Improved Jar Testing Optimization With TOC Analysis - Ca-nv-awwa

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Improved Jar Testing Optimization with TOC Analysis Dondra Biller, PhD GE Analytical Instruments Boulder, CO

Outline of Presentation 1. 2. 3. 4. What is total organic carbon (TOC)? Importance of jar testing Presentation of experimental data Discussion on the value of TOC

What is TOC? TOC Total Organic Carbon Total amount of organic carbon in natural water Where does TOC come from? Organic compounds come from plants, animals, etc. They can become bound to dissolved or suspended material in natural water sources Natural Organic Matter (NOM)

What is TOC? Examples of TOC and NOM Humic & Fulvic Acids Lignin Carbohydrates

Why is TOC important? Conventional Water Treatment: TOC removal is regulated Influent TOC Effluent TOC

Why is TOC important? Conventional Water Treatment: TOC removal is regulated Drinking water plants required to remove a certain percentage of the influent TOC based on the alkalinity of the water and the incoming concentration of TOC

Why is TOC important? Disinfection By-Products (DBPs) All water treatment plants NOM Disinfectant DBPs

Why is TOC important? Disinfection By-Products (DBPs) DBP Formation is dependent on: Temperature pH Time Currently regulated DBP’s: Trihalomethanes (THMs) Haloacetic Acids (HAAs) Chlorite Bromate more are coming

Why is TOC important? Disinfection By-Products (DBPs) Water treatment plants want to minimize microbial growth AND DBP formation Lowering TOC is the best solution for both! & Disinfectant TOC Microbial growth DBPs

Why is TOC important? Regulated TOC removal & Regulated DBP levels sometimes even meeting the regulated TOC percent removal doesn’t mean that you will meet the DBP regulation limits for the furthest point in the distribution system

Jar Testing Simulation of the coagulation and flocculation steps in the water treatment process Important for determining the optimal coagulant and dosage for a plant’s raw water

Jar Testing Jar testing is beneficial for plants so that they can optimize their treatment process Plants want to pick the right coagulant dosage and treatment so that they can: Maximize TOC removal to meet regulations Minimize sludge production Minimize costs

Jar Testing Simulation of the coagulation and flocculation steps in the water treatment process Add coagulant at different doses to raw water Replicate plant contactors with flocculation simulator

Jar Testing Simulation of the coagulation and flocculation steps in the water treatment process After flocculation and settling, sample the settled water to determine which coagulant dose was best Let the water settle

Jar Testing Parameters typically measured: Turbidity – measure of water clarity UV– measure of the aromatic content of the organic material in the water

Jar Testing Parameters typically measured: Turbidity – measure of water clarity UV– measure of the aromatic content of the organic material in the water Issues: Doesn’t distinguish between inorganic, organic, particulates. Is only a measure of how much light passes through water.

Jar Testing Parameters typically measured: Turbidity – measure of water clarity UV– measure of the aromatic content of the organic material in the water Issues: Not all organic molecules absorb in the UV spectrum, multiple interferences at 254 nm wavelength. SUVA UV/TOC

Jar Testing Experiment Collected natural surface water from 10 sites Water samples were representative of surface water feeding local water treatment plants 6 sites in Colorado river reservoir lake mountain plains

Jar Testing Experiment Collected natural surface water from 10 sites Water samples were representative of surface water feeding local water treatment plants Wyoming: reservoir Arizona: canal Texas: river and lake

Jar Testing Experiment Tested two different coagulants: Ferric Chloride (Ferric) Aluminum Sulfate (Alum) Measured Parameters Raw Water: Settled Water: o Alkalinity o TOC o pH o Turbidity o TOC o UV o Turbidity o UV

Jar Testing Experiment Tested two different coagulants: Ferric Chloride (Ferric) Aluminum Sulfate (Alum) Goal: To investigate how turbidity, UV, and TOC all Measured Parameters were influenced by different coagulant dosages Raw Water: Water: Spoiler alert: turbidity and UV were not alwaysSettled the best indicator of o TOC Alkalinity optimum removal o TOC o pH o Turbidity o TOC o UV o Turbidity o UV

Experimental Data TOC (ppm) Turbidity (NTU) Site 1: Saint Vrain River in Lyons, CO 2.0 1.5 Turbidity 1.0 0.5 0.0 3.0 2.0 TOC 1.0 0.0 Black, dotted line corresponds to the regulated TOC removal based on alkalinity and influent TOC UV (cm-1) 0.10 0.05 UV 0.00 0 10 20 Alum Dosage (ppm) 30 Coagulant type and dosage is indicated on the x-axis

Experimental Data TOC (ppm) Turbidity (NTU) Site 1: Saint Vrain River in Lyons, CO 2.0 1.5 Turbidity 1.0 0.5 0.0 3.0 2.0 TOC 1.0 0.0 UV (cm-1) 0.10 0.05 UV 0.00 0 10 20 Alum Dosage (ppm) 30 Lowest Turbidity was also lowest TOC and lowest UV

Experimental Data Turbidity (NTU) Site 2: Coot Lake in Boulder, CO 6.0 4.0 Turbidity 2.0 Lowest Turbidity was also lowest TOC TOC (ppm) 0.0 4.0 3.0 2.0 TOC 1.0 0.0 UV (cm-1) 0.06 0.04 UV 0.02 0.00 0 10 20 Alum Dosage (ppm) 30 Low turbidity at 5 ppm Alum dosage didn’t correspond to best TOC removal

Experimental Data Turbidity (NTU) Site 3: Canal water from Gilbert , AZ 15.0 10.0 Turbidity 5.0 0.0 UV (cm-1) TOC (ppm) 4.0 3.0 2.0 TOC 1.0 0.0 0.08 0.06 0.04 0.02 0.00 UV 0 10 20 Alum Dosage (ppm) 30 20 and 30 ppm Alum dosage had the same turbidity, but the TOC went down with the 30 ppm (even though UV went up)

Experimental Data Turbidity (NTU) Site 4: San Gabriel River from Austin, TX 3.0 2.0 Turbidity 1.0 0.0 TOC (ppm) 8.0 6.0 4.0 TOC 2.0 UV (cm-1) 0.0 0.20 0.15 0.10 0.05 0.00 20 and 30 ppm Alum dosage had the same turbidity, but there was slightly better TOC removal with the 30 ppm UV But 0 10 20 Alum Dosage (ppm) 30

Experimental Data Turbidity (NTU) Site 4: San Gabriel River from Austin, TX 3.0 2.0 Turbidity 1.0 0.0 The Ferric was actually a better coagulant than Alum for TOC removal TOC (ppm) 8.0 6.0 TOC 4.0 2.0 0.0 UV (cm-1) 0.20 0.15 0.10 UV 0.05 0.00 0 10 20 Ferric Dosage (ppm) 30 Could potentially dose less with the Ferric (20 ppm) than the Alum (30 ppm) based on TOC removal UV with Ferric has interferences, would have picked wrong chemical

Experimental Data Turbidity (NTU) Site 5: Lady Bird Lake in Austin, TX 4.0 3.0 2.0 Turbidity 1.0 TOC (ppm) 0.0 8.0 6.0 4.0 TOC 2.0 UV (cm-1) 0.0 0.20 0.15 0.10 UV 0.05 0.00 0 10 20 Alum Dosage (ppm) 30 Adjusting pH to 6.2 on this water with the 30 ppm alum was the only way to remove enough TOC (the turbidity also went way down with pH adjustment)

Experimental Data Turbidity (NTU) Site 6: Horsetooth Reservoir in Fort Collins, CO 6.0 4.0 Turbidity 2.0 0.0 TOC (ppm) 6.0 4.0 TOC 2.0 UV (cm-1) 0.0 0.15 0.10 UV 0.05 0.00 0 10 20 Ferric Dosage (ppm) 30 Even though the turbidity of the 30 ppm Ferric went up, the TOC went down

Experimental Data Turbidity (NTU) Site 7: Lake Estes in Estes Park, CO 4.0 3.0 2.0 Turbidity 1.0 TOC (ppm) 0.0 4.0 3.0 TOC 2.0 1.0 UV (cm-1) 0.0 0.15 With the Alum, the lowest turbidity (5 ppm Alum) had no TOC removal And 0.10 UV 0.05 0.00 0 10 20 Alum Dosage (ppm) 30

Experimental Data Turbidity (NTU) Site 7: Lake Estes in Estes Park, CO 4.0 3.0 2.0 Turbidity 1.0 0.0 TOC (ppm) 4.0 3.0 2.0 TOC 1.0 UV (cm-1) 0.0 0.20 0.15 0.10 0.05 UV 0.00 0 10 20 Ferric Dosage (ppm) 30 Even the lowest turbidity with the Ferric had almost no TOC removal

Experimental Data Turbidity (NTU) Site 8: Barker Reservoir in Nederland, CO 10.0 5.0 Turbidity 0.0 TOC (ppm) 3.0 2.0 TOC 1.0 0.0 UV (cm-1) 0.08 0.06 0.04 UV 0.02 0.00 0 10 20 Ferric Dosage (ppm) 30 There was no difference in TOC between the 20 and 30 ppm Ferric dosages – a plant could get the same TOC removal with less chemical Lower UV at 30 ppm Ferric, but no greater TOC removal

Experimental Data Turbidity (NTU) Site 9: Granite Springs Reservoir in Cheyenne, WY 3.0 2.0 Turbidity 1.0 TOC (ppm) 0.0 10.0 8.0 6.0 TOC 4.0 2.0 0.0 UV (cm-1) 0.20 0.15 UV 0.10 0.05 0.00 0 10 20 Alum Dosage (ppm) 30 Even with the low turbidity on the 30 ppm dosage, the TOC removal did not meet the regulatory limit But

Experimental Data UV (cm-1) TOC (ppm) Turbidity (NTU) Site 9: Granite Springs Reservoir in Cheyenne, WY 3.0 2.0 Turbidity 1.0 0.0 10.0 8.0 6.0 4.0 2.0 0.0 0.08 TOC 0.06 0.04 UV 0.02 0.00 0 10 20 Ferric Dosage (ppm) 30 With the Ferric, the lowest turbidity corresponded to the lowest TOC and lowest UV (and the plant would have met the TOC removal regulation)

Experimental Data TOC (ppm) Turbidity (NTU) Site 10: Pine Brook Reservoir in Boulder, CO 6.0 4.0 Turbidity 2.0 0.0 8.0 6.0 TOC 4.0 2.0 UV (cm-1) 0.0 0.10 UV 0.05 0.00 0 10 20 Alum Dosage (ppm) 30 The lowest turbidity corresponded to the best TOC removal but it isn’t low enough (2.8 ppm) to meet the DBP regulations for this plant Enhanced Coagulation

Enhanced Coagulation Where a plant removes more TOC than required by regulations so that they will not have issues passing their DBP limits everywhere in their distribution system Pine Brook Reservoir TOC (ppm) 8.0 6.0 4.0 TOC 2.0 0.0 Regulatory TOC removal if conventional treatment plant Needs to be below 2.8 ppm for passage of DBP regulations Measuring TOC gives much more information for enhanced coagulation

Data Summary The lowest turbidity and low UV also corresponded to the greatest TOC removal in less than half of the sites Sometimes a slightly higher turbidity corresponded to better TOC removal At some sites, less chemical dosage is better for TOC removal (but was slightly worse for turbidity)

Value of Using TOC TOC Removal Best TOC removal Lowest Turbidity doesn’t always correspond to the best TOC removal Lowest Turbidity Coagulant Dosage

Value of Using TOC Law of Diminishing Marginal Returns TOC Removal Best TOC removal More coagulant isn’t always better!! Coagulant Dosage Dosing coagulant blindly is not typically the best treatment option

Value of Using TOC Most comprehensive insight into TOC removal and how it relates to chemical dosage, cost, and sludge production TOC Removal DBP minimization Chemical Dosage Cost Sludge Production

Value of Using TOC Most comprehensive insight into TOC removal and how it relates to chemical dosage, cost, and sludge production But , sometimes these factors are actually on the same team! Turbidity and UV can give false information on process optimization. TOC Removal DBP minimization Chemical Dosage Cost Sludge Production Turbidity UV

Value of Using TOC Every plant is different AND every plant changes throughout the year Even the six sites in Colorado all showed great diversity in the optimal water treatment Site TOC (ppm) Alkalinity Coot Lake 3.7 175 Pine Brook Res. 6.1 135 Barker Res. 2.3 25 Lake Estes 3.6 20 Horsetooth Res. 4.9 40 Saint Vrain River 2.7 40

Value of Using TOC Every plant is different AND every plant changes throughout the year Jar testing is a simulation that can help with water treatment optimization as source water changes throughout the year or with other major perturbations (e.g., flood, fire, drought, etc.) Smarter jar testing using TOC can be extremely valuable to water treatment plants!

Value of Using TOC Choosing the right chemical and proper dosage Not all chemicals will work best for any given source water Not all optimal treatment steps (pH adjustment) make the most sense in a process environment Best to balance cost and treatment options for the long term Some chemical companies will do blends and/or help optimize chemical dosages for a plant’s source water (many of these chemical companies use TOC)

Value of Using TOC Case Study: City of Englewood, CO Problem: too much sludge and too much money spent on chemicals Goal: Reduce chemical costs and sludge production

Value of Using TOC Case Study: City of Englewood, CO Before: only using turbidity with jar testing After: expanded jar testing to include TOC and then scaled it up to the whole treatment process Plant saw a significant reduction in chemicals needed and sludge production 1 year savings of 100k in chemical and disposal costs

Size Distribution of Organics Technology to determine size distribution of organics in water Size Exclusion Chromatography with both UV and TOC detection Sample Size Exclusion Chromatography All organics combined (Total Organic Carbon) large small Separation of organics by size

Size Distribution of Organics Size Exclusion Chromatography (SEC) Why is this important? TOC detection because not all organics will be detected by UV Organics in some size fractions produce more DBP’s (humic acids, etc.) Complete picture or “footprint” of the organics to optimize treatment Shows changes in organic characteristics throughout the year

Size Distribution of Organics Raw water coming into the Pine Brook Plant

Size Distribution of Organics Raw water coming into the Pine Brook Plant This whole size fraction of organics is not detected by UV!

Size Distribution of Organics Raw water coming into the Pine Brook Plant Better understanding the characteristics of the organics coming into the plant - even smarter treatment

Summary TOC is important for regulatory requirements (DBP limits and %TOC removal) Jar testing that includes TOC as a measured parameter gives the most comprehensive information on optimizing the treatment process Every plant has different water that can change throughout the year, so optimization may change as well. Jar testing on site with TOC is a great way to help a plant minimize cost while still complying with regulatory limits.

Questions?

Jar Testing Experiment Tested two different coagulants: Ferric Chloride (Ferric) Aluminum Sulfate (Alum) Measured Parameters Raw Water: o Alkalinity o pH o TOC o Turbidity o UV Settled Water: o TOC o Turbidity o UV Goal: To investigate how turbidity, UV, and TOC all were influenced by different coagulant dosages

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