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Home My WebLink About25c_NCS000250_NCDOT_Metals Monitoring QAPP_September 2018_DRAFTQuality Assurance Project Plan for Stormwater Metals Monitoring (DRAFT) September 2018 PREPARED FOR NC Department of Transportation Hydraulics Unit 1590 Mail Service Center Raleigh, NC 27699 Tel 919-707-6700 PREPARED BY Tetra Tech One Park Drive, Suite 200 P.O. Box 14409 Research Triangle Park, NC 27709 Tel 919-485-8278 Fax 919-485-8280 tetratech.com NCDOT Highway Stormwater PROGRAM (This page was intentionally left blank.) Quality Assurance Project Plan for Stormwater Metals Monitoring September 2018 Plan approvals: Andy McDaniel, PE HSP Program Manager Signature Date Ryan Mullins, PE Research Program Manager Signature Date Name Title Signature Date Name Title Signature Date Name Title Signature Date (This page was intentionally left blank.) Highway storms. PROGR;..V TABLE OF CONTENTS QAPP for Stormwater Metals Monitoring (DRAFT) 1.0 INTRODUCTION..................................................................................................................................... 6 1.1 Project Background.......................................................................................................................... 6 1.2 Project Scope................................................................................................................................... 7 2.0 PROJECT ORGANIZATION.................................................................................................................. 8 2.1 Project Team.................................................................................................................................... 8 2.2 Quality Oversight..............................................................................................................................8 3.0 DATA QUALITY OBJECTIVES............................................................................................................. 9 3.1 Precision........................................................................................................................................... 9 3.2 Bias................................................................................................................................................. 10 3.3 Accuracy......................................................................................................................................... 10 3.4 Sensitivity........................................................................................................................................ 10 3.5 Representativeness........................................................................................................................ 10 3.6 Comparability.................................................................................................................................. 10 3.7 Completeness................................................................................................................................. 11 4.0 TRAINING AND SAFETY REQUIREMENTS....................................................................................... 12 4.1 Training...........................................................................................................................................12 4.2 Field Safety..................................................................................................................................... 12 5.0 MONITORING EXPERIMENTAL DESIGN...........................................................................................14 5.1 Sampling Site Selection.................................................................................................................. 14 5.2 Parameters of Concern.................................................................................................................. 14 5.3 Representative Storms................................................................................................................... 14 5.4 Sampling Size................................................................................................................................. 15 6.0 SAMPLING METHODS........................................................................................................................ 16 6.1 Water Quality Field Sampling Methods.......................................................................................... 16 6.1.1 Regulatory Considerations.................................................................................................... 16 6.1.2 Dissolved Metals Sampling Procedure................................................................................. 16 6.2 Sample Handling and Custody.......................................................................................................20 6.2.1 Sample Labeling................................................................................................................... 20 6.2.2 Sample Handling...................................................................................................................20 Highway Storms P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) 6.2.3 Sample Transport and Receipt............................................................................................. 21 7.0 ANALYTICAL METHODS.................................................................................................................... 22 8.0 QUALITY CONTROL............................................................................................................................23 8.1 Field Quality Control Procedures................................................................................................... 23 8.1.1 Field Instrument Quality Control........................................................................................... 23 8.1.2 Field Form/Data Sheet Quality Control................................................................................. 23 8.1.3 Field Quality Control Samples.............................................................................................. 23 8.2 Laboratory Quality Control Procedures.......................................................................................... 24 8.2.1 Laboratory Quality Control Samples.....................................................................................25 9.0 EQUIPMENT TESTING, INSPECTION, AND MAINTENANCE..........................................................27 10.0 DATA MANAGEMENT.......................................................................................................................28 10.1 Periodic Reporting........................................................................................................................ 28 10.2 Deliverables..................................................................................................................................28 10.3 Record Retention..........................................................................................................................28 11.0 DATA ANALYSIS AND PRESENTATION.........................................................................................29 11.1 Data Validation............................................................................................................................. 29 11.2 Handling of Censored Data.......................................................................................................... 29 11.3 Identification of Outliers................................................................................................................29 11.4 Data Presentation.........................................................................................................................30 12.0 DATA DISSEMINATION..................................................................................................................... 31 REFERENCES............................................................................................................................................ 32 APPENDIX A: EXAMPLE HEALTH & SAFETY PLAN............................................................................. 33 APPENDIX B: EXAMPLE CHAIN -OF -CUSTODY FORM......................................................................... 34 LIST OF TABLES Table 2-1. Research project management team ............................................ Table 5-1. Parameters of concern for stormwater metals monitoring ............ Table 8-1. Data validation criteria for field quality control samples ................ Table 8-2. Data validation criteria for laboratory quality control samples....... .8 14 24 26 Highway t P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) LIST OF FIGURES Figure 1-1. Key components of NCDOT's programmatic strategy for metals..............................................7 Figure 6-1. Example of a bioswale equipped for autsampling...................................................................17 Figure 6-2. Two ISCO 6712 autosamplers contained within a sampler enclosure....................................18 Figure 6-3. Teledyne ISCO 6712 automatic water quality sampler equipped with 10-liter carboy ............ 18 Figure 6-4. A standard rain gage (left) and tipping -bucket rain gage (right) for rainfall measurement ...... 19 Figure 6-5. Weir box of a stormwater BMP equipped with ISCO 730 Bubbler Module Flowmeter ...........19 Highway storms rsacw..�. DOCUMENT HISTORY 1.0 September 2018 Initial draft QAPP for Stormwater Metals Monitoring (DRAFT) iv Highway ok t P4OGR;..V. ACRONYMS & ABBREVIATIONS QAPP for Stormwater Metals Monitoring (DRAFT) BMP Best management practice CFR Code of Federal Regulations COC Chain -of -custody CWA Clean Water Act DEQ (North Carolina) Department of Environmental Quality DWR (North Carolina) Division of Water Resources EMC Event mean concentration DQO Data quality objective HASP Health and Safety Plan HSP Highway Stormwater Program LCS Laboratory control sample MDL Method detection limit MQO Measurement quality objective MS Matrix spike MSD Matrix spike duplicate NCDOT North Carolina Department of Transportation NOAA National Oceanic and Atmospheric Association NPDES National Pollutant Discharge Elimination System PCSP Post -Construction Stormwater Program PI Principal Investigator POC Pollutant (or Parameter) of Concern PPE Personal protective equipment PQL Practical quantitation limit QA Quality Assurance QAPP Quality Assurance Project Plan QC Quality Control QO Quality Officer QPR Quarterly progress report RL Reporting limit RPD Relative percent difference SOP Standard operating procedure STORMDATA (NCDOT) Stormwater Research Monitoring Database TMDL Total maximum daily load TN Total nitrogen TP Total phosphorus USEPA United States Environmental Protection Agency (EPA) USGS United States Geological Survey v Highway t ' P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) 1.1 PROJECT BACKGROUND The Highway Stormwater Program (HSP) is a statewide initiative of the North Carolina Department of Transportation (NCDOT) designed to protect and enhance stormwater quality while fulfilling the mission of providing and supporting a safe and integrated transportation system. In 2015 new water quality standards for metals became effective in North Carolina. Changes include alterations to both the numeric and narrative criteria including a shift in the expression of criteria to the dissolved fraction instead of total recoverable metals. In response to these changes, the HSP conducted a review of North Carolina's revised water quality standards for metals as part of compliance with its National Pollutant Discharge Elimination System (NPDES) permit. The HSP management objective related to these new standards is to develop a programmatic strategy for compliance with the NPDES permit as it relates to metals. Program areas informed by this strategy include the Post -Construction Stormwater Program (PCSP), the Retrofit Program, the Total Maximum Daily Load (TMDL) Program, and the Research Program. NCDOT intends for this strategy to represent a proactive step in assessing metals sources, monitoring and managing stormwater metals discharges, and contributing useful information for the agency and its partners (e.g., North Carolina Department of Environmental Quality (DEQ) and United States Geological Survey (USGS)). The strategy was developed in phases, with the first phase involving the compilation of background information on best practices for stormwater metals monitoring and assessment, and the second phase involving design and execution of a dissolved metals monitoring field study. Figure L-11F4gufe44 highlights key elements of the programmatic strategy for metals. Cei Highway t ' P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) • Investigation and report on NCDEQ Divison of Water Resources (DWR) metals monitoring program. • Research of TMDL calculation approaches for metals (with emphasis on EPA Region 4). • Development of annotated outline for a metals monitoring QAPP. • Development of detailed stormwater metals sampling plan. • Preparation of a white paper summarizing current policy and science related to zinc in transportation -related runoff. • Implementation of metals sampling plan in a field study. • Metals data analysis and report. • Development of a QAPP for dissolved metals monitoring. Figure 1-1. Key components of NCDOT's programmatic strategy for metals This stormwater metals monitoring QAPP represents the culmination of several years of proactive planning and research by NCDOT. This document leverages the efforts outlined in Figure 1-1 4 and is intended to serve as a template for future stormwater dissolved metals monitoring efforts by NCDOT and its partners. 1.2 PROJECT SCOPE NCDOT would like to be well-informed on best practices for conducting stormwater monitoring for metals to address criteria expressed as the dissolved fraction. To help achieve this goal, this QAPP was developed to serve as a template for future dissolved metals monitoring efforts. An important component of this QAPP is a discussion of the need for using "clean" sampling techniques and other challenges related to dissolved metals analysis such as sample preservation and holding times. This QAPP is organized into 12 primary sections and follows the general format of the HSP Research Program QAPP (NCDOT, 2013), including references to specific sections of the Program QAPP where applicable. This format is consistent with industry standards and the expectations of the NCDEQ Division of Water Resources (DWR) and United States Environmental Protection Agency (USEPA). The primary objective of this QAPP is to ensure consistent application of quality principles in the collection, handling, laboratory analysis, and data evaluation of dissolved metals samples. This document sets requirements to facilitate consistency among projects to allow comparison of results across studies. Following the implementation of this QAPP, all researchers performing research projects involving dissolved metals sample collection will be required to comply with the requirements herein. 7 Highway & torte PROGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) 2.1 PROJECT TEAM Table 2-lT�:e2=1 lists key personnel within the HSP organization. This table should be updated upon initiation of each new research project to include key personnel within the organization conducting research. Table 2-1. Research project management team Andy McDaniel, PE HSP Program Manager Ryan Mullins, PE Research Program Manager Quality Assurance Officer Project Manager Sampling Coordinator Sampling Field Lead Data Manager/Analyst Field Technician Field Technician 2.2 QUALITY OVERSIGHT The principal responsibility for oversight rests on the Principal Investigator (PI) for each individual project. NCDOT recommends a member on the project team be designated as a Quality Officer (QO) to coordinate compliance with this QAPP as well as providing quality oversight and training to the project team. The QO may be the PI, a staff member, or a graduate student, as appropriate to the specific project. To assist the Research Coordinator with ensuring compliance with the QAPP, the PI or QO for each research project shall be responsible for providing the following information: • Project QAPP: at the start of each research project, the researchers shall provide a project QAPP using this document as a template. • Quarterly Progress Reports (QPR): researchers shall submit quarterly project reports describing the following: status of the project, potential or ongoing issues, resources needed for continued project success, whether project is meeting data quality objectives (DQOs), and any proposed modifications to the monitoring approach, site, or design to address any data quality issues. QPRs shall include the cumulative dataset to date. • Draft and Final Reports: the draft and final reports for every research project shall include the project QAPP (as an appendix) and shall discuss DQOs and compliance with the QAPP. All data Highway t P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) are required to be submitted using the Stormwater Research Monitoring Database (STORMDATA) template (provided in Appendix B of the HSP Program QAPP). Per Section 3 of the HSP Program QAPP, Data Quality Objectives (DQOs) refer to the qualitative and quantitative objectives of the project with respect to the project purpose and scope, quality control, performance measures, and decision framework. All new research projects shall be required to establish DQOs during project initiation, to be presented at the project kickoff meeting or shortly after that, prior to initiation of any activities under the project. The overarching DQOs for NCDOT dissolved metals monitoring projects are as follows: 1. The data are generated according to set criteria and procedures for field sampling, sample handling and processing, laboratory analysis, and record keeping. 2. The data are representative of the monitoring site and are of a known precision, bias, and accuracy. 3. Data reporting and analytical sensitivity are clearly established and adequate for stormwater management program decisions and endpoints. To ensure that the project objectives are achieved, the quality of the data collected will be measured at each stage of data collection and analysis. Data quality will be assessed by determining the following characteristics of the data: • Precision • Bias • Accuracy • Sensitivity (detection and reporting limits) • Representativeness • Comparability • Completeness Detailed descriptions of these data quality indicators and specific limits for quality control (QC) samples are discussed in Section 8.0 (Quality Control). 3.1 PRECISION Precision is measure of the variability in the results of replicate measurements due to random error that is introduced during sample collection and processing in the field and the laboratory analytical procedure. Simply stated, precision expresses the degree to which sample results are repeatable. For dissolved metals sampling, evaluation of precision will be based on evaluation of field duplicates, laboratory duplicates, and matrix spike duplicates. Differences between results for these QC samples must be within the criteria presented in Section 8.0 (Quality Control) to meet measurement quality objectives (MQOs). 0 Highway t ' P4OGR;..V. 3.2 BIAS QAPP for Stormwater Metals Monitoring (DRAFT) Bias is a measure of the difference, due to systematic error, between an analytical result and the true value of an analyte. Example sources of bias may include sampling location (i.e., all stations located at road crossings, bridges, etc.) or timing of sampling (i.e., sampling performed only on business days, during daylight hours, etc.). Bias will be evaluated by analyzing field blanks, method blanks, spike blanks, matrix spikes, and laboratory control samples. Results for these QC samples must be within the criteria presented in Section 8.0 (Quality Control) to meet MQOs. 3.3 ACCURACY Accuracy is an estimate of the difference between a "true" or reference value and the associated measured value. The accuracy of a result is affected by both systematic errors (i.e., bias) and random errors (i.e., precision). Accuracy of the field measurements will be assessed by duplicate measurements. Accuracy of the analytical results will be evaluated using field blanks, method blanks, matrix spikes, and/or laboratory control samples. 3.4 SENSITIVITY Sensitivity is the measure of the concentration at which an analytical method can positively identify and report analytical results. The sensitivity of a method is commonly called the "detection limit." There are typically multiple limits used in analytical analyses and reporting, including: • Method detection limit (MDL) • Reporting limit (RL) or practical quantitation limit (PQL) The method detection limit is the minimum concentration of a substance that can be measured and reported with 99% confidence that the analyte concentration is greater than zero. The reporting limit refers to a limit established by the laboratory below which data are not reported and is the practical quantification limit established by the laboratory, not the method detection limit. 3.5 REPRESENTATIVENESS Representativeness is a qualitative measure of the degree to which sample data represent characteristic environmental conditions or, more specifically, site conditions. Representativeness of samples can be evaluated by analysis of field duplicates. To ensure representativeness, stormwater sampling must focus upon representative (or average) storm events. Refer to Section 5.3 (Representative Storms) for more information. 3.6 COMPARABILITY Comparability is a qualitative parameter expressing the confidence with which one data set can be compared with another. Comparability is addressed through use of standard techniques to collect and analyze representative samples, along with standardized data verification and reporting procedures 10 Highway t P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) described in this QAPP. Changes or updates to analytical methods and sampling techniques midway into the project must be tested, validated, and shown to be equivalent to existing methods. This validation must be approved by the Project Manager and QA Officer before being implemented. 3.7 COMPLETENESS Completeness is defined as the total number of samples analyzed for which acceptable analytical data are generated, compared to the total number of samples submitted for analysis. Sampling according to storm criteria, along with adherence to standardized sampling and testing protocols outlined in this QAPP, will aid in providing a complete set of data for this project. The samples from each event should produce at least 95 percent acceptable data under the QC conditions described in Section 8.0 of this QAPP. The goal for completeness also includes a minimum number of storms sampled at each sampling location; this is discussed in Section 5.4 (Sampling Size). Completeness will be calculated by dividing the number of valid values by the total number of values. Valid sample data consists of unflagged data and estimated data that has been assigned a "J" qualifier. A qualitative assessment will be made as to which "J" flagged data may need to be excluded from this calculation prior to annual reporting. If less than 95 percent of the samples submitted to the laboratory are judged to be valid, then additional samples will be collected until at least 95 percent are judged to be valid. See Section 8.0 (Quality Control) for additional information on data validation criteria. 11 Highway t ' P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) 4.1 TRAINING All staff performing field sampling shall receive training to ensure that the work is conducted correctly and safely. At a minimum, all field staff shall have demonstrated experience with the field guidelines and sample collection standard operating procedures (SOPS) included in this QAPP. Field staff shall demonstrate to the Field Lead their ability to properly operate the required sampling equipment. The Field Lead is responsible for assessing whether each field staff member is adequately trained and prepared to operate sampling equipment and collect samples. All work shall be performed under the supervision of a Field Sampling Coordinator experienced with the protocols described in the SOP. A copy of the safety training records will be maintained internally in the sampling project file by all entities contracted to perform field sampling. The project QA Officer is responsible for overseeing all training. Refer to Section 4 (Training Requirements) of the NCDOT Highway Stormwater Program QAPP (NCDOT, 2013) for additional guidance regarding training requirements. 4.2 FIELD SAFETY Prior to initiation of sampling, a Health and Safety Plan (HASP) shall be completed that includes, at minimum, the following information: • Hierarchy of responsibility for ensuring field safety and for incident reporting; • Health and safety requirements; • A field audit checklist and daily safety meeting form; • Locations, hours of operation, and phone numbers of nearest hospitals and urgent care centers; • Emergency contact information (primary and secondary) for each member of the field crew; and • Incident reporting procedure. An example HASP is included in Appendix A. Prior to initiating field sampling activities field crews will also review the project HASP as well as the field safety guidelines provided in the NCDOT Highway Stormwater Program QAPP (NCDOT, 2013). Appropriate personal protective equipment (PPE) shall be worn at all times while conducting field sampling activities including high -visibility safety vests and field boots. At the initiation of mobilization for each sampling event, the field team leader shall review HASP with field team members and complete the daily HASP checklist. Stormwater monitoring staff shall receive training for working in wet, cold, and poor -visibility conditions. During sampling, field staff may be exposed to traffic hazards and slippery conditions. It is an NCDOT requirement that field staff receive appropriate work zone safety training. Per the NCDOT Highway Stormwater Program QAPP, "[n]o individual shall engage in confined space entry at any time while performing NCDOT sponsored monitoring activities." However, if the Project Manager determines 12 Highway t P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) confined space entry to be necessary to successfully conduct monitoring, then they shall meet with NCDOT representatives to receive approval and ensure field staff receive proper training prior to conducting any work in confined spaces. 13 Highway t ' P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) 5.1 SAMPLING SITE SELECTION Field monitoring locations shall be in areas where traffic load and right-of-way width do not present significant risk exposure to researchers and equipment. Additionally, field sites selected for monitoring must allow sufficient space for sampling instrumentation and equipment installation and for safe sample collection. Refer to Section 5.2 (Sampling Site Selection) of the NCDOT Highway Stormwater Program QAPP (NCDOT, 2013) for additional site selection considerations. 5.2 PARAMETERS OF CONCERN Typical parameters of concern (POCs) for stormwater metals monitoring, accepted analytical methods (per USEPA), and standard reporting limits are summarized in Table 5-1T�;e5=1. Project -specific POCs should be determined at project initiation and be agreed upon by NCDOT and the project team. Table 5-1. Parameters of concern for stormwater metals monitoring EPA Method 200.7, Revision 4.4 (USEPA, 1994a) EPA Method 200.8, Revision 5.4 (USEPA, 1994b) EPA Method 200.9, Revision 2.2 (USEPA, 1994c) 5.3 REPRESENTATIVE STORMS Per the NCDOT Highway Stormwater Program QAPP (NCDOT, 2013): "[u]nless explicitly requested and approved by NCDOT, a representative storm must yield at least 0.1 inch of precipitation; must be preceded by at least 72 hours with less than 0.1 inch of precipitation; and, if possible, the total precipitation and duration should be within 50% of the average or median storm event for the area (USEPA, 1992; USDOT, 2001). Where the scope of work identifies a certain number of storms that will be monitored, only representative storms shall count towards this number." In order to determine if and when sampling will occur, two independent weather forecasting services shall be consulted. First, the National Oceanic and Atmospheric Association (NOAA) National Weather Service 14 Highway t P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) Forecast Office's point forecasts for the desired area will be examined. The NOAA point forecast system allows users to select a specific location on a map and returns a tailored forecast. Secondly, forecasts for the closest Wunderground® weather station will be assessed. Both forecasts include a precipitation depth estimate as well as a percentage chance precipitation will occur. 5.4 SAMPLING SIZE A sampling event is defined as a stormwater runoff producing event in which sufficient flow occurs at both the inlet and outlet locations of a subject stormwater best management practice (BMP). Samples will be collected at both inlet and outlet, or underdrain, locations of each BMP included in the monitoring program. The minimum number of sampling events to be monitored at each monitoring site should be specifically determined for each individual monitoring project. Refer to Section 5.5 (Sampling Size) of the Highway Stormwater Program QAPP (NCDOT, 2013) for additional considerations regarding sampling size. 15 Highway t ' P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) 6.1 WATER QUALITY FIELD SAMPLING METHODS 6.1.1 Regulatory Considerations The Clean Water Act (CWA) requires EPA to promulgate analytical methods for analyses required in NPDES permit applications; EPA codifies these approved test procedures at 40 CFR Part 136 (USEPA, 2007), "Guidelines Establishing Test Procedures for the Analysis of Pollutants." The analytical methods specified in 40 CFR Part 136 are required for all compliance monitoring performed under the NPDES Program, unless the permit specifically requires alternate methods. When performing monitoring for NPDES compliance, only approved analytical methods identified in 40 CFR Part 136 may be used to analyze for regulated constituents. Part 136 describes acceptable analytical methods for metals, including requirements regarding sample holding times, containers, sizes, and preservation requirements. An important consideration is that these requirements have been developed to facilitate ambient water quality studies; therefore, some of them do not necessarily apply to stormwater discharge monitoring, at least at the time this QAPP was written. For NCDOT's purposes, the methods outlined in 40 CFR 136 should be used as guidelines. However, from a regulatory standpoint, using these approved methods will likely help to streamline the review and approval process by regulatory agencies. 6.1.2 Dissolved Metals Sampling Procedure 6.1.2.1 Preparing for Sampling Prior to the initiation of sampling activities and continuously, as long as sampling efforts are underway or pending, the Sampling Coordinator should ensure that all supplies necessary for field sampling activities are on hand at all times. Stormwater sample containers should be cleaned and prepared for field use according to the procedures set forth in 40 CFR Part 136 (USEPA, 2007). Sample containers should be labeled after cleaning, and the laboratory should keep a record of the technician performing the cleaning as well as the date and time. This begins the required chain -of -custody procedure for legal custody (USEPA, 1992). Stormwater metals sampling will be conducted at the inlet and outlet of all stormwater BMPs selected for monitoring. Depending on the particular BMP configuration, two distinct outlet monitoring locations may be used: one location receiving flow from surface runoff and a second location receiving flow from the underdrain (where applicable). BMPs designated for monitoring shall be equipped with appropriate devices at the inlet and outlet monitoring locations to facilitate sample collection. Typically, V-notch weirs are sufficient, but the configuration may vary based on the specific BMP design. Figure 6-1;Figure 6-1 presents an example sampling configuration. 16 Highway t P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) Figure 6-1. Example of a bioswale equipped for autsampling (Left) wooden weir box at bioswale outlet equipped with autosamplers; (right) close-up of weir box outfitted with V-notch weirs for surface runoff and underdrain monitoring. 6.1.2.2 "Clean" Sampling Techniques Throughout sample collection and processing, field crews shall follow the "clean hands/dirty hands" sampling techniques as described in EPA's guidance on collection of ambient water for trace metals analysis also known as Method 1669 (USEPA, 1996). Field crew members should be well versed in these methods to prevent contamination and maintain sample integrity. 6.1.2.3 Sample Collection and Retrieval Stormwater discharge shall be collected through the use of automatic flow -weighted composite sampling using Teledyne ISCO 6712 (Full -Size Portable Sampler) automatic water quality samplers or equivalant (Figure 6-2 -6-2) equipped with 10-liter sample carboys (typically polyethylene Nalgene® containers; see Fiqure 6-3F4gufe-6=3Figure 6-2). The autosamplers will be programmed to collect samples (aliquots) at flow -proportional intervals throughout the storm event, which are then composited. Rain gages shall also be installed at each monitoring site to record rainfall depth, compare site rainfall to local meteorological sources (see Section 5.3), and determine "qualifying" events. The installation of a recording (automatic) rain gage coupled with a standard (manual) rain gage is recommended, because a manual rain gage can provide substitute information in the event of equipment failure. Figure 6-4€igu-re 6-4 shows an example rain gage installation at a BMP monitoring site. Flow meters (ISCO 730 Bubbler Module Flowmeter) or equivalent installed at each sample location will allow the collection of a flow -weighted composite sample (see Figure 6-5Figure 6-5). After a pre- determined volume of water passes by the flow meter, the autosampler is triggered to collect a pre- determined sample aliquot typically ranging in volume from 100 mL to 500 mL. The aliquot volume is set based on anticipated flow conditions using previous flow and rainfall monitoring data. 17 Highway torW rkacw..�. QAPP for Stormwater Metals Monitoring (DRAFT) Figure 6-2. Two ISCO 6712 autosamplers contained within a sampler enclosure LI Figure 6-3. Teledyne ISCO 6712 automatic water quality sampler equipped with 10-liter carboy 18 Highway t P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) Figure 6-4. A standard rain gage (left) and tipping -bucket rain gage (right) for rainfall measurement Figure 6-5. Weir box of a stormwater BMP equipped with ISCO 730 Bubbler Module Flowmeter 19 Highway t P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) At the end of a targeted storm event, field staff shall verify whether the event met criteria for storm qualification (see Section 5.3). Collected samples will remain in the autosampler until field crews are able to visit the site to retrieve them (typically within 24 hours of final aliquot collection). Metals samples will be retrieved from the autosamplers and processed following EPA Method 1669 ("clean hands/dirty hands"), with one field member (designated "dirty hands") handling the composite bottle and the other field member ("clean hands") handling the pre -labeled 500 mL bottles, with minimal handling, to be submitted to the laboratory for analysis. In the event that precipitation is occurring during sample collection, field crews may elect to deploy a rain shelter to provide a dry working environment for sample handling. Sample handling is discussed further in Section 6.2 (Sample Handling and Custody). 6.1.2.4 Sample Filtration and Preservation Per 40 CFR 136, "[f]or the determination of dissolved elements, the sample must be filtered through a 0.45 pm pore diameter membrane filter at the time of collection or as soon thereafter as practically possible. (Glass or plastic filtering apparatus are recommended to avoid possible contamination.)" Additionally, 40 CFR 136 states, "[f]or dissolved metals, filter grab samples within 15 minutes of collection and before adding preservatives. For a composite sample collected with an automated sampler..., filter the sample within 15 minutes after completion of collection and before adding preservatives." Because of the inherent difficulty in retrieving automatically collected samples on an expedited schedule, it is anticipated that all dissolved metals samples will be filtered outside of the 15-minute hold time. Therefore, all samples shall be filtered by the analytical laboratory upon receipt and shall be flagged "H" indicating that filtering occurred at more than 15 minutes following final aliquot collection. 40 CFR 136 also describes requirements for sample preservation. Per Table II (Required Containers, Preservation Techniques, and Holding Times), metals samples require preservative (HNO3 to pH <2) at least 24 hours prior to analysis. Approved containers for metals sample collection include polyethylene, glass, and Teflon®. 6.2 SAMPLE HANDLING AND CUSTODY 6.2.1 Sample Labeling Sample bottles shall be provided with preprinted labels. Upon retrieval, the Field Lead shall ensure that each label is completed with sample ID, date, and time of sample collection according to the predetermined and documented labeling plan. 6.2.2 Sample Handling Upon retrieval and transfer into the prelabeled 500 mL bottles for analysis, all samples shall be placed on ice in coolers provided by the analytical laboratory. The Field Lead shall verify that the field log and chain - of -custody (COC) forms have been completed, that all bottles are labelled appropriately, and that samples are placed in the coolers such that they are stable to protect from damage during transport. 20 Highway t P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) Samples should remain in the coolers until received by the applicable laboratory. The Sampling Coordinator shall ensure that the ice in each cooler is replenished as necessary so that sample temperature stays below 4°C. An example completed COC form is provided in Appendix B. 6.2.3 Sample Transport and Receipt Samples will be submitted to the analytical laboratory, which can provide pick-up/courier services to retrieve samples in iced coolers. Sample coolers should have completed COC forms placed on top of the cooler awaiting pick-up by courier. The Sampling Coordinator will be responsible for contacting the laboratory point of contact to schedule sample pick-up or drop-off. 21 Highway t ' P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) Laboratories performing each analytical method must be state certified, and their staff must have demonstrated experience with each method and be familiar with the laboratory SOPs. As a branch of the North Carolina Department of Environmental Quality (DEQ), the North Carolina Wastewater/Groundwater Laboratory Certification (NC WW/GW LC) program serves to ensure the quality of analytical data used for regulatory purposes. A list of certified laboratories is provided on the DEQ website and is updated annually: https://deg.nc.gov/about/divisions/water-resources/water-resources-data/water-sciences-home- page/laboratory-certification-branch. For stormwater metals sampling, the analytical laboratory must have demonstrated experience processing aqueous samples for total recoverable and dissolved metals analysis. Additionally, the laboratory should be able to readily provide thorough documentation and be able to demonstrate the following: • The laboratory processes metals samples following the approved analytical methods listed in Table 5-1Table 5 1 and can provide documentation of their procedures; • The laboratory is able to provide an accurate estimate of turnaround (sample processing) time and turnaround time is within an acceptable range (typically within 7 days of sample receipt); • The laboratory provides thorough documentation communicating receipt and processing of samples, including sample acknowledgement forms and reports of results; • As method detection limit and reporting limit may vary between laboratories, the laboratory is readily able to provide documentation of the limits applicable to their analysis methods; • Thorough laboratory QC procedures are followed, the procedures and acceptance limits are well - documented (see Section 8.2 for additional guidance), and the laboratory's QC procedures and results are transparent. Recommended analytical methods and reporting limits are provided in Section 5.2 (Parameters of Concern). Recommended data validation criteria for field and laboratory quality control samples are discussed in Section 8.0 (Quality Control). 22 Highway t ' P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) This section describes the field, laboratory, and data analysis quality control (QC) required for dissolved metals sampling programs. 8.1 FIELD QUALITY CONTROL PROCEDURES 8.1.1 Field Instrument Quality Control In order to maintain data quality, field equipment shall undergo routine cleaning, calibration, and maintenance at the recommended frequency specified by each manufacturer. 8.1.2 Field Form/Data Sheet Quality Control Field forms and/or data sheets shall be provided on Rite -in -the -Rain® water-resistant forms or recorded in weather -resistant tablet PCs. All entries shall be made in pencil or permanent ink. Field staff shall submit completed forms to the Field Lead, who shall review documents for errors and completeness and initial and date all corrections. Field documents shall then be submitted to data management staff for verification. 8.1.3 Field Quality Control Samples 8.1.3.1 Field Duplicates Field duplicates are analyzed to evaluate the precision of field sampling techniques. Composite field duplicate samples shall be collected at all sites at a rate of once per year or once per project duration, whichever is more frequent. Field duplicates are collected by splitting composited samples. The Sampling Coordinator shall maintain a schedule so that field crews know when to collect field duplicate samples at each site. Parameters analyzed in the field sample are also measured in the duplicate sample for a particular storm event. All field duplicates shall be labeled the same as other samples so that they have their own unique number and shall be submitted blind to the analytical laboratory with all other field samples. Field duplicates will be used to evaluate the Relative Percent Difference (RPD) between regular field samples and the corresponding duplicate samples. The measured value for each field sample shall be compared to the measured value for the corresponding field duplicate as follows: sample result — duplicate result %RPD = x 100% (sample result + duplicate result)12 For field duplicates, RPD shall be less than or equal to 25%. Field samples and corresponding duplicate samples not meeting acceptance criteria shall be flagged with a "J" and qualified as an estimate. 23 Highway t P4OGR;..V. 8.1.3.2 Field Blanks QAPP for Stormwater Metals Monitoring (DRAFT) Field blanks are used to evaluate whether contamination occurred during sampling, and include equipment rinsate blanks, transfer blanks, and transport blanks. All blank samples shall be submitted blind to the analytical laboratory. Equipment rinsate blanks shall be collected at all sites once per year or once per project duration, whichever is more frequent. Equipment rinsate blanks consist of laboratory - supplied, contaminant free water that is run through the autosampler into a clean sample bottle. Field staff then collect samples from the carboy using normal sampling procedures and clean sampling equipment. If contamination is detected, additional field blanks shall be collected to determine the source of contamination. A transfer blank is collected by pouring laboratory -provided deionized water into a clean sample bottle to determine whether field contamination is present and unrelated to the equipment. A transport blank is collected by transporting unopened bottles containing certified clean water from the laboratory into the field, then returning it to the laboratory (still unopened). If the field blank result is greater than the reporting limit (RL), the result and all associated sample results shall be flagged with a "B" to indicate blank contamination. If sample results are less than or equal to five times the contamination level found in the field blanks, the contamination may have biased the sample results; therefore, the corresponding field samples shall be qualified with a "J." The source of contamination shall be corrected and actions to prevent future contamination shall be documented. Table 8-1 Table summarizes the data validation schedule, acceptance criteria, and actions for field quality control samples. Table 8-1. Data validation criteria for field quality control samples Field duplicates One per site per year or project duration (whichever is more frequent). Field blanks One per site per year or project duration (whichever is more frequent). RPD <_ 25%. Field blank result < RL. Duplicate and sample flagged J. Field blank and associated samples flagged B. If sample result <_ 5x field blank result, associated samples qualified J. 8.2 LABORATORY QUALITY CONTROL PROCEDURES Contract laboratories shall make every effort to meet sample holding times and target reporting limits for all parameters. Laboratory QC procedures and results shall be closely monitored throughout the duration of sampling. 24 Highway Ok t P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) 8.2.1 Laboratory Quality Control Samples 8.2.1.1 Method Blanks Method blanks are analyzed to demonstrate that the analytical procedures do not result in sample contamination. Method blanks shall be prepared and analyzed at a rate of at least one for each analytical batch. Method blanks consist of laboratory -prepared blank (reagent) water processed along with the batch of samples. If the method blank result is greater than the reporting limit (RL), the result and all associated sample results shall be flagged with a "B" to indicate blank contamination. If sample results are less than or equal to five times the contamination level found in the method blanks, the contamination may have biased the sample results; therefore, the corresponding field samples shall be qualified with a "J." The source of contamination shall be corrected and actions to prevent future contamination shall be documented. 8.2.1.2 Laboratory Duplicates Laboratory duplicate samples shall be analyzed regularly to verify that the laboratory's analytical methods maintain their precision. Duplicates are selected at random from submitted samples that meet volume requirements. For lab duplicates, RPD shall be less than or equal to 20%. Field samples and corresponding duplicate samples not meeting acceptance criteria shall be flagged with a "J" and qualified as an estimate. 8.2.1.3 Matrix Spikes and Matrix Spike Duplicates Matrix spikes (MS) are field samples that are spiked in the laboratory with method -specific target analytes and then analyzed under the same conditions as the field samples. A matrix spike provides a measure of the recovery efficiency and accuracy for the analytical methods being used. Matrix spikes are typically analyzed in duplicate (MSD) to determine method accuracy and precision. Matrix spikes shall be prepared and analyzed at a rate of one pair for each analytical batch. Each matrix and matrix spike shall consist of an aliquot of laboratory -fortified environmental sample. For matrix spikes and matrix spike duplicates, the acceptance criteria shall be measured as percent recovery and RPD. Recovery is the accuracy of an analytical test measured against a known analyte addition to a sample and is calculated as: %Recovery — (matrix plus spike result — matrix result) expected matrix plus spike result x 100% If matrix spike or matrix spike duplicate recovery is outside of the acceptable range (70% to 130%), the associated sample results shall be flagged with J. If RPD for the matrix spike or matrix spike duplicate exceeds 20%, the associated sample results shall be flagged with J. 8.2.1.4 Laboratory Control Samples A laboratory control sample (LCS) is a sample of known analyte concentration(s) that is prepared in the lab from a separate source of analyte(s) relative to the calibration standards. The purpose of analyzing 25 Highway torW rkacw..�. QAPP for Stormwater Metals Monitoring (DRAFT) laboratory control samples is to demonstrate the accuracy and precision of the analytical methods. Laboratory control samples shall be analyzed at the rate of one per analytical batch. The acceptance criteria for laboratory control samples is percent recovery, calculated as: measured concentration %Recovery = x 100% true concentration If LCS recovery is outside of the acceptable range (85% to 115%), the associated sample results shall be flagged with J. Table 8-2Table 8-2 summarizes the data validation schedule, acceptance criteria, and actions for laboratory quality control samples. Table 8-2. Data validation criteria for laboratory quality control samples Method blanks One per analytical Method blank result < RL. Method blank and associated batch. samples flagged B. If sample result <_ 5x method blank result, associated samples qualified J. Lab duplicates One per analytical RPD <_ 20%. Duplicate and sample flagged J. batch. Matrix spike/matrix One per analytical spike duplicate batch. Matrix spike/matrix One per analytical spike duplicate batch. Laboratory control One per analytical sample batch. %Recovery 70-130 RPD <_ 20%. %Recovery 85-115 Associated sample flagged J. Associated sample flagged J. Associated sample flagged J. 26 Highway storms rsacw..�. QAPP for Stormwater Metals Monitoring (DRAFT) The following general recommendations are made for stormwater metals sampling equipment inspection and maintenance, per the Highway Stormwater Program QAPP (NCDOT, 2013): When DC power is used, verify the duration of continual operation permissible during continual operation of the equipment. Battery life reduces with time, so it is important to verify this periodically. • Flow monitoring equipment should be calibrated according to manufacturer specifications. Flow meters typically contain desiccant packets and moisture indicators to keep the internal components of the equipment dry. The moisture indicators should be checked during each site visit, or at least once between each monitoring event. The sensor(s) should be checked periodically and calibrated on an as -needed basis. The sensor cables should be inspected at least prior to each phase of intensive stormwater monitoring. All connections into the flow meter should be visually inspected prior to each monitoring event. • At a minimum, the autosampler calibration should be tested prior to major phases of monitoring. After each stormwater monitoring event, the volume of the sample should be verified against the expected value, and the autosampler calibrated if the deviation is outside of manufacturer's recommendations. • Rain gages should be inspected after every sampling event to make sure they are free from debris. They should be inspected and calibrated at least before every monitoring project, and ideally before every major phase of monitoring. The Sampling Coordinator shall be responsible for reviewing manufacturer's instructions for all sampling equipment and developing an appropriate maintenance protocol. Manufacturer's installation and operation guides for the ISCO 6712 and ISCO 730 models discussed in Section 6.0 (Sampling Methods) can be accessed from the Teledyne ISCO website: http://www.teledyneisco.com/en-us/waterandwastewater/Pages/6712-Sampler.aspx http://www.teledyneisco.com/en-us/waterandwastewater/Pages/730-Module.aspx 27 Highway & torte PROGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) NCDOT's use of data generated by a given research project may extend for many years after the conclusion of the project; therefore, the PI is expected to follow sound data management principles to ensure adequate documentation and the integrity of the data. To support these objectives, NCDOT requires several data management protocols by all researchers as discussed below. These protocols are consistent with the Highway Stormwater Program QAPP (NCDOT, 2013). 10.1 PERIODIC REPORTING Quarterly progress reports for all research projects shall include provisional data collected to date, including raw data along with data qualifiers. 10.2 DELIVERABLES The draft and final deliverable for each research project should include the entire raw dataset, with appropriate data qualifiers for data that were excluded or that is associated with other quality control issues. An Excel template for submission of this data is available by contacting the Research Coordinator and is included in Appendix B of the Highway Stormwater Program QAPP. 10.3 RECORD RETENTION Raw field and laboratory records, including notes by field personnel on site conditions and potential data quality concerns, should be retained by the Principal Investigator for a minimum of three (3) years after the completion of project and ideally longer. The Principal Investigator should notify NCDOT before destroying any historical records. WJ Highway t ' P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) The purpose of this section is to verify that data are of sufficient quality to support project objectives. These protocols are consistent with the Highway Stormwater Program QAPP (NCDOT, 2013). 11.1 DATA VALIDATION As part of the project closeout process, researchers are required to verify compliance with the project's DQOs prior to cessation of field activities and submission of the draft project report. Specifically, the following activities are required: • Verify the number of qualified sampling events (as defined in Section 5.3) exceeds the minimum requirements in Section 5.4 based on the variability of the data in question. • Submit the draft dataset in Excel in the format specified by the Research Coordinator, with appropriate data qualifiers for data, including presenting left -censored data (Section 11.2) and identifying data associated with site conditions that could result in compromised data quality. • Do not remove monitoring equipment from site until NCDOT signs off on the draft dataset, in the event it is deemed that additional sampling is required. 11.2 HANDLING OF CENSORED DATA Data that are below the reporting limit represent lower reliability, and the method of handling could influence the conclusions of a study. The Highway Stormwater Program QAPP (Section 11.2) recommends approved protocols for the handling of censored data (note that an "information -rich" method is one that is able to confirm the presence of the analyte in question, such as a spectrometric method). Briefly, the HSP Research Program's preferred protocols include: • When data value < MDL and method is not information -rich, report value as "<RL." • When data value > MDL but < RL and method is not information -rich, report value as recorded value preceded by "E" to indicate greater degree of uncertainty. • When data value < RL but method is information -rich, report recorded value with "E" qualifier even if value is < MDL. • When data value > RL, report as recorded. • Report MDL in all cases. 11.3 IDENTIFICATION OF OUTLIERS NCDOT recommends that each research project use a systematic process for identifying outliers. The project report should include a section discussing how outliers were identified and what verification processes were used to identify true outliers. See Section 11.3 (Identification of outliers) of the Highway Stormwater Program QAPP for a recommended method. 29 Highway t P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) 11.4 DATA PRESENTATION Per Section 11.5 (Data Presentation) of the Highway Stormwater Program QAPP: "Data from research projects should be presented in a variety of ways, including, at a minimum, the mean and median influent and effluent concentrations, with a description of how the EMCs [event mean concentrations] and loads were computed. Additional clarity can be achieved by presenting percentiles of concentration, typically the 25t" and 751" percentile and the interquartile range (IQR). It is also beneficial to compare the data presented to relevant benchmarks, e.g., a relevant drinking water standard, an instream water quality or receiving water -based benchmark..." NCDOT currently does not require a single method for computation of EMCs and loads; however, researchers are required to clearly document the method(s) used. Additionally, sample calculations should be provided in the project report. NCDOT requires all influent and effluent concentrations related to a BMP to be presented in the project report in the form of absolute concentrations and mass loadings. The report must also include a statistical evaluation of the significance of the difference between influent and effluent concentrations. 30 Highway t ' P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) The Highway Stormwater Program QAPP (NCDOT, 2013) provides guidelines for data dissemination for research projects under the Research Program, including the following: • Researchers are generally expected to produce at least one (1) journal article and two (2) conference proceedings based on each research project. • Researchers shall submit draft journal articles and conference abstracts for NCDOT approval prior to submission. • A minimum of three (3) days should be provided to the HSP Research Program team for review of conference abstracts. • A minimum of two (2) weeks should be provided to the HSP Research Program team for review of journal articles. NCDOT may be able to provide funding for participation in conferences; researchers should contact the Research Program Manager for more information. 31 Highway t ' P4OGR;..V. QAPP for Stormwater Metals Monitoring (DRAFT) NCDOT. 2013. Highway Stormwater Program Quality Assurance Project Plan. North Carolina Department of Transportation, Raleigh, NC. USDOT. 2001. Guidance Manual for Monitoring Highway Runoff Water Quality. Report FHWAEP-01-021. United States Department of Transportation, Washington, DC. USEPA. 1992. NPDES Storm Water Sampling Guidance Document (EPA/833/B-92-001). United States Environmental Protection Agency, Washington, D.C. USEPA. 1994a. Method 200.7: Determination of Metals and Trace Elements in Water and Wastes by Inductively Coupled Plasma -Atomic Spectrometry. Revision 4.4. U.S. Environmental Protection Agency. USEPA. 1994b. Method 200.8: Determination of Trace Elements in Waters and Wastes by Inductively Coupled Plasma -Mass Spectrometry. Revision 5.4. U.S. Environmental Protection Agency. USEPA. 1994c. Method 200.9: Determination of Trace Elements by Stabilized Temperature Graphite Furnace Atomic Absorption. Revision 2.2. U.S. Environmental Protection Agency. USEPA. 1996. EPA Method 1669: Sampling Ambient Water for Trace Metals at EPA Water Quality Criteria Levels. U.S. Environmental Protection Agency, Office of Water, Washington, D.C. USEPA. 2007. 40 CFR Part 122, 136, 141, 143, 430, 455, and 456; Guidelines Establishing Test Procedures for the Analysis of Pollutants under the Clean Water Act; National Primary Drinking Water Regulations; and National Secondary Drinking Water Regulations; Analysis and Sampling Procedures; Final Rule. Federal Register. U.S. Environmental Protection Agency, Washington, D.C. Additional references (not cited) Tetra Tech. 2017. NPDES Programmatic Strategy for Metals — Metals Sampling Plan (DRAFT). August 16, 2017. USEPA. 2001. USEPA Requirements for Quality Assurance Project Plans. United States Environmental Protection Agency, Washington, D.C. USEPA. 2002a. EPA Guidance for Quality Assurance Project Plans. (QA/G-5). (EPA/240/R-02-009). United States Environmental Protection Agency, Washington, D.C. USEPA. 2002b. Guidance on Environmental Data Verification and Data Validation. (QA/G-6). (EPA/240/R-02/004). United States Environmental Protection Agency, Washington, D.C. USEPA. 2006. Guidance on Systematic Planning Using the Data Quality Objectives Process (EPA QA/G- 4). United States Environmental Protection Agency, Washington, D.C. 32 Higw ay Ot " QAPP for Stormwater Metals Monitoring (DRAFT) 33 Higw ay Ot " QAPP for Stormwater Metals Monitoring (DRAFT) 34