Remotely measuring DBP’s and other Water Quality Trendsnysawwa.org/docs/pdfs/Session 4 Remotely...

Remotely measuring DBP’s and other Water Quality Trends

Tom Williams

+1 408 476 7768

[email protected]

[email protected]

“Enabling the Optimization of THM Control” 2

Who are we?


• Worked in DBP’s since 2008

• AMS is US based company with R&D and Technical Support in Sunnyvale, CA

and manufacturing in Lowell, MA

• Privately held with European and US private investors

• Founded in 2007 to focus on TTHM Monitoring now also HAA and Trace Metals

Monitoring

• Established presence across the USA and in UK and Spain with multiple units

at several clients

• THM-100 has been extensively tested independently by leading laboratories

and water utilities in USA and Europe

Disinfection By-Product Formation

Naturally-Occurring

Organic Matter (NOM)

e.g.

- Humic Acids

- Fulvic Acids

Chlorine Based Compounds for

Microbiological Disinfection

e.g.

- Chlorine

- Hypochlorite

- Chlorine Dioxide

DBPs

Disinfection By-Products*

e.g.

- Trihalomethanes- Haloacetic Acids

- Bromate

- Chlorite

Disinfection By-Products*

- Several thousand are known

- More than 500 have been toxicologically reviewed

- Several classes and compounds are regulated in drinking water:

◆ Trihalomethanes

◆ Haloacetic Acids 3

Typical Surface Water Source


DOC or TOC Detection


Hydrophilic or Hydrophobic ?


Halogens – the Halo’s in THM’s

halogen molecule structure modeld(X−X) / pm(gas phase)

d(X−X) / pm(solid phase)

fluorine F2 143 149

chlorine Cl2 199 198

bromine Br2 228 227

iodine I2 266 272


http://en.wikipedia.org/wiki/Fluorine

http://en.wikipedia.org/wiki/Chlorine

http://en.wikipedia.org/wiki/Bromine

http://en.wikipedia.org/wiki/Iodine

Bromine sources


• Mining areas – salt/coal

• Fire retardants

• Drugs and Pharmaceuticals

• DBDMH – Cooling

towers/Pulp and paper mills

• Dyes

• Organobromine Biocides –

water treatment

• Salt Water Intrusion

Trihalomethanes in Drinking Water

chloroform

bromodichloromethane

dibromochloromethane

bromoform9

Stage 1 Disinfection By Product Rule

Source: EPA, 40 CFR Parts 9, 141, and 142 National Primary Drinking Water Regulations:

Stage 2 Disinfectants and Disinfection Byproducts Rule; Final Rule, p 411

10

Stage 2 Disinfection By Product Rule

Source: EPA, 40 CFR Parts 9, 141, and 142 National Primary Drinking Water Regulations:

Stage 2 Disinfectants and Disinfection Byproducts Rule; Final Rule, p 411

11

DBP Mitigation Technologies

• Raw Water Blending

• Enhanced Coagulation

• Filtration – MIEX, GAC, Nanofiltration

• Disinfectants – Chloramines, Chlorine

Dioxide, UV, and Ozone

• Storage – Aeration, Tank mixing


Annual Operating Costs for a Typical Utility

Source: “Technologies and Costs Document for the Final Long Term

2 Enhanced Surface Water Treatment Rule and Final Stage 2

Disinfectants and Disinfection Byproducts Rule”, EPA, Dec 2005 13

Standard Method for DBP Analysis

• Operator collects a water sample

• Physically delivers it to the lab

• A skilled technician prepares the

sample

• The sample is analyzed on an

expensive piece of lab equipment

(GC-MS)

• Results are reported to the water

treatment plant in 3-10 days

• Operator makes an educated

adjustment to the treatment

process

• Water utility puts the report in a

binder

14

Operating a Plant Without a Monitor


Is Like

Driving a Car

Without a

Speedometer

…

First commercial in-line instrument for TTHM

and CHCl3 monitoring with manual sampling

capability

Installed at multiple water utilities with

excellent correlation to lab results

Unattended 24/7 results in 1 hour which can

immediately be used to modify the process

Self calibrating – no need for skilled operator

intervention at anytime

5-200 (in μg/L) range for TTHM and

Chloroform

2’ (W) x1.3’ (D) x 5’ (H)

100 lbs

AMS THM-100 – Another Option

16

W – 2.0’ (610mm), D - 1.33’ (406mm)

H – 5.0’ (1,524mm)

Weight – 100lbs (45.3kg)

Electronics Cabinet

Process Cabinet

Chemical Reagents and

Standards

Organization of THM-100 System

www.ams-h2o.com17

• Chloroform reacts more slowly than brominated THMs to form the Fujiwara reaction

• The THM Speciation of each water sample is deduced from the kinetics of the Fujiwara reaction

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0 100 200 300 400 500 600 700 800 900 1000

Ab

so

rban

ce

.e

Time / secs

Optimized Fujiwara Reaction Kinetics for the Four THMs

Cl3

Br2Cl

BrCl2

Br3

Rates of the Colorimetric ReactionsRates of the Colorimetric Reactions

Rates of Colorimetric Reactions

www.ams-h2o.com18

THM Speciation Ratios are Predictable (CHCl3 Dominant)

-10%

0%

10%

20%

30%

40%

50%

60%

0 20 40 60 80 100

% T

HM

% CHCl3 in THM Total

THM Ratios in Drinking Water Samples

(CHCl3 Dominant)

% CHBrCl2

% CHBr2Cl

% CHBr3

www.ams-h2o.com19

Data Reliability: Labs vs. Online (Spiked Samples)

20

-30

-20

-10

0

10

20

30

-30 -20 -10 0 10 20 30

THM-100 1 THM-100 2 THM-100 3

% Error CHCl3

% E

rror

CH

Br1

-3

-30

-20

-10

0

10

20

30

-30 -20 -10 0 10 20 30

Lab 1 Lab 2 Lab 3 Lab 4 Lab 5

% Error CHCl3

% E

rror

CH

Br1

-3

• 5 US-EPA Accredited Labs & 3 THM-100 Monitors

(current studying 60 labs nation wide)

• Sample Water Spiked at TTHM 79.5 ug/L (60% CHCl3)

21

Eyes wide shut

22

Unqualified Speculation………

• When was last calibration of Lab

equipment

• Who was the operator that day

• How and who prepared the sample

• Where was sample stored

• How long from sample taken to analysis

• What was temperature that day…

• Were some THM’s lost immediately…

• Many, many reasons….

1. Optimization of DBP Mitigation Technologies• Raw Water Blending

• Enhanced Coagulation

• Filtration – MIEX, GAC, Nano filtration

• Disinfectants – Chloramines, Chlorine Dioxide, UV, and

Ozone

• Storage – Aeration, Tank mixing23

Application of the THM-100

2. Contract compliance and quality

control in consecutive systems

3. Compliance monitoring

Independence Tank – NKWD Project Planning

• 1 million gallon capacity

• Source = FTTP/TMTP Blend

• Demand ≈ 2 MGD

• Influences 2 THM

compliance sites

• 3 drain/fill cycles daily

• 450,000 gallon per day

turnover

• ~20% flows through tank

• Booster chlorine up and

downstream

0

10

20

30

40

50

60

70

80

6/25/2013 8/14/2013 10/3/2013 11/22/2013 1/11/2014 3/2/2014 4/21/2014 6/10/2014

TTH

M C

on

cen

trat

ion

(u

g/L)

Date

NKWD Lab Results vs. On-Line Analyzer

Lab Total

AMS Total

Old Bridge Municipal Water Authority - NJ


• 10M gal tank fed

from a consecutive

source

• Few homes / low

demand

• Variable THMs


System Features, Functions, Benefits

Source Blend Variability in a Consecutive System

A

B

Castelldefels Water Storage – Spain


A B

• Near Barcelona

• 330k gals/tank

• A - aerated

• B - control

THM Mitigation by Aeration, RO, & Monitoring

29

• Reservoir filling between midnight and 6am (lower energy costs)

• Aeration reduces TTHM by ~30% daily

• Aeration changes THM speciation

• Extent of aeration and RO reduced on Sept 14th

0

10

20

30

40

50

60

70

80

90

0

5

10

15

20

25

30

35

40

45

8-Sep 9-Sep 10-Sep 11-Sep 12-Sep 13-Sep 14-Sep 15-Sep 16-Sep 17-Sep 18-Sep 19-Sep 20-Sep

% B

rom

ofo

rm

TTH

M (

ug

/L)

TTHM % Bromoform

Reduction in Extent of THM Mitigation

Contract Compliance Monitoring - Agbar

0

10

20

30

40

50

60

70

80

90

100

110

14-Mar 21-Mar 28-Mar 4-Apr 11-Apr 18-Apr 25-Apr 2-May 9-May 16-May

THM

/ u

g/L

THMs at Service Reservoir in NE Spain (#1)

CHBr3

CHBrCl2 +CHBr2ClCHCl3

Source: Miquel Paraira Faus, Director Water Quality

R. E. Badger Water Filtration Plant – So CA


• Rancho Santa Fe

• 40 MGD

• Challenging local

sources

• Blending with

imported water

THM Mitigation by Source Water Blending

32

• Local water TOC ~10-13 ppm; Imported water TOC ~2-3 ppm

• Imported water available once daily

• Increasing local water from 30% to 50% saves US > $2.0M

annually

0

10

20

30

40

50

60

70

80

90

100

4-Aug 11-Aug 18-Aug

TTH

M (

ug

/L)

City of Phoenix – South Mountain Reservoir


Optimizing Energy Use for THM Remediation


• System installed May 2012

• Location is the last point in the network where remediation can occur

• TTHM levels too close to MCL without remediation

• 10-30 ug/L daily swing – aeration, pumping, temperature, demand

• 8 15-HP aerators which can only be turned on or off

• 8 15-HP aerators, using 784MWH/year

0

10

20

30

40

50

60

70

80

90

100

0

10

20

30

40

50

60

70

80

90

9/2/12 9/4/12 9/6/12 9/8/12 9/10/12 9/12/12 9/14/12 9/16/12 9/18/12 9/20/12

% T

THM

ug/

L

TTHM

%CHCl3

City of Benicia Water Treatment – No. CA


• 12 MGD

• Seasonally variant

local sources

• Blending and

enhanced

coagulation

THM SUMMARY

0

20

40

60

80

100

120

Jan

-08

Fe

b-0

8M

ar-

08

Ap

r-08

Ma

y-0

8Jun

-08

Jul-0

8A

ug-0

8S

ep-0

8O

ct-

08

Nov-0

8D

ec-0

8Jan

-09

Fe

b-0

9M

ar-

09

Ap

r-09

Ma

y-0

9Jun

-09

Jul-0

9A

ug-0

9S

ep-0

9O

ct-

09

Nov-0

9D

ec-0

9Jan

-10

Fe

b-1

0M

ar-

10

Ap

r-10

Ma

y-1

0Jun

-10

Jul-1

0A

ug-1

0S

ep-1

0O

ct-

10

Nov-1

0D

ec-1

0Jan

-11

Fe

b-1

1M

ar-

11

Ap

r-11

Ma

y-1

1Jun

-11

Jul-1

1A

ug-1

1S

ep-1

1O

ct-

11

Nov-1

1D

ec-1

1Jan

-12

Fe

b-1

2M

ar-

12

Ap

r-12

Ma

y-1

2Jun

-12

Jul-1

2A

ug-1

2S

ep-1

2O

ct-

12

TH

M c

on

c. u

g/l

Quarterly Average Running Annual Average

DAILY THM-100 DATA

0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

10/01/12 10/15/12 10/29/12 11/12/12 11/26/12 12/10/12 12/24/12 01/07/13 01/21/13 02/04/13 02/18/13

Tota

l TH

M, p

pb

Daily Average TTHM, ppb

SOURCE WATER CHANGES

0

10

20

30

40

50

60

70

Tota

l TH

M, p

pb

Blend PSC NBA Avg Daily THM

Stockton East Water District – Central CA


• 45 MGD

• Retail / Wholesale

production

• Seasonally variant

local sources

• Agricultural runoff

• Chlorine gas

THM-100 Validates Wholesale Quality


0

10

20

30

40

50

60

70

80

90

100

1/26 3/17 5/6 6/25 8/14 10/3

µg/

L

Total THM from Stockton East into Distribution

Retailer had 4 of 19

locational measurements out

of compliance, ranging from

82 to 96 µg/L

East Bay Municipal Water District - Orinda


• 200 MGD

• 1.3 M Customers

• Largest of 6

EBMUD WTPs

• A Leader in Water

Quality

THM Levels Fluctuate 15-20 µg/L Daily


Why monitor THM’s in real time?

THM100 enables Real-Time Monitoring of THMs in Drinking Water

THM’s can vary dramatically over a few hours

WHO:• Engineers designing capital or operational changes need to accurately map the

fluctuations in the system to provide best solution

• Wholesalers and Purchase Water Systems - Contract compliance between

consecutive systems.

• Operators can test automatically at any location and also bring grab samples from

around the network.

WHY:• Capital and operational savings can be in the $millions

• Operational Benefits:– Reduced operating costs with process optimization of THM remediation

– Performance can be improved with correct blending

– Save Energy on aeration

– To identify when Bromo based THM’s occur in systems

• Regulatory Benefits:– Enables Compliance Management – Archival to Proactive

– Minimizes Public Health Hazards from exposure to contaminants

– Minimizes Potential Regulatory Breaches, and Fines based on Violations

43

Other Products coming to market

• HAA monitor currently being tested by Scottish Water

• Trace Detect Online trace metals monitors – arsenic,

selenium, iron, manganese, chromium, many more

metals……


Questions

Tom Williams

Aqua Metrology Systems

[email protected]

(408)476-7768

www.aquametrologysystems.com


mailto:[email protected]

http://www.aquametrologysystems.com/

Remotely measuring DBP’s and other Water Quality Trendsnysawwa.org/docs/pdfs/Session 4 Remotely...

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