Attachment 2 - Pages from CRPFY12-13QAPP.pdf

Attachment 2

Pages from

RIO GRANDE BASIN MONITORING PROGRAM QUALITY ASSURANCE PROJECT PLAN for FY2012 to 2013

Pages pertinent to Contract Lab include:

Section A7 QUALITY OBJECTIVES AND CRITERIA

Section A9 DOCUMENTS AND RECORDS

Section B (particularly Table 4 Sample Storage, Preservation and Handling Requirements and

Section B5 QUALITY CONTROL)

Appendix A (Table A7 MEASUREMENT PERFORMANCE SPECIFICATIONS)

Appendix D (COCs)

Entire document can be found online at:

http://www.ibwc.gov/CRP/documents/USIBWCFY12‐13QAPP_TableA7Final.pdf

USIBWC FY12-13 QAPP Page 1 Last revised on 08/09/2011 09:49 USIBWC FY12-13 QAPP.docx

RIO GRANDE BASIN MONITORING PROGRAM

QUALITY ASSURANCE PROJECT PLAN

INTERNATIONAL BOUNDARY AND WATER COMMISSION, UNITED STATES SECTION

4171 N. MESA, C-100

EL PASO, TEXAS 79902

CLEAN RIVERS PROGRAM

WATER QUALITY PLANNING DIVISION

TEXAS COMMISSION ON ENVIRONMENTAL QUALITY

P.O. BOX 13087, MC 234

AUSTIN, TEXAS 78711-3087

EFFECTIVE PERIOD: FY 2012 TO FY 2013

QUESTIONS CONCERNING THIS QAPP SHOULD BE DIRECTED TO:

ELIZABETH VERDECCHIA

USIBWC PROGRAM MANAGER

4171 N. MESA, C-100

EL PASO, TEXAS 79902

(915) 832-4701

ELIZABETH.VERDECCHIA@IBWC.GOV

USIBWC QAPP Page 29

A7 QUALITY OBJECTIVES AND CRITERIA

The purpose of routine water quality monitoring is to collect surface water quality data that can be used to characterize water quality conditions, identify significant long-term water quality trends, support water quality standards development, support the permitting process, and conduct water quality assessments in accordance with TCEQs Guidance for Assessing Texas Surface and Finished Drinking Water Quality Data. These water quality data, and data collected by other organizations (e.g., USGS, TCEQ, etc.), will be subsequently reconciled for use and assessed by the TCEQ.

Systematic watershed monitoring is defined by sampling that is planned for a short duration (1 to 2 years) and is designed to: screen waters that would not normally be included in the routine monitoring program, monitor at sites to check the water quality situation, and investigate areas of potential concern. Due to the limitations regarding these data (e.g., not temporally representative, limited number of samples, biological sampling does not meet the specimen vouchering requirements), the data will be used to determine whether any locations have values exceeding the TCEQ’s water quality criteria and/or screening levels (or in some cases values elevated above normal). The USIBWC will use this information to determine future monitoring priorities. These water quality data, and data collected by other organizations (e.g., USGS, TCEQ, etc.), will be subsequently reconciled for use and assessed by the TCEQ.

The measurement performance specifications to support the project purpose for a minimum data set are specified in Appendix A Table A7.1 and in the text following.

Ambient Water Reporting Limits (AWRLs)

The AWRL establishes the reporting specification at or below which data for a parameter must be reported to be compared with freshwater screening criteria. The AWRLs specified in Appendix A Table A7.1 are the program-defined reporting specifications for each analyte and yield data acceptable for the TCEQ’s water quality assessment. A full listing of AWRLs can be found at http://www.tceq.state.tx.us/compliance/monitoring/crp/qa/index.html.

The limit of quantitation (LOQ) is the minimum level, concentration, or quantity of a target variable (e.g., target analyte) that can be reported with a specified degree of confidence. The following requirements must be met in order to report results to the CRP:

The laboratory’s LOQ for each analyte must be at or below the AWRL as a matter of routine practice

The laboratory must demonstrate its ability to quantitate at its LOQ for each analyte by running an LOQ check sample for each analytical batch of CRP Samples analyzed.

Laboratory Measurement Quality Control Requirements and Acceptability Criteria are provided in Section B5

Precision

Precision is the degree to which a set of observations or measurements of the same property, obtained under similar conditions, conform to themselves. It is a measure of agreement among replicate

USIBWC QAPP Page 30 measurements of the same property, under prescribed similar conditions, and is an indication of random error.

Field splits are used to assess the variability of sample handling, preservation, and storage, as well as the analytical process, and are prepared by splitting samples in the field. Control limits for field splits are defined in Section B5.

Laboratory precision is assessed by comparing replicate analyses of laboratory control samples in the sample matrix (e.g. deionized water, sand, commercially available tissue) or sample/duplicate pairs in the case of bacterial analysis. Precision results are compared against measurement performance specifications and used during evaluation of analytical performance. Program-defined measurement performance specifications for precision are defined in Appendix A.

Bias

Bias is a statistical measurement of correctness and includes multiple components of systematic error.

A measurement is considered unbiased when the value reported does not differ from the true value.

Bias is determined through the analysis of laboratory control samples and LOQ Check Samples prepared with verified and known amounts of all target analytes in the sample matrix (e.g. deionized water, sand, commercially available tissue) and by calculating percent recovery. Results are compared against measurement performance specifications and used during evaluation of analytical performance.

Program-defined measurement performance specifications for bias are specified in Appendix A.

Representativeness

Site selection, the appropriate sampling regime, the sampling of all pertinent media according to TCEQ SOPs, and use of only approved analytical methods will assure that the measurement data represents the conditions at the site. Routine data collected under the Clean Rivers Program for water quality assessment are considered to be spatially and temporally representative of routine water quality conditions. Water Quality data are collected on a routine frequency and are separated by approximately even time intervals. At a minimum, samples are collected over at least two seasons (to include inter-seasonal variation) and over two years (to include inter-year variation) and include some data collected during an index period (March 15- October 15). Although data may be collected during varying regimes of weather and flow, the data sets will not be biased toward unusual conditions of flow, runoff, or season. The goal for meeting total representation of the water body will be tempered by the potential funding for complete representativeness.

Comparability

Confidence in the comparability of routine data sets for this project and for water quality assessments is based on the commitment of project staff to use only approved sampling and analysis methods and QA/QC protocols in accordance with quality system requirements and as described in this QAPP and in TCEQ SOPs. Comparability is also guaranteed by reporting data in standard units, by using accepted rules for rounding figures, and by reporting data in a standard format as specified in the Data Management Plan Section B10.

USIBWC QAPP Page 31

Completeness

The completeness of the data is basically a relationship of how much of the data is available for use compared to the total potential data. Ideally, 100% of the data should be available. However, the possibility of unavailable data due to accidents, insufficient sample volume, broken or lost samples, etc. is to be expected. Therefore, it will be a general goal of the project(s) that 90% data completion is achieved.

A8 SPECIAL TRAINING/CERTIFICATION

New field personnel receive training in proper sampling and field analysis. Before actual sampling or field analysis occurs, they will demonstrate to the QA Officer (or designee) their ability to properly calibrate field equipment and perform field sampling and analysis procedures. Field personnel training is documented and retained in the personnel file and will be available during a monitoring systems audit.

The requirements for Global Positioning System (GPS) certification are located in Section B10, Data Management.

Contractors and subcontractors must ensure that laboratories analyzing samples under this QAPP meet the requirements contained in section TNI Volume 1 Module 2, Section 4.5.5 (concerning Review of Requests, Tenders and Contracts).

A9 DOCUMENTS AND RECORDS

The documents and records that describe, specify, report, or certify activities are listed. The list below is limited to documents and records that may be requested for review during a monitoring systems audit.

Table 3 A9.1 Project Documents and Records

Document/Record Location Retention (yrs)

Format

QAPPs, amendments and appendices USIBWC 7 yrs.

Paper, electronic

Field SOPs USIBWC 7 yrs.

Laboratory Quality Manuals USIBWC/ Laboratories 7 yrs.

Paper

Laboratory SOPs USIBWC/ Laboratories 7 yrs.

QAPP distribution documentation USIBWC 7 yrs.

Field staff training records USIBWC 7 yrs.

Field equipment calibration/maintenance logs USIBWC 7 yrs.

Field instrument printouts (manuals, instructions, general information)

USIBWC 7 yrs.

USIBWC QAPP Page 32

Field notebooks or data sheets USIBWC 7 yrs. Paper, electronic

Chain of custody records USIBWC 7 yrs.

Laboratory calibration records Laboratories 7 yrs.

Laboratory instrument printouts Laboratories 7 yrs.

Laboratory data reports/results USIBWC/ Laboratories 7 yrs.

Laboratory equipment maintenance logs Laboratories 7 yrs.

Corrective Action Documentation USIBWC/ Laboratories 7 yrs.

Laboratory Test Reports

Test/data reports from the laboratory must document the test results clearly and accurately. Routine data reports should be consistent with the TNI Volume 1, Module 2, Section 5.10 and include the information necessary for the interpretation and validation of data. The laboratory supervisor validates the analytical data by comparing the various quality control measurements and by recalculating a random selection of the results produced by each analyst submitting data. The requirements for reporting data and the procedures are provided. The NELAC Standard provides for some flexibility in regard to the elements required in a test report. From the Clean Rivers Program perspective, it is important that data are reported unambiguously, are accurate, and that the necessary information for the review, verification, validation, and interpretation of data is included. At the very minimum, test reports (regardless of whether they are hard copy or electronic) should include the following:

Parameter Code Parameter Name Sample results Units of measurement Sample matrix Dry weight or wet weight (as applicable) Station information Collecting Entity Date and time of collection Dilution Factor Date Analyzed Holding time for SM9223-B LOQ and LOD (formerly referred to as the reporting limit and the method detection limit, respectively), and qualification of results outside the working range (if applicable) Certification of NELAP compliance Lab Method Prep Date/Time

Electronic Data

Data will be submitted electronically to the TCEQ in the Event/Result file format described in the most current version of the Surface Water Quality Monitoring Data Management Reference Guide (http://www.tceq.state.tx.us/compliance/monitoring/water/quality/data/wdma/dmrg_index.html). A

USIBWC QAPP Page 33 completed Data Review Checklist and Data Summary (see Appendix E) will be submitted with each data submittal. Data from CRP partners will be sent in paper format and kept on file at the USIBWC office.

B1 SAMPLING PROCESS DESIGN

See Appendix B for sampling process design information and monitoring tables associated with data collected under this QAPP.

B2 SAMPLING METHODS

Field Sampling Procedures

Field sampling will be conducted according to procedures documented in the TCEQ Surface Water Quality Monitoring Procedures Volume 1: Physical and Chemical Monitoring Methods for Water, Sediment, and Tissue, 2008.(RG-415) and Volume 2: Methods for Collecting and Analyzing Biological Community and Habitat Data (RG-416). Additional aspects outlined in Section B below reflect specific requirements for sampling under the Clean Rivers Program and/or provide additional clarification. In addition, USIBWC CRP partners using a YSI 556 for field parameter collection should follow USIBWC Clean Rivers Program Standard Operating Procedure: Calibration, Maintenance, and Troubleshooting of the YSI 556, dated April 2011 or later.

Sample volume, container types, minimum sample volume, preservation requirements, and holding time requirements.

Table 4 B2.1 Sample Storage, Preservation and Handling Requirements, Alamo Analytical

Routine Conventionals-in-Water Samples (5 containers: 2 unpreserved, 1 preserved with HNO3, 1 preserved with H2S04, 1 preserved with Na2S2O3)

Parameters Containers Sample Volume (ml)

Preservation Maximum Holding Time

CONTAINER 1

HDPE 500 Cool to 4 C

TSS (00530) 200 “ 7 days Chloride (Cl) (00940) 50 “ 28 days Sulfate (SO4) (00945) 50 “ 28 days Fluoride (00951) 50 “ 28 days TDS (70300) 50 “ 7 days Bromide (71870) 50 “ 28 days Alkalinity (00410) 50 “ 14 days

CONTAINER 2

HDPE 500 1-2 ml conc.HNO3 to pH <2 and cool to 4 C

Calcium (00916) 50 “ 6 months Magnesium (00927) 50 “ 6 months Sodium (00929) 50 “ 6 months Potassium (00937) 50 “ 6 months Hardness (00900) 50 “ 6 months

CONTAINER 3

USIBWC QAPP Page 34

HDPE 250 1-2 ml conc.H2SO4 to pH <2 and cool to 4 C

Ammonia (NH3) (00610) 50 “ 28 days TKN (00625) 50 “ 28 days Total Phosphorus (TPO4) (00665)

50 “ 28 days

Nitrate + Nitrite (00630)

(NO3 + NO2)

50 “ 28 days

CONTAINER 4

Chlorophyll a (32211) glass amber 500 dark and ice before filtration; dark and frozen after filtration

Filter within 48 hours.

Filters may be stored frozen up to 28 days

Pheophytin-a (32218) glass amber 500 dark and ice before filtration; dark and frozen after filtration

Filter within 48 hours Filters may be stored frozen up to 28 days

CONTAINER 5

E. coli bacteria (31699) Sterilized plastic container 100 Cool to 4 C

Sodium thiosulfate 6-8 hours

*extended 48 hours

Metals -In-Water

Parameters

Containers

Sample

Volume (ml)

Preservation

Maximum Holding

Time

TOTAL

HNO3 cleaned plastic bottle

500 Pre-acidified container with 5 ml ultra-pure HNO3 to pH<2

180 days

Total Mercury HNO3- cleaned glass or Teflon bottle

250 Preserved by lab 28 days

Metals in Sediment Metals glass jar with teflon lined lid

500 grams Cool 4 C 180 days

Total Mercury 1 pint glass jar with Teflon- lined lid

500 grams Dark and cool to 4 C 28 days

Organics in Water BTE 3- 40 ml VOA 120 Pre-acidified with 0.5 ml

HCl 14 days

Pesticides glass jar with teflon lined lid

1000 Cool 4 C 7 days

SVOC’s glass jar with teflon lined lid

1000 Cool 4 C 7 days

Organics in Sediment Pesticides glass jar with teflon lined lid 500 grams Cool 4 C 14 days

SVOC’s glass jar with teflon lined lid

500 grams Cool 4 C 14 days

** E.coli samples analyzed by SM 9223-B should always be processed as soon as possible and within 8 hours. When transport conditions necessitate delays in delivery longer than 6 hours, the holding time may be extended and samples must be processed as soon as possible and within 48 hours.

USIBWC QAPP Page 38

9. Custody transfer signatures and dates and time of transfer

10. Bill of lading (if applicable)

Sample Labeling

Samples from the field are labeled on the container (or on a label; please specify) with an indelible marker. Label information includes:

1. Site identification

2. Date and time of collection

3. Preservative added, if applicable

4. Indication of field-filtration (for metals) as applicable

5. Sample type (i.e., analysis(es)) to be performed

Sample Handling

Handling procedures for water, sediment and biological samples are discussed in detail in the TCEQ Surface Water Quality Monitoring Procedures Manual Volume I (2008 or subsequent edition) and Volume II (2007 or subsequent edition). Proper sample handling is a joint effort of the sampling crew, the sample transporter, and laboratory staff. Sample integrity must be protected by preventing sample contamination, whether intentional or accidental, after the sample is placed in a container. USIBWC, Rio Grande International Study Center, University of Texas at Brownsville, Sabal Palm Sanctuary, Sul Ross State University, Big Bend National Park, City of Laredo Environmental, El Paso Community College, Texas Parks and Wildlife Department, U.S. Fish & Wildlife Service, and the University of Texas at El Paso samples will be collected and shipped to Alamo Analytical, LTD. Please refer to the Chain of Custody section below for more details.

Field Data Reporting Forms (See Appendix C) will be required for reporting field data. The first form, “Field Data Reporting Form”, will be used when collecting grab samples. This form will include DO, temperature, pH, Specific conductance, Secchi disk, flow, flow severity, flow measurement method, stream width, stream depth, and days since significant precipitation (and turbidity for RGISC). A second form, “Field Data Reporting Form for 24 hr D.O. and Sediment Samples”, will be used for composite sampling of sediment samples. If a routine water chemistry sample is collected, the COC Form(s) are submitted to the laboratory with the sample(s).

Chain of Custody forms are submitted with all water and/or sediment chemistry samples. If both water and sediment sampled are collected, separate COC for the water samples and sediment samples will be submitted. Routine water chemistry and metals in water analyses are requested on the same form.

The receiving laboratory sample custodian will examine all arriving samples for proper documentation and preservation. Internal sample handling, custody, and storage procedures for laboratories are typically described in the laboratory quality assurance manual. It is assumed that samples in tape-sealed ice chests are secure whether being transported by staff vehicle, by common carrier, or by commercial package delivery.

Samples will be put in the ice chest with enough ice to fill to the top, and enough ice in the chest to keep the samples cold until they reach the laboratory. This is especially important in the warm months of the year. COC will be placed in an envelope and taped to the top of the ice chest or they may be

USIBWC QAPP Page 39 sealed in a plastic bag and taped to the inside of the ice chest lid. Ice chests will then be sealed with tape before shipping.

Sample Tracking Procedure Deficiencies and Corrective Action

All deficiencies associated with chain-of-custody procedures as described in this QAPP are immediately reported to the USIBWC Program Manager. These include such items as delays in transfer, resulting in holding time violations; violations of sample preservation requirements;

incomplete documentation, including signatures; possible tampering of samples; broken or spilled samples, etc. The USIBWC Program Manager in consultation with the USIBWC QAO will determine if the procedural violation may have compromised the validity of the resulting data. Any failures that have reasonable potential to compromise data validity will invalidate data, and the sampling event should be repeated. The resolution of the situation will be reported to the TCEQ CRP Project Manager in the project progress report. Corrective Action Plans will be prepared by the USIBWC QAO and submitted to TCEQ CRP Project Manager along with project progress report.

The definition of and process for handling deficiencies and corrective action are defined in Section C1.

B4 ANALYTICAL METHODS

The analytical methods, associated matrices, and performing laboratories are listed in Appendix A.

The authority for analysis methodologies under the Clean Rivers Program is derived from the TSWQS (''307.1 - 307.10) in that data generally are generated for comparison to those standards and/or criteria. The Standards state that “Procedures for laboratory analysis must be in accordance with the most recently published edition of the book entitled Standard Methods for the Examination of Water and Wastewater, the TCEQ Surface Water Quality Monitoring Procedures as amended, 40 CFR 136, or other reliable procedures acceptable to the commission, and in accordance with chapter 25 of this title.”

Laboratories collecting data under this QAPP are compliant with the TNI Standards. Copies of laboratory QMs and SOPs are available for review by the TCEQ.

Standards Traceability

All standards used in the field and laboratory are traceable to certified reference materials. Standards preparation is fully documented and maintained in a standards log book. Each documentation includes information concerning the standard identification, starting materials, including concentration, amount used and lot number; date prepared, expiration date and preparer’s initials/signature. The reagent bottle is labeled in a way that will trace the reagent back to preparation.

Analytical Method Deficiencies and Corrective Actions

Deficiencies in field and laboratory measurement systems involve, but are not limited to such things as instrument malfunctions, failures in calibration, blank contamination, quality control samples outside QAPP defined limits, etc. In many cases, the field technician or lab analyst will be able to correct the problem. If the problem is resolvable by the field technician or lab analyst, then they will document the problem on the field data sheet or laboratory record and complete the analysis. If the problem is not resolvable, then it is conveyed to the Alamo Analytical Laboratory Supervisor, who will make the

USIBWC QAPP Page 40 determination and notify the USIBWC QAO or the USIBWC Program Manager. If the analytical system failure may compromise the sample results, the resulting data will not be reported to the TCEQ.

The nature and disposition of the problem is reported on the data report which is sent to the USIBWC Program Manager. The USIBWC Program Manager or QAO will include this information in the CAP and submit with the Progress Report which is sent to the TCEQ CRP Project Manager.

The definition of and process for handling deficiencies and corrective action are defined in Section C1.

The TCEQ has determined that analyses associated with the qualifier codes (e.g.“holding time exceedance”, “sample received unpreserved”, “estimated value”, etc...) may have unacceptable measurement uncertainty associated with them. This will immediately disqualify analyses from submittal to SWQMIS. Therefore, data with these types of problems should not be reported to the TCEQ. Additionally, any data collected or analyzed by means other than those stated in the QAPP, or data suspect for any reason should not be submitted for loading and storage in SWQMIS.

B5 QUALITY CONTROL

Sampling Quality Control Requirements and Acceptability Criteria

The minimum Field QC Requirements are outlined in the TCEQ Surface Water Quality Monitoring Procedures. Specific requirements are outlined below. Field QC sample results are submitted with the laboratory data report (see Section A9.).

Field blank - Field blanks are required for total metals-in-water samples when collected without sample equipment (i.e., as grab samples). For other types of samples, they are optional. A field blank is prepared in the field by filling a clean container with pure deionized water and appropriate preservative, if any, for the specific sampling activity being undertaken. Field blanks are used to assess the contamination from field sources such as airborne materials, containers, and preservatives.

Field blanks are performed on 10% of samples taken. If less than 10 samples are collected in a month, one field blank is submitted per month.

The analysis of field blanks should yield values lower than the LOQ. When target analyte concentrations are high, blank values should be lower than 5% of the lowest value of the batch.

Field equipment blank - Field equipment blanks are required for metals-in-water samples when collected using sampling equipment. Field equipment blank is a sample of analyte-free media which has been used to rinse common sampling equipment to check the effectiveness of decontamination procedures. It is collected in the same type of container as the environmental sample, preserved in the same manner and analyzed for the same parameter. A set of field equipment blanks is submitted with every tenth sample. If less than 10 samples are collected in a month, submit one set of blanks per month.

The analysis of field equipment blanks should yield values lower than the LOQ, or, when target analyte concentrations are very high, blank values must be less than 5% of the lowest value of the batch, or corrective action will be implemented.

Field Split - A field split, also called a duplicate, is a single sample subdivided by field staff immediately following collection and submitted to the laboratory as two separately identified samples

USIBWC QAPP Page 41 according to procedures specified in the SWQM Procedures. Split samples are preserved, handled, shipped, and analyzed identically and are used to assess variability in all of these processes. Field splits apply to conventional samples only and are collected on a 10% basis or one per batch, whichever is greater. To the extent possible, field splits prepared and analyzed over the course of the project should be performed on samples from different sites.

The precision of field split results is calculated by relative percent difference (RPD) using the following equation:

RPD = |(X1 - X2)/{(X1+X2)/2} * 100|

A 30% RPD criteria will be used to screen field split results as a possible indicator of excessive variability in the sample handling and analytical system. If it is determined that elevated quantities of analyte (i.e., > 5 times the LOQ) were measured and analytical variability can be eliminated as a factor, than variability in field split results will primarily be used as a trigger for discussion with field staff to ensure samples are being handled in the field correctly. Some individual sample results may be invalidated based on the examination of all extenuating information. The information derived from field splits is generally considered to be event specific and would not normally be used to determine the validity of an entire batch; however, some batches of samples may be invalidated depending on the situation. Professional judgment during data validation will be relied upon to interpret the results and take appropriate action. The qualification (i.e., invalidation) of data will be documented on the Data Summary. Deficiencies will be addressed as specified in this section under Quality Control or Acceptability Requirements Deficiencies and Corrective Actions.

Trip blank - Trip blanks are required for volatile organic analyses (VOA) only. VOA trip blanks are samples prepared in the laboratory with laboratory pure water and preserved as required. A trip blank is submitted with each ice chest of VOA samples submitted to the laboratory. They are transported to the sampling site, handled like an environmental sample, and returned to the laboratory for analysis.

Trip blanks are not opened in the field. Their purpose is to check contamination of the sample through leaching of the septum. The analysis of trip blank should yield values less than the LOQ. When target analyte concentrations are very high, blank values should be less than 5% of the lowest value of the batch, or corrective action will be implemented.

Laboratory Measurement Quality Control Requirements and Acceptability Criteria

Batch – A batch is defined as environmental samples that are prepared and/or analyzed together with the same process and personnel, using the same lot(s) of reagents. A preparation batch is composed of one to 20 environmental samples of the same NELAP-defined matrix, meeting the above mentioned criteria and with a maximum time between the start of processing of the first and last sample in the batch to be 25 hours. An analytical batch is composed of prepared environmental samples (extract, digestates or concentrates) which are analyzed together as a group. An analytical batch can include prepared samples originating from various environmental matrices and can exceed 20 samples.

Method Specific QC requirements – QC samples, other than those specified later this section, are run (e.g., sample duplicates, surrogates, internal standards, continuing calibration samples, interference check samples, positive control, negative control, and media blank) as specified in the methods. The requirements for these samples, their acceptance criteria or instructions for establishing criteria, and

USIBWC QAPP Page 42 corrective actions are method-specific.

Detailed laboratory QC requirements and corrective action procedures are contained within the individual laboratory quality manuals (QMs). The minimum requirements that all participants abide by are stated below.

Limit of Quantitation (LOQ) – The laboratory will analyze a calibration standard (if applicable) at the LOQ published in Appendix A, Table A7, on each day calibrations are performed. In addition, an LOQ check sample will be analyzed with each analytical batch. Calibrations including the standard at the LOQ listed in Appendix A, Table A7 will meet the calibration requirements of the analytical method or corrective action will be implemented.

LOQ Sediment and Tissue Samples – When considering LOQs for solid samples and how they apply to results, two aspects of the analysis are considered: (1) the LOQ of the sample, based on the “real-world” in which moisture content and interferences affect the result and (2) the LOQ in the QAPP which is a value less than or equal to the AWRL based on an idealized sample with zero % moisture.

The LOQ for a solid sample is based on the lowest non-zero calibration standard (as are those for water samples), the moisture content of the solid sample, and any sample concentration or dilution factors resulting from sample preparation or clean-up.

To establish solid-phase LOQs to be listed in Appendix A Table A7 of the QAPP, the laboratory will adjust the concentration of the lowest non-zero calibration standard for the amount of sample extracted, the final extract volume, and moisture content (assumed to be zero % moisture). Each calculated LOQ will be less than or equal to the AWRL on the dry-weight basis to satisfy the AWRL requirement for sediment and tissue analyses. When data are reviewed for consistency with the QAPP, they are evaluated based on this requirement. Results may not appear to meet the AWRL requirement due to high moisture content, high concentrations of non-target analytes necessitating sample dilution, etc. These sample results will be submitted to the TCEQ with an explanation on the data summary as to why results do not appear to meet the AWRL requirement.

LOQ Check Sample – An LOQ check sample consists of a sample matrix (e.g., deionized water, sand, commercially available tissue) free from the analytes of interest spiked with verified known amounts of analytes or a material containing known and verified amounts of analytes. It is used to establish intra-laboratory bias to assess the performance of the measurement system at the lower limits of analysis. The LOQ check sample is spiked into the sample matrix at a level less than or near the LOQ published in Appendix A, Table A7, for each analyte for each analytical batch of CRP samples run. If it is determined that samples have exceeded the high range of the calibration curve, samples should be diluted or run on another curve. For samples run on batches with calibration curves that do not include the LOQ published in Appendix A, Table A7, a check sample will be run at the low end of the calibration curve.

The LOQ check sample is carried through the complete preparation and analytical process. LOQ Check Samples are run at a rate of one per analytical batch.

USIBWC QAPP Page 43

The percent recovery of the LOQ check sample is calculated using the following equation in which %R is percent recovery, SR is the sample result, and SA is the reference concentration for the check sample:

%R = SR/SA * 100

Measurement performance specifications are used to determine the acceptability of LOQ Check Sample analyses as specified in Appendix A Table A7.

Laboratory Control Sample (LCS) - An LCS consists of a sample matrix (e.g., deionized water, sand, commercially available tissue) free from the analytes of interest spiked with verified known amounts of analytes or a material containing known and verified amounts of analytes. It is used to establish intra-laboratory bias to assess the performance of the measurement system. The LCS is spiked into the sample matrix at a level less than or near the midpoint of the calibration for each analyte. In cases of test methods with very long lists of analytes, LCSs are prepared with all the target analytes and not just a representative number, except in cases of organic analytes with multipeak responses.

The LCS is carried through the complete preparation and analytical process. LCSs are run at a rate of one per preparation batch.

Results of LCSs are calculated by percent recovery (%R), which is defined as 100 times the measured concentration, divided by the true concentration of the spiked sample.

The following formula is used to calculate percent recovery, where %R is percent recovery; SR is the measured result; and SA is the true result:

%R = SR/SA * 100

Measurement performance specifications are used to determine the acceptability of LCS analyses as specified in Appendix A Table A7.

Laboratory Duplicates – A laboratory duplicate is an aliquot taken from the same container as an original sample under laboratory conditions and processed and analyzed independently. A laboratory control sample duplicate (LCSD) is prepared in the laboratory by splitting aliquots of an LCS. Both samples are carried through the entire preparation and analytical process. LCSDs are used to assess precision and are performed at a rate of one per preparation batch.

For most parameters except bacteria, precision is calculated by the relative percent difference (RPD) between duplicate LCS results as defined by 100 times the difference (range) of each duplicate set, divided by the average value (mean) of the set. For duplicate results, X1 and X2, the RPD is calculated from the following equation:

RPD = |(X1 - X2)/{(X1+X2)/2} * 100|

For bacteriological parameters, precision is evaluated using the results from laboratory duplicates. A bacteriological duplicate is considered to be a special type of laboratory duplicate and applies when bacteriological samples are run in the lab. Bacteriological duplicate analyses are performed on samples from the sample bottle on a 10% basis (or once per sampling run, whichever is more

USIBWC QAPP Page 44 frequent). These duplicates will be collected in sufficient volume (200 mL or more) for analysis of the sample and its laboratory duplicate from the same container.

The base-10 logarithms of the result from the original sample and the result from its duplicate will be calculated. The absolute value of the difference between the two logarithms will be calculated, and that difference will be compared to the precision criterion in Appendix A Table A7.

If the difference in logarithms is greater than the precision criterion, the data are not acceptable for use under this project and will not be reported to TCEQ. Results from all samples associated with that failed duplicate (usually a maximum of 10 samples) will be considered to have excessive analytical variability and will be qualified as not meeting project QC requirements.

The precision criterion in Appendix A Table A7 for bacteriological duplicates applies only to samples with concentrations >10 MPN/100 mL. Field splits will not be collected for bacteriological analyses.

Laboratory equipment blank - Laboratory equipment blanks are prepared at the laboratory where collection materials for metals sampling equipment are cleaned between uses. These blanks document that the materials provided by the laboratory are free of contamination. The QC check is performed before the metals sampling equipment is sent to the field. The analysis of laboratory equipment blanks should yield values less than the LOQ. Otherwise, the equipment should not be used.

Matrix spike (MS) – Matrix spikes are prepared by adding a known mass of target analyte to a specified amount of matrix sample for which an independent estimate of target analyte concentration is available.

Matrix spikes indicate the effect of the sample on the precision and accuracy of the results generated using the selected method. The frequency of matrix spikes is specified by the analytical method, or a minimum of one per preparation batch, whichever is greater. To the extent possible, matrix spikes prepared and analyzed over the course of the project should be performed on samples from different sites.

The components to be spiked shall be as specified by the mandated analytical method. The results from matrix spikes are primarily designed to assess the validity of analytical results in a given matrix, and are expressed as percent recovery (%R).

The percent recovery of the matrix spike is calculated using the following equation, where %R is percent recovery, SSR is the concentration measured in the matrix spike, SR is the concentration in the unspiked sample, and SA is the concentration of analyte that was added:

%R = (SSR - SR)/SA * 100

Matrix spike recoveries are compared to the acceptance criteria published in the mandated test method.

If the matrix spike results are outside established criteria, the data for the analyte that failed in the parent sample is not acceptable for use under this project and will not be reported to TCEQ. The result from the parent sample associated with that failed matrix spike will be considered to have excessive analytical variability and will be qualified by the laboratory as not meeting project QC requirements.

Depending on the similarities in composition of the samples in the batch, the USIBWC may consider excluding all of the results in the batch related to the analyte that failed recovery.

USIBWC QAPP Page 45

Method blank –A method blank is a sample of matrix similar to the batch of associated samples (when available) that is free from the analytes of interest and is processed simultaneously with and under the same conditions as the samples through all steps of the analytical procedures, and in which no target analytes or interferences are present at concentrations that impact the analytical results for sample analyses. The method blanks are performed at a rate of once per preparation batch. The method blank is used to document contamination from the analytical process. The analysis of method blanks should yield values less than the LOQ. For very high-level analyses, the blank value should be less than 5% of the lowest value of the batch, or corrective action will be implemented. Samples associated with a contaminated blank shall be evaluated as to the best corrective action for the samples (e.g. reprocessing or data qualifying codes). In all cases the corrective action must be documented.

The method blank shall be analyzed at a minimum of one per preparation batch. In those instances for which no separate preparation method is used (example: volatiles in water) the batch shall be defined as environmental samples that are analyzed together with the same method and personnel, using the same lots of reagents, not to exceed the analysis of 20 environmental samples.

Quality Control or Acceptability Requirements Deficiencies and Corrective Actions

Sampling QC excursions are evaluated by the USIBWC Program Manager, in consultation with the USIBWC QAO. In that differences in sample results are used to assess the entire sampling process, including environmental variability, the arbitrary rejection of results based on pre-determined limits is not practical. Therefore, the professional judgment of the USIBWC Program Manager and QAO will be relied upon in evaluating results. Rejecting sample results based on wide variability is a possibility.

Field blanks for trace elements and trace organics are scrutinized very closely. Field blank values exceeding the acceptability criteria may automatically invalidate the sample, especially in cases where high blank values may be indicative of contamination which may be causal in putting a value above the standard. Notations of field split excursions and blank contamination are noted in the quarterly report and the final QC Report. Equipment blanks for metals analysis are also scrutinized very closely.

Laboratory measurement quality control failures are evaluated by the laboratory staff. The disposition of such failures and the nature and disposition of the problem is reported to the USIBWC Program Manager and QAO by the Alamo Analytical laboratory manager. The USIBWC QAO will discuss with the USIBWC Program Manager. If applicable, the USIBWC Program Manager will include this information in the CAP and submit with the Progress Report which is sent to the TCEQ CRP Project Manager.

The definition of and process for handling deficiencies and corrective action are defined in Section C1.

B6 INSTRUMENT/EQUIPMENT TESTING, INSPECTION AND MAINTENANCE

All sampling equipment testing and maintenance requirements are detailed in the TCEQ Surface Water Quality Monitoring Procedures. Sampling equipment is inspected and tested upon receipt and is assured appropriate for use. Equipment records are kept on all field equipment and a supply of critical spare parts is maintained.

All laboratory tools, gauges, instrument, and equipment testing and maintenance requirements are contained within laboratory QM(s).

USIBWC QAPP Page 59

APPENDIX A:

MEASUREMENT PERFORMANCE SPECIFICATIONS (TABLE A7.1)

USIBWC QAPP Page 60

Measurement performance specifications define the data quality needed to satisfy project objectives.

To this end, measurement performance specifications are qualitative and quantitative statements that:

clarify the intended use of the data define the type of data needed to support the end use identify the conditions under which the data should be collected

Appendix A of the QAPP addresses measurement performance specifications, including:

analytical methodologies AWRLs limits of quantitation bias limits for laboratory control samples precision limits for laboratory control sample duplicates completeness goals qualitative statements regarding representativeness and comparability

The items identified above need to be considered for each type of monitoring activity. The CRP emphasizes that data should be collected to address multiple objectives, if possible, thereby maximizing the expenditure of resources. Caution should be applied when attempting to collect data for multiple purposes because measurement performance specifications may vary according to the purpose. For example, limits of quantitation may differ for data used to assess standards attainment and for trend analysis. When planning projects, first priority should be given to the main use of the project data and the data quality needed to support that use, then secondary goals should be considered.

Table A7 should be modified to reflect actual parameters, methods, etc. employed by the USIBWC and its participants. Alternative methods than those listed in the following table may be used. Procedures for laboratory analysis must be in accordance with the most recently published edition of Standard Methods for the Examination of Water and Wastewater, 40 CFR 136, or otherwise approved independently. Only data collected that have a valid TCEQ parameter code assigned in Table A7 are stored in SWQMIS. Any parameters listed in Table A7 that do not have a valid TCEQ parameter code assigned will not be stored in SWQMIS.

Based on a general review of available information regarding achievable recoveries of additional parameters, use the following bias limits (percent recovery of the LCS and LOQ Check Sample) in Table A7.1: metals-in solid samples (i.e., sediment and tissue) 60-140%; organics-in-water samples 65-135%; organics-in-solid samples (i.e., sediment and tissue) 40-160%. There may be poor performing analytes within these groups that do not perform well with specific methods and usually recover poorly. Before these compounds are included in the list of analytes to be submitted to the TCEQ, the USIBWC should discuss the situation with the TCEQ who will discuss if they are project specific analytes of concern, if low recoveries are acceptable or alternative methods should be run.

Table 2: A7.1 Measurement Performance Specifications

Please see the attached Excel file.

USIBWC QAPP Page 61

TABLE A7.1 Measurement Performance Specifications Field Parameters

Parameter

U ni ts

M at ri x

M et ho d

Pa ra m et er

C od e

A W

R L

O

Q

Q C he ck

Sa m pl e ec

Pr is io n

(R

PD

of

C

S/ L

C

SD

B ia s % R ec . o f L

C S ab

TEMPERATURE, WATER (DEGREES

CENTIGRADE)

DEG

C water

SM 2550 B

and TCEQ

SOP V1

00010 NA* NA NA NA NA Field

TEMPERATURE, AIR (DEGREES

CENTIGRADE)

DEG

C air TCEQ SOP

V1 00020 NA* NA NA NA NA Field

FLOW STREAM, INSTANTANEOUS (CUBIC

FEET PER SEC)

cfs water TCEQ SOP V1 00061 NA* NA NA NA NA Field

TRANSPARENCY, SECCHI DISC (METERS)

meters water TCEQ SOP

V1 00078 NA* NA NA NA NA Field

SPECIFIC CONDUCTANCE,FIELD (uS/CM @ 25C) us/cm water

EPA 120.1

and TCEQ

SOP, V1

00094 NA* NA NA NA NA Field

OXYGEN, DISSOLVED (MG/L)

mg/L water

SM 4500-O

G and TCEQ

SOP, V1

00300 NA* NA NA NA NA Field

PH (STANDARD UNITS)

s.u water

EPA 150.1

and TCEQ

SOP, V1

00400 NA* NA NA NA NA Field

TURBIDITY, FIELD NTU water SM 2130-B 82078 NA* NA NA NA NA Field

FLOW SEVERITY:1=No Flow,2=Low,3=Normal,4=Flood,5=High,6=Dry

NU water TCEQ SOP V1 01351 NA* NA NA NA NA Field

DAYS SINCE PRECIPITATION EVENT (DAYS)

days other TCEQ SOP

V1 72053 NA* NA NA NA NA Field

STREAM FLOW ESTIMATE (CFS)

cfs water TCEQ SOP, V1 74069 NA* NA NA NA NA Field

DEPTH OF BOTTOM OF WATER BODY AT

SAMPLE SITE MET

meters water TCEQ SOP V2 82903 NA* NA NA NA NA Field

FLOW MTH 1=GAGE 2=ELEC 3=MECH

4=WEIR/FLU 5=DOPPL

NU other TCEQ SOP V1 89835 NA* NA NA NA NA Field

STREAM WIDTH (M)

meters water TCEQ SOP

V1 89861 NA* NA NA NA NA Field

WIND INTENSITY

(1=CALM,2=SLIGHT,3=MOD.,4=STRONG)

NU other NA 89965 NA* NA NA NA NA Field

WIND DIRECTION

(1=North, 2=South, 3=East, 4=West, 5=NE, 6=SE, 7=NW, 8=SW)

NU other NA 89010 NA* NA NA NA NA Field

PRESENT WEATHER

(1=CLEAR,2=PTCLDY,3=CLDY,4=RAIN,5=OT

HER)

NU other NA 89966 NA NA NA NA NA Field

* Reporting to be consistent with SWQM guidance and based on measurement capability.

References:U.S. Environmental Protection Agency (USEPA) Methods for Chemical Analysis of Water and Wastes, Manual #EPA-600/4-79- 020American Public Health Association (APHA), American Water Works Association (AWWA), and Water Environment Federation (WEF), StandardMethods for the Examination of Water and Wastewater, 20th Edition, 1998. (Note: The 21st edition may be cited if it becomes available.)TCEQ SOP, V1 - TCEQ Surface Water Quality Monitoring Procedures, Volume 1: Physical and Chemical Monitoring Methods for Water, Sediment, and Tissue, 2008 (RG-415).TCEQ SOP, V2 - TCEQ Surface Water Quality Monitoring Procedures, Volume 2: Methods for Collecting and Analyzing Biological Community and Habitat Data, 2007 (RG-416)

USIBWC QAPP Page 62

TABLE A7.2 Measurement Performance Specifications for Alamo Analytical Laboratories, LTD.

Conventional and Bacteriological Parameters in Water

Parameter

U ri x

M et ho d

Pa ra m et er C od e

A W

Q C pl e is io n

C S/

L C

SD

B ia s % R ec . o f L

C S

RESIDUE, TOTAL

NONFILTRABLE (MG/L)

mg/L water EPA 160.2 00530 4 4 NA NA NA Alamo

NITROGEN, AMMONIA,

TOTAL (MG/L AS N)

mg/L water EPA 350.2 00610 0.1 0.1 70- 130 20 80-

120 Alamo

NITROGEN, KJELDAHL,

TOTAL (MG/L AS N)

mg/L water EPA 351.3 00625 0.2 0.2 70- 130 20 80-

120 Alamo

NITRITE PLUS NITRATE,

TOTAL 1 DET. (MG/L AS N)

mg/L water EPA 300.0 00630 0.05 0.05 70- 130 20 80-

120 Alamo

PHOSPHORUS, TOTAL, WET

METHOD (MG/L AS P)

mg/L water EPA 365.2 00665 0.06 0.06 70- 130 20 80-

120 Alamo

HARDNESS, TOTAL (MG/L AS

CACO3)*

mg/L water EPA 130.2 00900 5 5 NA 20 80- 120 Alamo

CHLORIDE (MG/L AS CL)

mg/L water EPA 300.0 00940 5 2 70-

130 20 80- 120 Alamo

SULFATE (MG/L AS SO4)

mg/L water EPA 300.0 00945 5 5 70-

130 20 80- 120 Alamo

CALCIUM, TOTAL (MG/L AS

CA)

mg/L water EPA 200.7, 6010 00916 0.5 0.5 70-

130 20 80- 120 Alamo

MAGNESIUM, TOTAL (MG/L

AS MG)

mg/L water EPA 200.7 00927 0.5 0.25 70- 130 20 80-

120 Alamo

SODIUM, TOTAL (MG/L AS NA)

mg/L water EPA 200.7, 6010 00929 NA 0.5 70-

130 20 80-

120 Alamo

POTASSIUM, TOTAL (MG/L AS

K) mg/L water EPA 200.7, 6010 00937 NA 0.5 70-

130 20 80- 120 Alamo

FLUORIDE, TOTAL (MG/L AS

F) mg/L water EPA 300.0 00951 0.5 0.5 70- 130 20 80-

120 Alamo

BROMIDE, TOTAL

mg/L water

EPA 300.0

71870 NA 5 70-

130 20 80- 120 Alamo

E. COLI, COLILERT, IDEXX

METHOD, MPN/100ML****

MPN/100

mL water SM 9223-

B*** 31699 1 1 NA 0.50** NA Alamo

E.COLI, COLILERT, IDEXX,

HOLDING TIME hours water NA 31704 NA NA NA NA NA Alamo

ALKALINITY, TOTAL (MG/L

AS CACO3)

mg/L water EPA 310.1 00410 20 10 NA 20 NA Alamo

PHEOPHYTIN-A UG/L

SPECTROPHOTOMETRIC

ACID. METH.

μg/L water SM 10200 H 32218 3 3 NA NA NA Alamo

CHLOROPHYLL-A UG/L

SPECTROPHOTOMETRIC

ACID. METH

ug/L water SM 10200

H 32211 3 3 NA 20 80-

120 Alamo

RESIDUE,TOTAL FILTRABLE

(DRIED AT 180C) (MG/L)

mg/L water EPA 160.1 70300 10 10 NA 20 80- 120 Alamo

USIBWC QAPP Page 63

*Hardness is not used for regulatory purposes but is used to assess metals in water at inland sites (estuarine sites do not require hardness analysis).

** This value is not expressed as a relative percent difference. It represents the maximum allowable difference between the logarithm of the result of a sample and the logarithm of the duplicate result. See Section B5.

*** E.coli samples analyzed by SM 9223-B should always be processed as soon as possible and within 8 hours. When transport conditions necessitate delays in delivery longer than 6 hours, the holding time may be extended and samples must be processed as soon as possible and within…