao-lu Zhang; Hone-wei Yang; Xiao-moa Wang; Tanju Karanfil; Yuefeng
F. Xie.
 The Journal of Physical Chemistry. College of physics and electronics, Shandong
Normal University, Jinan 250014, China. Hybrid Quantum Mechanical and Molecular
Mechanics Study of the SN2 Reaction of CCL4 + OH- in Aqueous Solution: The Potential
of Mean Force, Reaction Energetics, and Rate Constants. Tingting Want, Hongyun Yin,
Dunyou Wang, Marat Valiev.
 Curr Envir Health Rpt(2015) 2;107-115. Water and Health. Overview of Disinfection By-
Products and Associated Health Effects.

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Summer Research Presentation 1

  • 1. Determination of Chemical Mechanism for DBP + Nicotinamide + Basic Medium in Water Disinfection Device By: Samantha Espy
  • 2. Overview  How water is disinfected  Relevant chemicals  Purpose and goals  Methods  Conclusion
  • 3. Process of Drinking-Water Disinfection  Microorganisms must be removed to prevent illness  Disinfection removes organic matter  Must have a residual effect
  • 4. Disinfection By-Products  Disinfectants: chlorine, ozone, chlorine dioxide, or chloramines  Naturally occurring organic matter: anthropogenic contaminants, bromide, and iodide
  • 5. Disinfection By-Products  Specific article mentions 3 different categories  Many many DBP’s
  • 6. Health Risks  Increased risk of bladder cancer with men  Reproductive implications  Respiratory symptoms
  • 7. Haloacetic Acids  Carboxylic acids (+) halogen atom (-) hydrogen atom in acetic acid  Electronegative halogen results in higher acidity by stabilizing the negative charge of the conjugate base  Most common: minichloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, dibromoacetic acid  Formed by chlorination, ozonation, or chloramination of water + slightly acidic water +high organic content matter + elevated temperature
  • 8. HAA’s of Interest  Chloroacetic Acid  Dichloroacetic Acid  Trichloroacetic Acid  Bromoacetic Acid  Dibromoacetic Acid
  • 9. Trihalomethanes  Three hydrogen atoms of methane are replaced by halogen atoms  Used in industry as solvents or refrigerants  Environmental pollutants and may be carcinogenic  Bigger threat in swimming pools than drinking water
  • 10. THM’s of Interest  Chloroform  Bromoform  Bromodichloromethane  Dibromochloromethane
  • 11. Nicotinamide  Vitamin B group  Great fluorescing agent
  • 12. Specific Device  DBP + Nicotinamide + Base = Fluorescence Detection  Basic medium is used to detect fluorescence?  Or Nicotinamide?  Uses kinetics to determine rate law to create guidelines
  • 13. Purpose  Investigating the formation of complexes between toxins in water, such as trihalomethanes and haloacetic acids and nicotinamide in a basic medium  To come up with a reasonable mechanism for the reaction used in this device
  • 14. Mechanism of Interest Is the Fujiwara mechanism valid?
  • 15. Progress  Optimization of all THM’s, HAA’s, and any other reactants needed  First investigate the reaction of pyridine (and other nitrogen containing molecules) with CCl2 so that we may have a better understanding how nicotinamide may react with chloroform, etc  There is more literature on smaller nitrogen containing molecules such as pyridine
  • 16. Problems/Goals  Run pyridine reaction using Gaussian software to create a baseline for our unknown reaction with nicotinamide  Based on the previous mechanism, we can infer possible binding sites for CCl2 to the nitrogen ring of the nicotinamide  Another problem to be investigated is the production of CCl2 from CCl3- (after chloroform’s reaction with a base)
  • 17. Conclusion  To find a final reaction pathway that is the most optimized, and likely reaction mechanism of the water filter product  This equation can help further optimization of device and offer repair options
  • 18. References  What is water disinfection. Lenntech. http://www.lenntech.com/processes/disinfection/what-is-water-disinfection.htm Lenntech BV. (date accessed 4/19/16)  Water resources research center. University of the district of Columbia. Trihalomethane Removal and Formation Mechanism in Water. R.C. Chawla; M.M. Varma; A. Balram; M.M. Murali; and P. Natarajan.  ScienceDirect. Elsevier. Trihalomethan hydrolysis in drinking water at elevated temperatures. Xiao-lu Zhang; Hone-wei Yang; Xiao-moa Wang; Tanju Karanfil; Yuefeng F. Xie.  The Journal of Physical Chemistry. College of physics and electronics, Shandong Normal University, Jinan 250014, China. Hybrid Quantum Mechanical and Molecular Mechanics Study of the SN2 Reaction of CCL4 + OH- in Aqueous Solution: The Potential of Mean Force, Reaction Energetics, and Rate Constants. Tingting Want, Hongyun Yin, Dunyou Wang, Marat Valiev.  Curr Envir Health Rpt(2015) 2;107-115. Water and Health. Overview of Disinfection By- Products and Associated Health Effects.

Editor's Notes

  1. May be removed chemically (chlorine, chlorine dioxide, ozone, halogens, metals) or physically (UV light, electronic radiation, gamma rays, sounds, heat) Disinfection removes microorganisms as well as organic contaminants that serve as shelters or nutrients.
  2. Category 1 contains 8 DBP’s with some or all of the toxiologic characteristics of human carcinogen, four of which are regulated (bromodichloromethan, dichloroacetic acid, dibromoacedic acid, and bromate) and 4 that are not formaldehyde, acetaldehyde, MX and NDMA). Categories 2 and 3 contain 43 emerging DBP’s that are present at moderate levels. Category 2 contains 29 and category 3 contains 14, or which there is little to no toxilogical data on. Article
  3. Sperm quality, time to pregnancy menstrual cycle, pregnancy outcome such as fetal loss, fetal growth, preterm delivery and congenital malformation Higher rates of asthma. *discraimer: all about swimming pools and not drinking water. Also for the respiratory symptoms, the benefits of swimming out weigh the
  4. Question??