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Remotely measuring DBP’s and other Water Quality Trends
Tom Williams
+1 408 476 7768
“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 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
“Enabling the Optimization of THM Control” 7
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
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
“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.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
“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 Consecutive System
A
B
Castelldefels Water Storage – Spain
“Enabling the Optimization of THM Control” 28
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
“Enabling the Optimization of THM Control” 31
• 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
“Enabling the Optimization of THM Control” 33
Optimizing Energy Use for THM Remediation
“Enabling the Optimization of THM Control” 34
• 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
“Enabling the Optimization of THM Control” 35
• 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
“Enabling the Optimization of THM Control” 39
• 45 MGD
• Retail / Wholesale
production
• Seasonally variant
local sources
• Agricultural runoff
• Chlorine gas
THM-100 Validates Wholesale Quality
“Enabling the Optimization of THM Control” 40
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
“Enabling the Optimization of THM Control” 41
• 200 MGD
• 1.3 M Customers
• Largest of 6
EBMUD WTPs
• A Leader in Water
Quality
THM Levels Fluctuate 15-20 µg/L Daily
“Enabling the Optimization of THM Control” 42
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……
“Enabling the Optimization of THM Control” 44
Questions
Tom Williams
Aqua Metrology Systems
(408)476-7768
www.aquametrologysystems.com
“Enabling the Optimization of THM Control” 45