[PDF] - CEE/EHS 597B Class #15: Special Treatment Issues: DBPs Dave PDF Document

SLIDE 1

CEE 597B DBPs 1

CEE/EHS 597B

Class #15: Special Treatment Issues: DBPs

Dave Reckhow

2

SLIDE 2

CEE 597B DBPs 2

3

John #1: Dr. John Snow

 Cholera

 First emerged

in early 1800s

 1852-1860: The third cholera pandemic

 Snow showed the role of water in disease transmission  London’s Broad Street pump (Broadwick St)  Miasma theory was discredited, but it took decades to fully put

it to rest

1813-1858 2007

4

Picadilly Circus

Soho, Westminster

SLIDE 3

CEE 597B DBPs 3

John #2: Dr. John L. Leal

5

 Jersey City’s Boonton Reservoir  Leal experimented with chlorine,

its effectiveness and production

 George Johnson & George Fuller worked with Leal and designed

the system (1908)

“Full-scale and continuous implementation of disinfection for the first time in Jersey City, NJ ignited a disinfection revolution in the United States that reverberated around the world”

M.J. McGuire, JAWWA 98(3)123

1858-1914

Photo courtesy of the Leal family and Mike McGuire 6

Chlorination

Melosi, 2000, The Sanitary City, John Hopkins Press Greenberg, 1980, Water Chlorination, Env. Impact & Health Eff., Vol 3, pg.3, Ann Arbor Sci.

US Death Rates for Typhoid Fever

 1-2 punch of filtration &

chlorination

SLIDE 4

CEE 597B DBPs 4

7

Conventional Treatment: 1910-present

 Coagulation & solids separation

 rapid mix, flocculation, settling, filtration

 Disinfection

 including clearwell

for contact time  Most common for surface water

Dist. Sys.

Clear well

Coagulant

Chlorine

Settling

Corrosion Control Fluoride

raw water flocculation rapid mix Filtration

John #3: Johannes J. Rook

 Short Biography

 Education

 PhD in Biochemistry: 1949

 Work experience

 Technological Univ., Delft (~‘49-’54)

 Laboratory for Microbiology

 Lundbeck Pharmaceuticals in Copenhagen,

(~’55-?)

 Noury Citric acid Factory (in Holland)  Amstel Brewery  Rotterdam Water Works by 1963, chief chemist

(1964-1984).

 1984-1986; Visiting Researcher at Lyonnaise des

Eaux, Le Pecq.

 Early Research

 1955, Microbiological Deterioration of

Vulcanized Rubber

 Applied Micro.  1964, secured funds for a GC at

Rotterdam

 Carlo Erba with gas sample loop

8

1921-2010

SLIDE 5

CEE 597B DBPs 5

9

John Rook & DBPs

 Major Contributions

 Brought headspace analysis from the

beer industry to drinking water

 T&O problems

 Found trihalomethanes (THMs) in

finished water

 Carcinogens !?!

 Published in Dutch journal H2O, Aug 19,

1972 issue

 Deduced that they were formed as

byproducts of chlorination

 Proposed chemical pathways

Rook, 1974, Water Treat. & Exam., 23:234

DBP Epidemiology

 Bladder Cancer

 DBPs linked to 9,300 US cases every year

 Other Cancers

 Rectal, colon

 Reproductive & developmental effects

 Miscarriages & Low birth weight  Birth Defects

 e.g., Cleft palate, neural tube defects

 Other

 Kidney & spleen disorders  Immune system problems, neurotoxic effects

20 µg/L THMs - high risk Hwang et al., 2008 Basis for current EPA regulation 80 µg/L THMs 60 µg/L HAAs

SLIDE 6

CEE 597B DBPs 6

11

HOCl O3 NH2Cl ClO2 NOM Oxidized NOM Reduced Inorganics Oxidized Inorganics Cl- OH- NH4

+

ClO2

Reactants

Products

& inorganic DBPs & Organic DBPs

SLIDE 7

CEE 597B DBPs 7

Formation of Cl2-driven DBPs

13

Natural Organic Mater

Anthropogenic Chemicals

(PPCPs, Ag & industrial products)

Cl2 NaOCl

NH3 Br-, I-

OBr-, I3-

~90%

CO2 + Oxidized Organic Compounds

Acids
Aldehydes
Ketones
Nitrosamines

NH2Cl The non- halogenated DBPs

The Halogenated DBPs

THMs
HAAs and other haloacids
Haloaromatics
N-halo compounds
Halo-nitriles, aldehydes, nitros, etc

~10%

Reactions with Disinfectants: Chlorine

14

HOCl + natural organics (NOM)

Oxidized NOM and inorganic chloride

Aldehydes

Chlorinated Organics

TOX
THMs
HAAs

Cl Cl Cl C H Br Cl Cl C H Br Cl Br C H Br Br Br C H Chloroform Bromodichloromethane Chlorodibromomethane Bromoform

The THMs

The Precursors!

SLIDE 8

CEE 597B DBPs 8

The Haloacetic Acids

15

 HAA5 & HAA6 include the two monohaloacetic acids (MCAA & MBAA) plus

 One of the trihaloacetic acids:  And 2 or 3 of the

dihaloacetic acids Cl Cl Cl C COOH Br Cl Cl C COOH Br Cl Br C COOH Br Br Br C COOH Trichloroacetic Bromodichloroacetic Chlorodibromoacetic Tribromoacetic Acid Acid Acid Acid

(TCAA)

Cl Cl H C COOH Br Cl C COOH Br Br H C COOH Dichloroacetic Bromochloroacetic Dibromoacetic Acid Acid Acid

(DCAA)

H

HAA6 only

15

Haloacetonitriles

16

 Others that are commonly measured, but not regulated include

the:

 Dihalo-

acetonitriles

 Trihaloacetonitriles

Cl Cl H C C Br Cl C Br Br H C Dichloroacetonitrile Bromochloroacetonitrile Dibromoacetonitrile

(DCAN)

H N C N C N

(BCAN) (DBAN)

Cl Cl Cl C C Trichloroacetonitrile

(TCAN)

N

16

SLIDE 9

CEE 597B DBPs 9

Halopropanones

17

 As well as the:  dihalopropanones trihalopropanones

Cl Cl Cl C C Br Cl Cl C 1,1,1-Trichloropropanone

(TCP)

O H H C H C O H H C H 1,1,1-Bromodichloropropanone

etc.

Cl Cl H C C 1,1-Dichloropropanone

(DCP)

O H H C H

etc

17

“I think you should be more explicit here in step two”

Factors Affecting DBP Formation

18

 Time  pH  Dose  Temperature  Bromide/Ammonia  Pretreatment  Reactions with pipe

walls & attached materials

SLIDE 10

CEE 597B DBPs 10

Time

19

 Major

Byproducts

Time (hrs)

20 40 60 80 100 120 140 160 300 350

TOX Concentration (g/L)

100 200 300 400 500 600 700 800 900 1000 1100 1200 1300

THM, HAA Concentration (g/L)

100 200 300 400 500 600

TOX TCAA TTHM DCAA

20 mg/L chlorine dose pH 7.0 20oC

(after Reckhow & Singer, 1984)

Aquatic NOM

20

pH

2 4 6 8 10 12

Concentration (g/L)

200 400 600 800 1000 1200 1400

TCAA + DCAA TTHM TOX

pH Effects

SLIDE 11

CEE 597B DBPs 11

Significance of Bromide

21

 Present in surface and groundwaters  Concentrations are highly variable  Not removed by most treatment processes  Readily oxidized by chlorine

HOCl Br HOBr Cl

k

    

 

k x M s x M s C

T

  

     

4 7 10 37 10 25

2 754 9 1 1 3 1 1

. [exp( )] . @

.

Therefore, bromide has a 13 second half life at pH 7, and 1 mg/L residual chlorine

Impact of Bromide on THM Formation

22

Bromide Concentration (mg/L)

0.0 0.4 0.8 1.2 1.6 2.0

Percent of TTHM

20 40 60 80 100 CHCl3 CHBrCl2 CHBr2Cl CHBr3

Data from: Minear & Bird, 1980

96 hours, pH 7.0 5 mg/L Chlorine Dose 1 mg/L Humic Acid

SLIDE 12

CEE 597B DBPs 12

Bromide: THAA Formation

23 Bromide Concentration (mg/L)

1 2 3 4 5

Concentration (g/L as Cl-)

30 60 90 120 150 180 210 240 270 300 330

CCl3COOH CCl2BrCOOH CClBr2COOH pH 7, 25oC, 7 days 25 mg/L chlorine dose 2.9 mg/L TOC CBr3COOH

From Pourmoghaddas, 1990

Note that TCAA is the only regulated THAA

Case Study: Impact of time & chlorine dose

24

Cl2 Demand

Time (hrs)

20 40 60 80 100 120

Chlorine Demand (mg/L)

1 2 3 4 5 6 10 mg/L 5 mg/L 2.5 mg/L Loss of Residual Chlorine Dose

SLIDE 13

CEE 597B DBPs 13

Case Study: Impact of time & chlorine dose

25

THM

Time (hrs)

20 40 60 80 100 120

Total Trihalomethanes (g/L)

20 40 60 80 100 120 140 160 180 200 220 10 mg/L 5 mg/L 2.5 mg/L Loss of Residual Chlorine Dose

THMs from Chlorination

Reaction Time (hours)

20 40 60 80 100

THM Formation (g/L)

5 10 15 20 25 30 35 40 45 50 55 60 1-Chlorine: std dose: low temp 2-Chlorine: std dose: high temp 3-Chlorine: opt dose: low temp 4-Chlorine: opt dose: high temp

 Chlorine Residual @ 48 hrs

 std = 0.8 mg/L  opt = 0.2 mg/L

 Temp

 Low = 13 C  High = 23 C

26

SLIDE 14

CEE 597B DBPs 14

THMs from Chloramination

 Addition of ammonia after 5 hrs free contact time

Reaction Time (hours)

20 40 60 80 100

THM Formation (g/L)

5 10 15 20 25 30 35 40 45 5-Chloramine: mid dose: 4.0 Cl2/N: low temp 6-Chloramine: mid dose: 4.9 Cl2/N: low temp 7-Chloramine: mid dose: 6.0 Cl2/N: low temp 8-Chloramine; low dose: 4.9 Cl2/N: low temp 9-Chloramine: high dose: 4.9 Cl2/N: low temp 10-Chloramine: mid dose: 4.9 Cl2/N: high temp End of Initial Free Chlorine Contact Period

27

DBP Modeling

 Power function models (Empirical)

 simple to use  greater experience

 Chemical kinetic models (Semi-mechanistic)

 depends on time-varying concentrations of the precursors

(reactants)

 better adapted for use with a more integrated framework

 combine with degradation terms  combine with hydraulic/reactor models  Chlorine boosting

28

SLIDE 15

CEE 597B DBPs 15

DBP Formation: Empirical Model

29

 Montgomery Watson, 1992 Compound a b c d e f g h i

Chloroform 0.064 0.329 0.874 0.01

0.404

1.161 0.561 0.269 1.018 Bromodichloromethane1 0.0098 0.181 2.55 0.497 0.256 0.519 Bromodichloromethane2 1.325

0.725

0.794 0.632 0.204 0.519 Chlorodibromomethane3 15.0

1.67

1.24 0.73 0.261 0.989 Chlorodibromomethane4 0.028

1.08
1.18

1.57 1.97 1.07 0.200 0.596 Bromoform 6.53

2.03

1.39 1.60 1.06 0.136 Monochloroacetic Acid 1.63 0.75 0.01

0.085
1.12

0.51 0.300 Dichloroacetic Acid 0.605 0.29 0.73 0.01

0.57

0.48 0.239 0.665 Trichloroacetic Acid 87.2 0.36 0.90 0.01

0.70
1.73

0.88 0.264 Monobromoacetic Acid 0.176 1.66

0.62

0.80

0.93

0.145 0.450 Dibromoacetic Acid 84.9

0.62

0.65 1.07

0.20

0.120 0.657

             

i h g f e c b

Temp Time dose Cl pH d Br UV TOC a DBPs

2 254

 

Descriptive, but not much insight

1Cl2/Br <75; 2Cl2/Br >75; 3Cl2/Br <50; 4Cl2/Br >50

DBPs in µg/L, UV254 in cm-1, Time in hrs, Temp in oC, all others in mg/L

Annual TOC Cycles: Small NE Tributary

30 Date

Mar Apr May Jun Jul

Flow (cfs)

50 100 150 200

DOC (mg/L)

2 4 6 8 Flow DOC

2017

 Mill River in Amherst

SLIDE 16

CEE 597B DBPs 16

Monroe: quarterly THMs

 Monroe

31

Monroe, MA

Date

2 2 2 3 2 4 2 5 2 6 2 7 2 8 2 9 2 1 2 1 1 2 1 2 2 1 3 2 1 4 2 1 5 2 1 6 2 1 7 2 1 8 2 1 9

THM (g/L)

20 40 60 80 100 120 140 160 Collected vs THMs, ug/L Standard

Monroe: THMs LRAA

 xcv

32

Monroe, MA

Date

2 2 2 3 2 4 2 5 2 6 2 7 2 8 2 9 2 1 2 1 1 2 1 2 2 1 3 2 1 4 2 1 5 2 1 6 2 1 7 2 1 8 2 1 9

THM (g/L)

30 40 50 60 70 80 90 100 110 Collected vs LRAA Standard

SLIDE 17

CEE 597B DBPs 17

Monroe: THMs OEL

 dsf

33

Monroe, MA

Date

2 2 2 3 2 4 2 5 2 6 2 7 2 8 2 9 2 1 2 1 1 2 1 2 2 1 3 2 1 4 2 1 5 2 1 6 2 1 7 2 1 8 2 1 9

THM (g/L)

20 40 60 80 100 120 Collected vs OEL Standard

 sd

34

Hinsdale, MA

Date

2 2 2 3 2 4 2 5 2 6 2 7 2 8 2 9 2 1 2 1 1 2 1 2 2 1 3 2 1 4 2 1 5 2 1 6 2 1 7 2 1 8 2 1 9

THM (g/L)

20 40 60 80 100 120 System THMs, ug/L Standard

Hinsdale: Quarterly THMs

SLIDE 18

CEE 597B DBPs 18

Hinsdale: THM LRAA

35

Hinsdale, MA

Date

2 4 2 5 2 6 2 7 2 8 2 9 2 1 2 1 1 2 1 2 2 1 3 2 1 4 2 1 5 2 1 6 2 1 7 2 1 8

THM (g/L)

20 40 60 80 100 120 LRAA Standard

Hinsdale: THM OEL

 sd

36

Hinsdale, MA

Date

2 4 2 5 2 6 2 7 2 8 2 9 2 1 2 1 1 2 1 2 2 1 3 2 1 4 2 1 5 2 1 6 2 1 7 2 1 8

THM (g/L)

20 40 60 80 100 120 OEL Standard

SLIDE 19

CEE 597B DBPs 19

Hinsdale: Quarterly HAA5

 ad

37

Hinsdale, MA

Date

2 2 2 3 2 4 2 5 2 6 2 7 2 8 2 9 2 1 2 1 1 2 1 2 2 1 3 2 1 4 2 1 5 2 1 6 2 1 7 2 1 8 2 1 9

HAA5 (g/L)

20 40 60 80 Quarterly HAA5, ug/L Standard

Hinsdale HAA5 RAA

38

Hinsdale, MA

Date

2 4 2 5 2 6 2 7 2 8 2 9 2 1 2 1 1 2 1 2 2 1 3 2 1 4 2 1 5 2 1 6 2 1 7 2 1 8

HAA5 (g/L)

10 20 30 40 50 60 70 LRAA Standard

SLIDE 20

CEE 597B DBPs 20

Hinsdale: HAA5 OEL

39

Hinsdale, MA

Date

2 4 2 5 2 6 2 7 2 8 2 9 2 1 2 1 1 2 1 2 2 1 3 2 1 4 2 1 5 2 1 6 2 1 7 2 1 8

HAA5 (g/L)

10 20 30 40 50 60 70 OEL Standard

Analysis of DBP Precursors

40

Laboratory Precursor Test

Time (hrs)

50 100 150 200

TTHM (g/L)

50 100 150 200 250

Available Precursors Instantaneous

Time of Chlorine Addition

Terminal

r Formation

Potential

40

Use a standard:

chlorine dose
reaction time
pH (maybe)

SLIDE 21

CEE 597B DBPs 21

Significance

41

 Formation potential are important for controlling organic

precursors

 assess process performance  compare waters

THMs HAAs Stage 1&2 0.080 0.060

 Only instantaneous

concentrations are regulated

 Formation kinetics

are important for managing systems

(mg/L)

41

National Database

42

Cumulative Frequency

0.0 0.2 0.4 0.6 0.8 1.0

Specific THMFP (g/mg-C)

20 40 60 80 100 120

Specific THM-SDS (g/mg-C)

10 20 30 40 50 60 Surface Waters Groundwaters

From: Reckhow et al., 2006 AWWARF report (in press)

42

From: Reckhow et al., 2007 WRF Report #91186

SLIDE 22

CEE 597B DBPs 22

Mean TTHMs from US Surveys

43

Occurrence Assessment for the Final Stage 2 DBPR, 12/05, USEPA

43

From Seidel et al., 2016

TOX: Known & Unknown

44

Data from the Mills Plant (CA) August 1997 (courtesy of Stuart Krasner)

44 Trihalomethanes 20% Sum of 5 Haloacetic Acids 10% Bromochloroacetic Acid 3% Unknown Organic Halogen 64% Chloral Hydrate 1% Haloacetonitriles 2% Haloketones Chloropicrin

SLIDE 23

CEE 597B DBPs 23

DBP Control Strategies

 Source Selection  Precursor Removal

 Most commonly used: better coagulation, GAC, MIEX,

membranes

 Changing Treatment Sequence/conditions  Alternative disinfectants

 Also common: chloramines, chlorine dioxide, ozone

 DBP removal  Distribution System Modification

45

See: Chapter 19 in Water Quality and Treatment; 6th edition; 2011

Some 2009 Projected Costs

46

Plant Capacity (MGD)

1 10 100

Total Annual Costs ($ per MGD capacity)

1x103 10x103 100x103 Nanofiltration Low-pressure Membranes Ozone GAC UV Chlorine Dioxide Chloramines

 Comparison from Roy, 2010 [JAWWA 102(3)44-51]

SLIDE 24

CEE 597B DBPs 24

Alternative Secondary Disinf.

47

 Chloramines

 About 30% now use chloramines

 Seidel et al., 2005

 Unique chloramine DBPs

 Anecdotal reports of health effects

 Reduction of chlorine DBPs  Nitrification and regrowth (free ammonia)

 Modeling: Fleming et al., 2005; Liu et al., 2005  Control techniques: e.g., Rosenfeldt et al., 2009 [JAWWA 101:10:60]

 Lead solubilization

 If Pb(IV) controls solubility

 Lytle & Schock, 2005 [JAWWA 97:11:102]  Vasquez et al., 2006 [JAWWA 98:2:144]

 Possible role in controlling bromate

Utility Case Studies

48

 Biodegradation

 Elizabethtown, NJ

 Weisel study

 Norwood, MA

 Distribution System

Evaluation

 Woburn, MA

SLIDE 25

CEE 597B DBPs 25

Seasonal Variability & Biodegradation

49

 Chen & Weisel study  JAWWA, April 1998  Intensive study of Elizabethtown, NJ system

 125 MGD conventional plant  4.9 mg/L DOC (raw water average)  pH 7.2

Elizabethtown, NJ: THMs

50

SLIDE 26

CEE 597B DBPs 26

Elizabethtown, NJ: TCAA

51

HAA Degradation

52

 Biodegradation:  dihaloacetic acids degrade more readily than

trihaloacetic acids

 On BAC

 MHAA>DHAA>THAA

 Wu & Xie, 2005 [JAWWA 97:11:94]

 In distribution systems

 DHAA>MHAA>THAA

 Many studies

SLIDE 27

CEE 597B DBPs 27

Biodegradation in Dist. Systems

53 Town Hall; Norwood, MA

Date

1 / 1 / 1 9 9 9 1 / 1 / 2 1 / 1 / 2 1 1 / 1 / 2 2 1 / 1 / 2 3 1 / 1 / 2 4 1 / 1 / 2 5 1 / 1 / 2 6

Concentration (g/L)

20 40 60 80 100 120 TTHM HAA5

Pier 1; Norwood, MA

Date

1 / 1 / 1 9 9 9 1 / 1 / 2 1 / 1 / 2 1 1 / 1 / 2 2 1 / 1 / 2 3 1 / 1 / 2 4 1 / 1 / 2 5 1 / 1 / 2 6

Concentration (g/L)

20 40 60 80 100 120 TTHM HAA5

Example: Norwood, MA

Biodegradation of HAAs

54

 Norwood, MA example

Percentile

20 40 60 80 100

HAA/THM Ratio (g/g)

0.0 0.2 0.4 0.6 0.8 1.0 1.2 Town Hall Pier 1 No Degradation Degradation

SLIDE 28

CEE 597B DBPs 28

Woburn System Description

55

 Local supplies of 4 MGD from five municipal wells located at

Horn Pond

 Free chlorine

 The MWRA supplies an average of 2.5 MGD through

connections at Meter 230 and 200 to supplement local supply

 chloramines

 Ave day demand is 6.2 MGD

 Max (summer) is 12.5 MGD  Min (winter) is 4.5 MGD

Mixing

56

 Percent MWRA water

 Based on Maximum daily

demand

Courtesy of CDM and City of Woburn

SLIDE 29

CEE 597B DBPs 29

Mixing

57

 Same as before, but:

 Including THM sampling

locations

Courtesy of CDM and City of Woburn

North Woburn FS Senior Center Red Roof Inn Central Woburn FS Dix Road Shaker Glenn BS West Woburn FS South Woburn FS

Mixing

58

 Percent MWRA water

 Based on minimum day

demands

Courtesy of CDM and City of Woburn

Central Woburn FS

SLIDE 30

CEE 597B DBPs 30

Water Age

59

 Based on Maximum Day

demands

Courtesy of CDM and City of Woburn

Water Age

60

Courtesy of CDM and City of Woburn Whispering Hill Tank Janis Terrace Waltham St. Tank DPW Rag Rock Tank Hurld School Health East Rehab Country Club City Hall Blueberry Hill FS Shamrock School East Woburn FS

 Based on minimum day

demands

SLIDE 31

CEE 597B DBPs 31

Water Age

61

 Max Day  With bacterial

sampling locations

Whispering Hill Tank Janis Terrace Waltham St. Tank DPW Rag Rock Tank Hurld School Health East Rehab Country Club City Hall Blueberry Hill FS Shamrock School East Woburn FS

D a te

6 /1 /2 0 0 4 1 0 /1 /2 0 0 4 2 /1 /2 0 0 5 6 /1 /2 0 0 5 1 0 /1 /2 0 0 5 2 /1 /2 0 0 6 6 /1 /2 0 0 6

Chlorine Residual (mg/L)

0 .0 0 .5 1 .0 1 .5 2 .0 2 .5 S O U T H W O B U R N F IR E S T A T IO N R E D R O O F IN N N O R T H W O B U R N F IR E S T A T IO N C E N T R A L S Q . F IR E S T A T IO N W E S T W O B U R N F IR E S T A T IO N S H A K E R G L E N B O O S T E R S T A T IO N

Chlorine Residuals at Stage 1 sites

62

MWRA Local

SLIDE 32

CEE 597B DBPs 32

63

All Stage 1 Sites; Woburn, MA

Date

1/1/2001 1/1/2002 1/1/2003 1/1/2004 1/1/2005 1/1/2006 1/1/2007 1/1/2008 1/1/2009

TTHM Concentration (g/L)

20 40 60 80 100 120 City Hall Dix Road Janis Terrace North Woburn FS Red Roof Inn Senior Center Shaker Glen BS South Woburn FS West Woburn FS Central Square FS 64

IDSE Sites; Woburn, MA

Date

1/1/2008 1/1/2009

TTHM Concentration (g/L)

10 20 30 40 50 #1: 5 Cove St. (entry) #2: 679 Main St (Wyman Sch) #3: 6 Packard St. #4: 15 Parliament Ln #5: 69 Mt. Pleasant St #6: 1 Nichols St Ext #7: 14 Hiawatha Rd #8: 5 Winter Rd

SLIDE 33

CEE 597B DBPs 33

Chloramines – many more reactions

65

NH2OH

NH2Cl

HNO ClNHOH NO2

H2N2O2

NH3 N2O X1 X2 N2 NO3

Pb(IV)

Pb+2

AMO HAO

AOB NOB

Chemical Reduction Chemical Oxidation Biodegradation AMO 66