THM Formation And Control

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THM Formation And Control By Ken Roberts Safe Drinking Water Seminar Gander, Newfoundland March 26/27 2001

THM Formation And Control DISINFECTION DISINFECTION BYPRODUCTS DBPs HEALTH RISKS DBP REDUCTION/REMOVAL FUTURE - REGULATIONS; PATHOGENS; DBPs

Disinfection A process designed specifically to destroy pathogenic organisms Prevents waterborne disease Other WT processes such as filtration, or coagulation-flocculation-sedimentation nay achieve reductions; not generally the primary goal

Disinfection Waterborne disease is the most significant health risk A variety of chemical and physical agents may be used The disinfecting agents most commonly used today are chlorine and its compunds Chlorine Dioxide, Ozone, UV, membrane

Common Disinfecting Agents Chlorine: - early 1900s - affected by contact time, ph, temperature,turbidity, ammonia Chloramines - reaction of aqueous chlorine and ammonia - less power than free Cl 2, O 3 or ClO 2

Common Disinfecting Agents - assist in T & O control - good penetration of biofilms Chlorine Dioxide - potency not affected by ph or ammonia - controls phenolic T & O - does not form THMs but chlorite and chlorate - must be produced on-site

Common Disinfecting Agents Ozone - in some respects superior to chlorine - unaffected by ph, ammonia - unstable and no long-time residual - must be produced on-site - no chlorinated byproducts - has its own DBPs: aldehydes, ketones, caboxylic acid and bromate

Common Disinfecting Agents Ultra-Violet Iraradiation - can kill bacteria, cysts and viruses - raw water quality affects - turbidity and colour can block UV - a viable alternative for Giardia and Cryptosporidium inactivation - no residual

Disinfectant Use - 1998 AWWA GW Type of Disinfectant Systems Using - % Chlorine gas Sodium Hypochlorite -Bulk - Generated on-site Calcium Hypochlorite -Powder -Tablet Other 61 34 31 3.3 4.5 1.7 2.8 3.9

Surface Water 1998 AWWA Treatment Process Systems - % Filtration Clearwell (BW) Coagulation Flocculation Sedimentation Fluoridation Corrosion Control Disinfection Contact Basin Other PreOx; Softg, Raw storage 97 94 85 76 72 56 52 50 10-25

DBPs of Current Interest Halogenated organic compopunds - THMs and HAAs Inorganic Byproducts -Bromate; Chlorite; Chlorate Disinfection Residuals - Chlorine; Chloramines; Chlorine Dioxide

Disinfectants as Oxidants Nuisance Zebra Mussels Control Iron and Manganese Residual to prevent regrowth in DS Tastes and Odours Improve coagulation efficiency Prevent algal growth in sed basins and filters Indicators of DS integrity

Health Effects THMs formed by chlorination Chlorine has virtually eliminated waterborne microbial disease Classified as: probably carcinogenic to humans IMAC of 0.1 mg/l based on chloroform risk Extrapolation model - Lifetime risk: 3.64 x 10-8

Health Effects DW standards set on basis of: - health impacts - occurrence (conc. and frequency) - exposure - cost benefit - analytical - treatment availability

Health Effects Based on similar health effects data, including animal studies, jurisdictions can have different standards. For example: US EPA have a THM standard of 80 µg/l Ongoing discussion re chloroform NOEL Australia consider a NOEL and have a standard of 250 µg/l

Canadian THM Guideline IMAC is 0.1 mg/l based on a running quarterly average Based on the chloroform risk Interim until all other DBP risks are determined Not expected that all supplies will meet immediately Efforts to meet as expansion/upgrade Precursor removal is preferred Any DBP reduction MUST NOT compromise disinfection

DBP Production Trihalomethanes are produced by chlorination of raw water precursors e.g.: - humic and fulvic (peaty) materials. Most common THMs. - Chloroform. - Bromodichloromethane. - Chlorodibromomethane. - Bromoform.

Modeling DBP Formation Mechanistic models have been developed to predict DBP formation These models have included: - Colour -TOC - UV absorbance - chlorine decay kinetics Some general trends have been noted but definitive concentrations difficult Best results are obtained from on-site testing

DBP Reduction/Removal Three basic treatment approaches for THM reduction: Removal after formation Removal of precursors before Chlorine addition Use of alternative disinfectant

DBP Reduction/Removal Removal of THMs - + and -: No need for change of disinfectant + Lack of precursor removal and so free chlorine continues to react THMs are transferred to another medium e.g. air or activated carbon, and disiposal issue -

DBP Reduction/Removal THM removal: By Air Stripping potential air pollution; energy intensive; winter operation difficult By GAC an advantage is that the process is reversible and GAC can be regenerated (energy and air issues); problems are short bed lives and possible desorption Overall not optimum solution

DBP Reduction/Removal Disinfection process changes: Moving point of disinfectant addition Changing type of disinfectant (e.g. chlorine to ozone, UV) Process change e.g. contact chamber layout, ph Raw water source change

THM Reduction Changing location of disinfectant addition: Issues Zebra mussel control Adequate disinfection contact time Precursor removal can achieve 50% reductions through conventional coagulation and settling

US EPA TOC % Removals TOC mg/l Alk y; mg/l 0 60 Alk y; mg/l 60-120 Alk y; mg/l > 120 % % % 2.0 4.0 35 25 15 4.0 8.0 45 35 25 >8.0 50 40 30

THM Reduction Membrane Filtration (ultrafiltration, nanofiltration and reverse osmosis) Effective removal of: - particles - TOC, DOC and THM precursors - other organic compounds - microorganisms eg. Giardia and Cryptosporidium - ionic dissolved salts

THM Reduction Biological treatment Slow sand filtration - simple operation - up to 15 20% THM reductions through precursor removal - disadvantage is the large filter area required High Rate e.g. bilogical GAC (possibly 40% but relatively costly and complex)

THM Reduction Developing a strategy for THM reduction should consider: Ability to meet guidelines (can colour be relaxed?) THM reduction potential Cost capital and O&M Reliability and ease of water quality change adjustment Complexity of operation Flexibility Climate sensitivity

Alternative Disinfectants Ozone - Effective disinfectant - good for colour removal, T & O, iron and manganese - must be produced on-site - not persistent and therefore requires a second DS disinfectant

Alternative Disinfectants Free Chlorine plus ammonia - chloramines do not produce THMs - must have adequate disinfection prior to ammonia addition - persistent in DS - chloramine toxicity being evaluated

Alternative Disinfectants Chlorine Dioxide - strong disinfectant - does not form THMs - residual will persist in DS - chlorite and chlorate toxicity Iodine - historical use in emergency situation - relatively high cost - iodinated THMs & pot l physiological effects

Disinfection/Disinfection ByProducts (DBPs) Optimal disinfection is important too much of a good thing e.g. in chlorine application - it is not DBP production occurs with disinfectant addition Chlorine produces trihalomethanes, haloacetic acids Ozone can produce ketones, aldehydes, bromates Chlorine dioxide chlorate and chlorite Chlorine and Chloramines

What s in the Future?

Disinfection Needs Health Canada has established a Chlorinated Disinfection ByProducts (CDBP) Task Group to comprehensively assess the risks from THMs in Canadian drinking water supplies and develop risk management recommendations. - work is ongoing

Disinfection Needs Groundwater (unless exclusion is granted) - Disinfection minimum level of treatment - Chlorine, or other equivalent, for disinfection and DS residual - GW under direct surface water influence likely to require contact time and disinfectant concentration (CT) as per developed tables

Disinfection Needs Surface water - a minimum 3 Log removal/inactivation (99.9%) of Giardia cysts and 4 Log viruses - CT tables will define - higher requirements for poor source bacterial qualities

Disinfection Needs US EPA considering additional treatment based on raw water Cryptosporidium concentrations Additional treatment may need to use: -ozone - chlorine dioxide -UV - membranes - bag/cartridge filtration, or - in-bank filtration

Down the Road DBPs DBPs TO HAVE GUIDELINES Disinfection residuals -chlorine - chloramines - chlorine dioxide Inorganic ByProducts - Bromate ion - chlorite ion

Down the Road DBPs Halogenated Organic Byproducts - THMs (chloroform, Bromodichloromethane, Dibromochloromethane, Bromoform) - Haloacetic Acids (Monochloroacetic, Dichloroacetic, Trichloacetic, Monobromoacetic, and Dibromoacetic)