Not all THMs are Created Equal

CA/NV AWWA FALL CONFERENCE October 3, 2013

SMURPH SAYS: “NEVER write a NUMBER without UNITS!”

Regulated and unregulated THM basics, and the future of THM regulation Why Total THM results can be exactly the same

number, yet have completely different properties How to find the source of THM formation Making the most of what your data is telling you Steps in implementing operational changes

5 Key Points to Learn

Disinfection by-products most notably chloroform and other trihalomethanes were first found in DW in

1974, and regulated in 1979. Trihalomethane and Halo acetic acids are currently

regulated in DW. Halogens are a group of nonmetallic elements with

similar properties. Fluorine, Chlorine, Bromine, Iodine, and Astatine. All are toxic!

What are THMs?

Chlorine is one of the PRIMARY disinfectants in DW, and Bromine can frequently be found in water sources. TTHM: Bromodichloromethane, Bromoform, Dibromochloromethane, and Chloroform (only 4 ?) Haloacetic acids: Dichloroacetic acid, Trichloroacetic acid, Monochloroacetic acid, Bromoacetic acid, and Dibromoacetic acid (only 5 ?)

Which halogens are we interested in?

International Union of Pure and Applied Chemistry

Trichloromethane = Chloroform and a few other names…..

Trichloromethane; Formyl trichloride; Methane trichloride; Methyl trichloride; Methenyl trichloride; TCM; Freon 20; Refrigerant-20; R-20; UN 1888 How could ANYONE get chemical names “mixed’ up?

Tribromomethane = Bromoform and a couple other names….. Methenyl tribromide, Methyl tribromide

These are simple organic molecules

Bromodichlormethane Chloroform

Bromoform Chlorodibromomethane

How Many DBPs could be regulated?

More than 500 disinfection by-products (DBPs) have been reported in the literature for the major disinfectants currently used (chlorine, ozone, chlorine dioxide, chloramines), as well as their combinations

Priority DBPs selected for Nationwide Occurrence Study-

3-Chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone, 3-Chloro-4-(dichloromethyl)-2-(5H)-furanone, 2-Chloro-3-(dichloromethyl)-butenedioic acid, 2-Chloro-3-(dichloromethyl)-4-oxobutenoic acid, 2,3-Dichloro-4-oxobutenoic acid, 3-Chloro-4-(bromochloromethyl)-5-hydroxy-2(5H)-furanone, 3-Chloro-4-(dibromomethyl)-5-hydroxy-2(5H)-furanone, 3-Bromo-4-(dibromomethyl)-5-hydroxy-2(5H)-furanone, 2-Chloro-3-(bromochloromethyl)-4-oxobutenoic acid, 2-Chloro-3-(dibromomethyl)-4-oxobutenoic acid, 2-Bromo-3-(dibromomethyl)-4-oxobutenoic acid , 3,3-Dichloropropenoic acid, Bromomethane, Dibromomethane, Bromochloromethane, Bromochloroiodomethane, Dichloroiodomethane, Dibromoiodomethane, Chlorodiiodomethane , Bromodiiodomethane, Iodoform, Chlorotribromomethane, Carbon tetrachloride, Bromonitromethane, Chloronitromethane, Dibromonitromethane, Dichloronitromethane, Bromodichloronitromethane, Dibromochloronitromethane, Tribromonitromethane, Bromopicrin, Bromoacetonitrile, Chloroacetonitrile, Tribromoacetonitrile, Bromodichloroacetonitrile, Dibromochloroacetonitrile AND……

Chloropropanone, 1,3-Dichloropropanone, 1,1-Dibromopropanone, 1,1,3-Trichloropropanone, 1-Bromo-1,1-dichloropropanone, 1,1,1,3-Tetrachloropropanone, 1,1,3,3-Tetrachloropropanone, 1,1,3,3-Tetrabromopropanone , 1,1,1,3,3-Pentachloropropanone, Hexachloropropanone Haloaldehydes: Chloroacetaldehyde, Dichloroacetaldehyde, Bromochloroacetaldehyde, Tribromoacetaldehyde Haloacetates: Bromochloromethyl acetate Haloamides: Monochloroacetamide, Monobromoacetamide, Dichloroacetamide, Dibromoacetamide, Trichloroacetamide Non-Halogenated Aldehydes and Ketones: 2-Hexenal, 5-Keto-1-hexanal, Cyanoformaldehyde, Methylethyl ketone (2-butanone), 6-Hydroxy-2-hexanone, Dimethylglyoxal (2,3-butanedione) Volatile organic compounds (VOCs) and Miscellaneous DBPs: 1,1,1,2-Tetrabromo-2-chloroethane, 1,1,2,2-Tetrabromo-2-chloroethane, Methyl-tert-butyl ether, Benzyl chloride

Disinfection byproducts are created by chemical reactions when water is disinfected. Of the hundreds of known, or suspected, disinfection byproducts possibly created by disinfection processes, the brominated forms are among the most toxic. The water was examined for 29 different disinfection byproducts, including brominated and non-brominated disinfection byproducts. The brominated disinfection byproducts were detected more frequently and at much higher levels in river water impacted by disinfected produced waters than at other sites.

Technical Announcement: Disinfection of Energy Wastewater Can Lead to Toxic Byproducts Released:

9/4/2013

You have to look at the individual components!!

Philip C. Singer, Ph.D., P.E. Daniel A. Okun Distinguished Professor of Environmental Engineering University of North Carolina at Chapel Hill http://www.nwri-usa.org/laureates.htm

U.S. EPA orders Solano Irrigation District to remove chemical from drinking water Release Date: 5/10/2005 Contact Information: Mark Merchant (415) 947-4297 SAN FRANCISCO - The U.S. Environmental Protection Agency recently ordered the Solano Irrigation District to reduce levels of disinfection byproducts from drinking water treated by the district’s Gibson Canyon water system. The EPA promulgated new disinfection byproduct regulations in December 1998 to protect public health from potentially harmful byproduct chemicals formed when chlorine reacts with natural organic compounds during the treatment process. This is the first action taken by the EPA against a small water system in California under the agency’s disinfection byproduct regulation. “Chemical byproducts in treated drinking water need to be monitored, reported and reduced to meet federal health standards,” said Alexis Strauss, the EPA’s water division director for the Pacific Southwest region. “In this case, the district notified the public and has begun changing their operations to prevent the byproduct from forming.” Although detected in trace amounts over the federal drinking water standard, the district is required to notify the public when detection goes above health-based standards. The drinking water standard for total trihalomethanes is 80 parts-per-billion; the Gibson Canyon system had a range from 98 to 107 parts-per-billion. While the system exceeds the standard, no effects on human health are anticipated from this short-term exposure. The district was required to monitor its water system for these chemicals on a quarterly basis beginning January 2004. The district violated the standard from January 1, 2004 to March 31, 2005. The order requires the district to submit a compliance plan within 21 days of receiving the order and to reduce disinfection byproducts to below federal standards no later than September 30, 2006. BUT WAIT THERE IS A HAPPY ENDING!

WE WON THE CLAIR HILL AWARD FOR SOLVING THE PROBLEM!

87%

1% Non-Detect

Typical TTHM Components in SID Treated Water

12%

VOLATILE? Or

SEMIVOLATILE?

COMPOUND Molecular Weight

Boiling Point

Vapor

Pressure

Solubility

(mg/L)

Henry’s law constant

(atm-m3/mol)

chloroform 119.38 g/mol 61.2 °C 159 mm Hg 7.22 x 103 3.00 x 10-3

bromodichloromethane 163.83 g/mol 90.1 °C 50 mm Hg 4.5 x 103 2.41 x 10-3

dibromochloromethane 208.28 g/mol 120 °C 76 mm Hg 2.7 x 103 0.99 x 10-3

bromoform 252.73 g/mol 149.1 °C 5 mm Hg 3.10 x 103 0.56 x 10-3

Volatile organic compounds (VOCs) Generally speaking, volatiles have been defined as compounds with boiling points below 150°C, and low molecular weight. Semi-volatile organic compounds (SVOCs) Substances composed primarily of carbon and hydrogen atoms that have boiling points greater than 150°C, and higher molecular weight.

Physical characteristics of VAPOR PRESSURE:

Liquids may change to a vapor at temperatures below their boiling points through the process of evaporation. Evaporation is a surface phenomenon in which molecules located near the vapor/liquid surface escape into the vapor phase. At any given temperature, for a particular substance, there is a pressure at which the gas of that substance is in “dynamic equilibrium” with its liquid or solid forms. The equilibrium vapor pressure is an indication of a liquid's evaporation rate. A substance with a high vapor pressure at normal temperatures is often referred to as volatile.

The Challenge

Troubleshooting THM sources

Don’t wait for compliance dates, get “sneak peaks” Worst case scenario get some Total Potential data Develop ONE LOOK data tables, and graphs Change one focus point, and keep everything else constant Try a new method, lab, time of day, date, split samples Brainstorm with as many people as possible Do some demo projects/pilot studies on a small scale Start at the source, and follow the water timeline Pay attention to WHICH THMs or HAs are present Phone a friend, READ, AWWA conference, LEARN MORE!

TANKS can be important locations to evaluate!

FULL SCALE TEST

Water into Air The flow rate on the pump was 65 gpm, and the tank contained about 1 million gallons of treated water with a known level of TTHMs.

The water in the tank was completely recirculated and aerated between sampling dates and no water was added to the tank during testing.

Make the MOST of your DATA COMPARISON of THM to TPTHM

Date THM (ppb)

TP THM (ppb)

Difference

7/5/06 10 20 10 11/21/06 98 * 129 31* 10/18/06 128 120 +8 8/16/06 115 122 7 8/9/06 110 120 10 8/2/06 119 137 18 7/26/06 101* , 133 136 35*, 3 7/19/06 118 124 6 7/12/06 123 129 6 7/5/06 116 139 23 6/28/06 106 137 31 6/21/06 118 118 0 6/14/06 104*, 113 123 19*, 10 6/7/06 108 126 18 5/31/06 112 116 4 5/24/06 129 122 7 5/10/06 116 120 4 5/3/06 104 104 0 4/26/06 90 105 15 4/19/06 90 104 14 4/12/06 82 92 10 1/18/06 111 114 3

Date Time Location THM ppb

Cl2 ppm

Comments

SSWA 6/8/11 8:55 am Plant #1

Settled 29 0.0 Pre-chlorine on

6/8/11 9:05 am Plant #1 Finished

46 1.2 Pre-chlorine on

6/8/11 9:15 am Plant #2 Settled

30 0.0 Pre-chlorine on

6/8/11 9:20 am Plant #2 Finished

47 0.8 Pre-chlorine on

6/22/11 8:10 am Plant #1

Settled ND 0.0 Pre-chlorine off

6/22/11 9:20 am Plant #1 Finished

19 1.2 Pre-chlorine off

6/22/11 9:25 am Plant #2 Settled

ND 0.0 Pre-chlorine off

6/22/11 9:35 am Plant #2 Finished

20 0.9 Pre-chlorine off

THM STAGE 2 Extra Sample Results

ID 10/22/09 1/21/10 3/25/10 4/14/11 THM1

92 ppb

10:15 am 1.6 ppm 67.0 °F

81 ppb 9:30 am 1.3 ppm 46.1 °F

110 ppb 9:45 am 1.0 ppm 55.3 °F

100 ppb 9:10 am 0.9 ppm 52.0 °F

HAA1

66 ppb 10:00 am

0.7 ppm 65.2 °F

63 ppb 9:10 am 1.8 ppm 45.9 °F

72 ppb 9:00 am 1.2 ppm 52.7 °F

Stage 2 “sneak peaks”

Look at it in a variety of ways Put it in tables by date Graph it with related data Add other data: time, temp Do small “studies” Show it to others Take additional samples

Cement Hill WTP and Putah South Canal

I fell in LOVE again with the Periodic Table!! Preparing for this talk!!

For questions or help:

Sue Murphy Water Quality Specialist Solano Irrigation District murphys@sidwater.org 707-455-4021