Quality Assurance Project Plan (QAPP)
Removal of Strontium from Drinking Water by Coagulation/Filtration, & Lime Softening.
Submitted on:
June 7, 2013
By
Darren A. Lytle
Environmental Engineer
TTEB, WSWRD, NRMRL, ORD, USEPA
Cincinnati, OH 45268
And
Alissa O’Donnell
MS Environmental Engineering Student
SEEBME, CEAS, UC
Cincinnati, OH 45221-0012
Approved by:
______
Darren A. Lytle/Alissa O’Donnell, Principal InvestigatorsDate
______
Darren A. Lytle, TTEB Branch Chief Date
______
Steve Musson, WSWRD QA ManagerDate
TABLE OF CONTENTS
1. DISTRIBUTION LIST
2. PROJECT ORGANIZATION
3. PROBLEM DEFINITION/BACKGROUND
3.1. Problem/Background
3.2. Purpose
4. PROJECT DESCRIPTION AND SCHEDULE
4.1. Project Description
4.2. Project Schedule
5. QUALITY OBJECTIVES AND CRITERIA FOR MEASUREMENT DATA
6. SPECIAL TRAINING REQUIREMENTS
7. DOCUMENTATION AND RECORDS
8. MEASUREMENT/DATA ACQUISITION
8.1. Experimental Design
8.2. Sampling Methods Requirements
8.3. Sample Handling and Custody Requirements
8.3.1. Sample labeling
8.3.2. Chain of custody
8.3.3. Sample login, verification, and tracking
8.4. Analytical Methods Requirements
8.4.1. General Analytical Methods
8.4.2. X-Ray Diffraction and Scanning Electron Microscopy Analysis
8.4.3. Waste Disposal Requirements
8.4.4. Corrective Action in Event of Failure
8.4.5 Water
8.4.6. Chemicals
8.5. Quality Control Requirements
8.5.1. General
8.5.2. Identified QA Objectives
8.5.3. Action taken when QA objectives are not met
8.6. Instrument/ Equipment Testing, Inspection, and Maintenance Requirements
8.7. Instrument Calibration and Frequency
8.7.1. Graphite Furnace Atomic Absorption Spectrometry
8.7.2. Inductively Coupled Plasma Emission Spectrometry
8.7.3. pH Measurements
8.7.4. Analytical Balances
8.8. Inspection/Acceptance Requirements for Supplies and Consumables
8.9. Data Acquisition Requirements (Non-direct Measurements)
8.10. Data Management
8.10.1. General
8.10.2. Data Reporting Units
8.10.3. Data Reduction Procedures
8.10.4. Data Validation Procedures
9. ASSESSMENT/OVERSIGHT
9.1. Assessments and Response Actions
9.2. Reports to Management
10. DATA VALIDATION AND USABILITY
10.1. Data Review, Validation, and Verification Requirements
10.2. Validation and Verification Methods
11. REFERENCES
12. APPENDIX
12.1. Operating & Maintenance Guide to pH, DO, and REDOX Probes
12.1.1. HACH EC40 Benchtop pH/ISE Meters
12.1.2. HACH DO175 Dissolved Oxygen Meter
12.1.3. ORION Portable pH/ISE 230Apluse Meter
12.1.4. YSI Dissolved Oxygen Model 5100 Meter
TABLE OF FIGURES
Figure 1: Jar Testing Apparatus with Six Cells.
Figure 2: Jar Testing Controls.
Figure 3: Example sample label.
Figure 4: Sample log-in sheet.
TABLE OF TABLES
Table 1: Parameters for Coagulation/Filtration & Lime Softening Jar Testing.
Table 2: Requirements for Aqueous Sample Collection, Preservation, & Holding Time.
Table 3: Analytical Methods Used for Chemical Analysis of Water Samples.
Table 4: QA Objectives for MDL, Precision, Accuracy, and Completeness.
Table 5: Data Reporting Units.
1. DISTRIBUTION LIST
Darren A. Lytle
26 W MLK Dr.
Mail Code: 681
Cincinnati, OH 45268
513-569-7432
Christy M. Muhlen
26 W MLK Dr.
Mail Code: B17
Cincinnati, OH 45268
513-569-7901
Steve Musson
26 W MLK Dr.
Mail Code: G75
Cincinnati, OH 45268
513-569-7969
2. PROJECT ORGANIZATION
Responsibility: Principle investigator (PI), experimental design and experiment operation:
Darren Lytle, Environmental Engineer, TTEB, WSWRD, NRMRL, ORD, USEPA
Alissa O’Donnell, MS Environmental Engineering Student, Grantee, UC
Responsibility: Data evaluation and interpretation:
Darren Lytle, Environmental Engineer, TTEB, WSWRD, NRMRL, ORD, USEPA
Alissa O’Donnell, MS Environmental Engineering Student, Grantee, UC
Responsibility: Analytical procedures, analysis/analytical data base operation and management
Keith Kelty, Chemist, TTEB, WSRD, NRMRL, ORD, USEPA
Maily Pham, Chemist, TTEB, WSRD, NRMRL, ORD, USEPA
Responsibility: QA manager
Steve Harmon, TTEB, WSWRD, NRMRL, ORD, USEPA
3. PROBLEM DEFINITION/BACKGROUND
3.1. Problem/Background
Strontium (Sr) is a natural and commonly occurring alkaline earth metal which has an oxidation state of +2 under normal environmental conditions.[1] Stable strontium is suspended in water and is dissolved after water runs through rocks and soil. Typically, the amount of strontium that has been measured in drinking water in different parts of the United States by the EPA is less than 1 mg/L.[1]In February 21, 2008, the EPA published a Federal Register notice for the draft Contaminant Candidate List 3 (CCL3). The final list includes 104 chemicals or chemical groups and 12 microbiological contaminants, including strontium, which are known or anticipated to occur in public water systems. These candidates all have the potential to present health risks through drinking water exposure.[2]Having searched for journal articles to provide material for a literature review and background, it was noted that only a handful of papers had been published on drinking water treatment systems removing strontium. More research is needed to determine how effective widely practiced drinking water treatment processes, such as coagulation, filtration, and lime softening techniques, are at removing strontium. Such information will be useful in the regulatory determination process and valuable to water systems that have water supplies with elevated strontium levels.
3.2. Purpose
The objective of this research is to evaluate the effectiveness of conventional coagulation (aluminum and iron) and lime softening to remove strontium from water. The effectiveness of chemical doses, pH, or turbidity have on the removal rates will be explored.
4. PROJECT DESCRIPTION AND SCHEDULE
4.1. Project Description
Precipitation experiments will be performed using the six-cell jar testing apparatus and the experimental parameters are listed in Table 1 below:
Table 1: Parameters for Coagulation/Filtration & Lime Softening Jar Testing.
Alum Coagulation / Nanopure WaterTreatment Dose / Initial Turbidity / Initial pH / Initial Strontium Spike
Test 1 / varied dose (0-50 mg/L) / constant (0 NTU) / constant (6.5) / constant (5 mg/L)
Alum Coagulation / River Water
Treatment Dose / Initial Turbidity / Initial pH / Initial Strontium Spike
Test 1 / varied dose (0-50 mg/L) / constant (25 NTU) / constant (7.5) / constant (5 mg/L)
Test 2 / constant (25 mg/L) / constant (25 NTU) / varied (5.5-9.0) / constant (5 mg/L)
Test 3 / constant (25 mg/L) / constant (25 NTU) / constant (9.0) / varied (1-10 mg/L)
Test 4 / constant (25 mg/L) / varied (0-200 NTU) / constant (9.0) / constant (5 mg/L)
Ferric Chloride Coagulation / Nanopure Water
Treatment Dose / Initial Turbidity / Initial pH / Initial Strontium Spike
Test 1 / varied dose (0-50 mg/L) / constant (0 NTU) / constant (5.5) / constant (5 mg/L)
Ferric Chloride Coagulation / River Water
Treatment Dose / Initial Turbidity / Initial pH / Initial Strontium Spike
Test 1 / varied dose (0-50 mg/L) / constant (25 NTU) / constant (7.5) / constant (5 mg/L)
Test 2 / constant (25 mg/L) / constant (25 NTU) / varied (6.0-9.0) / constant (5 mg/L)
Test 3 / constant (25 mg/L) / constant (25 NTU) / constant (9.0) / varied (1-10 mg/L)
Test 4 / constant (25 mg/L) / varied (0-200 NTU) / constant (9.0) / constant (5 mg/L)
Softening / Ground Water
Treatment Dose / Initial Hardness (as CaCO3) / Initial pH / Initial Strontium Spike
Test 1 / varied dose (0-450 mg/L) / constant (300 mg/L) / constant (7.5) / constant (5 mg/L)
Test 2 / constant (450 mg/L) / constant (300 mg/L) / constant (7.5) / varied (1-10 mg/L)
4.2. Project Schedule
If there are no budget constraints related to the project, it is expected to run from August 2013 to December 2013 with additional four months for data analysis, internal review, and journal article submissions.
5. QUALITY OBJECTIVES AND CRITERIA FOR MEASUREMENT DATA
The QA objectives for this project are designed to ensure that the sample analysis meets accuracy and precision standards described in the following sections. Additional QA objectives may be considered during the project implementation period. Changes in the form of an amendment will be submitted for formal approval.The intended use of the data collected during this project will be research in nature and eventually be published in peer-reviewed research journals and presented at professional symposia.
6. SPECIAL TRAINING REQUIREMENTS
No special training requirements are necessary beyond educational experience and standard training. Existing standard operating procedures (SOPs) and instrument manuals will be adequate with initial minor oversight from the principle investigator.
7. DOCUMENTATION AND RECORDS
Daily laboratory experiment records will be maintained in a project lab-book. Analyst initials, date, experimental conditions, measurements, etc. will be recorded in pen as the work is conducted.Project documentation and records will be maintained in hard copy reports and electronic files. Data will be maintained in a Microsoft Excel spreadsheets, written reports will be created in Microsoft Work documents, and graphs will be made in Jandel Scientific Sigma Plot.All project reporting will be done in the form of presentations at technical conferences, conference proceedings publications, and peer-reviewed journal articles. A final project summary document will also be produced most likely as an EPA publication. All records and documents will be filed by the principle investigator for a period of beyond 10 years after project completion.
8. MEASUREMENT/DATA ACQUISITION
8.1. Experimental Design - Coagulation/Filtration & Lime Softening Jar Testing
Add 1.5 liter of double deionized (DDI) water to each of the six cells on the jar testing apparatus. DDI water was prepared by passing distilled water through a Milli-Q deionized water system.
Figure 1: Jar Testing Apparatus with Six Cells.
Start the mixing process by turning the jar testing apparatus and turning speed dial to 20-25 rpm. This speed is ideal so that particles can form but not break apart.
Figure 2: Jar Testing Controls.
Adjust the water to the desired pH using sodium hydroxide, potassium hydroxide, hydrochloric acid, sulfuric acid, or nitric acid.Add in the desired amount of strontium.Adjust the water back to the desired pH. Add in the desired treatment process chemical: aluminum sulfate, ferric chloride, calcium hydroxide, or sodium carbonate.Adjust the water back to the desired pH as quickly as possible. Immediately take the following initial samples from each cell: one-60ml HDPE bottle for ICAP (metals), one-250ml HDPE bottle for Inorganics (alkalinity, nitrate, nitrite, ammonia), one-30mL clear vial for turbidity (no headspace), and 110mL to test the HACH reagent powder pillows and color.Write down the pH, DO, redox potential, and temperature.Allow the jar testing apparatus to run for at least 30 minutes.Once the time has been reached, immediately take the following final samples from each cell: one-60ml HDPE bottle for ICAP, one-250ml HDPE bottle for Inorganics, one-30mL clear vial for turbidity (no headspace), and 110mL to test the HACH reagent powder pillows and color.Write down the pH, DO, redox potential, and temperature.Collect 350ml of water from each cell and filter all of it through the desired size Whatman filter.Collect the final filtered samples from each cell: one-60ml HDPE bottle for ICAP, one-250ml HDPE bottle for Inorganics, one-30mL clear vial for turbidity, and 10mL to test the HACH color.
8.2. Sampling Methods Requirements
Tests for chlorine, ammonium, and phosphate will be measured by the Hach kits (method described later) for each cell test. Temperature, pH, DO, free chlorine, and orthophosphate will be processed immediately following collection and will not require preservation.A list of required sample size, sample container type, preservative, and recommended sample holding times is provided in Table 2. Note that all analysis are not critical to this project (see section 8.3), but are included as part of the overall laboratory capabilities. In the event of a sample failure, the principle investigator will be responsible for corrective action. If the principle investigator can easily address the problem, the corrective action will be implemented and documented in the laboratory record book. Otherwise, a major sample failure may dictate a rerun in the test which will also be documented in the project record book.
Table 2: Requirements for Aqueous Sample Collection, Preservation, & Holding Time.
Analyte / Sample SizeRequired for
Analysis / Container Type / Preservation / Holding Time
Alkalinity / 200 mL / Plastic / Cool, 4°C / 14 days
pH / 50 mL / Glass / NA / (a)
Calcium / 30 mL / Plastic / HNO3 to pH<2 / 6 months
Manganese / " / " / " / "
Copper / " / " / " / "
Ferrous Iron / " / " / " / "
Total iron / " / " / " / "
Total aluminum / " / " / " / "
Dissolved iron(b) / 1 L / Plastic / Cool, 4°C / 6 months
Dissolved aluminum(b) / " / " / " / "
Chloride / 50 mL / Plastic / Cool, 4°C / 28 days
Sulfate / 50 mL / Plastic / Cool, 4°C / 28 days
Arsenic / 30 mL / Plastic / HNO3 to pH<2 / 6 months
Orthophosphate(b) / 100 mL / Plastic / Cool, 4°C / 48 hours
Fluoride / 50 mL / Plastic / Cool, 4°C / 28 days
Free and total chlorine / 200 mL / Amber glass / No headspace / (a)
Turbidity / 30 mL / Glass / none / none
Electrophoretic mobility / 15 mL / Plastic syringe / none / none
Particle counts / 200 mL / Glass / none / none
Nitrate / 50 mL / Plastic / Cool, 4°C / 28 days
Silica / 200 mL / Plastic / Cool, 4°C / 28 days
(a) Analyzed immediately after sample receiving.
(b) Filter on-site through a 0.45-micron filter.
8.3. Sample Handling and Custody Requirements
All analysis work will be conducted in-house so shipping does not apply in this project.
8.3.1. Sample labeling
This section describes labeling procedures for water samples and solids samples (XRD analysis and TEM analysis). An example label is shown as Figure 3:
SAMPLE I.D. NUMBER:TYPE OF SAMPLE:
SAMPLER INITIALS:
DATE/TIME OF COLLECTION:
ANALYSIS REQUIRED:
PRESERVATIVES:
Figure 3: Example sample label.
I.D. Number: The sample number should be assigned in sequence for each test beginning with the date followed by an identifier that will be keyed and recorded in the laboratory book. For example, a sample taken at the end of the first test run on the date 1/12/02 might be given the I.D. number 011202-01.
Conditions in which sample was formed: A brief description of the experimental conditions or objective will be written.
Sampler Initials: The initials of the person responsible for filling out each sample label and preparation of samples will be identified.
Date/Time: The date and time of sample collection will be documented.
Analysis Required: This applies to aqueous samples only.
Preservatives: This applies to aqueous samples only.
8.3.2. Chain of custody
The level of security and project sophistication does not warrant complicated chain-of-custody requirements. A system has been in place within the WSWRD for tracking samples submitted for analysis (metals, organics, and wet chemistry).
8.3.3.Sample login, verification, and tracking
Samples are taken in the appropriate bottle (see Table 2), preserved accordingly, and labeled as already described. Samples are given I.D. numbers corresponding to date of test and sample number as already described. The samples are then entered into the WSWRD sample tracking system. A sample submission form (Figure 4) is filled out to enter the samples into the system. Samples and forms are left in the designated sample login and storage area in room B-22.The sequence of sample handling events are:
Laboratory: Designated laboratory personnel (PI, operators, etc.)
Sample login:Maily Pham (sample custodian)
Laboratory:Designated laboratory personnel (analysts)
Database maintenance:Keith Kelty
All sample bottles will be sealed prior to submission for analysis. When samples are received by the sample custodian, verification will be performed that all samples indicated on the laboratory log-in forms are included and intact. Discrepancies will be addressed with the PI. The sample custodian and PI will randomly check samples for the appropriate preservative (i.e., pH test strips to ensure appropriate preservation pH) when applicable. Wet chemistry samples will be stored at or below 4ºC upon arrival in a refrigerator located in room B22.
Analytical results are submitted electronically to the sample database manager (Keith Kelty) where they are merged with the master SAS computer based software database system. The data are returned to the analyst on a regular schedule electronically in a spreadsheet-type format.
Figure 4: Sample log-in sheet.
8.4. Analytical Methods Requirements
A summary of analytical methods (appropriately referenced and numbered) used during this project as well as their corresponding detection limits are listed in Table 3. Note that not all analytes in Table 3 were applicable to this study (see Section 8.1.). Additional detail of the analytical methodology including the instrumentation required is provided in the following sections.
8.4.1. General Analytical Methods
The pH will be measured with a Hach Company (Loveland, CO) EC40 benchtop pH/ISE meter (model 50125) and a Hach Company (Loveland, CO) combination pH electrode (model 48600) with temperature corrections. The instrument will be standardized daily using a two-point calibration with pH 7 and 10 standard solutions (Whatman, Hillsboro, OR). Standard operating procedures (SOPs) for several instruments are provided in the appendix along with appropriate filling solutions for various electrodes All other metals will be analyzed with a Thermo Jarrel Ash (Franklin, MA) 61E® purged inductively coupled argon plasma spectrometer (ICAPS). Color, orthophosphate, copper, and free and total chlorine will be analyzed with a Hach DR/2000 spectrophotometer (Loveland, CO). Turbidity will be measured using a Hach 2100N turbidimeter. Total inorganic carbon (TIC) will be analyzed by a coulometric procedure on a UIC Model 5011 CO2 coulometer (Joliet, IL) with Model 50 acidification module operated under computer control. Syringe filters (0.45, 0.2, 0.02 μm) (Whatman, Inc., Clifton, NJ) will be used to separate colloidal copper and lead for measurements.
Table 3: Analytical Methods Used for Chemical Analysis of Water Samples.
Analysis / Method / Method # / ReferenceTotal Alkalinity / Potentiometric Titration / 2320 b.4.6 / Std. Methods (1)
Ammonia (as N) / Automated Colorimetric / 350.1 / EPA (2)
Anions (F, Cl, ClO2, ClO3, Br, BrO3, NO2, NO3, PO4 SO4) / Ion Chromatography / 300 / EPA (2)
Chloride / Potentiometric Titration / 4500-Cl D / Std. Methods (1)
Nitrate+Nitrite (as N) / Automated Colorimetric / 353.2 / EPA (2)
Orthophosphate / Automated Colorimetric / 365.1 / EPA (2)
TIC / Coulometric / D-513-92 / ASTM (3)
As Pb U Se Bi / ICP-MS / 200.8 / EPA (4)
Al, As_icap, Ba, Be, Bi, Ca, Cd, Cr, Cu, Fe, K_icap, Mg, Mn, Na, Ni, P, Pb_icap, S, Sb, Sulfate, Si, Silica, Sn, Zn / ICP_AES / 200.7 / EPA (4)
TOC / Combustion / 5310 C / Std. Methods (1)
THM HAN / GC ECD / 551.1 / EPA (5)
Dissolved Oxygen / Winkler (Azide Modification) / 4500-0 D. / Std. Methods7
Temperature / -- / -- / --
Ammonia / Automated Colorimetric / 350.1 / EPA5
Particle Counts / Light-Blockage / 2560-C. / Std. Methods7
Turbidity / Nephelometric / 2130 / Std. Methods7
Apparent Color / Platinum-Cobalt / 8025 / Hach10
Ferrous Iron / Phenanthroline / 8146 / Hach10
Phosphorus / Ascorbic Acid / 8048 / Hach10
Total Iron / Phenanthroline / 8145 / Hach10
* Detection limit can be adjusted by changing sample volume
1 RREL SW846, Sept. 1986.
2 Modified from methods for Determination of Inorganic Substances in Water & Fluvial Sediments, U.S. Geological Survey Open-File Report, (85-495) 1985.
3 Alpkem Research, Inc., Clackamas, OR.
4 Orion Research, Inc., Boston, MA.
5 USEPA, "Methods for Chemical Analysis of Water and Wastes," EPA-600/14-79-020 (1983).
6 USEPA, "Methods for the Determination of Metals in Environmental Samples," EPA-600/14-91-010 (1994).
7 "Standard Methods for the Examination of Water and Wastewater," 18th Edition (1992).
8 USEPA, AMethod 300.1 Determination of Inorganic Anions in Drinking Water by Ion Chromatography,@ Revision1.0, NERL, ORD, Cincinnati, OH (1993).
9 "1994 Annual Book of ASTM Standards," section 11, volume 11.01, Water (I).
10 Hach Company, Loveland,Co.
11 Drinking Water Research Division, USEPA, Internal Method. References: Journal AWWA 72:5:304(1980); Schock & Lytle, Proc. AWWA WQTC (1994).
8.4.2. X-Ray Diffraction and Scanning Electron Microscopy Analysis
X-Ray Diffraction (XRD) will be used to identify crystalline phases. Colloids and particles will be filtered from suspension onto a 47 mm diameter 0.45 μm filter (Millipore Corp., Bedford, MA) or a 0.1 μm filter (Costar Corp., Cambridge, MA) using a vacuum filtration apparatus. Unused filters will be also analyzed to determine background contributions. A Scintag (Scintag, Inc., Santa Clara, CA) XDS-2000 theta-theta diffractometer with a copper x-ray tube will be used to acquire x-ray patterns. The tube will be operated at 30 kV and 40 mA, and scans will typically cover the range of 5 to 60 degrees 2 theta, with 0.03 degree step sizes that will be held for 3 seconds each. Pattern analysis will be performed using the computer software provided by the manufacturer, which generally followed ASTM procedures (ASTM, 1996).