Achieving Stage 2 Compliance by Online Monitoring In Surface Water
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1 Achieving Stage 2 Compliance by Online Monitoring In Surface Water Tom Williams twilliams@aquametrologysystems.com Tom.Williams@enebio.com
2 Who are we? Worked in DBP s since 2008 with MIEX and UV treatment systems 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 today exclusively focused on TTHM 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 Enabling the Optimization of THM Control 2
3 Disinfection By-Product Formation DBPs Naturally-Occurring Organic Matter (NOM) e.g. - Humic Acids - Fulvic Acids Chlorine Based Compounds for Microbiological Disinfection e.g. - Chlorine - Hypochlorite - Chlorine Dioxide 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
4 DBP Contamination: A Global Issue Country THM MCL (ppb or µg/l) HAA5 MCL (ppb or µg / L) Switzerland 25 Austria, Belgium, Italy, Ecuador 30 Germany, Luxembourg, Sweden 50 United States UK, France, Ireland, Israel, Norway, Spain, Canada 100 Columbia, Brazil, Argentina, Japan 100 South Korea 100 design, operate United Kingdom and maintain the disinfection 100 process so as to keep disinfection by-products as low as possible without compromising the effectiveness Australia of the disinfection 250 4
5 Evolution of DBP Regulations Evolution of DBPs (THMs) Regulations US-EPA Stage 2 DBPR in force with levels of THMs to 80 µg /L US-EPA Stage 1 DBPR proposed levels of 80 µg /L 2012 WHO published guideline values for THMs U.S. EPA regulation to control THMs at 100 µg /L NCI published results linking chloroform to cancer 1975 NOM Survey reported high THMs in US Chlorinated Drinking water NOR Survey reported high THMs in US Chlorinated Drinking water Rook reported first THM Chloroform in chlorinated drinking water Over 1000 US cities were using chlorinated drinking water US First Chlorination, Jersey City, New Jersey, began chlorination of drinking water 1850 Chlorine was widely used as a disinfectant of drinking water. Snow used Chlorine to disinfect London s water supply during now-famous cholera epidemic WHO-World Health Organization NCI- US National Cancer Institute NORS-US National Organics Reconnaissance Survey US-EPA- USA Environmental Protection Agency NOMS-US National Organic Monitoring Survey 5
6 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 6
7 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 7
8 Trihalomethanes in Drinking Water chloroform bromodichloromethane dibromochloromethane bromoform 8
9 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
10 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 10
11 Operating a Plant Without a Monitor Is Like Driving a Car Without a Speedometer Enabling the Optimization of THM Control 11
12 AMS THM-100 Another Option First commercial in-line instrument for TTHM and CHCl 3 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 (in μg/l) range for TTHM and Chloroform 2 (W) x1.3 (D) x 5 (H) 100 lbs 12
13 Organization of THM-100 System W 2.0 (610mm), D (406mm) H 5.0 (1,524mm) Weight 100lbs (45.3kg) Electronics Cabinet Process Cabinet Chemical Reagents and Standards 13
14 THM-100 Principal of Operation Analysis Steps THM-100 Process Flow Draw Finished Water Sample Fill Reservoir (Purge Vessel) Extract THMs Purge Reservoir and Trap THMs Concentrate THMs Desorb Trap and Dissolve THMs into Reagents React THMs with Reagents Initiate the Fujiwara Reaction Measure change in Absorbance Spectrophotometric Detection at 540 nm Determine Concentration of the dominant THM and TTHM Quantitative Determination of dominant THM and TTHM Concentrations Report total THM and Chloroform results Make Results Available on the System and via 4-20 ma and the Ethernet 14
15 Rates of the Colorimetric Reactions Rates of Colorimetric Reactions 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 Optimized Fujiwara Reaction Kinetics for the Four THMs Absorbance.e Cl3 Br2Cl BrCl2 Br Time / secs 15
16 % THM THM Speciation Ratios are Predictable (CHCl 3 Dominant) 60% THM Ratios in Drinking Water Samples (CHCl 3 Dominant) 50% 40% % CHBrCl2 % CHBr2Cl % CHBr3 30% 20% 10% 0% -10% % CHCl3 in THM Total 16
17 % Error CHBr1-3 % Error CHBr1-3 Data Reliability: Labs vs. Online (Spiked Samples) 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% CHCl 3 ) Lab 1 Lab 2 Lab 3 Lab 4 Lab 5 THM THM THM % Error CHCl % Error CHCl3 17
18 Eyes wide shut 18
19 TTHM and % CHCl3 70 THM Measuremnts Online vs Three Analytical Labs CHCl3 Conc - Lab [ALS] 60 TTHM Conc - Lab [ALS] TTHM - Lab [Microbac Harrisburg] TTHM - Lab [Benchmark] 50 CHCl3 Conc - Online TTHM Conc - Online /14 11/28 12/12 12/26 1/9 1/23 2/6 2/20 19
20 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. 20
21 Application of the THM 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 2. Contract compliance and quality control in consecutive systems 3. Compliance monitoring 21
22 Real-time TTHM Analysis for Local Water Quality Control and Consecutive System Monitoring
23 Independence Tank - NKWD 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
24 TTHM Concentration (ug/l) NKWD Lab Results vs. On-Line Analyzer Lab Total AMS Total /06/ /08/ /10/ /11/ /01/ /03/ /04/ /06/2014 Date
25 Old Bridge Municipal Water Authority - NJ 10M gal tank fed from a consecutive source Few homes / low demand Variable THMs Enabling the Optimization of THM Control 25
26 Source Blend Variability in a Consecutive System System Features, Functions, Benefits Enabling the Optimization of THM Control 26
27 Castelldefels Water Storage Spain B A A B Near Barcelona 330k gals/tank A - aerated B - control Enabling the Optimization of THM Control 27
28 TTHM (ug/l) % Bromoform THM Mitigation by Aeration, RO, & Monitoring Reservoir filling between midnight and 6 am (lower energy costs) Aeration reduces TTHM by ~30% daily Aeration changes THM speciation Extent of aeration and RO reduced on Sept 14 th Reduction in Extent of THM Mitigation TTHM % Bromoform 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
29 THM / ug/l Contract Compliance Monitoring - Agbar THMs at Service Reservoir in NE Spain (#1) CHBr3 CHBrCl2 + CHBr2Cl CHCl Mar 21-Mar 28-Mar 4-Apr 11-Apr 18-Apr 25-Apr 2-May 9-May 16-May Source: Miquel Paraira Faus, Director Water Quality
30 R. E. Badger Water Filtration Plant So CA Rancho Santa Fe 40 MGD Challenging local sources Blending with imported water Enabling the Optimization of THM Control 30
31 TTHM (ug/l) THM Mitigation by Source Water Blending 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 > $2.0 M annually Aug 11-Aug 18-Aug 31
32 City of Phoenix South Mountain Reservoir Enabling the Optimization of THM Control 32
33 ug/l % TTHM 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 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 /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 TTHM %CHCl3 Enabling the Optimization of THM Control 33
34 City of Benicia Water Treatment No. CA 12 MGD Seasonally variant local sources Blending and enhanced coagulation Enabling the Optimization of THM Control 34
35 THM SUMMARY Jan-08 Feb-08 Mar-08 Apr-08 May-08 Jun-08 Jul-08 Aug-08 Sep-08 Oct-08 Nov-08 Dec-08 Jan-09 Feb-09 Mar-09 Apr-09 May-09 Jun-09 Jul-09 Aug-09 Sep-09 Oct-09 Nov-09 Dec-09 Jan-10 Feb-10 Mar-10 Apr-10 May-10 Jun-10 Jul-10 Aug-10 Sep-10 Oct-10 Nov-10 Dec-10 Jan-11 Feb-11 Mar-11 Apr-11 May-11 Jun-11 Jul-11 Aug-11 Sep-11 Oct-11 Nov-11 Dec-11 Jan-12 Feb-12 Mar-12 Apr-12 May-12 Jun-12 Jul-12 Aug-12 Sep-12 Oct-12 THM conc. ug/l Quarterly Average Running Annual Average
36 Total THM, ppb DAILY THM-100 DATA Daily Average TTHM, ppb /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
37 Total THM, ppb SOURCE WATER CHANGES Blend PSC NBA Avg Daily THM
38 Stockton East Water District Central CA 45 MGD Retail / Wholesale production Seasonally variant local sources Agricultural runoff Chlorine gas Enabling the Optimization of THM Control 38
39 µg/l THM-100 Validates Wholesale Quality 100 Total THM from Stockton East into Distribution Retailer had 4 of 19 locational measurements out of compliance, ranging from 82 to 96 µg/l /26 3/17 5/6 6/25 8/14 10/3 Enabling the Optimization of THM Control 39
40 East Bay Municipal Water District - Orinda 200 MGD 1.3 M Customers Largest of 6 EBMUD WTPs A Leader in Water Quality Enabling the Optimization of THM Control 40
41 THM Levels Fluctuate µg/l Daily Enabling the Optimization of THM Control 41
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 42
43 Other Products coming to market HAA pre-concentration unit for labs Trace Detect Online trace metals monitors arsenic, selenium, iron, manganese, chromium, many more metals Enabling the Optimization of THM Control 43
44 Questions Tom Williams Aqua Metrology Systems (408) Enabling the Optimization of THM Control 44
45 45
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