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  • Remotely measuring DBP’s and other Water Quality Trends

    Tom Williams

    +1 408 476 7768

    twilliams@aquametrologysystems.com

    Tom.Williams@enebio.com

  • “Enabling the Optimization of THM Control” 2

    Who are we?

    “Enabling the Optimization of THM Control” 2

    • 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

    “Enabling the Optimization of THM Control” 4

  • DOC or TOC Detection

    “Enabling the Optimization of THM Control” 5

  • Hydrophilic or Hydrophobic ?

    “Enabling the Optimization of THM Control” 6

  • Halogens – the Halo’s in THM’s

    halogen molecule structure model d(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

    “Enabling the Optimization of THM Control” 7

    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

    “Enabling the Optimization of THM Control” 8

    • 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

    bromoform 9

  • 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

    “Enabling the Optimization of THM Control” 12

  • 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

    “Enabling the Optimization of THM Control” 15

    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.com 17

  • • 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

    A b

    s o

    rb a n

    c e

    .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.com 18

  • THM Speciation Ratios are Predictable (CHCl3 Dominant)

    -10%

    0%

    10%

    20%

    30%

    40%

    50%

    60%

    0 20 40 60 80 100

    % T

    H M

    % CHCl3 in THM Total

    THM Ratios in Drinking Water Samples

    (CHCl3 Dominant)

    % CHBrCl2

    % CHBr2Cl

    % CHBr3

    www.ams-h2o.com 19

  • 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

    rr o r

    C H

    B r1

    -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

    rr o r

    C H

    B r1

    -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 mixing 23

    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

    TT H

    M C

    o n

    ce n

    tr at

    io n

    ( u

    g/ L)

    Date

    NKWD Lab Results vs. On-Line Analyzer

    Lab Total

    AMS Total

  • Old Bridge Municipal Water Authority - NJ

    “Enabling the Optimization of THM Control” 26

    • 10M gal tank fed

    from a consecutive

    source

    • Few homes / low

    demand

    • Variable THMs

  • “Enabling the Optimization of THM Control” 27

    System Features, Functions, Benefits

    Source Blend Variability in a C

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