DRAFT Technical Memorandum.

Prepared by: Akin Okupe, Senior Water Quality Engineer, Water Quality Lab and R&D; James Hogan,
Water Quality Chemist, Water Quality Lab and R&D

To: Pravani Vandeyar, Water Quality Superintendent, Water Quality Lab and R&D

Subject: Draft Standard Operating Procedure for the Chemtrac Laboratory Charge Analyzer at
Sacramento River Water Treatment Plant

Date: November 28, 2016

Background

Recently, the Sacramento River Water Treatment Plant (SRWTP) acquired a Chemtrac Laboratory Charge
Analyzer (LCA). Treatment plant operators intend to use this instrument to determine the amount of
coagulant needed for water treatment under different water conditions. Staff believes that this
instrument can be used as a backup to jar testing for the determination of the optimal amount of
coagulant needed for water treatment under different flow conditions.

Currently, SRWTP relies on historical data and jar tests to determine an optimum coagulant dose. Jar
testing yields an optimal coagulant dose by maximizing settled turbidity, using a set of different
coagulant doses. Alternatively, the LCA measures particle charge to determine an optimal coagulant
dose. The differences between jar testing and LCA methods are further detailed in the Principal
Differences in Methodology section of this protocol.

Due to the differences in methodology, jar testing and the LCA may yield different results for optimal
coagulant dose. One concern is the method of pH depression; while the manufacturer suggests using
acetic acid, current jar testing procedures rely on alum for pH depression. This difference will likely
affect the determination of optimal coagulant doses, especially for high turbid water. In this regard, it is
hypothesized that the LCA method would underestimate the amount of alum needed for treatment
when compared to the results of jar testing. This hypothesis will be evaluated. Similarly, other
differences between jar testing and LCA methods must be considered for both low turbid and high
turbid waters.Research Objective

The objective of this research is to evaluate the LCA as a viable analytical tool for operators and
laboratory staff in optimizing the water treatment process; as compared to jar test analysis. Both high
turbid water and low turbid water shall be analyzed to determine any correlation therefrom.

Definitions

1. Streaming Current Value (SCV): A reciprocating piston with electrode sensors detecting ionic
charge variations within solution.
2. Isoelectric Point (IEP): The IEP is defined as the pH at which a particle or compound carries a net
zero electrical charge, and is the point of optimal floc formation.
 3. Signal Health: > 90% indicates that the probe within the optimal range for analysis. < 90%
indicates either too much particulate matter within solution and/or that the probe needs to be
cleaned.

Principal Differences in Methodology

The following list summarizes the principal differences between jar testing and LCA procedures:

 Jar testing determines optimal coagulant doses by maximizing settle turbidity; this process is
manually done. Conversely, the LCA determines optimal coagulant doses by neutralizing particle
charge.
 The LCA can determine the optimal pH for coagulation by determining the IEP. The jar test
procedure relies on operator-discretion to determine necessary pH adjustment.
 Both methods use NaOH solutions to increase pH. However, the manufacturer’s representative
suggested using store-bought vinegar or an acetic acid solution to decrease the pH. In this
study, pH reduction is done with reagent grade hydrochloric acid for both jar testing and LCA
procedures.

Procedure

The following lists a simplified procedure based on the Operations Manual for the Chemtrac LCA:
Models LCA-1, LCA-2, and LCA-3 (revision 9/24/2015).

1. Unit LCA-3 Overview

a. Components
i. Primed Automatic Titrators
1. Coagulant; i.e.: 1% Alum Solution.
2. pH Adjustment Chemicals; i.e.: 1% Caustic Soda Solution and/or 1%
Hydrochloric Acid Solution.
ii. Magnetic Stir Plate with stir bar magnet.
iii. Sensors at specified depths within sample. Refer to Figure 4 – Optimum Depth
of Probe in Sample, on page 19 of the Manual for more information.
1. SCV (mV)
2. pH (0 to 14)
3. Temperature (⁰C)
iv. Sample Size
1. 225 mL to 2000 mL, with 2000 mL preferred.
v. Sample Source
1. Tap 2 Post-Chlorination Grit Basin
2. Preliminary Water Quality Assessment at Process Taps at SRWTP
a. Intake – Tap 1, Grit Basin – Tap 2, and Sedimentation Basin Effluent – Tap 6 and/or Tap
6A.
 i. Turbidity
ii. pH
iii. Temperature
iv. Alkalinity
v. NOM/TOC*
*Application note: For purposes of this experiment, NOM/TOC evaluation shall be
omitted due to the time required for complete analysis. It is understood that
NOM/TOC components within solution add a significant negative charge to the net
charge SCV of the sample. Therefore, the mV readout of the LCA may provide enough
information for treating these constituents.
3. Survey of Current Process Chemical Application Concentrations at Water Treatment Plant
A preliminary evaluation of the following process chemical applications currently in use at the
water treatment plant will provide a starting point for the operators and lab staff in applying
initial chemical dosages.
a. Coagulant Applied
b. pH Adjustment
c. Non-ionic Polymer
4. pH Adjustment Determination
Several factors dictate whether pH adjustment may be necessary for the sample, including: pH,
alkalinity, temperature, turbidity, NOM/TOC, etc. It is up to the Operator’s discretion to the
apply the correct pH adjustment technique, if necessary; i.e.: increasing or lowering pH to
maintain the optimal pH for coagulation, flocculation, sedimentation, and filtration.
a. Caustic Soda: Increases pH.
b. Hydrochloric Acid: Decreases pH.
5. 1% Reagent Concentration Preparation Protocol
a. 1% HCl Solution using 1.0 N HCl Stock Reagent
Calculation note: 1% = 10,000 ppm; 10,000 ppm = 10,000 mg/L; 10,000 mg = 10 g.
If there are 36.46064 g HCl per 1 mol HCl; and 1 mol/L = 1 Molar; 1 Molar = 1 Normal,
for monoprotic acids. Then, 68.567 mL of 1 N HCl must be added to 250 mL for a 1%
HCl solution.
i. Materials Needed
Note: The following procedure is meant as an operational guideline. With
regards to the materials listed and the procedure given, any component
therein may be substituted with an equivalent material or procedural
technique; i.e.: (1) 50 mL Volumetric Pipette Tip may be substituted for (1) 50
mL Graduated Cylinder, etc.
1. (1) 250 mL Volumetric Flask filled approximately 1/3 of the way with
laboratory grade reagent water.
2. (1) 50 mL Graduated Cylinder, (1) 20 or 25 mL Graduated Cylinder, and
(1) Adjustable 1000 µL Pipette calibrated to 567 mL.
3. (1) Squirt Bottle containing laboratory grade reagent water.
ii. Procedure
 1. Fill the 50 mL graduated cylinder to the 50 mL mark with the 1.0 N HCl
stock reagent, then fill the 20 or 25 mL graduated cylinder to the 18 mL
mark with the 1.0 N HCl stock reagent. Using the 1000 µL adjustable
pipette dispense exactly 567 µL of the 1.0 N HCl stock reagent into the
250 mL volumetric flask.
2. Combine the entire contents into of the 50 mL and 20 or 25 mL
graduated cylinders to the 250 mL volumetric flask.
3. Fill to the mark 250 mL mark using the lab grade reagent water squirt
bottle.
4. Invert gently several times, then label as “1% HCl Solution” with the
date of preparation, and aliquot to a 250 mL plastic titrant container
provided by the LCA-3 unit.
b. 1% NaOH Solution using Sodium Hydroxide solid pellets
i. Materials Needed
Note: The following procedure is meant as an operational guideline. With
regards to the materials listed and the procedure given, any component
therein may be substituted with an equivalent material or procedural
technique; i.e.: (1) 1000 mL Volumetric Flask containing 10 g NaOH may be
substituted for (1) 250 mL Volumetric Flask containing 2.5 g NaOH, etc.
1. (1) 250 mL Volumetric Flask filled approximately 1/3 of the way with
laboratory grade reagent water.
2. (1) Weigh Boat, (1) Analytical Balance, (1) Spatula, and (1) Container of
Reagent Grade Sodium Hydroxide (NaOH) solid pellets.
3. (1) Squirt Bottle containing laboratory grade reagent water.
ii. Procedure
1. Using the spatula, accurately transfer exactly 2.5 g of NaOH solid pellets
to a weigh boat resting on a tared analytical balance.
2. Quantitatively transfer the entire contents of the weigh boat into the
250 mL volumetric flask by rinsing the interior surface of the weigh boat
with the lab grade reagent water squirt bottle.
3. Swirl the contents of the volumetric flask until completely dissolved and
fill to the mark 250 mL mark using the same squirt bottle in the previous
step.
4. Invert gently several times, then label as “1% NaOH Solution” with date
of preparation and aliquot to a second 250 mL plastic titrant container
provided by the LCA-3 unit.
c. 1% Alum Solution using Concentration Alum from the Day Tank at SRWTP
Note: The following procedure is meant as an operational guideline. With regards to
the materials listed and the procedure given, any component therein may be
substituted with an equivalent material or procedural technique. However, for the
1% Alum Solution preparation it is advised that the procedure listed below be
followed closely; due to variations and inconsistencies that may arise.
 i. Materials Needed
1. (1) 1000 mL Volumetric Flask filled approximately 1/3 of the way with
laboratory grade reagent water.
2. (1) Weigh Boat, (1) Analytical Balance, (1) glass Pasteur pipette with
rubber bulb, and (1) Container of Concentrated Alum Day Tank Solution;
note the percentage of “active alum” in solution from the Safety Data
Sheet (SDS); e.g.: 48.5% Active Alum or Aluminum Sulfate.
3. (1) 50 mL Graduated Cylinder.
4. (1) Squirt Bottle containing laboratory grade reagent water.
ii. Procedure
1. Due to any differences in viscosity, density, or concentration of alum
solution due to evaporation, temperature, and/or variations of a specific
batch of alum from the manufacturer; the specific gravity of the alum
solution held in the day tank will be determined by direct measurement
of the mass of a specified volume; i.e.: mass of 50 mL of concentrated
alum day tank solution.
2. With a 50 mL graduated cylinder resting on a tared analytical balance,
accurately dispense 50 mL of concentrated alum day tank solution to
the 50 mL mark using the glass Pasteur pipette, and record the exact
mass. Divide the recorded mass by the volume to obtain the specific
gravity or relative density of the solution.
Note: If there are 66.31 g Concentrated Alum Day Tank Solution per
50 ml Concentrated Alum Day Tank Solution, then the Relative Density
= 1.3262 g/mL. Given that the solution is comprised of approximately
48.5% Aluminum Sulfate, a 1% Aluminum Sulfate solution may be
obtained by adding 20.6186 mL of Alum Day Tank Solution to 1000 mL
in the Volumetric Flask with lab grade reagent water. For an
alternative gravimetric approach, multiply 20.6186 mL by the Relative
Density 1.3262 g/mL to get 27.3443g of Concentrated Alum Day Tank
solution to be added to the Flask detailed above. Given the viscosity
of the Alum Day Tank solution, this is the preferred method for
accurate quantitative transfer.
3. Using a glass Pasteur pipette and rubber bulb, accurately transfer
exactly 27.3443 g of Concentrated Alum Day Tank Solution to a weigh
boat resting on a tared analytical balance.
4. Quantitatively transfer the entire contents of the weigh boat into the
1000 mL volumetric flask by rinsing the interior surface of the weigh
boat with the lab grade reagent water squirt bottle.
5. Swirl the contents of the volumetric flask until completely dissolved and
fill to the mark 1000 mL mark using the same squirt bottle in the
previous step.
 6. Invert gently several times, then label as “1% Alum Solution” with the
date of preparation, Relative Density, and mass of Concentrated Alum
Day Tank Solution added. Then aliquot the entire contents of the 1000
mL Volumetric Flask to a screw-top plastic container and transfer as
needed to the 250 mL Coagulant Titrant container provided by the LCA-
3 unit.

6. Static Chemical Composition

a. Non-ionic Polymer: 0.04 ppm Non-ionic Polymer dosed using 1.333 mL of a 60 ppm
Intermediate Stock Polymer Reagent into a 2000 mL sample volume.
b. Residual Chlorine: 1.8 to 2.7 ppm Cl2, or whatever the current Grit Basin process
condition is at the Plant.
7. Current Process Treatment in Use at Plant Starting Point for Jar Test and LCA Analyses
The results of Step 3 – Survey of Current Process Chemical Application Concentrations at Water
Treatment Plant, may be used as a resource in providing a starting point for adjusting and
optimizing process chemical application for both jar tests and LCA analyses.

8. Comparative Analysis of Methods from Data Obtained with Low Turbid Water and High Turbid
Water Sources
The research shall be divided into two phases:
a. Phase 1: Low Turbid Water Assessment
i. LCA-3 Procedure
1. Collect water from Tap 2 or the Grit Basin at SRWTP in a 2000 mL
Beaker.
Note: The benefit of sourcing the water from Tap 2 is that prior pH
adjustment for both Jar Test and LCA-3 analyzers will not be needed.
2. With reference to Step 2 - Preliminary Water Quality Assessment at
Process Taps at SRWTP, record the initial water quality parameters for
SRWTP Tap 2 in the Template LCA Data Entry Sheet located in Appendix
A, below.
3. Based on the data entered above, setup the LCA-3 coagulant and
titration parameters in accordance with Section 2.1.2.1 – Titration
Control on page 11 of the Chemtrac LCA Operations Manual.
4. Calibrate the SCV probe on the LCA-3 by immersing the probe in Tap 1
water at the time of Tap 2 collection, per Section 2.2 – Calibration, page
12 of the Chemtrac LCA Operations Manual. In other words, the probe
will be submersed to the specified depth and conditioned with an
aliquot of raw water containing no chemical application. Then SCV mV
readout shall be adjusted to -200 mV and calibrated by pressing enter.
Record the results in the Template LCA Data Entry Sheet in Appendix A.
5. Rinse the probe using the squirt bottle containing lab grade reagent
deionized water and dry with a chem wipe.
 6. Place the clean and dry probe in the 2000 mL Beaker containing the Tap
2 water detailed in Step 1 of the Phase 1 LCA Procedure.
7. Add a magnetic stir bar and place the beaker on a magnetic stir plate
and commence stirring at a medium speed; i.e.: slight vortex present on
the surface of the water in the beaker.
8. Turn the SCV on and note the change in mV on the display. The piston
should be reciprocating within the SCV probe, circulating sample
through the internal surfaces of the probe. Note the Signal Health listed
on the display, ensuring that > 90% is indicated before proceeding.
9. Insert the pre-calibrated pH probe in the solution. Wait until both pH
probe and SCV mV reading have stabilized before taking a reading, then
record the stabilized values in the Template LCA Data Entry Sheet
located in Appendix A.
10. Add 1.333 mL of the 60 ppm Non-ionic Polymer Solution to the sample
for a final concentration of 0.04 ppm Non-ionic polymer in the sample.
Then record the SCV mV and pH readings on the data entry sheet.

Note: The dose of Non-ionic Polymer is based on the current process

dose at SRWTP.

11. In accordance with Section 2.1.3.1 – Target pH, on page 11 of the

Chemtrac LCA Operations Manual, enter a pH Target of 6.5, since Alum
is the primary coagulant. Given that the current process chemical dose
at SRWTP at the time of sampling = 35 ppm Alum, set the LCA-3
Coagulant Dosage as follows:
a. Initial Dose = 20 ppm Alum
b. Minimum Dose = 1 ppm Alum
c. Maximum Dose = 50 ppm Alum
12. Begin the coagulant titration and record the final SCV mV, final pH, final
temperature, final alkalinity, and enter the concentrations of coagulant
and pH adjustment applied. These values will be compared to the
values obtained by the jar test.
ii. Jar Test Procedure
1. The dosage of alum applied to each jar shall be determined by the data
obtained from Step 7 – Current Process Treatment in Use at Plant; i.e.:
35 ppm Alum process application at SRWTP, etc. Given that there are
six jars for the Jar Test, Table 2, Example Jar Test Data Entry Sheet,
provides a suggested dosing order for each jar. The values of the jar
test may also serve to validate or optimize the current process chemical
treatment in use at SRWTP.

Table 2, Example Jar Test Data Entry Sheet*

 Alum Tap 2 Water Parameters
Concentrationa
Jar #
Applied (mg i f
i
Alkalinit f
Alkalinit i
Turbidit f
Turbidit i
Chlorine f
Chlorine
Alum/L) pH pH
y y y y Residual Residual
7.3 6.5
1 33 60 45 15.52 0.35 2.50 0.75
0 1
7.3 6.5
2 34 60 44 15.35 0.42 2.51 0.72
5 3
7.3 6.5
3 35 60 42 15.45 0.25 2.49 0.73
4 4
7.3 6.5
4 35 60 42 15.56 0.23 2.50 0.74
3 1
7.3 6.5
5 36 60 41 15.39 0.38 2.52 0.76
5 3
7.3 6.5
6 37 60 40 15.50 0.45 2.49 0.75
1 2

*Table 2 is not representative of actual raw data collected from a jar test experiment; it is merely an
example as to the type of data that will be collected.
a
Regarding Alum Concentration Applied in Table 2 above, the data collected from Jars 3 and 4 will allow
a statistical average to be computed. These jar will also represent the current process chemical
application of alum at the water treatment plant.

Note: The superscript i = initial, taken upon filling the jars, and the superscript f= final, was taken at the
end of the jar test.

a. Phase 2: High Turbid Water Assessment

During a High Turbid Water event last winter at SRWTP, approximately 20 L of 200 NTU
water was collected from the continuous sampling tap in the Operator’s lab at Tap 1,
representing the Intake. This will be the source of water for both the LCA analysis and
jar testing of high turbid water.

iii. LCA-3 Procedure

1. Dispense the High Turbid Water described above in a 2000 mL Beaker
for LCA analysis.
Note: Though this ‘old’ water is not ideal to correlate and suggest any
process treatment chemical applications to current plant water quality
conditions, the comparison of both the LCA and Jar Test data sets will
still provide insight as to how either technique differs from each other.
2. Based on historical research of the High Turbid water event at SRWTP
during the time of collection, note the previous process chemical
 application at the time. Additionally, record the initial water quality
parameters in the Template LCA Data Entry Sheet located in Appendix
A, below.
3. Based on the data entered above, setup the LCA-3 coagulant and
titration parameters in accordance with Section 2.1.2.1 – Titration
Control on page 11 of the Chemtrac LCA Operations Manual.
4. Calibrate the SCV probe on the LCA-3 by immersing the probe in the
well-mixed High Turbid water, per Section 2.2 – Calibration, page 12 of
the Chemtrac LCA Operations Manual. In other words, the probe will be
submersed to the specified depth and conditioned with an aliquot of
raw water containing no chemical application. Then SCV mV readout
shall be adjusted to -200 mV and calibrated by pressing enter. Record
the results in the Template LCA Data Entry Sheet in Appendix A.
5. Add a magnetic stir bar and place the beaker on a magnetic stir plate
and commence stirring at a medium speed; i.e.: slight vortex present on
the surface of the water in the beaker.
6. Turn the SCV on and note the change in mV on the display. The piston
should be reciprocating within the SCV probe, circulating sample
through the internal surfaces of the probe. Note the Signal Health listed
on the display, ensuring that > 90% is indicated before proceeding.
7. Insert the pre-calibrated pH probe in the solution. Wait until both pH
probe and SCV mV reading have stabilized before taking a reading, then
record the stabilized values in the Template LCA Data Entry Sheet
located in Appendix A.
8. Add 1.333 mL of the 60 ppm Non-ionic Polymer Solution to the sample
for a final concentration of 0.04 ppm Non-ionic polymer in the sample.
Then record the SCV mV and pH readings on the data entry sheet.

Note: The dose of Non-ionic Polymer is based on the historical process

dose at SRWTP during the time of sampling.

9. In accordance with Section 2.1.3.1 – Target pH, on page 11 of the

Chemtrac LCA Operations Manual, enter a pH Target of 6.5, since Alum
is the primary coagulant. Given that the historic process chemical dose
at SRWTP at the time of sampling = 50 ppm Alum, set the LCA-3
Coagulant Dosage as follows:
a. Initial Dose = 25 ppm Alum
b. Minimum Dose = 2 ppm Alum
c. Maximum Dose = 75 ppm Alum
10. Begin the coagulant titration and record the final SCV mV, final pH, final
temperature, final alkalinity, and enter the concentrations of coagulant
 and pH adjustment applied. These values will be compared to the
values obtained by the jar test.
iv. Jar Test Procedure
Similar to the Low Turbid Water Jar Test procedure, the dose of alum applied to
each jar is entirely dependent upon the historical data of the process chemical
application at the time of sampling. In other words, if the historic process
chemical dose = 50 ppm, then Jars 3 and 4 shall be dosed with 50 ppm Alum.
With the dosing order as follows: Jar 1 = 46 ppm, Jar 2 = 48 ppm, Jar 5 = 52 ppm,
and Jar = 54 ppm Alum. This applies to other process chemical applications; i.e.:
non-ionic polymer and pH adjustment chemicals.

10. Final Analysis

After all the data is compiled from both the High Turbid and Low Turbid water experiments
using both the Jar Tests, LCA-3, and process chemical applications; i.e.: current and historic; a
final analysis will be conducted. Pursuant to the results of the final analysis, Staff will evaluate
whether the LCA unit will offer the functional utility required to be a back-up analytical method
for water treatment process control.
APPENDIX A

Template LCA Data Entry Sheet

Date:
Analyst(s):
Location: SRWTP

Preliminary Water Quality Assessment    

Alkalinity (ppm
Process Sample Taps  Turbidity (NTU) pH Temperature (⁰C)
CaCO₃)
Tap 1
Tap 2
Tap 6
Tap 6A

Calibration and Setup

Tap 1 SCV:

Alum
Concentration (%):
Initial (ppm):
Maximum (ppm):
Increment (ppm):

pH Adjustment (Check applicable box)

Target pH = 6.5
Acid Solution (%): Base Solution (%):
Initial (ppm): Initial (ppm):
Maximum (ppm): Maximum (ppm):

Coagulant Dose Determination

Tap 2
  pH SCV (mV)

Initial  

Polymer Addition
   
Dose (ppm): __________

Final    

Results
Optimal Coagulant Dose (ppm):

pH Adjustments (if applicable)

Acid Added (ppm): Base Added (ppm):