Comprehensive Quality Assurance Plan

Transcription

1 Comprehensive Quality Assurance Plan For University of Florida Institute of Food and Agricultural Sciences Analytical Services Laboratories 2390 Mowry Road 631 Wallace Building Gainesville, FL (352) NELAC Certification # _ E72850 September 2016

2 Comprehensive Quality Assurance Plan EWQLQAManual-6.2.2doc.doc 09/21/2016 Rev Page 2 of 44 For University of Florida Institute of Food and Agricultural Sciences Analytical Services Laboratories 2390 Mowry Road 631 Wallace Building Gainesville, FL (352) Prepared by University of Florida Institute of Food and Agricultural Sciences Analytical Services Laboratories 2390 Mowry Road 631 Wallace Building Gainesville, FL (352) Dr. Rao Mylavarapu UF/IFAS ASL Laboratory Director (Date) William d Angelo UF/IFAS ASL Laboratory Coordinator (Date) Nancy S. Wilkinson UF/IFAS ASL QA Officer (Date) DOH QA Officer or Designee (Date)

3 09/21/2016 Rev Page 3 of 44 TABLE OF CONTENTS QA Plan Elements Section Title Page # Rev. Date 1.0 Title Page 1 07/ Table of Contents 3 07/ Statement of Policy 8 07/ Organization and Responsibility 9 07/ Analytes and QA Targets 13 07/ Sampling Procedures 15 07/ Contract Review 16 07/ Sample Chain of Custody 17 07/ Field Sampling Custody 17 09/ Laboratory Custody 17 07/ Sample Change of Custody to the EWQL 17 07/ Sample Custody Tracking within the EWQL 18 07/ Sample Holding Time 19 07/ Sample Disposal 19 07/ EWQL Laboratory Information Management System 19 07/ Analytical Procedures 21 07/ Method Modifications 21 09/ EPA UF Ammonia 21 09/ All Methods Minimum QC Requirements 21 07/ Reagent Storage 22 07/ Waste Disposal 23 07/ Laboratory Glassware Cleaning 23 07/ Calibration Procedures and Frequency 24 07/ Metals 24 07/ Nutrients/Major Ions 24 07/10

4 09/21/2016 Rev Page 4 of ph Meter 25 07/ Conductivity Meter 25 07/ Analytical Balances 25 07/ Digestion Blocks 25 07/ Autoclave 26 09/ Other Equipment 26 07/ Standard Sources, Receipt and Traceability 26 09/ Preventive Maintenance 28 09/ QC Checks 29 07/ Blind QC Check Sample Analysis 29 07/ Definitions and Methods of Calculations for QC Terms 29 09/ Precision 29 09/ Accuracy 29 09/ Standard Deviation and Control Limits 30 07/ Method Detection and Practical Quantitation Limits 31 07/ Method Detection Limit (MDL) 31 07/ Practical Quantitation Limit (PQL) 31 07/ Data Reduction, Validation, and Reporting 33 07/ Corrective Action 36 07/ In-House Corrective Actions 36 07/ Client Complaints 37 09/ Performance and System Audits 38 07/ Internal System Audit 38 07/ Internal Performance Audits 40 07/ External Performance Audits 40 07/ Annual Management Review 40 07/ Quality Assurance Reports 42 07/ Uncertainty Estimation 43 07/ Appendix 45 07/11

5 09/21/2016 Rev Page 5 of 44 FIGURES Figure Description Page # Rev. Date 4.1 Organizational Chart 12 07/ In-House Laboratory Audit Check List 39 09/02

6 09/21/2016 Rev Page 6 of 44 TABLES Table Description Page # Rev. Date 5.1 Analytical Methods and QA Targets 14,43 07/ Preservation Techniques and Holding Times 15 07/ Chemical Storage Procedures 22 09/ Standard Sources, Receipt and Traceability 27 09/ Preventive Maintenance 28 09/ Quality Control Checks 32 07/ Data Qualifier Codes 35 11/11

7 09/21/2016 Rev Page 7 of 44 ATTACHMENTS Attachment Description Ref Page # Rev. Date 1 Certified Analysis Request Form 17 06/11 2 Code of Ethics 8 08/11

8 09/21/2016 Rev Page 8 of STATEMENT OF POLICY The mission of the University of Florida, Institute of Food and Agricultural Sciences, Analytical Services Laboratories which includes the Environmental Water Quality Laboratory (EWQL), the Analytical Research Laboratory (ARL), the Extension Soil Testing Laboratory (ESTL), and the Livestock Waste Testing Laboratory (LWTL) (henceforth referred to as the UF/IFAS ASL) is to offer UF/IFAS researchers high quality analytical services for an appropriate selection of standard tests in a timely manner, through adoption of The NELAC Institute (TNI) certification protocols. This document is the Comprehensive Quality Assurance Program manual for the Environmental Water Quality Laboratory (henceforth referred to as the EWQL). Its purpose is to detail the activities and evaluation criteria necessary to ensure that the data generated at the EWQL are of high and known quality and as such meet the scientific needs of UF/IFAS researchers working with the Florida Department of Environmental Protection (FDEP). This Quality Assurance (QA) manual also documents the procedures used by the EWQL to ensure that all data generated by the laboratory are subjected to sound quality assurance management practices. Management is committed to compliance with TNI standards and a Code of Ethics (Attachment 2) which is annually approved by management. All laboratory personnel will be familiar with the quality documentation and implement the policies and procedures in their work.

9 09/21/2016 Rev Page 9 of ORGANIZATION AND RESPONSIBILITY The UF/IFAS EWQL is an inorganic sample preparation and analysis laboratory only. The EWQL offers these services to UF/IFAS researchers only. The EWQL does not provide any field sampling services. The internal management organizational structure for the EWQL is detailed in Figure 4-1. Dr. Rao Mylavarapu, Mr. William M. d Angelo and Ms. Nancy S. Wilkinson are the approved signatories of the UF/IFAS ASL. The UF/IFAS ASL is headed by its Director, Dr. Rao Mylavarapu. The Director, under the advisement of the UF/IFAS ASL Oversight Committee, is responsible for the development and implementation of the technical and administrative policies for the EWQL. The Director is committed to the QA Program described in this manual. The UF/IFAS ASL Director is supported by William M. d Angelo, UF/IFAS ASL Coordinator, and by Nancy S. Wilkinson, UF/IFAS ASL QA Officer. The Laboratory Coordinator is responsible for overseeing the daily operation of the laboratory and for overseeing the processing, analysis and generation of sample results by the laboratory. In addition, the Coordinator ensures the EWQL s compliance with quality assurance objectives by supervising the implementation of the procedures described in this manual. The Quality Assurance Officer is responsible for ensuring the actual implementation of the QA protocols as described in this manual. The QA Officer s responsibilities include the timely development and revision of the EWQL QA Manual and Standard Operating Procedures (SOP s), ensuring the EWQL s compliance with audit requirements and the Department of Health (DOH) Proficiency Examination Program, and reviewing and validating data prior to release of certified reports to clients. All analyses performed at the EWQL are carried out by well-trained and experienced laboratory personnel using the latest revision of the laboratory SOP s. Under the supervision of the QA Officer, laboratory personnel are required to annually review and update (if necessary) all SOP s that pertain to the analyses they perform. Any revisions to laboratory SOP s must be approved by the Laboratory Coordinator and Director prior to implementation. It is the responsibility of the Laboratory QA Officer and the Coordinator to ensure and document that employees have read, understood and adopted the latest version of the approved SOP manual. All analysts are required to demonstrate initial and continuing proficiency (annually) for the analysis they are performing. Proficiency may be demonstrated by either successfully analyzing a blind Performance Evaluation (PE) sample or by successfully analyzing three consecutive Laboratory Control Samples. In addition, all analysts must complete annual MDL (method detection limit) studies for the parameters that they are responsible for. Results of the initial and continuing proficiency demonstrations as well as the MDL studies are to be maintained by the QA Officer. All analysts shall participate in annual data integrity and ethics training sessions. Topics covered will include all data integrity procedures and examples of breaches of ethical behavior. These sessions are documented in writing and provided to all employees. Employees are required to understand that any infractions of laboratory data integrity procedures will result in investigation that could lead to serious consequences including termination. The data integrity training session will have a signature attendance sheet that demonstrates all staff have participated and understand their obligations related to data integrity.

10 09/21/2016 Rev Page 10 of 44 The following is a list of key laboratory personnel and responsibilities: William d Angelo, Lab Coordinator. Responsible for overseeing the daily operation of the lab. Backup analyst on AQ2 for EPA Methods 365.1, 350.1, 353.2, and and ICP EPA Nancy S. Wilkinson, QA/QC Officer. Responsible for day-to-day implementation of the EWQL s Quality Assurance and Quality Control programs. Back-up analyst for TKN EPA Cassandra Bonds, Information Technology Specialist. Responsible for processing on-line sample submission requests and answering ing queries from clients. Enters all client information into the LIMS and processes paperwork and labels for sample submissions. Responsible for analysis of ph by EPA Method and Specific Conductance by EPA Method Also responsible for certified sample receiving and sample check-in including all documentation for Chain of Custody purposes. Terrace James, Office Assistant. Serves as the customer contact point and is responsible for processing invoices. Also responsible for overseeing non-certified sample check-in and storage. Mary Cathy MacLeod, Laboratory Technician. Responsible for analysis of nitrate plus nitrite (NO 2 + NO 3 ) by EPA Method Also responsible for certified sample receiving and sample check-in including all documentation for Chain of Custody purposes and backup analysis of Ammonia by EPA Method modified, no distillation and backup analysis of Phosphorus (all forms) by EPA Derek Tornwall, Chemist. Responsible for analysis of ph by EPA Method and Specific Conductance by EPA Method Also responsible for certified sample receiving and sample check-in including all documentation for Chain of Custody purposes. Xiao-Li Yi, Laboratory Technician. Responsible for receiving all samples for the ESTL. Responsible for prepping and running ph and extracting for soil ICP analysis, organic matter, EC, and BpH. Joel Walle, OPS Laboratory Technician. Responsible for Total Kjeldahl Nitrogen digestion by EPA Method and sample processing in the Livestock Waste Testing Lab. Andrew Ziadie, OPS. Analysis of Ammonia by EPA Method modified, no distillation. Responsible for analysis of Phosphorus (all forms) by EPA and for digestion of samples for Total-Phosphorus analysis by EPA Laura Clark, Student OPS. Backup for digestion of samples for Total-Phosphorus analysis by EPA

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12 Personnel Chart UF/IFAS Analytical Services Laboratories, Gainesville, Soil & Water Science Department EWQLQAManual-6.2.2doc.doc 09/21/2016 Rev Page 12 of 44 Dr. Rao Mylavarapu Director, IFAS ASL William d Angelo Lab Coordinator Nancy S. Wilkinson, QA Officer Extension Soil Testing Lab (ESTL) Livestock Waste Testing Lab (LWTL) Environmental Water Quality Lab (EWQL) Analytical Research Laboratory (ARL) ICP Analyst NOx-N Analyst NH4-N Analyst TP/OP Analyst ph/ec Analyst TKN Analyst Figure 4.1 Organizational Chart for the UF/IFAS ASL

13 09/21/2016 Rev Page 13 of ANALYTES AND QA TARGETS A list of analytes, analytical methods, matrices, accuracy and precision targets, MDL s and PQL s (practical quantitation limits) used by the UF/IFAS ASL is given in Table 5-1. MDL s are determined using 40 CFR Part 136, Appendix B. The procedure used by the EWQL to establish MDL s involves analyzing 7 replicate standard solutions with a concentration at 1 to 5 times the estimated MDL, as per EPA protocol. The standard deviation of the measured standard concentrations is then determined and the MDL is set to the student s T value (corresponding to the appropriate degrees of freedom; = 0.01) times the calculated standard deviation. MDL s are recalculated/verified annually. MDL s may be set higher than experimentally determined due to data interpretation parameters or instrument limitations. PQL s are set at 3 to 5 times the reported MDL unless method demonstration indicates the need for a different and higher PQL. Both MDL s and PQL s are reported in mgl -1 unless otherwise noted. The QA targets for all analytes are within the range of % recovery for accuracy and < 10% relative percent difference (RPD) for precision (25% at low level concentrations of < 20x the MDL) unless laboratory generated data indicates that tighter control limits can be routinely maintained. All samples must be analyzed within the calibration range. All sample concentrations greater than the highest calibration standard must be diluted to read within calibration range. Therefore the linear range for each element/ nutrient is the concentration of the high calibration standard and no sample reported will exceed the high standard concentration.

14 09/21/2016 Rev Page 14 of 44 Table 5.1 Analytical Methods and QA Targets for the UF/IFAS ASL ANALYTE EPA METHOD MATRIX ACCURACY PRECISION MDL (mg/l) PQL (mg/l) Aluminum water % Boron water % Cadmium water % Calcium water % Copper water % Iron water % Lead water % Magnesium water % Manganese water % Nickel water % Phosphorus water % Potassium water % Sodium water % Zinc water % Total Kjeldahl Nitrogen water % Nitrate + Nitrite water % Ortho Phosphorus water % Total Phosphorus water % PH water n/a ph units 0.1 ph units Specific Conductance water n/a μmho/cm 10 μmho/cm Ammonia 350.1UF water %

15 Page 15 of SAMPLING PROCEDURES Sample collection and field handling procedures are not addressed in this document. The EWQL does not provide any field sampling supplies or services to researchers. Solution samples are currently delivered to the EWQL by the researcher in 20-mL scintillation vials. These sample vials are purchased and prepared by the researcher prior to their delivery to the EWQL. If requested, unused sample and/or the empty sample vials are returned to the researcher. Used sample vials are not cleaned by the EWQL prior to their return to the researcher. Cleaning is the responsibility of the researcher. Any necessary sample preservation at the time of sampling, including refrigeration and acidification, is the responsibility of the researcher or field sampling team. Upon delivery of the samples to the laboratory, the sample preservation technique is verified and any deviations noted on the sample custody form. Appropriate storage of the samples is then provided by the EWQL in accordance with EPA guidelines. Table 6-1 outlines the appropriate preservation techniques and holding times recommended by the EPA for various analytes. Table 6.1 Preservation Techniques and Holding Times Analyte Preservation Holding Time EC Cool, 4 o C 28 days ph None required 48 hours Nitrate + Nitrite Cool, 4 o C, H 2SO 4 to ph < 2 28 days Nitrogen, Ammonia Cool, 4 o C, H 2SO 4 to ph < 2 28 days Nitrogen, Total Kjeldahl Cool, 4 o C, H 2SO 4 to ph < 2 28 days Phosphorus, Ortho Cool, 4 o C 48 hours Phosphorus, Total Cool, 4 o C, H 2SO 4 to ph < 2 28 days ICP Metals HNO 3 to ph < 2 6 months

16 Page 16 of CONTRACT REVIEW As of January 1, 2007, it is a mandatory policy of the EWQL to require for review one or all of the following documents from clients prior to beginning analysis for any new research project: 1. Project Summary 2. Scope of Work 3. Quality Assurance Plan The purpose of this policy is to ensure that the client s requests are adequately defined, documented and understood by the laboratory (including appropriate method selection and reporting limits) and that the laboratory has the capabilities and resources to meet the client s requirements. The documents listed above will serve as written contracts outlining agreed on services between the lab and the client. The ASL Lab Coordinator and QA Officer will review the required documentation prior to the beginning of the project and provide written approval/refusal for work that is cited as being performed by the EWQL. Any differences between the contract requests and what the lab is capable of providing must be resolved in writing before any work commences. In addition, any deviations by the lab from normal TNI protocols and procedures will be discussed with the client and documented by the lab during this review process. A unique identification number will be assigned to each project and that information entered into the Laboratory Information Management System (LIMS) for internal tracking purposes. In addition, the Certified Sample Analysis Request Form will be updated and the assigned unique identification number for the project will become a required field. Forms without the required information will not be processed and will be returned to the client for completion.

17 Page 17 of SAMPLE CHAIN OF CUSTODY The EWQL is considered to have assumed custody of a sample when the procedures described below (in the Laboratory Custody section) are properly carried out and completed. The EWQL does not assume custody of samples if the procedures described below are not carried out by an authorized EWQL employee. It is the responsibility of the designated Sample Custodian(s) or the Laboratory Coordinator or an authorized designee to perform the procedures as described prior to assuming custody of any sample. Errors in paperwork must be corrected prior to sample acceptance. Corrections should be made in indelible ink by placing one line through the improper entry, initialing and dating the correction, and writing in the new information clearly and legibly next to the deleted entry. 8.1 Field Sampling Custody Not applicable to this laboratory QA document. 8.2 Laboratory Custody Sample Change of Custody to the EWQL EWQL policy requires that the researcher complete a Research Certified Sample Analysis Request Form prior to the arrival of any sample at the EWQL (Attachment 1). This form provides client information, sampling dates, preservation information, number of samples and sample matrix, scheduled sample arrival date, and analytes requested for analysis. Once this form is received by the EWQL, a unique set number, unique series of laboratory identification numbers and an appointment date for sample arrival will be assigned and noted on the form. The IT Specialist enters the information into LIMS and a unique set number is assigned. The set number begins with a C followed by a four digit sequential number based on the order that requests are received. The unique series of laboratory identification numbers are also assigned by LIMS as a C followed by five sequential numbers. A copy of this form will then be sent to the researcher to be returned with the samples on their assigned appointment date. The researcher copy of this form must accompany the samples when they arrive at the EWQL in order to assure proper identification and analysis of the samples. In addition, a Chain of Custody form must also accompany the samples. Appropriate signatures and date for Relinquished By and Received By are required on the Sample Chain of Custody forms. If samples are shipped via a commercial shipping company (i.e. FedEx, UPS, etc), a copy of the shipping label must be attached to the Chain of Custody for internal tracking purposes. The EWQL will only accept custody of samples after the following additional requirements are met: All samples submitted to the EWQL must be identified using unique field identification numbers assigned by the researcher. The EWQL requires that these identifiers be a series of sequential numbers. Each sample must be labeled on the side of the sample vessel with this unique sample identifier using waterproof labels and/or indelible ink. In no instance should the sample identification be placed only on the cap of the sample vessel. Sample identification should include location, time and

18 Page 18 of 45 date of sample collection except where client prior to submitting samples asks for location not to be revealed. Sample condition, if other than acceptable (i.e., leaking, broken or cracked vials, missing fractions, etc.), shall be noted on the Chain of Custody Form and in the EWQL Sample Receipt Log. When provided with minimal sample volume by the client, it is the policy of the EWQL to analyze the sample first followed by a sample replicate and then by sample matrix spikes if there is sufficient volume remaining. Upon sample arrival, if insufficient sample volume is provided to the EWQL by the client for analysis of replicates and/or matrix spikes, it will be assumed by the EWQL that the analysis of these QC types is not required by the client for those samples. A notation will be made in the Set Comment area of the final data package if any particular QC is not analyzed due to insufficient sample volume. Sample data will be reported to the client without further flagging. All samples which require thermal preservation shall be considered acceptable if the arrival temperature is either within 2 C of the required temperature or the method specified range. For samples with a specified temperature of 4 C, samples with a temperature ranging from just above the freezing temperature of water to 6 C shall be acceptable. Samples that are hand delivered to the laboratory on the same day they are collected may not meet this criteria. In these cases, the samples shall be considered acceptable if the samples were received on ice. Shipping temperature upon arrival will be noted in the EWQL Sample Receipt Log and on the Chain of Custody Form. Inappropriate shipping or preservation technique should be brought to the attention of the Laboratory Coordinator and/or QA Officer. Samples will be flagged with a Y data qualifier for improper preservation. The laboratory checks chemical preservation such as ph prior to sample prep or analysis. ph >2 are noted by the analyst on the Run Summary Log and samples are flagged with a Y data qualifier for improper preservation. All required information must be completed on the Research Certified Sample Analysis Request Form including number of samples, requested analyses, sample disposition, etc. The Sample Custodian (or designee) should initial and date all entries to the EWQL Sample Receipt Log and the Research Certified Sample Analysis Request Form. The EWQL need not accept custody of samples unless the above conditions are met Sample Custody Tracking within the EWQL Upon accepting custody of a set of samples, the EWQL confirms the identity of the sample set using the Certified Analyses Solution Sample Information Sheet Control Number, the assigned unique sample set number and the laboratory identification numbers (Lab Numbers) previously assigned. Lab numbers are generated using the Laboratory Information Management System (LIMS) and are cross-referenced to the unique researcher identification numbers. Once the assigned set number and laboratory numbers have been confirmed as correct, a label (listing the set number and the assigned lab numbers) is prepared by the IT Specialist and affixed to the box containing that particular set of samples. This label is used in tracking and identifying the samples within the laboratory. The EWQL provides refrigeration units (4 o C ± 2 o C) and freezers (0 o C ± 2 o C) for the storage of samples, if necessary. Once the samples have been properly identified for tracking, they are transferred to the appropriate refrigeration unit for storage and entered into that refrigerator s Sample Check-out Log. Only authorized laboratory personnel shall have access to the refrigeration units. Standard solutions must be stored in an area separate from the samples.

19 Page 19 of 45 All sample preparations and analyses (including digestion, filtration and dilutions) are conducted only by the technicians indicated in Figure 4-1 (or by their trained designee). Prior to removing a sample set from its storage refrigerator, the analyst is required to log their name, the time and date of the removal and the new work area where the samples may be found in the Refrigerator Sample Check-out Log. Additional activities involving the samples should be noted in the pertinent Sample Run Log or Digestion Log along with the initials of the technician performing the activity and the date and time the activity was preformed Sample Holding Time The sample collection date is required for tracking analysis holding times. If the client provides a range of dates for a set of samples, the earliest sampling date for the entire set will be used for holding time tracking purposes at the EWQL. If the sample collection date is not provided by the client, the EWQL will use the laboratory sample receipt date as the collection date for holding time tracking purposes. If the client provides only the month and year of collection (i.e. June 2006), the EWQL will use the first day of the month for holding time tracking purposes. A comment will be included in the Set Comment area of the final data package if a date other than the client sampling date is used for tracking and flagging holding times for data. It is the responsibility of the client to be aware that holding times commence upon sample collection and samples should be received at the lab with adequate time left for digestion (if appropriate) and analysis (refer to Table 6.1). Samples received or analyzed after holding time expires will be flagged with a Q qualifier Sample Disposal Researchers are given an option concerning the disposition of samples. Samples may be returned to the researcher in the original containers at the researcher's request or samples may be destroyed and properly disposed of according to University regulations. Should a researcher wish to have samples returned to them, transfer of sample custody is documented by use of the Research Certified Sample Analysis Request Form and the Sample Check-Out Log. In those situations where the researcher requests that the EWQL dispose of the samples, the sample set number and the date is entered into the LIMS. Samples are then moved to the designated sample disposal holding area for later pick-up by representatives of the UF Environmental Health and Safety Department. The EWQL does not supply either new or used containers to researchers to replace those disposed of in this manner. 8.3 EWQL Laboratory Information Management System (LIMS) The EWQL LIMS is a controlled-access computer program in residence on the UF/IFAS main server with controlled access back-up program copies and data archives in residence on the UF/IFAS central computer system. Access to any of the LIMS systems requires knowledge of account and password information as well as directory information. Technical level of access involves discrete satellite programs for ICAP, colorimetric analyses, and classical wet chemistry methods. These programs do

20 Page 20 of 45 not have direct access to the LIMS but create working electronic files from which final data is transferred. The IT Specialist (or designee) is responsible for entering client information into the LIMS and for supplying the sample set labels. Raw data from all analyses are entered either by automatic upload or manually depending on the analysis. In both cases, a manual calculation may be requested to confirm that the program is properly processing raw data and that the final calculated values are correct. Any corrections made to raw data must be properly documented by the correcting analyst. Proper correction of data is accomplished by drawing a single line through the incorrect entry and initialing and dating the new entry. Upon completion of analysis for a particular parameter for a set of samples, a hard copy report (known as a batch ) is produced. The data and QC included in the batch is reviewed and signed off on by the analyst involved in its production and hard copies of all raw data are attached. The batch is sent to the QA Officer and/or Laboratory Coordinator for final review. The batch is then finalized and the data locked in the LIMS. An electronic copy of the data is sent to the client by the QA Officer and/or Laboratory Coordinator. The finalization date and client date is documented in the LIMS by the QA Officer and/or Laboratory Coordinator. No further corrections can be made to that data once it is finalized and sent to the client without authorization from the Laboratory Coordinator (or designee). Submission of a corrective action form may be required and the client will be notified by the Laboratory Coordinator (or designee) of any changes made after data finalization and the cause of the change. The hard-copy of the batch and all associated documentation is filed until all requested parameters are complete. Once all requested parameters for a particular set of samples are completed and all batches are finalized, the batches are consolidated and a final report for all data (known as a set ) is generated. The set (including all batch information) is reviewed for a final time by the QA Officer and/or the Laboratory Coordinator (or designee) and upon approval, the completed data package is finalized and a copy ed to the client. The completed hard-copy data package including all supporting documentation, raw data, etc is maintained on file at the EWQL for 5 years after the end of the project in a locked filing area. Reports are filed by the EWQL assigned set number. Revisions and upgrades to the EWQL LIMS may be conducted by either the UF/IFAS Information Technology group or by an authorized computer consultant. Changes to the program are made first to a back up copy of the program and are tested fully using dummy data to insure that the full effect of programming changes can be determined prior to incorporating the changes into the working program. Changes to the working version of the LIMS program are made only after testing is complete and changes have been approved by the EWQL management. A log book of all changes to the LIMS is maintained in the laboratory. Electronic back-up files for each day s data are created and maintained by the UF/IFAS Information Technology group on an authorized access only server. Daily s are sent to the Lab Laboratory Coordinator documenting that the back-up files are being created of the LIMS database by the UF/IFAS IT Group. These electronic records are maintained for a period of 5 years after the end of project. Any upgrades or alterations to the LIMS or the computer resources at the EWQL must be authorized by the Laboratory Coordinator and/or the Laboratory Director.

21 Page 21 of ANALYTICAL PROCEDURES The EWQL will have in place and use as a basis for day to day activities a current Quality Assurance Plan and current Standard Operating Procedures for all analytical methods in order to ensure that the lab meets the requirements of the most current TNI Standards. All SOP s and the EWQL QAP will have the revision number and effective date noted in the header of each page. All SOP s will be signed by the analyst(s) responsible for that analysis at the time of the SOP production as well as by the Laboratory Coordinator and QA Officer. The Laboratory Coordinator or the QA Officer will be responsible for reviewing and updating SOP s and the QAP as required. A master list will be maintained for logging all revisions to the QAP, SOP s, manuals, etc. and the time periods they were in place. Retired SOP s and QAP s will be archived in the Laboratory Coordinator s office. It is the policy of the EWQL that all employees will have access to the most current version of the lab s QAP, SOP s, and reference methods. In addition, all employees will be provided information on UF policies for lab safety and chemical hygiene to ensure personal safety in the lab while performing analyses, etc. All analytical methods utilized by the UF/IFAS EWQL are listed in section 5.0 of this Quality Assurance Manual. All methods listed in this section are taken from the EPA publications, Methods for Chemical Analysis of Water and Wastes; EPA 600/ and Methods for the Determination of Inorganic Substances in Environmental Samples; EPA 600/R-93/100;USEPA Office of Research and Development, Cincinnati, OH, 8/93.Several modifications of these methods are based on recommendations from Standard Methods for the Examination of Water and Wastewater, 19th Edition, Method Modifications The following modifications have been made to methods indicated in Table EPA 350.1UF Ammonia Method has been modified in several ways. First, the sample is analyzed without the performing the preliminary distillation step. Second, Potassium Sodium Tartrate/Sodium Citrate is used in place of Disodium-EDTA in the color development step as per instrument manufacturer s recommendation All methods Minimum QC Requirements: The EWQL maintains the normal TNI requirement of a minimum of 10% Quality Control (QC) samples for replicate samples and matrix spiked samples.

22 Page 22 of Reagent Storage All reagents and solvents are dated upon receipt. Reagents that do not have a manufacturer s expiration date are given an in-house expiration date and labeled to reflect this date. Certificates of Analysis for analytical standards and reagents are maintained by the EWQL QA Officer or by the analyst. Table 9.1 outlines the storage of various laboratory chemicals in the EWQL. Table 9.1 Chemical Storage Procedures Reagent Storage Location Conditions Nonhalogenated Solvents Vented Storage Cabinets Sample Prep Room Air Conditioning Alcohols Vented Storage Cabinets Sample Prep Room Air Conditioning Inorganic Chemicals Shelving Cabinets Metals Analysis Area, Inorganic Analysis Area, Sample Prep Room Air Conditioning Trace Metals Standards Standards Refrigerator Metals Lab Cool, 4 o C Acids, Inorganic Vented Storage Cabinets Sample Prep Area Air Conditioning Acids, Organic Vented Storage Cabinets Sample Prep Area Air Conditioning Inorganic Standards Standards Refrigerator Inorganic Analysis Area Cool, 4 o C

23 Page 23 of Waste Disposal Methods All chemical waste generated by the EWQL will be disposed of in accordance with UF Environmental Health and Safety (EH&S) protocols. Instrument waste will be captured in appropriately sized carboys, labeled as to content and placed in the designated satellite accumulation point for pick-up. Vials containing sample will be placed in drums provided by EH&S. Full drums will be placed in the designated satellite accumulation point for pick-up. Waste containing chromium will be placed in the appropriate drum provided by EH&S. When full the drum will be picked up by EH&S. Non-hazardous aqueous solutions may be are poured down the sink drain while flushing with tap water. 9.4 Laboratory Glassware Cleaning General procedures for cleaning and storing laboratory glassware and other labware for various applications are outlined below. 1. Remove all labels using sponge or acetone. 2. Using a scrub brush to clean insides of glassware, stopcocks, etc., wash with hot tap water and a suitable laboratory-grade detergent (Liquinox or equivalent). 3. Rinse thoroughly with hot tap water. 4. Rinse thoroughly with deionized water. 5. Heat at > 105 o C for 3-4 hours or air dry. 6. Store inverted or capped with suitable material or suitable container stopper.

24 Page 24 of CALIBRATION PROCEDURES AND FREQUENCY 10.1 Metals Calibration Protocols ICP-AES (axial instrument) PerkinElmer 5300DV The Inductively Coupled Plasma-Atomic Emission Spectrometer (ICP-AES) is calibrated daily and/or whenever the response of the continuing calibration verification standard (CCV) varies by greater than + 10% from the initial calibration. The initial calibration curve is generated using an instrument blank and a minimum of two standards per analyte. The curve fit is linear, first order. The initial calibration curve must meet the following criteria: 1. The correlation coefficient for the linear regression must be > Instrument Performance Check (IPC) solution must be in the range of %. 3. Accuracy of a daily Initial Calibration Verification Standard (ICV or QC Check Standard) must be in the range of %. 4. Calibration/instrument blank must exhibit a response equal to or below ½ the PQL. 5. A Continuing Calibration Verification Standard (CCV), a method blank (MB), a laboratory control standard (LCS), and an instrument blank (CCB) are analyzed every 10 samples and at the end of the run to insure the continuing validity of the initial calibration. The CCV s must agree within + 10 % of the initial calibration. In addition, the blank must exhibit a response equal to or below ½ the PQL of the analysis components. 6. All samples must be analyzed within the calibration range. All sample concentrations greater than the highest calibration standard must be diluted to read within calibration range. Therefore the linear range for each element is the concentration of the high calibration standard and no sample reported will exceed the high standard concentration. 7. All calibration runs and sample results associated with that calibration curve are recorded on the system hard disk. All data are archived to the UF/IFAS centralized computer server. All records are filed by run date and analyst initials Nutrients/Major Ions Calibration Protocols Segmented Flow Auto Analyzers Alpkem Flow Solution IV (4), Astoria Pacific A2, SEAL AAIII Discrete Analyzers SEAL AQ2+ (2) A calibration curve containing 4 to 7 calibration standards and a blank covering the working range of the instrument is analyzed daily. The curve generated may be first or second order depending on the method and the linear working range. A second source initial calibration verification standard (ICV) is used to verify the accuracy of the calibration curve. In addition, the calibration curve must meet the following criteria: 1. The correlation coefficient for the linear regression must be > Accuracy of the daily ICV must be in the range of % or within the manufacturer s accuracy acceptance range, unless historical data indicate that tighter control limits can be routinely maintained. 3. Calibration/instrument blank must exhibit a response equal to or below ½ the PQL. 4. Continuing Calibration Verification Standard (CCV)), a method blank (MB), a laboratory control standard (LCS), and an instrument blank (CCB) are analyzed every 10 samples and again at the end of the run to insure the continuing validity of the initial calibration. The CCV s must agree within +/-10 % of the response of the initial calibration to be valid. If this check fails, the instrument is re-calibrated. In addition, the calibration/instrument blank, which is analyzed every 10 samples, must exhibit a response equal to or below ½ the PQL.

25 Page 25 of All samples must be analyzed within the calibration range. All sample concentrations greater than the highest calibration standard must be diluted to read within calibration range. Therefore the linear range for each nutrient is the concentration of the high calibration standard and no sample reported will exceed the high standard concentration. 6. Calibration information is recorded on the computer printout of raw data. The calibration runs are also recorded on the system hard drive. All initial calibration raw data is filed by run date and method identification. The sample numbers associated with the calibration curve are recorded on the system hard drive. Applicable calibration run dates are recorded on sample raw data records ph meter Thermo-Orion Model 370 (1) The ph meter is calibrated on a daily need basis using a series of ph buffer solutions. Generally, the ph 4.0, 7.0 and 10.0 buffers are employed for this purpose although other ph ranges may be employed if needed. In addition, the instrument calibration is checked every 10 samples and at the end of each analytical run using a ph 7.0 buffer. The result for this Continuing Calibration Verification Standard (CCV) must agree within ph units of the true value or the instrument must be recalibrated and the samples reanalyzed. Calibration information should be recorded in the ph Run Log Conductivity Meter Markson Model 1054 The conductivity meter is calibrated on a daily use basis using a 720 μs/cm conductivity standard. Calibration reading is recorded in the sample analysis Run Log. The meter is then checked with two other standards to validate higher and lower readings. The instrument calibration is checked after every 10 samples and at the end of each analytical run using the 720 μs/cm conductivity standard. The result for this Continuing Calibration Verification Standard (CCV) must agree within + 10% of the true value or the instrument must be recalibrated and the samples reanalyzed. Calibration information should be recorded in the Run Log Analytical Balances Mettler AE 50 (1), Mettler PL300 (1), Denver XP-600 (1) All analytical balances used by the EWQL are checked for proper calibration and function each morning prior to use using certified Class 1 weights. The calibration check is recorded in the Balance Calibration Log along with the test weights, analyst s name, and the date and time of calibration. In addition to daily calibration checks, all analytical balances are calibrated and certified by an independent company on an annual basis Digestion Blocks MIC 6000, BDC Inc (1), Watlow F4 (2)

26 Page 26 of 45 All digestion block temperatures are checked on a daily use basis. A NIST traceable thermometer is checked against the temperature reported by the instrument. Should the temperature of the thermometer and that of the instrument not match within 5 o, the digestion should be halted, the Laboratory Coordinator notified and corrective action taken Autoclave Tuttnauer-Brinkmann 3850 M The temperature and pressure of the autoclave is checked on a daily use basis and calibrated annually. Autoclave sensitive tape is placed on sample trays being inserted into the autoclave. The time at which the required temperature and pressure is reached is recorded in the analysis Digestion Log. The autoclave tape is checked after digestion is complete to insure that the indicated temperature and pressure were actually achieved Other Equipment In addition to the instruments listed above, the EWQL has a variety of hot plates, vortex mixers, stir plates, drying ovens, pipettes, repipetters, and diluters. All pipettes, repipetters and diluters are calibrated on a quarterly basis. In addition, each is calibrated and certified by an independent company on an annual basis. Calibration data is recorded in the analyst s Pipette Calibration Log. Oven temperatures are checked on a daily use basis using a NIST traceable thermometer Standard Sources, Receipt and Traceability Sources and traceability for the stock standards used in the UF/IFAS ASL are presented in Table The QA Officer is responsible for maintaining the Certificate of Analysis for all stock standards received in the laboratory. In addition, all dilutions made to the stocks must be recorded in the appropriate Standard Preparation Log and must reference the Manufacturer, the Lot Number, the stock expiration date, the date prepared and the expiration date of the diluted solution.

27 Page 27 of 45 Table 10.1 Standard Sources, Receipt and Traceability Analyte, Stock Conc. Sources Shelf Life Storage Traceability Nutrients 1000 mg/l Fisher, Spex, Exaxol, ERA, Ultrascientific Manufacturer s exp. date or 1 year from date of receipt (exp. date can be extended by certifying against an independent ref. check std) Refrigerator, 4 o C Commercial stock standards are dated upon receipt and upon opening. Dilutions of stocks are documented in the pertinent Standard Prep Log. Certificates of Analysis are kept on file by the QA Officer. Metals 1000 mg/l Fisher, Spex, Exaxol, ERA, Ultrascientific Manufacturer s exp. date or 1 year from date of receipt (exp. date can be extended by certifying against an independent ref. check std) Refrigerator, 4 o C Commercial stock standards are dated upon receipt and upon opening. Dilutions of stocks are documented in the pertinent Standard Prep Log. Certificates of Analysis are kept on file by the QA Officer. ph Neat Fisher Manufacturer s exp. date Room temp, lab bench Commercial stock standards and reagents are dated upon receipt and upon opening. Certificates of Analysis are kept on file by the QA Officer. EC 720 μs/cm Markson Manufacturer s exp. date Room temp, lab bench Commercial stock standards and reagents are dated upon receipt and upon opening. Certificates of Analysis are kept on file by the QA Officer.

28 Page 28 of PREVENTATIVE MAINTENANCE Table 11.1 lists the types of analytical equipment utilized to perform routine analyses and the frequency of preventative maintenance tasks performed to ensure data quality. All maintenance or repair to equipment is documented in the pertinent Instrument Maintenance Log. Documentation includes a description of the problem(s), work performed, date and analyst's initials. In the case of instrument failure, sample analysis using that particular instrument will be moved to a back-up or loaner instrument if at all possible. If a loaner or back-up instrument is not available and holding time is not an issue, sample analysis will be completed once the instrument has been repaired. If holding time becomes an issue (i.e. specified holding times will not be met due to instrument failure), the client will be notified and given the option of retrieving their samples for analysis by a different laboratory. Table 11.1 Preventative Maintenance Instrument Analyte Group Routine Maintenance Task Frequency 1 Alpkem Flow Solution IV and RFA 300 Auto analyzers Nutrients Change pump tubing Flush system Clean pump rollers/replace platens Check detector Check light source Check heating bath Bi-Weekly or as needed Daily As needed Daily Daily Daily 2 ph meter ph Clean and refill electrode Change electrode Prior to use Every 6 months or as needed 3 Conductivity Meter EC Clean electrode Change electrode Prior to use As needed 4 ICP Metals Check optical alignment Clean torch assembly Check gases Change pump tubing Check optic profile Check chiller temperature Clean OPI Upon torch replacement When fouled Daily Weekly or as needed Monthly Daily Weekly

29 Page 29 of QUALITY CONTROL CHECKS The types of quality control (QC) samples used by the UF/IFAS ASL and the frequency at which they are performed are listed in Table Target values for each QC sample are defined in terms of either relative precision (P) or accuracy (A) Blind QC Check Sample Analysis The EWQL participates in the bi-annual DOH Performance Evaluation (PE) Study. Samples for these Performance Evaluation studies are provided by ERA (Environmental Resource Associates), a DOH approved provider. The Laboratory Coordinator and QA Officer evaluate the results of these tests and corrective actions (if any are necessary) are completed. In addition to these programs, the laboratory also regularly receives blind QC check samples from its clients Definitions and Methods of Calculations for QC Terms Precision The relative percent difference (RPD) between replicate samples A and B is calculated using the formula: RPD = A - B A + B x Accuracy Percent recoveries are calculated as: Where: % Recovery = SC - UC EV x 100 SC = Concentration in the spiked sample UC = Concentration in the unspiked sample EV = Expected value

30 Page 30 of Standard Deviation and Control Limits A statistical program housed on the LIMS handles the calculations of mean and standard deviation and also calculates warning and control limits for QC elements. QC data are uploaded from electronic QC analysis to the LIMS for storage. The statistical program looks at historical data and at a specified frequency, re-calculates accuracy and precision acceptance limits for a specific sample matrix, instrument type and QC element. Warning and control limits are initially calculated when at least seven or more data points are available. They are updated when at least 7 new data points are obtained or when there are significant changes made to the instrument or analytical method. Method warning limits are set at two standard deviations from the mean and the control limits are set at three standard deviations from the mean. In general, the EWQL utilizes method or laboratory defined warning and control limits for reporting data. Method limits may be modified utilizing statistical information collected over time. The precision and recovery data are used for the diagnosis of analytical problems. The formulae used for the calculation of standard deviation, mean, upper and lower control and warning limits are shown below. (Reference chapter 6 of "Handbook for Analytical Quality Control in Water and Wastewater Laboratories" - EPA 600/ , March 1979). a. Standard deviations are calculated based on the formula: n 2 n 2 i 1 i i 1 i Sp = [ P ( P) / n] / n 1 Where Sp = standard deviation of the population n = total number of points in the population Pi = the value for each point b. The mean is calculated as the average of all points: P = n i = 1 n Pi c. Upper and lower control limits are based on 99% confidence levels UCL = P + t (0.99)Sp LCL = P - t (0.99)Sp d. Upper and lower warning limits for recovery are based on 95% confidence levels UWL = P + t (0.95)Sp LWL = P - t (0.95)Sp

31 Page 31 of 45 Where t (0.99) and t (0.95) are Student s t factors for 99% and 95% confidence, respectively. Because levels of statistical confidence vary with sample size, a fixed level of statistical confidence is employed that approximates 2 and 3 standard deviations. Those control limits are based on requirements specified in various EPA methods and in EPA s Handbook for Analytical Quality Control in Water and Wastewater Laboratories. The statistical program utilizes a Student s t table, setting warning limits at 95% confidence and control limits at 99% confidence. Those Student s t factors correspond approximately to 2 and 3 standard deviations for 7 collected datum points (~1.9 Sp and ~3.1 Sp, respectively). The advantage of using Student s t factors is that control limits are based on known confidence limits regardless of the number of datum points in the population. e. For precision on duplicate samples, the upper warning and control limits are based on a 95% and 99%confidence levels, respectively. UWL = D 3P UCL = D 4P Where D 3 and D 4 are Shewhart factors representing 95% and 99% confidence limits for pairs of duplicate s and P is the mean for the population of precision values (as %RPD measurements) Method Detection Limits (MDL) and Practical Quantitation Limits (PQL) MDL The MDL is defined as the minimum concentration of an analyte that can be measured by the method with 99% confidence of its presence in the sample matrix. The procedure used by the EWQL to establish MDL s if not enough sample sets are analyzed to validate the above procedure involves analyzing 7 replicate standard solutions at a concentration 1 to 5 times the estimated MDL, as per EPA protocol. The standard deviation of the measured replicate concentrations is then determined and the MDL is set to the student s T value (corresponding to the appropriate degrees of freedom; = 0.01) times the calculated standard deviation. MDL s are recalculated/verified annually PQL The PQL is the lowest level of concentration that can be reliably achieved within specified limit of precision and accuracy during routine laboratory operating conditions. The EWQL generally sets the PQL at 3 to 5 times the MDL depending on the method of analysis and the analyte although higher PQL s may be set if the instrument does not provide sufficient sensitivity to determine a PQL standard at the 3-5x MDL level.

32 Page 32 of 45 Table 12.1 Quality Control Checks Analysis Group QC Check Frequency Performed Quality Assurance Target Metals Reagent Blank (ICB, CCB) > 10% of samples ½ PQL Initial Calibration Verification 1x, initial calibration A, ± 10% (ICV) Initial Performance Check 1x, initial calibration A, ± 5% (IPC) Continuing Calibration > 10% of samples A, ± 10% Verification (CCV) Laboratory Control Sample > 10% of samples A, ± 10% (LCS) Method Blank (MB) > 10% of samples ½ PQL Replicate sample > 10% of samples P Matrix Spike > 10% of samples A PQL Check Standard 1x, initial calibration A Nutrients Reagent Blank (ICB, CCB) > 5 % of samples ½ PQL Initial Calibration Verification (ICV) 1x, initial calibration A, ± 10% (digested) A, ± 10% (non-digested) Continuing Calibration > 10% of samples and A, ± 10% Verification (CCV) at end of run Laboratory Control Sample > 10% of samples A, ± 10% (LCS) Method Blank (MB) > 10% of samples ½ PQL Replicate Sample > 10% of samples P Matrix Spike > 10% of samples A PQL Check Standard 1x, initial calibration A ph Reagent Blank (ICB, CCB) 1x, initial calibration Initial Calibration Verification 1x, initial calibration A, ± 0.1 ph units (ICV) Continuing Calibration > 10% of samples A, ± 0.1 ph units Verification (CCV) Laboratory Control Sample > 10% of samples A, ± 10% (LCS) Method Blank (MB) > 10% of samples ½ PQL Replicate Sample > 10% of samples P EC Reagent Blank (ICB, CCB) 1x, initial calibration Initial Calibration Verification 1x, initial calibration A, ± 10% (ICV) Continuing Calibration > 10% of samples A, ± 10% Verification (CCV) Laboratory Control Sample > 10% of samples A, ± 10% (LCS) Method Blank (MB) > 10% of samples ½ PQL Replicate Sample > 10% of samples P

33 Page 33 of DATA REDUCTION, VALIDATION AND REPORTING Raw data from analyzed samples or digestates are first processed by the analyzing instrument s PCbased data system or chromatography software. The analyst who performed the analysis then electronically downloads the results from the analytical instrument via appropriate analytical spreadsheets to the EWQL LIMS. For those instruments not interfaced to a PC, the analyst performing the analysis manually enters the results into the LIMS. The analyst performing the digestion or analysis is also responsible for entering any associated sample preparation/analysis data (amount sample digested, final digestion volume, dilution factors, spiking level/solution used, etc.) into the appropriate logbooks. After sample results have been processed by the LIMS, each analyst is responsible for reviewing his/her data and confirming that the results of each analytical determination have all associated QC measurements and that the acceptance criteria are met and documented according to protocol. Acceptance criteria for data and associated QC samples are given in Table 5.1. Failure to follow the protocols outlined in this QA Manual or QC samples that do not meet acceptance criteria must be brought to the immediate attention of the QA Officer or Laboratory Coordinator or their designee for corrective action. In addition to reviewing his/her own data, it is the analyst s responsibility to check calculations, complete sample preparation, calibration, analysis and instrument logs, and complete all internal custody documentation associated with the analyses that they performed. The QA Officer and/or (or their designee) are responsible for reviewing all processed data packages for completion and correctness adding data qualifiers (Table 13.1) as required prior to authorizing release of the results to the client. In addition, it is the QA Officer s responsibility to review all logbooks (run logs, digestion logs, instrument maintenance logs, refrigerator/heating block logs, chain of custody logs, etc.) on a regular basis. Upon completion of analysis for a particular parameter for a set of samples, a hard copy report (known as a batch ) is produced. The data and QC included in the batch is reviewed and signed off on by the analyst involved in its production and hard copies of all raw data are attached. The batch is sent to the QA Officer and/or Laboratory Coordinator for final review. The batch is then finalized and the data locked in the LIMS. An electronic copy of the data is sent to the client by the QA Officer and/or Laboratory Coordinator. The finalization date and client date is documented in the LIMS by the QA Officer and/or Laboratory Coordinator. No further corrections can be made to that data once it is finalized and sent to the client without authorization from the Laboratory Coordinator (or designee). Submission of a corrective action form may be required and the client will be notified by the Laboratory Coordinator (or designee) of any changes made after data finalization and the cause of the change. The hard-copy of the batch and all associated documentation is filed until all requested parameters are complete. Once all requested parameters for a particular set of samples are completed and all batches are finalized, the batches are consolidated and a final report for all data (known as a set ) is generated. The set (including all batch information) is reviewed for a final time by the QA Officer and/or the Laboratory Coordinator (or designee) and upon approval, the completed data package is finalized and a copy ed to the client. The completed hard-copy data package including all supporting documentation, raw data, etc is maintained on file at the EWQL for 5 years in a locked filing area. Reports are filed by the EWQL assigned set number. EWQL does not release data to second or third parties without the written permission of the client.

34 Page 34 of 45 In the event that the EWQL should go out of business or should have ownership changed for any reason, possession of all hard-copy data and all electronic copies and archived back-ups of data reports will be given over to the Chairman of the Department of Soil and Water Science whose responsibility it will be to ensure that the data in all of its forms are released to the proper personnel for each client or are disposed of in whatever manner the client requests.

35 Page 35 of 45 Table Data Qualifier Codes I J The reported value is greater than or equal to the laboratory method detection limit but less than the laboratory practical quantitation limit. Estimated value. A J value shall be accompanied by a detailed explanation to justify the reason(s) for designating the value as estimated. Where possible, the organization shall report whether the actual value is estimated to be less than or greater than the reported value. A J value shall not be used as a substitute for K, L, M, T, V, or Y, however, if additional reasons exist for identifying the value as an estimate (e.g., matrix spiked failed to meet acceptance criteria), the J code may be added to a K, L, M, T, V, or Y. Examples of situations in which a J code must be reported include: instances where a quality control item associated with the reported value failed to meet the established quality control criteria (the specific failure must be identified); instances when the sample matrix interfered with the ability to make any accurate determination; instances when data are questionable because of improper laboratory or field protocols (e.g., composite sample was collected instead of a grab sample); instances when the analyte was detected at or above the method detection limit in a blank other than the method blank (such as calibration blank or field-generated blanks and the value of 10 times the blank value was equal to or greater than the associated sample value); or instances when the field or laboratory calibrations or calibration verifications did not meet calibration acceptance criteria. K Off-scale low. Actual value is known to be less than the value given. This code shall be used if: L 1. The value is less than the lowest calibration standard and the calibration curve is known to be non-linear; or 2. The value is known to be less than the reported value based on sample size, dilution. This code shall not be used to report values that are less than the laboratory practical quantitation limit or laboratory method detection limit. Off-scale high. Actual value is known to be greater than value given. To be used when the concentration of the analyte is above the acceptable level for quantitation (exceeds the linear range or highest calibration standard) and the calibration curve is known to exhibit a negative deflection. Q Sample held beyond the accepted holding time. This code shall be used if the value is derived from a sample that was prepared or analyzed after the approved holding time restrictions for sample preparation or analysis. T Value reported is less than the laboratory method detection limit. The value is reported for informational purposes only and shall not be used in statistical analysis. V Indicates that the analyte was detected in both the sample and the associated method blank. Note: the value in the blank shall not be subtracted from associated samples. Y The laboratory analysis was from an improperly preserved sample. The data may not be accurate.

36 Page 36 of CORRECTIVE ACTION 14.1 In-House Corrective Actions Corrective actions are initiated whenever there is a significant deviation from the protocols outlined in this QA Manual or the Laboratory SOP s. In-house corrective actions may be initiated by either the bench analyst, the QA Officer or the Laboratory Coordinator. It is the responsibility of the QA Officer to initiate the proper forms to document the corrective action, to follow up on the corrective action to insure implementation of the actions to be taken and to maintain appropriate files documenting any corrective actions taken. In addition, corrective actions may also be initiated based on findings from certain certifying authority audits (DOH or DEP QA Officer/Auditor) or when cause is found during internal or external performance evaluation studies or method audits. If necessary, changes to inhouse protocols and/or procedures are documented using the EWQL s in-house corrective action form. In addition, the date on which the change took place is documented in the QA/QC Changes Logbook along with the actions taken and the authorizing entity. Corrective action in the laboratory may occur prior to, during and after initial analyses. A number of conditions such as broken sample containers, low/high ph readings, potentially high concentration samples may be identified during sample log-in or just prior to analysis. The SOPs specify conditions during or after analysis that may automatically trigger corrective action or optional procedures. These conditions may include dilution of samples, additional sample extract cleanup, and automatic reanalysis when certain QC criteria are not met. Any QC sample result outside of acceptance limits requires corrective action. Once the problem has been identified and addressed, corrective action may include the reanalysis of samples, or appropriately qualifying the results. If a quality control measure is found to be out of control, and the data is to be reported, all samples associated with the failed quality control measure are reported with the appropriate data qualifier(s). Sample results may also be qualified when holding times are not met, improper sample containers and/or preservatives or used or when other deviations from laboratory standard practices and procedures occur. The analyst must address in writing any QC sample failures. The analyst comments concerning the QC failure must be reviewed by the QA Officer and/or Laboratory Coordinator (or their designee) and the comments must be included with the data. Samples that were received and accepted by the EWQL without proper preservation must be documented and flagged on the sample chain of custody report. All other significant observations that do not conform to accepted practices or policies are documented and reported along with analytical results. Documentation may include corrective action forms, letters, interoffice memorandum or appendices to analytical reports. Responses to routine QC failures identified prior to sample analysis and data reduction are outlined in the EWQL s Standard Operating Procedures and are generally not documented These include such items as initial calibration failure, initial or continuing calibration verification failure, and blank failure. Acceptance criteria for these QC types are outlined in both Table 11.1 and in the Standard Operating Procedures. In cases where a documented corrective action is necessary, the following protocols are followed: 1. The appropriate personnel are notified that a corrective action has been initiated. If an analyst is initiating a corrective action, they should report their findings to the QA Officer and the Laboratory

37 Page 37 of 45 Coordinator for further review. It is the Laboratory Coordinator s responsibility to notify all other affected parties including analysts, clients and the Laboratory Director. 2. All pertinent records should be examined to determine extent of problem. 3. Determine the appropriate corrective action to be taken. Initiate and document the actions to be taken to correct the situation and the personnel responsible for implementing the action. 4. Follow up assessment by the QA Officer to determine the effectiveness of the implemented corrective actions. Corrective actions are performed prior to release of the data from the laboratory. The corrective action will be documented in both a corrective action log (signed by analyst, Laboratory Coordinator, and QA Officer), and in the narrative in the data report Client Complaints All client complaints, concerns, special requests, etc., whether verbal or written, shall be referred to the Laboratory Coordinator for assessment and response. If the client contact is by phone, the call shall be logged into the Laboratory Coordinator s phone log along with pertinent information and response, if made at that time. If the client contact is by (via either soilslab@ifas.ufl.edu, arl@ifas.ufl.edu, or through the Laboratory Coordinator s personal account), the response shall also be made by with a CC to the lab director and/or department chair. All s involved in the exchange will be archived to the computer s hard drive and backed up electronically on a periodic basis. If contact is in person, a written summary of the meeting shall be logged into the Laboratory Coordinator s personal log along with the corresponding response and/or follow-up information. A copy shall also be provided to the director, department chair and/or client upon written request. If the Laboratory Coordinator is unable to resolve the issue with the client, the lab director shall be notified and the client referred to him/her. All documentation and/or a summary of events shall be provided to the director to aid in the response to the client.

38 Page 38 of PERFORMANCE AND SYSTEM AUDITS The EWQL conducts internal system and performance audits on select certified laboratory methodologies on an annual basis. These internal audit procedures follow the general guidelines listed below. In addition, external system assessments are conducted by a representative of DOH at regular intervals in compliance with the NELAP regulations. The EWQL will submit to any assessments conducted by DOH/DEP organizational units necessary to maintain the EWQL s DEP/DOH NELAP certification Internal System Audits Selected systems within the EWQL will be audited annually. The QA Officer is responsible for conducting all internal audits and providing the findings of these audits to the Laboratory Coordinator and the Director. Audits will consist of the random selection of a previously reported sample project, tracking of these samples through the system, evaluation of sample results, and a follow-up laboratory audit. System components to be audited will include, but are not limited to: All documentation associated with sample and data handling including mechanisms employed to track sample data and documentation for any particular sample point/set; The use and proper execution of the established and approved EWQL procedures as outlined in the EWQL QA Manual and current EWQL Standard Operating Procedures; Sample and data handling activities including sample log-in, chain of custody, laboratory tracking, and sample/waste disposal; Documentation of sample preparations, analyses, method validations (calibrations and QC); Data reduction, validation and reporting; Preventive maintenance and repair procedures; Standard and reagent preparations and storage; Container and laboratory glassware cleaning/decontamination; QC management practices and assessment of analytical precision, accuracy and sensitivity; Deficiency lists and associated corrective action orders.

39 Page 39 of 45 Figure 15.1 Example of an In-House Laboratory Audit Check List Sample Log-In/Receipt Section 1. Are up-to-date SOPs available? 2. Are refrigerator temperature logs for refrigerators up-to-date? Are thermometers calibrated and traceable? Are refrigerator temperatures set correctly? 3. Is sample preservation checked and documented during sample receipt process? 4. Is the sample check-in area clean and well maintained? 5. Is proper chain-of -custody maintained and documented? Inorganic Section 1. Are standards and samples stored separately? 2. Are std. prep logs, run logs, maintenance logs, etc. adequate and up-to-date? 3. Are logbooks easily traceable and stored for easy retrieval? 4. Are current up-to-date SOPs readily available and being used? 5. Are instrument maintenance logs properly maintained? 6. Are refrigerator temperature logs up to date? 7. Are balances, thermometers and auto-pipettes (if used) calibrated on a regular basis? 8. Do technicians and analysts seem to understand the analytical concepts being utilized in the performance of their duties? Are analysts familiar with the methodologies and QA/QC requirements concerning the performance of their daily duties? 9. Are data calculations and data review being carried out correctly and sufficiently? 10. Are raw data records properly and adequately maintained and stored for easy retrieval? 11. Are calibration records adequate and up-to date? Are instruments being calibrated and calibration verified at appropriate time intervals?

40 Page 40 of Internal Performance Audits Internal performance audits are carried out annually by the QA Officer to insure that the methods performed at the EWQL are in compliance with National standards and are capable of producing data within the acceptance criteria for National Performance Evaluation Samples. In addition, a special performance audit may be initiated if there is an observed or suspected problem with specific system or method. Performance audits consist of submission and analysis of two sets of duplicate QC samples (obtained from ERA, SPEX, Ultra or other commercial PE sample provider). Samples are prepared by the QA Officer and analyzed as routine samples by the EWQL. Results are submitted to the QA Officer and Laboratory Coordinator for examination. The QA Officer will maintain copies of the results along within any deficiencies found and corrective actions initiated as a result of failures. Reports will be available for examination by external auditing agencies if requested External Performance Audits The EWQL will submit to any external performance audits conducted by DOH/DEP or their authorized organizational units. In compliance with the new NELAP regulations, the EWQL will submit 2 initial Performance Evaluation (PE) samples prior to DOH certification and will submit PE sample results annually after receiving certification or as required by DOH/DEP in order to maintain the EWQL s DEP/DOH NELAP certification Annual Management Review The ASL Laboratory Director shall perform a Management Review of the Analytical Research Laboratory s policies, procedures and Quality Assurance System on an annual basis. This review shall include: Review of reports from supervisory personnel including the ASL Technical Director (Lab Coordinator) and QA Officer. Review of findings and outcomes from internal audits. Review of findings and outcomes from external audits. Review of outcomes from Performance Evaluations studies or other inter-laboratory testing. Assessment of changes in laboratory workloads. Review of internal corrective actions and/or preventative actions. Review of client/laboratory interactions and feedback. Review of current Quality Assurance Plan (QAP) and Standard Operating Procedures (SOP s) Review of analyst training records including laboratory data integrity training.

41 Page 41 of 45 Following the Management Review, the Laboratory Director will meet with the Laboratory Coordinator and QA Officer to discuss any findings, deficiencies, proposed changes to policy, corrective actions, etc.

42 Page 42 of Quality Assurance Reports The EWQL LIMS currently generates quality assurance reports as an appendix to each analytical report. The quality assurance reports summarize the batch quality assurance results associated with the reported data. This report undergoes several levels of review including analyst review, QA review and/or coordinator review. Any deviations above or below the accepted control limit criteria presented in this QA manual are noted and an analyst comment is required along with a corrective action form if necessary. In addition to the quality assurance reports associated with each data report, the QA Officer is also responsible for generating control charts on a regular basis and for updating MDL s and PQL s annually. A brief summary of performance and system audits is prepared by the QA Officer after each in-house audit or external audit and is submitted to the management for review and action or approval. Along with these reports, The QA Officer also submits a summary of all corrective actions taken over that period and the outcome of those actions.

43 Page 43 of Estimation of Uncertainty of Measurements Uncertainty is defined as the parameter associated with the result of a measurement that characterizes the dispersion of values that could reasonably be attributed to that measurement (Heinbaugh, AIHA Guidelines for Measurement of Uncertainty, 2005) Uncertainties allow the client to properly interpret data in a report and are used in determining how good a test result actual is. It is generally accepted that there are two major contributors to uncertainty. The first is termed Type A and includes values that may be determined statistically (aka random contributors ). The second is the Type B contributor and are those that can not be determined by statistical means. Type A uncertainties may include but are not limited to: Uncertainty in repeatability Uncertainty due to instrument drift Uncertainty due to instrument non-linearity Uncertainty due to rounding of instrument readings Uncertainty of volumes associated with Class A glassware Uncertainty of volumes associated with glass pipettes and/or Eppendorf pipettes Uncertainty associated with temperature/volume changes Uncertainty associated with analytical balance weighing Type B uncertainties may include but are not limited to: Uncertainty associated with chemical purity of reference materials and standards Uncertainty in atomic weights Once both Type A and Type B errors have been determined, they may be combined using the technique of root-mean square to obtain an estimate of total uncertainty: µ o = µ i 2 However, in most cases for chemical analyses, the Type B contribution is usually insignificant and may be ignored. Given this assumption, then only error associated with Type A uncertainties need be considered. Uncertainty resulting from Type A contributors can be estimated using the overall uncertainty in the entire analytical procedure. This can be determined by measuring the dispersion of values obtained from a known certified reference standard using the proper number of data points (20-30 points is typically recommended). Both bias (average % yield 100) and precision (standard deviation of % yield) can be determined and reported for any given analytical technique. Due to the nature of the services provided by the EWQL, estimating a numerical value for uncertainties of measurement associated with sampling is not possible. The EWQL does not provide its own

44 Page 44 of 45 sampling group and how the sample is handled prior to its arrival at the lab is an unknown quantity. The client should be aware that the EWQL s estimate of uncertainty does not include any error associated with sampling handling or collection prior to that sample s arrival at the laboratory. Estimates of uncertainty will be updated by the lab on an annual basis (See Table 5.1). Final data package reports to the client will reference how to access and obtain the most current estimates of uncertainty for the parameter of interest.

45 Page 45 of APPENDIX Selected References Definition and Procedure for the Determination of the Method Detection Limit- Revision 1.11, 40 CFR Part 135, Appendix B. Methods for Chemical Analysis of Water and Wastes, USEPA Office of Research and Development, Rev. 2, 8/93. Cincinnati, OH, EPA 600/ Methods for Determination of Inorganic Substances in Environmental Samples, USEPA Office of Research and Development, 8/93. Cincinnati, OH, EPA 600/R-93/100. Methods for Determination of Metals in Environmental Samples, USEPA Office of Research and Development, Supp. 1, 5/94. Cincinnati, OH, EPA 600/R-94/111. Standard Methods for the Examination of Water and Wastewater (designated SM), 18th Edition, American Public Health Association, Washington, DC, TNI Standard. Environmental Laboratory Sector. Vol.1. The NELAC Institute, Weatherford, Texas

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