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VIRGINIA DEPARTMENT OF ENVIRONEMTNAL QUALITY Revision: 3page 1 of 36

QUALITY ASSURANCE PROJECT PLAN FOR

THE INVESTIGATION OF STREAM CONCENTRATIONS OF TOTAL AND

DISSOLVED TRACE METALS, MAJOR ANIONS AND CATIONS, AND

SUSPENDED AND DISSOLVED SOLIDS IN THE MAINSTEM CLINCH RIVER

BETWEEN NORRIS LAKE, TENNESSEE AND NASH FORD, VIRGINIA

Prepared By: Virginia Department of Environmental QualityOffice of EcologyWater Monitoring and Assessment629 East Main StreetRichmond, Virginia 23219

Date: March 2015

Special Study Number: 15019

Key Words: MUSSELS, CLINCH RIVER, CPCRI, DISSOLVED METALS, TOTAL RECOVERABLE METALS

document.docx Tuesday, March 10, 2015


A1 Title and Approval Sheet

Name: Braven Beaty, The Nature ConservancyTitle: Project Manager

Signature:__________________________ Date:_____________

Name: Beverly Brown, Tennessee Department of Environment and ConservationTitle: Tennessee Team Leader

Signature:__________________________ Date:_____________

Name: Roger Stewart, Virginia Department of Environmental QualityTitle: Virginia Team Leader

Signature:__________________________ Date:_____________

Name: James Beckley, Virginia Department of Environmental QualityTitle: Quality Assurance Officer

Signature:__________________________ Date:_____________



A2 Table of ContentsA1 Title and Approval Sheet.....................................................................................................2A2 Table of Contents.................................................................................................................3A3 Distribution List...................................................................................................................5A4 Project/Task Organization....................................................................................................5A5 Project Definition / Background..........................................................................................6A6 Project/ Task Description.....................................................................................................6A7 Quality Objectives and Criteria for Measurement Data.....................................................14

A7.1 Data Quality Objectives............................................................................................................................14A.7.1.1 Comparability...................................................................................................................................14A.7.1.2 Representativeness............................................................................................................................14A.7.1.3 Precision and Bias.............................................................................................................................14A.7.1.4 Completeness....................................................................................................................................15

A8 Special Training Needs/ Certification................................................................................15A9 Documents and Records.....................................................................................................15

A9.1 Field Data Documentation........................................................................................................................15A9.2 Instrument Calibration and Maintenance Documentation........................................................................20A9.3 Laboratory Data Documentation..............................................................................................................20

B1 Sampling Design................................................................................................................20B2 Sampling Methods..............................................................................................................21B3 Sampling Handling and Custody........................................................................................23B4 Analytical Methods............................................................................................................24B5 Quality Control...................................................................................................................24

B5.1 Quality Assurance Objective....................................................................................................................24B5.2 QC Procedures for Field Operation..........................................................................................................24B5.3 QC Procedures for Laboratory Operation.................................................................................................25

B6 Instrument/Equipment Testing, Inspection, and Maintenance...........................................29B7 Instrument/Equipment Calibration and Frequency............................................................29

B7.1 Field Operations........................................................................................................................................29B7.2 Laboratory Operations..............................................................................................................................29

B8 Inspection/Acceptance of Supplies and Consumables.......................................................29B9 Data Management..............................................................................................................30C1 Assessment and Response Actions....................................................................................30

C1.1 Field Crew.................................................................................................................................................30C1.2 Field Reviews............................................................................................................................................30C1.3 Laboratory Activities................................................................................................................................31

C1.3.1 System Audit......................................................................................................................................31C 1.3.2 Performance Audit............................................................................................................................32

C2 Reports to Management.....................................................................................................32C2.1 Field Activities..........................................................................................................................................32C2.2 Final Report...............................................................................................................................................32

D1 Data Review, Verification, and Validation........................................................................32D2 Verification and Validation Methods.................................................................................33

D2.1 Data Verification.......................................................................................................................................33D2.2 Data Validation.........................................................................................................................................33

D3 Reconciliation with User Requirements............................................................................34



TablesTable 1 Station Identification..................................................................................................................................7Table 2 Measured Parameters................................................................................................................................12Table 3 Solid Speciation........................................................................................................................................22Table 4 Sample Containers and Preservations.......................................................................................................23Table 5 Acceptance Criteria for Field Parameters.................................................................................................25Table 6 Analytical Test Methods...........................................................................................................................25

FiguresFigure 2 State Scale Location of Clinch River Trace Elements Special Study Sites..........Error! Bookmark not

defined.Figure 1 Clean Metals Bridge Bottle.....................................................................................................................10Figure 3 Monthly Run Schedule for Clinch River Tennessee...............................................................................16Figure 4 Field Data Sheet for Run TNCLINCH....................................................................................................17Figure 5 Electronic Field Data Sheet, partial.........................................................................................................17Figure 6 Container Labels.....................................................................................................................................18Figure 7 Wire Tag..................................................................................................................................................19



A3 Distribution List

Project Manager: Braven Beaty

Team Leaders: Beverly Brown and Roger Stewart

VADEQ WQMA Quality Assurance Officer: James Beckley

VADEQ Southwest Regional Office: Allen Newman and Stewart Phipps

Clinch Powell Clean River Initiative Science Team: Carl Zipper, Jess Jones, Craig Lott, Jen Krstolic, Greg Johnson

A4 Project/Task Organization

The associated personnel responsibilities for this project are as follows:

Team Leaders:

Beverly Brown 423.854.5448 and Roger Stewart 804.370.8043 M, 804.698.4449 O

1) Coordinates project activities. Ensures field teams are properly trained and equipped to conduct sampling and that QA/QC procedures outlined in this QAPP are followed.

2) Point of contact for field activities.3) Data entry of field and lab activities.

VADEQ WQMA QA Officer: James Beckley 804.698.4025 O

1) Coordinates Quality Assurance (QA) activities to ensure quality in field data, analytical results, and data validity.

2) Oversees field audits to ensure QA/QC procedures are followed. 3) Recommends corrective actions when necessary.

Field Support:

Stuart Torbeck 804.385.8886 M, 804.698.4461 O

1) Responsible for calibrating field equipment.2) Preparation and organization of sampling equipment and containers.



3) Collection and preparation of samples for shipment to the contract laboratory.4) Data entry of field and lab activities.

Project Manager:

Braven Beaty 276.608.6508 M, 276.676.2209 O

1) Assures that activities meet the requirements of the project as defined in this project plan.2) Responsible for development, implementation and management of the project.

A5 Project Definition / BackgroundRecent assessments of freshwater mussels in portions of the mainstem Clinch River Virginia, USA, indicate impacted assemblages; those containing lower population densities, lower species richness and lack of age class distribution that is characteristic of successful reproduction. These impacted sections of the Clinch River are found beginning from the confluence of Stock Creek at Clinchport (RKM 343.3; RM 213.3) to Lick Creek near St. Paul (RKM 411.5; RM 255.7)1.

Trace element sampling conducted from August 2012 to September 2013 n = 5 at eight stations from river mile 192.4 to 274.71 indicated that there were differences in concentrations of several inorganic and trace elements between the impacted reach and reference sites.

In order to better identify the inorganic, ionic, and trace elemental constituents present in the water column throughout the impacted zone sampling and analyses using clean techniques will occur at eight sites along the mainstem Clinch River and one on the Guest River. Three stations downstream of the impacted reach in Tennessee and two upstream of the impacted reach will serve as reference condition sites. Three stations will be distributed in the impacted reach. One ambient long term station on the Guest River a tributary to the Clinch in the impacted zone will also be sampled as part of this study.

A6 Project/ Task DescriptionEight sites will be sampled for trace elements, ionic constituents, and various other associated variables, and field parameters. Bimonthly sampling will be targeted to low flow or base flow conditions.

Sampling locations are listed in on page 6 along with the rationale for site selection2. The CPCRI Science Team was very deliberate in the selection of these sampling locations. Members of the Science Team that made the selections have many years of experience working on the Clinch and represent some of the most knowledgeable of any researchers working in the watershed.

1 Water Monitoring Strategies to Inform Imperiled Species Conservation and Management in the Clinch River, Virginia and Tennessee A White Paper Prepared by: Clinch-Powell Clean Rivers’ Initiative (CPCRI) Science Team August 25, 2014.2 Ibid, Table 3. Proposed monitoring locations.document.docx Tuesday, March 10, 2015


Table 1 Station Identification

STA_ID STATION DESCRIPTION LATITUDE LONGITUDE RATIONALE

6BCLN177.47 36.515630 ### 177.47

6BCLN189.10 36.569420 ### 189.10

6BCLN199.15 36.572870 ### 199.15

6BCLN219.26 36.708140 ### 219.26

6BCLN227.25 36.765860 ### 227.25

6BCLN237.33 36.831360 ### 237.33 Within impacted reach.

6BCLN271.50 36.943250 ### 271.50

6BCLN279.43 36.967560 ### 279.43

RIVERMILE

Clinch River mile 177.4, Rt 33 bridge south of Sneedville

Reference for best-case mussel populations. Site is both easily accessible and upstream from the Swan Island sampling site (mile 172.4), which has been sampled for multiple years, upstream of Briery Creek (mile 174.5, sampled in 2006), and immediately downstream from the mile 178.4 sampling site at Sneedville (2006).

Route 70 bridge near Kyles Ford

Reference for high quality mussel assemblage (Kyles Ford, sampled 2004); downstream from North Fork Clinch River tributary influx. Provides a bridge for sampling, unlike the Wallens Bend (mile 192.5) location, sampled by Cooperative Monitoring, which requires wading.

Horton Ford, Tennessee

Reference for high quality mussel populations; also at USGS gage.

Rt. 645 bridge at Craft Mill

Closer to Pendleton Island, and thus more clearly within the impacted reach, than Clinchport sampling point used for Cooperative Monitoring. Upstream from USGS gage at Speers Ferry. [note: a possible alternative sampling site would be the Slant swinging bridge at river mile 223.5, which is closer to Pendleton Island and a VDGIF mussel sampling site].

Ft Blackmore, Old 72 Bridge.

Within impacted reach, close to and upstream from Pendleton Island.

DUNGANNON RT 65 SINKING CREEK HWY

RT. 82 BRIDGE AT CLEVELAND

Bridge access point within the upstream reference reach and located coincident with a USGS stream gaging station.

Nash Ford, Rt. 645 Bridge

Upstream end of reference reach, providing a bridge for sampling efficiency.



Figure 1 State Scale Location of Clinch River Trace Elements Special Study Sites on page 8 provides a scaled map of the study area and sample locations.

Figure 1 State Scale Location of Clinch River Trace Elements Special Study Sites



Field measurements for temperature, pH, dissolved Oxygen, and specific conductivity, at the thalweg and each of the predefined cross sectional sampling intervals established for the depth and width integrated sampling are to be recorded. A clean metals Bridge Bottle sampling device, (Figure 2 Clean Metals Bridge Bottle page 10) will be used to collect the trace elements by evenly sampling the entire river cross section from 10% to 90% of the wetted width3.

Sampling is to occur when the flow conditions at the reference flow gages are at or below the “median daily statistic” as defined by the US Geological Survey. Field staff will verify the flow conditions the morning of each sampling event. The reference gages are:

USGS 03527220 CLINCH RIVER NEAR LOONEYS GAP, TN. http://waterdata.usgs.gov/tn/nwis/uv?site_no=03527220

USGS 03527000 CLINCH RIVER AT SPEERS FERRY, VA.http://waterdata.usgs.gov/va/nwis/uv?site_no=03527000

USGS 03524000 CLINCH RIVER AT CLEVELAND, VA.http://waterdata.usgs.gov/va/nwis/uv?site_no=03524000

This project is being done in cooperation with the Tennessee Department of Environment and Conservation (TDEC) and The Nature Conservancy (TNC). Coordination of sampling events between TDEC, TNC, and VADEQ will ensure sampling at all eight sites are completed in the same two day window for each of the six annual sampling events.

TDEC is responsible for sampling the three downstream reference sites; Rt 33 Bridge south of Sneedville (6BCLN177.47), Route 70 Bridge near Kyles Ford (6BCLN189.10), and Horton Ford (6BCLN199.15).

VADEQ is responsible for sampling Rt. 645 Bridge at Craft Mill (6BCLN219.26), the old Route 72 bridge at Ft Blackmore(6BCLN227.25), Route 65 bridge (Sinking Creek Highway) at (6BCLN237.33), Route 82 bridge at Cleveland (6BCLN271.50), and Rt. 645 Bridge at Nash Ford (6BCLN279.43).

TNC, TDEC and VADEQ will coordinate the transfer of field data sheets and samples from TDEC to VADEQ so that VADEQ can enter the data into the Comprehensive Environmental Database Water Quality Monitoring module, (CEDSWQM). The CEDSWQM module is the VADEQ database application that provides storage of field data, electronic notification of sample analytical requests to the State lab, the Division of Consolidated Laboratory Services, (DCLS), Chain of Custody tracking, and storage of electronic submission of analyte results. Samples received from TDEC will be transferred to VADEQ coolers, iced and packed for shipment to DCLS according to the VADEQ Standard Operating Procedure4 section referenced for overnight shipping of routine samples, referred to as the SOP in this document.

3 Guidance Memorandum No. 01-2003, Virginia Department of Environmental Quality, Office of Water Quality Programs, Water Quality Monitoring and Assessment, March 5, 2001. http://www.deq.virginia.gov/Programs/Water/Laws,Regulations,Guidance/Guidance/MonitoringAssessmentGuidance.aspx4 STANDARD OPERATING PROCEDURES MANUAL FOR THE DEPARTMENT OF ENVIRONMENTAL QUALITY WATER QUALITY MONITORING AND ASSESSMENT PROGRAM, Commonwealth of Virginia Department of Environmental Quality Water Quality Monitoring and Assessment 629 East Main Street Richmond, VA 23219, Revision No.: 19 Rev. Date: 02/27/2014. http://www.deq.virginia.gov/Programs/Water/WaterQualityInformationTMDLs/WaterQualityMonitoring/QualityAssuranceQualityControl.aspxdocument.docx Tuesday, March 10, 2015

http://waterdata.usgs.gov/va/nwis/uv?site_no=03524000

http://waterdata.usgs.gov/va/nwis/uv?site_no=03527000

http://waterdata.usgs.gov/tn/nwis/uv?site_no=03527220

http://waterdata.usgs.gov/tn/nwis/uv?site_no=03527220


VADEQ will provide all the sample containers, clean metals Bridge Bottles, clean metals filter tubing kits, preservatives, field data sheets, sample containers, tags, and labels.

Figure 2 Clean Metals Bridge Bottle



Samples for dissolved and total metals and various other chemical parameters (Table 2 Measured Parameters) are to be collected at each station. . These parameters are included in the laboratory parameter group codes, DCMET1, TCMET1, SSC-C2, TN, TNUTL, TOC, TPLL and PROB4-2. One field blank for each of the parameter group codes will be collected during the first event of the project by each of the two field teams.

Sample analyses will be conducted by The Virginia Department of General Services, Division of Consolidated Laboratory Services (DCLS) using approved methods as specified in the Virginia Environmental Laboratory Accreditation Program and for which DCLS is certified to perform these analyses.



Table 2 Measured ParametersPG_PARM_NAME PG_STORET_CODE PG_MEASUREMENT_UNITALUMINUM, DISSOLVED (UG/L AS AL) 01106 ug/lANTIMONY, DISSOLVED (UG/L AS SB) 01095 ug/lARSENIC, DISSOLVED (UG/L AS AS) 01000 ug/lBARIUM, DISSOLVED (UG/L AS BA) 01005 ug/lBERYLLIUM, DISSOLVED (UG/L AS BE) 01010 ug/lCADMIUM, DISSOLVED (UG/L AS CD) 01025 ug/lCALCIUM, DISSOLVED (MG/L AS CA) 00915 ug/lCHROMIUM, DISSOLVED (UG/L AS CR) 01030 ug/lCOPPER, DISSOLVED (UG/L AS CU) 01040 ug/l

DHARD mg/lIRON, DISSOLVED (UG/L AS FE) 01046 ug/lLEAD, DISSOLVED (UG/L AS PB) 01049 ug/lMAGNESIUM, DISSOLVED (MG/L AS MG) 00925 ug/lMANGANESE, DISSOLVED (UG/L AS MN) 01056 ug/lMERCURY-TL,FILTERED WATER,ULTRATRACE METHOD NG/L 50091 ug/lNICKEL, DISSOLVED (UG/L AS NI) 01065 ug/lSELENIUM, DISSOLVED (UG/L AS SE) 01145 ug/lSILVER, DISSOLVED (UG/L AS AG) 01075 ug/lTHALLIUM, DISSOLVED (UG/L AS TL) 01057 ug/lZINC, DISSOLVED (UG/L AS ZN) 01090 ug/lALUMINUM, DISSOLVED (UG/L AS AL) 01106 ug/lANTIMONY, DISSOLVED (UG/L AS SB) 01095 ug/lARSENIC, DISSOLVED (UG/L AS AS) 01000 ug/lBARIUM, DISSOLVED (UG/L AS BA) 01005 ug/lBERYLLIUM, DISSOLVED (UG/L AS BE) 01010 ug/lCADMIUM, DISSOLVED (UG/L AS CD) 01025 ug/lCALCIUM, DISSOLVED (MG/L AS CA) 00915 mg/lCHROMIUM, DISSOLVED (UG/L AS CR) 01030 ug/lCOPPER, DISSOLVED (UG/L AS CU) 01040 ug/l

DHARD mg/lIRON, DISSOLVED (UG/L AS FE) 01046 mg/lLEAD, DISSOLVED (UG/L AS PB) 01049 ug/lMAGNESIUM, DISSOLVED (MG/L AS MG) 00925 mg/lMANGANESE, DISSOLVED (UG/L AS MN) 01056 ug/lMERCURY-TL,FILTERED WATER,ULTRATRACE METHOD NG/L 50091 ng/lNICKEL, DISSOLVED (UG/L AS NI) 01065 ug/lPOTASSIUM, DISSOLVED (MG/L AS K) 00935 ug/l

HARDNESS, CA MG CALCULATED (MG/L AS CACO3) AS DISSOLVED




Table 2 Measured Parameters, continued

PG_PARM_NAME PG_STORET_CODE PG_MEASUREMENT_UNITALUMINUM, DISSOLVED (UG/L AS AL) 01106 ug/lANTIMONY, DISSOLVED (UG/L AS SB) 01095 ug/lARSENIC, DISSOLVED (UG/L AS AS) 01000 ug/lBARIUM, DISSOLVED (UG/L AS BA) 01005 ug/lBERYLLIUM, DISSOLVED (UG/L AS BE) 01010 ug/lCADMIUM, DISSOLVED (UG/L AS CD) 01025 ug/lCALCIUM, DISSOLVED (MG/L AS CA) 00915 ug/lCHROMIUM, DISSOLVED (UG/L AS CR) 01030 ug/lCOPPER, DISSOLVED (UG/L AS CU) 01040 ug/l

DHARD mg/lIRON, DISSOLVED (UG/L AS FE) 01046 ug/lLEAD, DISSOLVED (UG/L AS PB) 01049 ug/lMAGNESIUM, DISSOLVED (MG/L AS MG) 00925 ug/lMANGANESE, DISSOLVED (UG/L AS MN) 01056 ug/lMERCURY-TL,FILTERED WATER,ULTRATRACE METHOD NG/L 50091 ug/lNICKEL, DISSOLVED (UG/L AS NI) 01065 ug/lSELENIUM, DISSOLVED (UG/L AS SE) 01145 ug/lSILVER, DISSOLVED (UG/L AS AG) 01075 ug/lTHALLIUM, DISSOLVED (UG/L AS TL) 01057 ug/lZINC, DISSOLVED (UG/L AS ZN) 01090 ug/lALUMINUM, DISSOLVED (UG/L AS AL) 01106 ug/lANTIMONY, DISSOLVED (UG/L AS SB) 01095 ug/lARSENIC, DISSOLVED (UG/L AS AS) 01000 ug/lBARIUM, DISSOLVED (UG/L AS BA) 01005 ug/lBERYLLIUM, DISSOLVED (UG/L AS BE) 01010 ug/lCADMIUM, DISSOLVED (UG/L AS CD) 01025 ug/lCALCIUM, DISSOLVED (MG/L AS CA) 00915 mg/lCHROMIUM, DISSOLVED (UG/L AS CR) 01030 ug/lCOPPER, DISSOLVED (UG/L AS CU) 01040 ug/l

DHARD mg/lIRON, DISSOLVED (UG/L AS FE) 01046 mg/lLEAD, DISSOLVED (UG/L AS PB) 01049 ug/lMAGNESIUM, DISSOLVED (MG/L AS MG) 00925 mg/lMANGANESE, DISSOLVED (UG/L AS MN) 01056 ug/lMERCURY-TL,FILTERED WATER,ULTRATRACE METHOD NG/L 50091 ng/lNICKEL, DISSOLVED (UG/L AS NI) 01065 ug/lPOTASSIUM, DISSOLVED (MG/L AS K) 00935 ug/lSELENIUM, DISSOLVED (UG/L AS SE) 01145 ug/lSILVER, DISSOLVED (UG/L AS AG) 01075 ug/lSODIUM, DISSOLVED (MG/L AS NA) 00930 mg/lTHALLIUM, DISSOLVED (UG/L AS TL) 01057 ug/lZINC, DISSOLVED (UG/L AS ZN) 01090 ug/lPG_PARM_NAME PG_STORET_CODE PG_MEASUREMENT_UNITACID NEUTRALIZING CAPACITY ANCXX mg/lACIDITY, TOTAL (MG/L AS CACO3) 00435 mg/lALKALINITY, TOTAL (MG/L AS CACO3) 00410 mg/lCHLORIDE, DISSOLVED IN WATER MG/L 00941 mg/lNITRATE NITROGEN, DISSOLVED (MG/L AS N) 00618 mg/lNITRATE NITROGEN, TOTAL (MG/L AS N) 00620 mg/lNITRITE NITROGEN, DISSOLVED (MG/L AS N) 00613 mg/l





A7 Quality Objectives and Criteria for Measurement Data

A7.1 Data Quality Objectives

Data Quality Objectives (DQOs) are qualitative and quantitative statements that specify the quality of data supporting project decisions. Data are to be collected and analyzed in accordance with the Department’s Water Quality Monitoring Standard Operating Procedures5, referred to in this document as the SOP. Data are to be reported uncensored for the purpose of statistical analyses. Trace elements are determined by methods of standard additions so data censoring is not appropriate and will not be considered for data analyses.

The quality of data generated by this project can be expressed in terms of comparability, representativeness, precision, bias, and completeness using the following criteria.

A.7.1.1 Comparability

Comparability refers to the extent to which the data generated by this project is comparable to data collected from the sites from previous studies. To ensure comparability, this project requires the use of standardized sampling and analytical methods, uniform units of reporting, and standardized site selection procedures. The comparability of laboratory data produced for VADEQ is provided by utilizing the Division of Consolidated Laboratory Services where standardized methods are utilized where possible, including USEPA approved analytical methods, Standard Methods, USGS Methods, or documented modifications thereof which provide equal or better results. The sampling methods have been reviewed by a team of water quality assessment experts and determined appropriately similar to previous studies for comparison.

A.7.1.2 Representativeness

The representativeness of the data is mainly dependent on site selections and the utilization of sampling procedures that produce results adequately representing the true condition of the site sampled. The goal for meeting total representation of the site will be tempered by the types and number of potential sampling points and media as well as the potential funding required for meeting complete representativeness.

A.7.1.3 Precision and Bias

The precision and bias of data are determined by the procedures used by the analytical laboratory and field staff. The precision of data is a measure of the reproducibility of the measurement when the analysis is repeated. It is reported in Relative Percent Difference (RPD). The bias of an analysis is a measure of how much of a constituent actually present is determined. It is measured, where applicable, by adding a known amount of a constituent to a sample and determining how much of the added constituent (spike) is then measured. It is reported as Percent Recovery. The acceptable percent deviations and acceptable percent recoveries are dependent on many factors including: analytical method used, laboratory used, media of sample, and constituent being measured.

5 STANDARD OPERATING PROCEDURES MANUAL FOR THE DEPARTMENT OF ENVIRONMENTAL QUALITY WATER QUALITY MONITORING AND ASSESSMENT PROGRAM, Commonwealth of Virginia Department of Environmental Quality Water Quality Monitoring and Assessment 629 East Main Street Richmond, VA 23219, Revision No.: 19 Rev. Date: 02/27/2014. http://www.deq.virginia.gov/Programs/Water/WaterQualityInformationTMDLs/WaterQualityMonitoring/QualityAssuranceQualityControl.aspxdocument.docx Tuesday, March 10, 2015


A.7.1.4 Completeness

The completeness of data is the relationship of how much usable data are available compared to the total amount of data expected to be available. Ideally, 100% of the data should be available. However, the possibility of data becoming unavailable due to laboratory error, insufficient sample volume, or samples broken during shipment must be expected. Also, unexpected situations may arise where field conditions do not allow for 100% data completeness. Therefore, 90% data completeness is considered sufficient for this project.

A8 Special Training Needs/ Certification

Proper training of field personnel represents a critical aspect of sampling collections. Biologists have been trained to conduct sampling using standardized protocols to ensure comparability in data collection across geographic locales. Field teams should be certified in the clean metals sampling protocol.

A9 Documents and Records

A9.1 Field Data Documentation

The project requires that each data generating activity be thoroughly documented. Field staff record field data on hardcopy field data sheets containing station ID, date and time collected, collector, group code, and the field measurement results. At the end of each sampling day, all the field data are transcribed into the central database CEDSWQM. It is recommended that the field data sheets be secured in filing cabinets at the regional offices and maintained for a seven year period. Field data sheets and container labels are generated from the Monthly Run Schedule in CEDS, see Figure 3 Monthly Run Schedule for Clinch River Tennessee on page 16. Figure 4 Field Data Sheet for Run TNCLINCH (Figure 4, page 17) can be used by the field team members to record measurements and any notes relevant to the collection event. A convenient alternative to the Field Data Sheet for the Tennessee field crew could be the use of an electronic spreadsheet that can be easily transferred to VADEQ staff for data entry, such as the Figure 5 Electronic Field Data Sheet, partial (Figure 5, page 17).

Figure 6 Container Labels (Figure 6, page 18), is an example of the container labels which print on Avery Laser Labels 5163. For sample containers like cubitainers where the Avery 5163 label has a hard time sticking we use the VADEQ wire tag around the neck of the container and place the Avery 5163 on the back of the wire tag (Figure 7 Wire Tag, page 19. VADEQ will provide wire tags for all samples.



Figure 3 Monthly Run Schedule for Clinch River Tennessee, TNCLINCH



Figure 4 Field Data Sheet for Run TNCLINCH

Figure 5 Electronic Field Data Sheet, partial

TDEC STATION Run ID VADEQ STA Collector Date Time Water Temp

TNCLINCH 6BCLN177.47 BB 06/24/2015 1100

TNCLINCH 6BCLN189.10 BB 06/24/2015 1300

TNCLINCH 6BCLN199.15 BB 06/24/2015 1500

Clinch River mile 177.4, Rt 33 bridge south of Sneedville

Route 70 bridge near Kyles FordHorton Ford, Tennessee



Figure 6 Container Labels



Figure 7 Wire Tag



A9.2 Instrument Calibration and Maintenance Documentation

Complete procedures for operating, maintaining and calibrating instruments used in field environmental measurements are contained in Water Quality Monitoring SOPs. Personnel using field instruments are expected to read and be thoroughly familiar with all procedures detailed in the SOPs. A calibration and maintenance log shall be kept for each instrument. Dates of calibration and any other pertinent data shall be routinely entered in the logsheet. All maintenance activities will also be entered in the logsheet. Records shall be maintained for seven years.

A9.3 Laboratory Data Documentation

Documentation for analytical data is kept on file at the participating laboratories and recommended to be maintained on site for five years before being archived at the state library. Documents should be readily available for review during external audits and should include the analyst’s comments on the condition of the sample, progress of the analyses, primary standard certification, working standard preparations, instrument calibration results, results of QC check sample/measurements or instrument printouts, and final data calculations.

B1 Sampling Design

The focus of this study is to conduct trace element, major ion, and various solid species sampling at a section of the Clinch River where freshwater mussel communities are impacted as indicated by low densities, low species diversity, and lack of age class distribution. Sampling upstream and downstream just outside of the impacted area is designed to determine if there are significant differences in concentrations of target analytes present in the impacted zone as compared to these upstream and downstream reference sites.

A most important consideration of this study has been the discussion of depth and width isokinetic sampling versus cross sectional non isokinetic sampling versus a single grab sample at the thalweg. Typically when following the VADEQ clean metals SOP, cross sectional field specific conductivity (SC) measurements will determine if the stream is well mixed. SC measurements must be within 10% of the thalweg SC for the stream to be considered well mixed. Because this study is focused on low or base flow conditions, when the ratio of total to dissolved metals approximates 1:1, low suspended sediments equates to most of the trace elements existing in their dissolved moieties, isokinetic sampling involving multiple grab samples composited into pre cleaned churn splitters is considered not to be necessary. Additionally because sampling is targeted towards low flow conditions, we assume stream velocities are below 1.5 meter sec-1.

Integrated continuous sampling by moving the Bridge Bottle sample collection device at a constant rate during sample collection is considered a more representative sample than the traditional fixed interval grabs composited into one sample. The integrated nature of continuous sampling across 80% center wetted width (10% to 90%) of the river versus only five discreet interval samples likely reflects the true concentrations of target analytes present in the system.



Sampling every other month will target flow conditions that are at or below the median daily flow for the period of record. These base flow sampling events are thought to be representative of typical conditions experienced by stream infauna.

The solids series parameters will be used to infer sample constituents based on the Table 3 Solid Speciation table (Table 3, page 23). Toxic metal concentrations will be compared to the Virginia Water Quality Standards6 to determine the potential for aquatic life impairment. Major ion charge balances will be calculated to verify analytical quantitation and that all major ions have been accounted for when the charge balance is within approximately 5%.

The null hypothesis of this study is that there is not a statistically significant difference among the target analytes in the impacted reach and those of the downstream or upstream reference stream sites.

B2 Sampling Methods

In addition to collecting field parameters and standard chemical parameters covered in the Water Quality Monitoring SOP7, clean metal samples will be collected following the Standard Operating Procedure for the Collection of Freshwaters, Saltwaters, and Wastewaters for the Determination of Trace Elements8, also known as the Clean Metals SOP or simply clean hands dirty hands method. The clean metals sample collection procedure documented in this SOP is extremely rigorous and requires field staff using the method to be trained by experts in the application of this SOP.

Because of the large volumes of water sample needed for the extensive list of analytes, a modification to the standard bridge bottle configuration will be used such that a single width integrated sample will be collected. The standard Bridge Bottle holds 3,750 ml when completely filled and would require three separate deployments to obtain the volume for all sample containers. The total sample volume required is derived from the sum of all containers and equals 8,285 ml plus 125 ml to purge the clean metal capsule filter of entrained ultrapure water.

Substituting the standard Bridge Bottle configuration with a larger 2.5 gallon, 9,500 ml pre-cleaned plastic jerry can will facilitate sample collection efficiency and integrity. Giving the unique sealed design of the Bridge Bottle, and the moderately slow siphoning of sample water, it has been decided to collect a near surface, integrated cross sectional sample with the Bridge Bottle. Starting from within 10% of the left ascending wetted bank, the Bridge Bottle is to be deployed. Once siphoning has begun the bottle will be gently and steadily dragged to the 90% right ascending wetted bank width within the time it takes to completely fill a bridge bottle. It takes on average 5 minutes to completely fill the large Bridge Bottle when 10 pounds of ballast are used.

Once the sample has been collected, the Bridge Bottle is transported off the bridge to a safe location where the processing of individual samples occurs. Typically, for routine samples that do not require the use of the clean 6 STATE WATER CONTROL BOARD 9 VAC 25-260 Virginia Water Quality Standards. Statutory Authority: § 62.1-44.15 3a of the Code of Virginia. WITH AMENDMENTS EFFECTIVE January 6, 2011. http://www.deq.virginia.gov/Programs/Water/WaterQualityInformationTMDLs/WaterQualityStandards.aspx7 STANDARD OPERATING PROCEDURES MANUAL FOR THE DEPARTMENT OF ENVIRONMENTAL QUALITYWATER MONITORING AND ASSESSMENT PROGRAM Commonwealth of Virginia Department of Environmental QualityWater Quality Monitoring and Assessment 629 East Main Street Richmond, VA 23219, Rev. Date: 02/27/2014.8 Guidance Memorandum No. 01-2003, Virginia Department of Environmental Quality, Office of Water Quality Programs, Water Quality Monitoring and Assessment, March 5, 2001. http://www.deq.virginia.gov/Programs/Water/Laws,Regulations,Guidance/Guidance/MonitoringAssessmentGuidance.aspxdocument.docx Tuesday, March 10, 2015

http://www.deq.virginia.gov/Programs/Water/Laws,Regulations,Guidance/Guidance/MonitoringAssessmentGuidance.aspx

http://www.deq.virginia.gov/Programs/Water/Laws,Regulations,Guidance/Guidance/MonitoringAssessmentGuidance.aspx


hands dirty hands procedure, stainless steel bucket sampling is specified in the Water Quality Monitoring SOP. For this study all parameters will be collected out of the clean metals Bridge Bottle.



Table 3 Solid Speciation

SOLIDS DISSOLVED SUSPENDEDTOTAL RESIDUE FILTRABLE RESIDUE NONFILTRABLE RESIDUE00500 TS = 00515 TDS + 00530 TSS00505 TV = 00520 TDV + 00535 TSV00510 TF = 00525 TDF + 00540 TSFTS = TV + TF TDS = TDV + TDF TSS = TSV + TSF

TV =

OH

TDV =

OH

TSV =

SO4CO3 CO3 organicsHCO3 HCO3 PO4

SO4 00945 Cl SiO2Cl 00940 PO4 00671 BO3

PO4 SiO2 00955SiO2 BO3BO3 DOC

TOC 00680

TF = inorganics TDF = inorganics TSF = inorganics

70300 TDS

MOIETY MW MAJOR CATION CONTRIBUTION IN FRESHWATERSCa 40 Ca 40.0% 16.0

mean, mg/LMg 24 Mg 15.3% 6.1Na 23 Na 40.2% 16.1K 39 K 4.5% 1.8Al 27 Al traceFe 56 Fe traceMn 55 Mn trace

CO2 44 00435 Acidity

CO3 60 00410 Alkalinity

SO4 96 00900 and HARDNESS Hardness

Cl 35 00095 and FDT_SPECIFIC_CONDUCTANCE Conductivity

OH 17

measure of hydrogen ion capacity

measure of titratable bases, CO3 HCO3 PO4 SiO2 BO3

measure of Calcium and Magnesium

measure of electron potential, correlated to cation and anion concentration



Sample container count, size, type, and preservation for each of the parameter group codes are listed in Table 4 Sample Containers and Preservations

Table 4 Sample Containers and Preservations

CT_CONT_TYPE CT_CONT_COLOR PS_PRESER_TYPE_DESC

CMETB 1 250ml No Preservative Required

CMETB 1 1000ml CLEAR No Preservative Required

DCMET1 1 250ml No Head Space

DCMET1 1 1000ml CLEAR No Preservative Required

PROB4-2 1 4000ml Cubitainer No Preservative RequiredPROB4-2 1 250ml Plastic Bottle Clear Sulfuric Acid to pH < 2SSC-C2 1 1000ml Cubitainer No Preservative Required

TCMET1 1 250ml No Head Space

TCMET1 1 1000ml CLEAR No Preservative Required

TN 1 125ml plastic bottle No Preservative Required

LC_PARM_GROUP_CODE

CG_CONT_COUNT

CT_CONT_SIZE

CT_CONT_SIZE_UNITS

Double bagged Nalgene (FLPE) with pre-cleaningClean Metals Certified loop Nalgene bottle with pre-cleaning and tubing kitNalgene (FLPE) with special tubing and cleaningClean Metals Certified loop Nalgene bottle with pre-cleaning and tubing kit

Double bagged Nalgene (FLPE) with pre-cleaningClean Metals Certified loop Nalgene bottle with pre-cleaning and tubing kit

B3 Sampling Handling and Custody

Upon collecting each sample that is destined for laboratory analysis, the corresponding preprinted label will be placed on the container and the time of sample collection will be recorded in the TIME block. For cubitainers, the label will be placed on the back of the wire tag label which is then fastened around the neck of the container. When handling clean metals containers, the clean hand holds each container in a manner that provides access to the surface so that dirty hands can attach the label without coming in direct contact with the container surface.

In the field, all samples will be packed in wet ice after collection and during shipment so that they will be kept at approximately 6oC. Sample containers will be clearly labeled with printed labels or sample tags. All caps and lids will be checked for tightness prior to placement in the cooler.

Samples collected by TDEC will be transferred to VADEQ for shipping to DCLS using the overnight courier. VADEQ will provide shipping coolers to TDEC that meet the courier’s and DCLS’s requirements for overnight transportation of environmental samples.

Field staff will drain the water from the cooler at the end of the sampling day and refill the cooler with ice to maintain the samples at 6oC. Samples are shipped in the cooler overnight to the Division of Consolidated Laboratory Services (DCLS) via contract courier service. Upon receipt of the samples, DCLS will check the information on the labels against the information field staff has entered into CEDSWQM. If the information does not match, the lab staff will try to reconcile the differences or reject the sample(s). DCLS will also measure the temperature of the samples using a temperature bottle kept in the cooler throughout the collection and shipment process and check acidified preserved samples to ensure proper acidification, pH. If any of the



measurements exceed a limit, the lab qualifies the sample result or rejects the sample. Once the samples have been logged, the lab staff will transfer them to the refrigerator and store them at 4oC. All samples will be handled, prepared, transported and stored in a manner so as to minimize bulk loss, analyte loss, contamination and/or biological degradation.

Ideally, all analyses are completed within a few days after processing to allow for review of the results and possible reanalysis of suspect samples within fourteen days. Critical holding times for the analyses are the maximum allowable holding time as defined by USEPA and Standard Methods.

The data for this project are not to be used for legal purposes, therefore, formal chain of custody procedures are not required.

B4 Analytical Methods

The analytical methods used by DCLS for this project are in accordance with currently approved procedures given in Standard Methods for Examination of Water and Wastewater or USEPA Methods for Chemical Analysis of Water and Wastes or VADEQ Guidance. Sample analyses will be conducted by DCLS using approved methods as specified in the Virginia Environmental Laboratory Accreditation Program and for which DCLS is certified to perform these analyses. A detailed description of analytical procedures and the instruments used for each analysis are included in the laboratory’s Standard Operation Procedures.

B5 Quality Control

B5.1 Quality Assurance Objective

For duplicate samples, precision across batches is estimated as the pooled standard deviation of all samples at the lower concentration range, and as the pooled percent relative standard deviation of all samples at the higher concentration range. Bias (systematic error) is reported as net bias. Net bias is estimated as the difference between the mean measured value and the target value of a performance evaluation and/or internal reference samples at the lower concentration range measured across batches. Precision and bias are monitored at the point of measurement (field or analytical lab) by several types of QC samples described in the Section B.5.3.

B5.2 QC Procedures for Field Operation

For in-situ measurements, each field instrument must be calibrated prior to use and calibration information should be recorded on a calibration logsheet. A calibration logsheet is maintained by each regional office for every piece of field instrumentation. The field instrument should be checked at the end of each sampling day for drift in calibration. The acceptance criteria for the drift of field parameters are listed in Table 5 Acceptance Criteria for Field Parameters.



Table 5 Acceptance Criteria for Field Parameters

Check Description Acceptance CriteriaDO ±0.50 mg/lpH ± 0.20 unitConductivity ±10%Verify performance of temperature probe Functionality ± 0.5 oC Field QC Samples;

Each of the two field crews (TN and VA) will collect one equipment blank during the first sampling event of this project. Each of the two field crews (TN and VA) will collect one field split sample at a randomly selected site during the second sampling event of the study.

B5.3 QC Procedures for Laboratory Operation

The services performed by DCLS as requested in this project are approved methods for which DCLS has been certified to perform on environmental samples. Each of the methods contains rigorous quality control steps that document data integrity. The laboratory methods are listed in Table 6 Analytical Test Methods beginning page 26.

Table 6 Analytical Test Methods

I3750 70331 %

I3750 mg/l

I3750 SSC-FINE mg/l

I3750 SSC-TOTAL mg/l

APHA NITROGEN, TOTAL (MG/L AS N) 00600 mg/l

USEPA 351.2 00625 mg/l

USEPA 365.4 PHOSPHORUS, TOTAL (MG/L AS P) 00665 mg/l

APHA 5310-B CARBON, TOTAL ORGANIC (MG/L AS C) 00680 mg/l


USDOI/USGS

SUSPENDED SED SIEVE DIAMETER,% FINER THAN .062MM

USDOI/USGS

SUSP. SED. CONC. - >62 um,MG/L, (Method C)

SSC-COARSE

USDOI/USGS

SUSP. SED. CONC. - <62 um,MG/L, (Method C)

USDOI/USGS

SUSP. SED. CONC. TOTAL, MG/L,(Method B)

4500-N-C

NITROGEN, KJELDAHL, TOTAL, (MG/L AS N)




USEPA 1638 ZINC, DISSOLVED (UG/L AS ZN) 01090 ug/l

USEPA 1638 ANTIMONY, DISSOLVED (UG/L AS SB) 01095 ug/l

USEPA 200.7 ALUMINUM, DISSOLVED (UG/L AS AL) 01106 ug/l

USEPA 1638 SELENIUM, DISSOLVED (UG/L AS SE) 01145 ug/l

USEPA 245.7 50091 ng/l

USEPA 200.7 DHARD mg/l

PG_PARM_NAME

APHA 2510B SPECIFIC CONDUCTANCE (UMHOS/CM @ 25C) 00095 umho/cm

APHA 150.1 PH, LAB, STANDARD UNITS SU 00403 None

APHA 2320-B ALKALINITY, TOTAL (MG/L AS CACO3) 00410 mg/l

APHA 2310 ACIDITY, TOTAL (MG/L AS CACO3) 00435 mg/l

I3750 TS RESIDUE, TOTAL (MG/L) 00500 mg/l

I3750 TV RESIDUE, TOTAL VOLATILE (MG/L) 00505 mg/l

I3750 TF RESIDUE, TOTAL FIXED (MG/L) 00510 mg/l

I1750 00520 mg/l

I1750 TDF RESIDUE, FIXED FILTRABLE (MG/L) 00525 mg/l

I3765 00530 mg/l

I3765 00535 mg/l

I3765 00540 mg/l


ASTM 00608 mg/l

I4523 NITROGEN, AMMONIA, TOTAL (MG/L AS N) 00610 mg/l

00613 mg/l

353.2 NITRITE NITROGEN, TOTAL (MG/L AS N) 00615 mg/l

00618 mg/l

353.2 NITRATE NITROGEN, TOTAL (MG/L AS N) 00620 mg/l

USEPA 365.1 00671 mg/l

MERCURY-TL,FILTERED WATER,ULTRATRACE METHOD NG/L


ME_METHOD_CODE

MC_CODE_ID

PG_STORET_CODE

PG_MEASUREMENT_UNIT

USDOI/USGSUSDOI/USGSUSDOI/USGSUSDOI/USGS

TDV RESIDUE, VOLATILE FILTRABLE (MG/L)

USDOI/USGSUSDOI/USGS

TSS RESIDUE, TOTAL NONFILTRABLE (MG/L)

USDOI/USGS

TSV RESIDUE, VOLATILE NONFILTRABLE (MG/L)

USDOI/USGS

TSF RESIDUE, FIXED NONFILTRABLE (MG/L)

4500-N-CD6919-03

NITROGEN, AMMONIA, DISSOLVED (MG/L AS N)

USDOI/USGS

D3867-04

NITRITE NITROGEN, DISSOLVED (MG/L AS N)

D3867-04

NITRATE NITROGEN, DISSOLVED (MG/L AS N)

PHOSPHORUS, DISSOLVED ORTHOPHOSPHATE (MG/L AS P)




PG_PARM_NAME

USEPA 200.7 CALCIUM, DISSOLVED (MG/L AS CA) 00915 mg/l

USEPA 200.7 MAGNESIUM, DISSOLVED (MG/L AS MG) 00925 mg/l

USEPA 200.7 SODIUM, DISSOLVED (MG/L AS NA) 00930 mg/l

USEPA 200.7 POTASSIUM, DISSOLVED (MG/L AS K) 00935 mg/l

USEPA 1638 ARSENIC, DISSOLVED (UG/L AS AS) 01000 ug/l

USEPA 200.7 BARIUM, DISSOLVED (UG/L AS BA) 01005 ug/l

USEPA 1638 BERYLLIUM, DISSOLVED (UG/L AS BE) 01010 ug/l

USEPA 1638 CADMIUM, DISSOLVED (UG/L AS CD) 01025 ug/l

USEPA 1638 CHROMIUM, DISSOLVED (UG/L AS CR) 01030 ug/l

USEPA 1638 COPPER, DISSOLVED (UG/L AS CU) 01040 ug/l

USEPA 200.7 IRON, DISSOLVED (UG/L AS FE) 01046 mg/l

USEPA 1638 LEAD, DISSOLVED (UG/L AS PB) 01049 ug/l

USEPA 1638 MANGANESE, DISSOLVED (UG/L AS MN) 01056 ug/l

USEPA 1638 THALLIUM, DISSOLVED (UG/L AS TL) 01057 ug/l

USEPA 1638 NICKEL, DISSOLVED (UG/L AS NI) 01065 ug/l

USEPA 1638 SILVER, DISSOLVED (UG/L AS AG) 01075 ug/l

USEPA 1638 ZINC, DISSOLVED (UG/L AS ZN) 01090 ug/l

USEPA 1638 ANTIMONY, DISSOLVED (UG/L AS SB) 01095 ug/l

USEPA 200.7 ALUMINUM, DISSOLVED (UG/L AS AL) 01106 ug/l

USEPA 1638 SELENIUM, DISSOLVED (UG/L AS SE) 01145 ug/l

USEPA 245.7 50091 ng/l

USEPA 200.7 DHARD mg/l

PG_PARM_NAME

ME_METHOD_CODE

MC_CODE_ID

PG_STORET_CODE

PG_MEASUREMENT_UNIT

MERCURY-TL,FILTERED WATER,ULTRATRACE METHOD NG/L


ME_METHOD_CODE

MC_CODE_ID

PG_STORET_CODE

PG_MEASUREMENT_UNIT




USEPA 1638 SELENIUM, TOTAL (UG/L AS SE) 01147 ug/l

USEPA 200.7 46570 mg/l

USEPA 245.7 50092 ng/l

PG_PARM_NAME

I3750 70331 %

I3750 mg/l

I3750 SSC-FINE mg/l

I3750 SSC-TOTAL mg/l


USEPA 351.2 00625 mg/l


APHA 5310-B CARBON, TOTAL ORGANIC (MG/L AS C) 00680 mg/l


HARDNESS, CA MG CALCULATED (MG/L AS CACO3)

MERCURY-TL,UNFILTERED WATER,ULTRATRACE METHOD NG/L

ME_METHOD_CODE

MC_CODE_ID

PG_STORET_CODE

PG_MEASUREMENT_UNIT

USDOI/USGS

SUSPENDED SED SIEVE DIAMETER,% FINER THAN .062MM

USDOI/USGS

SUSP. SED. CONC. - >62 um,MG/L, (Method C)

SSC-COARSE

USDOI/USGS

SUSP. SED. CONC. - <62 um,MG/L, (Method C)

USDOI/USGS

SUSP. SED. CONC. TOTAL, MG/L,(Method B)

4500-N-C

NITROGEN, KJELDAHL, TOTAL, (MG/L AS N)



B6 Instrument/Equipment Testing, Inspection, and Maintenance

To minimize downtime of the measurement system, all field and lab instruments must be maintained in working condition. Environmental field specialists and lab technicians will inspect instruments and equipment daily. Corrective action will be taken immediately when problems are found. Backup instruments/equipment or common spare parts will be available so that if any piece of an instrument/equipment fails during use, repairs or replacement can be made as quickly as possible and the measurement tasks resumed. Preventive maintenance should be performed according to the manufacturer’s recommendations.

B7 Instrument/Equipment Calibration and Frequency

Field and lab instruments and equipment require routine calibration checks to verify that their performance is within acceptable quality standards. The following sections will discuss procedures and frequencies for the instrument calibrations.

B7.1 Field Operations

Each field instrument must be inspected prior to use and calibrated with standards bracketing the expected concentration of the samples. The field instruments are then verified for accuracy at the end of the sample day by comparing readings to standards as outlined in Table 5 Acceptance Criteria for Field Parameters.

B7.2 Laboratory Operations

Calibration of DCLS’s analytical instruments is required to assure that the data generated meet Data Quality Objectives (DQOs). Detailed calibration frequencies and acceptance criteria are specified in the analytical methods SOPs. Calibration activity performances are documented and are available for review during internal and external lab audits.

In general, reference standards used will bracket the expected concentration of the samples. At a minimum, this generally will require the use of three to five different standard concentration levels to quantify the instrument’s linear range. Calibration of the instruments must be performed prior to sample analyses and then at periodic intervals during the analyses to verify that the instruments are still in calibration. Sample concentrations exceeding the calibration ranges need to be diluted and reanalyzed.

B8 Inspection/Acceptance of Supplies and Consumables

This project will only utilize supplies and consumables that are of adequate quality to sustain confidence that data generated in the sample collection, processing, and laboratory analyses will meet the DQOs. Purchased supplies and consumables will not be used until they have been inspected, calibrated, or otherwise verified to ensure compliance with any relevant standard specifications for use in this project.



B9 Data Management Constituents measured in the field are recorded manually on a field data sheet and entered by the field specialist into the Department’s environmental database, CEDSWQM, upon returning to the office. The CEDSWQM system has been designed to check valid values for key field measurements, e.g. pH between 0.0 and 14.0. Field data sheets will be kept in the file for five years.

Analytical results are certified by each Principal Chemist at DCLS and then loaded into the CEDSWQM database via an automated File Transfer Protocol (FTP). Laboratory files processed by the system are archived on the server to retain the original data files.

Retrieval of the data can be accomplished through SAS. VADEQ Central Office staff will perform the queries and statistical analyses of all data relevant to this project. Data, results, and interpretations will be documented in a final report that will be stored with the raw data in CEDSWQM under the Special Study number 15019.

The data from this project will also be available to the public via the USEPA Water Quality Exchange database application, STORET, under the Organization ID 21VASWCB, Virginia Department of Environmental Quality being the official owner of the data.

C1 Assessment and Response Actions

C1.1 Field Crew

Field staff are trained by the Virginia Team Leader and follow the Water Quality Monitoring Program’s Standard Operating Procedures (SOP) to ensure the consistency between regions. The TDEC and VADEQ Team Leaders will accompany each of the field crews during all sampling events.

C1.2 Field Reviews

To ensure that actual field collections are conducted in accordance with the SOP, the performance of field staff will be evaluated by the QA Officer. The format for the evaluations will be more of a field procedural review than audit. The goal is to conduct at least one collection activity review during the whole project. The evaluator will use an approved checklist to systematically document acceptable/unacceptable performance on all pertinent aspects of the sampling.

Any minor deficiencies observed during a field procedure review should be immediately pointed out to the staff and corrective actions imposed on-the-spot. If significant deficiencies are observed, the evaluator will make the appropriate on-the-spot correction, and if the case warrants, stop the field activities until the problems are resolved to the satisfaction of the WQM QA Officer. All cases of this nature will be documented.



C1.3 Laboratory Activities

Internal and external audits are conducted regularly at DCLS to monitor the overall effectiveness of the quality assurance system. Internal audits are performed by the DCLS QA department, which is responsible for all QA/QC functions in the laboratory, and/or members of the professional laboratory staff that do not normally work in the section or analytical unit being audited. External audits are conducted by the persons who are not direct employees of DCLS to provide an independent and unbiased review of laboratory operation.

There are two types of audits: system audits and performance audits. 1) System audits involve an in-depth review and evaluation of some or all of the components of the analytical laboratory to determine if guidelines listed in the QA plans are properly applied. 2) Performance audits require the analysis of blind samples or other samples whose values are not known to the analytical lab. These results are used to evaluate the accuracy of the lab analytical system.

The DCLS laboratory facilities for this project have been approved under the Virginia Environmental Laboratory Accreditation Program (VELAP) to maintain regimented QA/QC records and performance.

C1.3.1 System Audit

1) System Internal Audits

The DCLS QA department conducts several system audits each calendar year. During these audits, one or more components of the lab will be reviewed to determine if that part is functioning in compliance with the lab QA plan, the approved SOPs, and approved methodologies. An audit report will include a list of deficiencies that must be addressed in order to correct or improve the lab operations.

System components to be audited during the internal audit will include, but are not limited to:

All documentation associated with sample and data handling, to include linkage mechanism employed between all records for tracking documentation for any sample data result.

Use of established approved procedures as outlined in the QA plan. Personnel training records. Proper execution of established procedures. Follow-up to corrective actions from previous audits. Sample and data handling activities: all sample login, routing and disposal; sample preparations; method

calibrations; sample analyses; data reduction, validation and reporting; preventative maintenance and repair procedures; standard and reagent preparation, documentation and storage; sample and waste disposal; container and labware decontamination; QC management practices and assessment of analytical precision, accuracy and sensitivity.

Deficiency lists and associated corrective action orders will be formally communicated to responsible staff.

2) System External Audits



External audits are performed when certifying agencies or clients submit samples for analysis and/or conduct on-site inspections. External laboratory systems and periodic performance audits are conducted by an authorized National Environmental Laboratory Accreditation (NELAC) inspection team.

C 1.3.2 Performance Audit

The laboratory is involved in external performance audits conducted annually through the analysis of performance evaluation samples provided by the QA department or third party.

The QA department and VADEQ conduct performance evaluations using commercially prepared samples as blind samples. The results of these audits will be documented and reported to managers so that any necessary adjustments can be made.

Blind sample audits are performed by submitting QC samples to the analyst. The true values are only made known after the test is completed. Blind sample audits are carried out by the QA department, clients and certifying agencies as necessary to assure the lab is capable of achieving success with a blind QC sample.

C2 Reports to Management

C2.1 Field Activities

The Team Leaders should update the progress on the general status of the field team’s activities on a regular basis to the project manager. These updates can be informal and be communicated by telephone or e-mail.

C2.2 Final Report

The Virginia Team Leader will prepare the data assessment and final report to the project manager when the project is completed.

D1 Data Review, Verification, and Validation

The most critical component of data review, validation and verification of data generated in this project will be conducted by staff at the regional offices and laboratory staff when it is generated through the analytical results. The overall data quality of each parameter will be evaluated in terms of accuracy and precision by the WQM QA Officer using the quality criteria described in this QAPP (see section B5.3). Data sets that meet all the prescribed quality criteria will be accepted without further qualification for use in development of nutrient standards. Data that do not meet all of the acceptable criteria because of minor deficiencies will be assigned data qualifier codes to flag them as questionable values. These data may still be included in the data set to allow the data users to decide for themselves whether the data are acceptable for their specific purpose. Data that consistently fail one or more quality criteria assessment by a significant margin will be rejected and deleted from the data set.document.docx Tuesday, March 10, 2015


D2 Verification and Validation Methods

D2.1 Data Verification

Data verification is a process of evaluating the completeness, correctness and conformance/compliance of a specific data set against the cited method, procedure or expected results.

Field data verification should include: a review of data for correctness, use of correct units, data reality in relation to the range of expected results, and data completeness. For example, an evaluation needs to be conducted for transcription errors that occur when transcribing the information from field data sheets into electronic format. This evaluation will be performed on all sites for this study.

When lab results are transmitted to the VADEQ CEDSWQM database the QA Officer will conduct the verification process as follows:

1) Each result will be compared to historic data collected from the same site. The datum will be flagged if it falls more than three standard deviations from the mean for a given parameter.

2) The values of split samples will be flagged if the coefficient of variation of the difference in the split samples exceeds 20%.

3) The datum will be flagged if the holding time was exceeded.4) If internal logic checks (the sum of individual species is greater than total concentration) are violated, then all results involved will be flagged.

D2.2 Data Validation

Data validation is an analyte and sample specific process that extends the evaluation of data beyond method or procedure to determine the analytical quality of specific data set.

Measurements of field parameters taken directly in the field will be evaluated for accuracy by verifying the results by calibration and checking for instrument drift. These checks should be performed by the field staff on a daily basis and, if the instruments are out of specifications, they should be recalibrated. Any field data that was collected while the instrument was out of compliance will be removed from the database.

The WQM QA Officer will be responsible for conducting data validation of the data before submitting the data to the project manager. The data set will be assessed by a critical comparison of the submitted QA/QC results to the quality criteria or standards established by this QAPP for that analysis. If the evaluation indicates that the data meet the quality standards overall, with no or only minor deficiencies, then the data set will be considered acceptable for the project without further qualification. If the data consistently fail one or more quality criteria then the data set will be flagged with an appropriate data qualifier code. Depending on the degree of the deficiency, the data might still be used for some purpose or may be removed entirely from the database.



D3 Reconciliation with User Requirements

It is essential that the data quality is at the highest level. Data rejected during laboratory analysis or during the data validation process are considered unusable. It is recommended that the samples should be reanalyzed or additional samples should be collected.



Table 7 Glossary

Term Definition

CEDSWQM Comprehensive Environmental Data System Water Quality Monitoring module

DCLS Division of Consolidated Laboratory Services

DQO Data Quality Objective

NELAC National Environmental Laboratory Accreditation

RKM River kilometer as measurement from mouth.

RM River mile as measurement from mouth.

RPD Relative Percent Difference

SOP Water Quality Monitoring Standard Operating Procedures

TDEC Tennessee Department of Environment and Conservation

TDEC Tennessee Department of Environment and Conservation

TNC The Nature Conservancy

USEPA U.S. Environmental Protection Agency

USGS U.S. Geologic Survey

VADEQ Virginia Department of Environmental Quality

WQM ADMIN Administrator role for WQM

WQMA Office of Water Quality Monitoring and Assessment

WQX Water Quality Data Exchange Network for STORET data


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