# Quality Assurance Project Plan for the Chlorine and Chlorinated Hydrocarbons Analytical Data Review and Validation

Prepared for:



# U.S. Environmental Protection Agency Engineering and Analysis Division Office of Water 1200 Pennsylvania Avenue, NW Washington, DC 20460

Prepared by:



# Eastern Research Group, Inc. 14555 Avion Parkway Suite 200 Chantilly, VA 20151-1102

June 2009

EPA Contract No . 68-C2-095 Work Assignment 5-18

### iii TABLE OF CONTENTS

Page

1.0 I NTRODUCTION 

### ..................................................................................................... 1-1

2.0 P ROJECT 

### M ANAGEMENT 

### E LEMENTS 

### ..................................................................... 2-1 2.1 Element A.3: Distribution List ................................................................. 2-1 2.2 Element A.4: Project Organization ......................................................... 2-2 2.3 Element A.5: Problem Definition/Background ....................................... 2-5 2.3.1 Statement of Key Questions and Project Outcome ...................... 2-5 2.3.2 Background .................................................................................. 2-6 2.4 Element A.6: Project/Task Description .................................................. 2-8 2.5 Element A.7: Quality Objectiv es and Acceptance Criteria ..................... 2-9 2.6 Element A.8: Special Tr aining/Certification ........................................ 2-14 2.7 Element A.9: Project Documents and Records ...................................... 2-15

3.0 D ATA 

### G ENERATION AND 

### A CQUISITION 

### ................................................................. 3-1 3.1 Element B.3: Sample Handling and Custody .......................................... 3-1 3.2 Element B.4: Analytical Methods ............................................................ 3-2 3.3 Element B.5: Quality Control .................................................................. 3-2 3.4 Element B.6: Instrument/Equipment Testing, Inspection, and Maintenance ............................................................................................. 3-2 3.5 Element B.7: Instrument/Equipment Calibration and Frequency ............ 3-3 3.6 Element B.10: Project Data Management ................................................ 3-3

4.0 A SSESSMENT AND 

### O VERSIGHT 

### E LEMENTS 

### ............................................................ 4-1 4.1 Element C.1: Assessments and Response Actions .................................. 4-1 4.1.1 Technical Support ........................................................................ 4-1 4.1.2 Analytical Data Review ............................................................... 4-2 4.1.3 Corrective Action ......................................................................... 4-2 4.2 Element C.2: Reports to Management ..................................................... 4-3

5.0 D ATA 

### V ALIDATION AND 

### U SABILITY 

### E LEMENTS 

### ................................................... 5-1 5.1 Elements D.1 and D.2: Data Revi ew, Verification, and Validation ........ 5-1 5.2 Element D.3: Reconciliation with User Requirements ............................ 5-2

6.0 R EFERENCES 

### ......................................................................................................... 6-1

Attachment 1: DATA REVIEW PROCEDURES

### iv LIST OF TABLES

Page

1-1 Chemicals in the Chlorine and Chlori nated Hydrocarbon Manuf acturing Segment1-3

2-1 QAPP Distribution List ........................................................................................ 2-2

2-2 Standard Analytical Me thods and Procedures ................................................... 2-16

3-1 Typical Database Structure .................................................................................. 3-5

### v LIST OF FIGURES

Page

2-1 ERG CCH Data Review and Validation QA Organization ................................. 2-3

### Section No. 1 Revision No. 0 March 2009

Page 1 of 4

1.0 I NTRODUCTION



### ERG is providing technical support to th e U.S. Environmental Protection Agency (EPA) to evaluate the potential revision of effluent limitations, guidelines, and standards (ELGs)

for facilities that manufacture chlorine a nd chlorinated hydrocarbons (including polyvinyl
chloride (PVC)). EPA refers to the manufacturers of chlorine and chlorinated hydrocarbons as the Chlorine and Chlorinated Hydrocar bon (CCH) manufacturing segments. CCH manufacturing involves the production of the chemicals listed in Table 1-1.

EPA is collecting information and data regarding the sources and characteristics of discharges from CCH manufacturing. EPA is conducting a sampling program to collect: 1)

wastewater characterization data and 2) wastewater treatment technology/pollution prevention performance data. EPA will use these data in combination with other CCH data to evaluate pollution prevention and treatm ent of CCH wastewater.

As directed by Work Assignments 2- 18, 3-18, and 4-18 of Contract No. 68-C02- 095, ERG prepared several Quality Assurance Project Plans (QAPPs) to address various parts of the CCH technical evaluation. Specifica lly, ERG has prepared the following QAPPs:

 

### Final Quality Assurance Project Plan for the Chlorine and Chlorinated Hydrocarbon Sampling Program dated May 4, 2006 and approved June 14, 2006;

 

### Final Quality Assurance Project Plan for the Chlorine and Chlorinated Hydrocarbon Sampling Program 2007 Addendum dated July 9, 2007 and approved July 9, 2007;

 

### Draft Quality Assurance Project Plan for the Technical Portion of the Chlorine and Chlorinated Hydrocarbons Manufacturing Segments Effluent Guidelines Questionnaire dated November 28, 2006; and

 

### Draft Quality Assurance Project Plan for the Chlorine and Chlorinated Hydrocarbons Effluent Guidelines Regulatory Support Secondary Data Collection and Analysis dated February 28, 2007.

### Section No. 1 Revision No. 0 March 2009

Page 2 of 4

EPA is currently working with CCH indus try representatives to collect additional data to characterize discharges of chlorinate d dibenzo(p)dioxin and ch lorinated dibenzofuran congeners (dioxin and furans) from CCH facilities. Therefore, due to changes in priorities, EPA has not approved the Questionnaire and Secondary Data QAPPs since work on these topics has been postponed.

As directed by a Technical Dir ective dated January 7, 2008 under Work Assignment 5-18 of Contract N o. 68-C02-095, ERG prepared this QAPP to address the review and validation of analytical data for two CCH sampling ep isodes (Episodes 6542 and 6543). This QAPP is responsive to all a pplicable elements specified in EPA Requirements for Quality Assurance Project Plans (1) and will be used by EPA and ERG.

Section 6.0 presents the references ci ted in this QAPP. Throughout this document, each time a reference is cited, a number corresponding to the Section 6.0 listing is shown in parentheses.

### Section No. 1 Revision No. 0 March 2009

Page 3 of 4

Table 1-1. Chemicals in the Chlorine a nd Chlorinated Hydrocarbon Manufacturing Segment

International Union of Pu re and Applied Chemistry (IUPAC) Name Common Name
Chlorinated Paraffins
Chlorine Chlorine
Chlorobenzene Monochlorobenzene 2-Chlorobutadiene Chloroprene 1-Chlorobutane Butyl Chloride
Chloroethane Ethyl Chloride 1-Chlorohexane Hexyl Chloride Chloromethane Methyl Chloride Chloromethyl Benzene Benzyl Chloride 1-Chloro-2-methylpropene Methyl Allyl Chloride 1-Chloropropane n-Propyl Chloride 3-Chloro-1-propene Allyl Chloride Chlorotoluene o,m,p-Chlorotoluene 1,2-Dichlorobenzene o-Dichlorobenzene 1,3-Dichlorobenzene m-Dichlorobenzene 3,4-dichloro-1-butene 1,4-dichloro-2-butene 1,1-dichloro-2-chloroethylene Trichloroethylene 1,1-Dichloroethane Ethylidene Chloride 1,2-Dichloroethane Ethylene Dichloride 1,1,-Dichloroethene Vinylidene Chloride 1,2-Dichloroethene Acetylene Dichloride Dichloromethane Methylene Chloride 1,1-Dichloropropane Propylidene Chloride 1,2-Dichloropropane Propylene Dichloride 1,3-Dichloropropane Trimethylene Dichloride 2,2-Dichloropropane Dimethyl-dichloromethane 1,2-Dichloropropene 1,2-Dichloropropylene Hexachlorobenzene (HCB) Amatin
Hexachlorobutadiene Perchlorobutadiene Hexachlorocyclopentadiene Perchlorocyclopentadiene 1,1,1,2,2,2-Hexachloroethane Hexachloroethane Monochloroethylene Vinyl Chloride 1,2,3,4,5-Pentachlorobenzene Pentachlorobenzene Pentachloroethane Ethane pentachloride Polyvinyl Chloride Polyvinyl Chloride

### Section No. 1 Revision No. 0 March 2009

Page 4 of 4 Table 1-1 (Continued)

International Union of Pu re and Applied Chemistry (IUPAC) Name Common Name 1,2,3,4-Tetrachlorobenzene Tetrachlorobenzene 1,1,1,2-Tetrachloroethane Chloromethyltrichloromethane 1,1,2,2-Tetrachloroethane Acetylene Tetrachloride 1,1,2,2-Tetrachloroethylene Perchloroethylene trans-1,4-Dichloro-2-butene trans-2-Butylene Dichloride
Trichlorobenzene Trichlorobenzene 1,1,2-Trichloroethane Vinyl Trichloride
Trichloromethane Chloroform 1,2,3-Trichloropropane Allyl trichloride 1,2,3-Trichloropropene Trichloropropene

### Section No. 2 Revision No. 0 March 2009 Page 1 of 16

2.0 P ROJECT 

### M ANAGEMENT 

### E LEMENTS



### This section addresses project mana gement, including project history and objectives, roles and responsibilities, and project goals. In addition, this section presents the

mechanisms EPA and ERG will use to ensure that all participants understand the goals and the approach to be used for the CCH data review and validation. EPA has identified nine elements

to be discussed in this section.

 

### A.1: Title and Approval Sheet;

 

### A.2: Table of Contents;

 

### A.3: Distribution List;

 

### A.4: Project Organization;

 

### A.5: Problem Definition/Background;

 

### A.6: Project/Task Description;

 

### A.7: Quality Objectives;

 

### A.8: Special Training / Certification; and

 

### A.9: Project Documents and Records.

Elements A.1 and A.2 have been provided earlier in this document. The remaining elements are presented below.

2.1 Element A.3: Distribution List

Table 2-1 presents the dist ribution list for this data re view and validation QAPP. As additional ERG staff members are required to participate in the project, ERG will notify the

EPA WAM.

### Section No. 2 Revision No. 0 March 2009 Page 2 of 16

Table 2-1. QAPP Distribution List

Organization Role US EPA/OW EPA QA Coordinator US EPA/OW EPA Work Assignment Manager US EPA/OW EPA Alternate Work Assignment Manager US EPA/OW EPA Project Officer ERG ERG Program Manager ERG ERG Work Assignment Manager

ERG ERG Lead for Data Review and Validation ERG ERG Project QA Coordinator
ERG ERG Senior Chemists



### 2.2 Element A.4: Project Organization

Figure 2-1 shows the project organization for the CCH data revi ew and validation. Under EPA Contract No. 68-C02-095, ERG is provi ding technical support to EPA to evaluate and potentially revise discharge regulations for CCH operations. Under this contract, ERG conducted two sampling episodes in July 2007 (Episodes 6542 and 6543) following the procedures outlined in the site-specific sampling plans and the Final Quality Assurance Project Plan for the Chlorine and Chlorinated Hydrocarbon Sampling Program (2) and Final Quality Assurance Project Plan for the Chlorine and Chlorinated Hydrocarbon Sampling Program 2007

Addendum (3). This document describes ERG’s pro cedures for reviewing and validating the results of chemical analysis of samples co llected in Episodes 6542 and 6543 to ensure their quality for use in CCH technical analyses. This document will be used in conjunction with the guidelines and standard operating procedures described in ERG’s Draft Data Review Procedures for Office of Water Effluent Guidelines Sampling Data (Data Review Plan) (Attachment 1).Section No. 2Revision No. 0March 2009Page 3 of 16ERG DataReview StaffLines of CommunicationReporting and AuthorityERGWork AssignmentManagerERGData Review LeadERGProgramManagerERGProject QACoordinatorEPAWork AssignmentManagersEAD QACoordinatorERG DataReview StaffLines of CommunicationReporting and AuthorityERGWork AssignmentManagerERGData Review LeadERGProgramManagerERGProject QACoordinatorEPAWork AssignmentManagersEAD QACoordinatorFigure 2-1. ERG CCH Data Reviewand Validation QA Organization

### Section No. 2 Revision No. 0 March 2009 Page 4 of 16

A Senior Chemical Engineer, will se rve as ERG’s Work Assignment Manager (WAM). The ERG WAM will be responsible for en suring the project staff follows this QAPP. The WAM is also responsible for all manageme nt and administrative aspects of the work performed and for ensuring that the quality of work, schedule, and budget meet the requirements of the CCH effluent guidelines project. The ERG WAM will be the principal contact for the
EPA WAM on data review tasks, issues, delive rables, and schedule. The ERG WAM will also keep the Project QA Coordinator and the ERG Program Manager advised of any quality problems that arise.

The ERG Project QA Coordinator is re sponsible for developing and executing ERG’s QA activities throughout the c ourse of the data review tas k. Additional details on ERG’s project QA organization can be found in ERG's April 2007 Quality Management Plan (a successor to the June 2002 Quality Management Plan for Technical Support for the Strategy for National Clean Water Industrial Regulations) (4). ERG's QMP details the responsibilities of the ERG Quality Assurance (QA) coordinators a nd Project Management Team and describes procedures used to plan, implem ent, and assess project quality.

A Senior Analytical Chemist will serve as ERG’s lead for the data review and validation task and will oversee ERG laboratory and data review staff in conducting this work.

Senior ERG chemists will perform the data review.

As additional ERG staff are required to pa rticipate in this project, ERG will notify

the EPA WAM. The ERG WAM will ensure that any new staff members re ceive a copy of this QAPP. Additional details on ERG’s project QA or ganization can be found in the QMP, Section

1.2 Project Organization and Staff Responsibilities (4).

### Section No. 2 Revision No. 0 March 2009 Page 5 of 16

2.3 Element A.5: Problem Definition/Background

This subsection explains the primar y purpose of the CCH sampling program, provides background information on the sampling progr am, and a describes the data review that will be performed for Episodes 6542 and 6543.

2.3.1 Statement of Key Questi ons and Project Outcome

The sampling program included the collec tion of in-process wastewater sampling points to characterize the CCH pr ocesses and paired influent and effluent sampling points to evaluate CCH pollution prevention and treatmen t techniques. The CCH sampling program will evaluate end-of-pipe or in-p rocess pollutant control techno logies that may reduce dioxin discharges. The analytical results from the CCH sampling program will support EPA in answering the following key questions:

 

### What pollutants are being di scharged by CCH operations?

 

### What are the sources of dioxin from CCH operations?

 

### What are the concentrations and quantities of pollutants currently being discharged (i.e., “bas eline” concentration)?

 

### What is the performance/efficiency of pollution prevention and wastewater treatment technologies being used to reduce pollutants discharged from CCH operations?

The purpose of the data review and valida tion project is to ensure the results of the chemical analyses of samples collected in Episodes 6542 and 6543 are appropriate for use in answering the overall project key questions. For the data review, ERG will support EPA in answering the following questions:

 

### Did the analytical laboratory document the sample receipt and receipt conditions properly?

### Section No. 2 Revision No. 0 March 2009 Page 6 of 16

 

### Did the analytical laboratory follow the sample handling and preparation procedures specified in the method (e.g., hold times)?

 

### Did the laboratory follow met hod-specific QC requirements (e.g., instrument performance and calibra tion, method blanks, recovery of labeled compounds)?

 

### Should any data qualifiers be added to the analytical database prior to using the results in technical analyses?

2.3.2 Background

Section 304(m) of the Clean Water Act re quires EPA to publish a plan every two years to establish a schedule for the annual review and revision of effluent guidelines required by Section 304(b). During the 2004 annual review, EP A selected the Organic Chemicals, Plastics, and Synthetic Fibers (OCPSF) Point Source Ca tegory (40 CFR Part 414) for further review because it ranked highest in terms of toxic, pr iority, and nonconventional pollutant discharges among all industrial point source cat egories. One of the polluta nts driving the OCPSF pollutant discharges in the screening analysis was dioxi n. EPA identified the manufacture of ethylene dichloride (EDC), vinyl chloride monomer (V CM), and polyvinyl chloride (PVC) as possible sources of dioxin and conducted a detailed study of these manufacturing processes in 2004.

In addition, because many chlor-alkali operations are collocated with vinyl chloride manufacturing, and because these opera tions discharge significant quantities of pollutants, EPA also selected the chlor-alkali industrial segment of the inorganic chemical industry for review. Wastewater from chlorine manufacturing via the chlor-alkali process is regulated by the Inorganic Chemicals Manufactur ing Point Source Category (40 CFR Part 415).

During 2005, EPA identified other manufacturing processes for regulatory review. First, EPA is including all chlorine manufacturers in the CCH manufacturing segments to obtain a complete overview of the chlori ne industry. Second, EPA identified several additional chlorinated hydrocar bons currently regulat ed under OCPSF that are manufactured via direct chlorination, oxychlorination, and dehydroc hlorination. Because their manufacturing

### Section No. 2 Revision No. 0 March 2009 Page 7 of 16

processes may also discharge toxic pollutant s, EPA is including manufacturing of these chlorinated hydrocarbons in the project scope. Chlorinated hydrocarbon ma nufacturing that is regulated under the Pesticide Chemicals Manuf acturing (40 CFR Part 455) and Pharmaceutical Manufacturing (40 CFR Part 439) Point Source Categories are not included in the CCH manufacturing segments. In summary, the scope of this regulatory review project includes all

chlorine manufacturers and manuf acturers of the chlorinated hydro carbons listed in Table 1-1.

Although the CCH manufacturing segments were selected fo r potential revision primarily due to high levels of dioxin discharge d, EPA will also evaluate other pollutants that contribute significantly to the overall polluta nt discharge, such as chlorine, metals, polychlorinated biphenyls, and other organic pollutants.

ERG supported EPA in planning and ex ecuting a CCH sampling program in 2006 and 2007. The sampling program comprised five samp ling episodes at four different facilities. ERG developed site-specific sampling plans to serve as the primary source of procedural information and as guides for the field sampling crew and facility personnel.

In 2007, EPA conducted two-day sampli ng episodes at two facilities that manufacture EDC and VCM (Episo des 6542 and 6543). At each faci lity, EPA collected samples of the influent to and the effluent from the pl ant’s wastewater treatment system and of several intermediate points within the system. The samples were collected as manual composites comprising six aliquots. The six aliquots were co mposited to create one representative sample for each 24-hour time period. Details for the sampling episodes are site-specific and are
confidential business information (CBI). See Section 2.6 for information on ERG’s CBI handling procedures.

ERG will document information and data collected during all five episodes in sampling episode reports (SERs) and the data will be used by EPA and ERG in conducting additional technical analyses. The SERs are considered CBI.

### Section No. 2 Revision No. 0 March 2009 Page 8 of 16

2.4 Element A.6: Project/Task Description

Prior to use in the SER and technical anal yses, results of chemi cal analyses of the wastewater samples must be reviewed for comp leteness, comparability, precision, accuracy, and sensitivity. For the first three sampling episodes, EPA provided ERG with analytical data that had already undergone QC review. For the ne xt two sampling episodes (Episodes 6542 and 6543), ERG has outlined procedures it will use to conduct the data quality review in the Data Review Plan (Attachment 1). This QAPP will be used in conjunction with the Data Review Plan to assess the quality of the results of chemical analyses received from the laboratories for these two episodes.

ERG has received electronic data pack ages consisting of Microsoft® Excel spreadsheets containing the analytical results and documentation packages consisting of traffic reports and sample receipt information, laborator y analysis sheets and checklists, instrument data, and analyte chromatograms, where applicab le. ERG will review, verify, and validate the chemical results and supporting documentation provided by the laboratory using method-specific checklists. The checklists provide the method-sp ecific QC objectives for each parameter in the review (e.g., acceptable instrument signal to nois e ratio, use of correct spiking concentration, acceptable recovery ranges). Each checklist contai ns the following standard sections that list the detailed criteria ERG will use to verify and validate the results of chemical analyses:

 

### General Review of Sample Identity and Handling – ERG will use Sections A and B of the checklist to verify sa mple identity and traceability. ERG will confirm that all data required fo r the data review, verification, and validation are contained in the labora tory data package and will review information in the data package to ve rify that the laboratory identified and handled samples properly;

 

### Review of General QC Requirements – ERG will use Sections C and D of the checklist to evaluate the common QC requirements in all methods which include sample preparati on and extraction procedures; and

 

### Detailed Review of Method-Specific Parameters – ERG will use Sections E through H of the checklists to pe rform method-specific QC validation

### Section No. 2 Revision No. 0 March 2009 Page 9 of 16

which includes reviewing the prim ary instrument calibrations and performance evaluation samples.

ERG will provide a completed checklist fo r each sample number and each analyte in the final analytical data review, verification, and validation package. ERG will also provide a

data review narrative that summ arizes the results documented in the checklist for each group of compounds shown in Table 2-2 at the end of th is section. Project documentation will be discussed in greater detail in Section 3.6.

2.5 Element A.7: Quality Object ives and Acceptance Criteria

The QA objectives for the collection of the samples were documented in sitespecific sampling plans, the Sampling QA PP, and 2007 Sampling QAPP Addendum. The primary objective of the data review is to assess whether the results from chemical analyses from Episodes 6542 and 6543 are of the quality necessary for use in developing effluent guidelines for this industry. This QAPP, the Data Review Plan, and the method-spec ific checklists document the procedures for the quality review. ERG will re view the results of chemical analyses and the supporting documentation provided by the laboratory to assess the completeness, comparability, precision, accuracy, and sens itivity of the data.

Completeness

Completeness for Episodes 6542 and 6543 is de fined in terms of the percentage of samples collected, analyzed, and deemed to be acceptable for use in this study. Completeness is

assessed in three different area s and is defined as follows:

Sampling completeness is the number of samples co llected and received in the laboratory relative to the number of samples planned for collection;

Analytical completeness is the number of valid sample measurements relative to the number of samples collected; and

### Section No. 2 Revision No. 0 March 2009 Page 10 of 16

Overall completeness is the number of valid sample measurements relative to the number of samples planned for collection.

The number of samples planned for collec tion is documented in the site-specific sampling plans and any deviations are noted in the sampling episode reports. The traffic reports list all the samples that were sent to the laboratory for analysis.

This project goal is a minimum of 90% for both sampling and analytical completeness and a minimum of 81% for overall completeness (determined by multiplying sampling and analytical completeness goals). Co mpleteness may also be evaluated in terms of subsets of samples (e.g., completeness for influe nt samples versus completeness for effluent samples).

ERG will use Sections A and B of the method-specific checklists to verify analytical completeness.

Comparability

Comparability is a qualitative measure of the confidence with which datasets can be compared. This project will ensure data comparability by following approved, standard analytical procedures and by reporti ng the results in the standard uni ts of measure required in the methods. ERG will use Sections C and D of the method-specific checklists to document data comparability. ERG will check that all data we re generated with the appropriate method, the laboratory followed the procedures for sample ha ndling and sample preparation/extract handling
listed in the method, and the resu lts were reported using the st andard units required by the

method.

### Section No. 2 Revision No. 0 March 2009 Page 11 of 16

Precision

Precision is a measure of the agreement among repeated measurements. To evaluate precision, the laborat ories calculate the relative pe rcent difference (RPD) among the results from one or more types of “duplic ate” analyses using the following equation:



### 100 D S D S RPD       

 


where: RPD = Relative percent difference; S = First sample result; and D = Duplicate sample result.

Laboratories use the results of duplicate anal yses to evaluate the precision of their operations. Laboratories often use matrix spike (MS) /matrix spike duplicate (MSD) samples to evaluate both precision and accuracy.

Table 2-2 (located at the end of this sec tion) presents the analytical methods used for samples collected in these two episodes. The method-specified QC limits for duplicate precision will serve as the DQO for th is project. If the method does not contain QC limits for the RPD value, the RPD should not exceed 20 percent. This is not intende d to be a required precision, but to be a target. ERG will use Sec tion H of the checklist to validate laboratory performance evaluation sample s in terms of precision.

Accuracy



### Accuracy is a measure of the agr eement between a measured value and a

reference or “true” value. Because the “true” co ncentration of an analyte in a field sample is never known, spiked samples (e.g., a matrix sp ike (MS)) are used to evaluate accuracy. Laboratories prepare an MS samp le by adding known amounts of the compounds of interest to the field sample. The spiked samples receiv e the same handling, ex traction, cleanup, and

### Section No. 2 Revision No. 0 March 2009 Page 12 of 16

analysis steps as the field samples. The labor atories then perform a percent recovery (%R) calculation to determine their accuracy:

100 SA SR

- SSR Recovery Percent       





### where: SSR = Spiked sample result; SR = Sample result; and SA = Spike added.

The successful evaluation of accuracy depends on the choice of spiking concentration. To determine the appropriate spiking concentration for the MS sample, the laboratory must first analyze the original sample. In general, the spiki ng concentration must be

at least twice the c oncentration of the analyte present in the origin al sample, and ideally, should

be no more than ten times that concentration.

The QC limits for the recovery of spiked analytes for most of the analytical
methods listed in Table 2-2 (locat ed at the end of this section) will serve as the DQO for this project. These limits are based primarily on met hod validation studies using matrices as treated

effluents from wastewater treatme nt plants. If the method does not specify percent recovery, it should be between 50 and 150 percent. This is no t intended to be a required percent recovery, but to be a target.

In addition to MS/MSD sample, the laboratory analyzes a laboratory blank, which consists of reagent water or “clean matrix” material that does not contain th e analytes of interest or interfering compounds. ERG will review labora tory blank results to verify the absence of contamination originating at the laboratory.

ERG will use Section H of the checklis t to validate laboratory performance evaluation samples to validate the accuracy of the results of chemical analyses.

### Section No. 2 Revision No. 0 March 2009 Page 13 of 16

Sensitivity



### Sensitivity is the ability of the method or instrument to detect the target analytes
at the level of interest (method or instrument de tection limit). Sensitivity can be evaluated using the following:

 

### Method Detection Limits - A method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99 percent confidence th at the analyte concentration is greater than zero. For organics and metals analytical methods, laboratories are required to perform MD L studies for each instrument with which analyses will be performed and any time a modification is made that will effect the MDL. Laboratorie s must demonstrate that they obtain an MDL value that is less than or eq ual to either of the following: (1) the MDL (if listed in the method) or (2) one-third the minimum level (if listed in the method). Appendix B of 40 CFR Part 136 describes the EPA procedure used for establishing MDLs.

ERG was not responsible for selecting analytical laboratories or reviewing MDL studies. For methods that have MDL studies, ERG will review the laboratory-supplied MDL or reporting limit to ensure the laboratories’ MDL meets the method requirements. ERG will not evaluate MDLs for classical pollutants.

 

### Aqueous Performance Standard - To assess laboratory performance and evaluate error sources in the labo ratory, the laboratory prepares an aqueous performance standard (ongoi ng precision and recovery (OPR)) sample by adding known amounts of the analytes of interest to a matrix with known characteristics. Reagent wa ter is usually used as the reference matrix. The laboratory processes the standard through all sample preparation and analysis steps and ev aluates analyte recoveries against method specific limits.

ERG was not responsible for selecting analytical laboratories or verifying the selected laboratorie s are qualified through a ce rtification process or through the use of performance evaluation samples.

 

### Instrument Calibration Check Standard - To ensure that the instrument calibration remains in control, the laboratory performs a calibration check standard by adding analytes of interest to a laboratory reagent blank over a range of concentrations as required by the method. Analyte recoveries are evaluated using limits specified in the applicable method.

### Section No. 2 Revision No. 0 March 2009 Page 14 of 16

ERG will verify that the laborator y performed appropriate initial calibration and periodic calibration checks by reviewing criteria in listed in Section E of the checklists.

 

### Surrogates and Internal Standards for Organic Analyses - Organic analysis methods that have solvent extraction steps require the use of surrogate compounds or, in the case of isotope d ilution methods, isotopically labeled analogue compounds to monitor extracti on efficiency and extract handling procedures. Because these steps can greatly impact the recovery of the target analytes, the laboratories must monitor these steps carefully to ensure data quality. The applicable methods specify the surrogate and isotope compound recovery limits , based on method validation study results.

ERG will compare the reported recovery of the isotopically labeled compounds by reviewing criteria in listed in Sections F and G of the checklists.

2.6 Element A.8: Special Training/Certification



### All information and data collected via this sampling program has been claimed CBI by the CCH facilities. ERG did not use site names or sample point descriptions when transmitting samples to the analytical laboratories. The analytical results received from the lab

are not CBI because the results are identified only by episode number, sampling point number, and Sample Control Center (SCC) numb er. ERG data review staff will not have access to CCH

CBI data for this task and therefore do not need to be trained in handl ing CBI. ERG has handled CBI for other portions of the CCH project under Work Assignment 5- 18 of Contract 68-C2-095.

All ERG staff that have access to CBI have been trained in CBI handling procedures as outlined in ERG’s CBI security plan entitled Security Plan for Handling Confidential Business Information Under the Clean Water Act 

### , dated March 5, 2004 and approved by Ahmar Siddiqui,
EPA’s Document Control Officer for this contract, on March 19, 2004 (5).

### Section No. 2 Revision No. 0 March 2009 Page 15 of 16

2.7 Element A.9: Project Documents and Records



### ERG has developed and instituted docume nt control mechanisms for reviewing, revising, and distributing QAPPs. Each QAPP ha s a signed approval form, title page, table of contents, and EPA-approved document control format (see header that appears at the top of each page in this QAPP).

Table 2-1 presents the dist ribution list for this QAPP. During the course of the project, any revision to the QA PP will be circulated to ever yone on the dist ribution list.

Section 5 of ERG’s QMP (4) presents sta ndard controls for pr oject-related data, documents, and records. ERG’s WAM is responsi ble for designating an i ndividual to maintain all project files. All information collected, gene rated, and analyzed on th e project is handled and

stored in a centralized re cord, as described in the Chlorine and Chlorinated Hydrocarbons Project File Management Plan 

### , dated May 16, 2005 (6). This cen tralized record contains all

information collected or accessed from other sour ces, documents the analytical data review, and documents analyses of any data collected (e.g ., site visit reports, sampling plans, sampling episode reports, laboratory data packages). Th e contents of the reco rd are indexed using a

Microsoft® Access database.

Management of project data is specif ically described in Element B.10, Data Management (Section 3.6).

### Section No. 2 Revision No. 0 March 2009 Page 16 of 16

Table 2-2. Standard Analytical Methods and Procedures

Method Number Title Method Type
Classicals EPA 160.2 Total Suspended Solids (TSS) Gravimetric EPA 160.1 Total Dissolved Solids (TDS) Gravimetric EPA 300.1, Rev 2.1 Sulfate Colorimetric, Gravimetric, or Turbidimetric EPA 300.1, Rev 2.1 Chloride Colorimetric or Titrimetric EPA SM2320 B Alkalinity Colorimetric or Titrimetric EPA SM5210 B Carbonaceous Biochemical Oxygen Demand (CBOD 5 ) 5 day; DO Depletion EPA SM5210 B Biochemical Oxygen Demand (BOD 5 ) 5 day; DO Depletion EPA 410.4, Rev 2 Chemical Oxygen Demand (COD) Colorimetric or Titrimetric EPA SM5310 C Total Organic Carbon (TOC) Combustion or Oxidation
Metals EPA 200.7, 245.1 Total Metals – 27 Element Quantification Mercury ICP and GFAA

Organics EPA 1624C Volatile Organic Compounds GC/MS EPA 1625C Semivolatile Organic Compounds GC/MS
Other EPA 1668A Chlorinated Biphenyls Congeners by Isotope Dilution HRGC/MS EPA 1613B Tetra- Through Octa-Chlorinated Dioxins and Furans by Isotope Dilution HRGC/MS

GC/MS: Gas chromatography with mass spectrometry. HRGC/MS: High resolution gas chromatography with mass spectrometry. GFAA: Graphite furnace atomic adsorption. ICP: Inductively coupled plasma. CVAA: Cold vapor atomic adsorption. GC/FID: Gas chromatography with flame ionization detection.

### Section No. 3 Revision No. 0 March 2009

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3.0 D ATA 

### G ENERATION AND 

### A CQUISITION



### EPA’s sample collection procedures were documented in the site-specific sampling plans, Sampling QAPP, and 2007 Sampling QAPP A ddendum. The site-specific sampling plans include the following:

 

### EPA’s criteria for selecting the CCH facility for sampling;

 

### Samples to be collected (number of samples and location);

 

### Sample collection procedures (manual composites or grabs);

 

### Analytes for each sampling point;

 

### Analytical methods;

 

### Sample handling and preser vation requirements; and

 

### Collection of QC samples.

EPA has identified 10 elements to be di scussed related to data generation and acquisition (1). Most of these elements we re covered by the Sampling QAPP and 2007 Sampling
QAPP Addendum. This section discusses the followi ng elements that pertain to the analytical data
review, verification, and validati on for Sampling Episodes 6542 and 6543:

 

### B.3: Sample handling and custody;

 

### B.4: Analytical methods;

 

### B.5: Quality control;

 

### B.6: Instrument/equipment testi ng, inspection, an d maintenance;

 

### B.7: Instrument/equipment cal ibration and frequency; and

 

### B.10: Project data management.

3.1 Element B.3: Sample Handling and Custody



### During the data review, ERG will compare documentation for sample receipt to the actual handling of the sample on ce received in the laboratory to ensure all method requirements

were met. ERG data review checklists includ e items pertaining to storage requirements and sample hold time requirements to verify the la boratory’s sample handling procedures and
documentation (Sections B and C).

### Section No. 3 Revision No. 0 March 2009

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3.2 Element B.4: Analytical Methods



### Table 2-2 at the end of Section 2.0 list s the analytical methods that EPA used in Episodes 6542 and 6543. ERG will verify that the laboratory followed all method-specified requirements and document the findings in the me thod-specific checklists. The attached Data

Review Plan contains the method checklists.

3.3 Element B.5: Quality Control



### EPA’s data generation quality control pr ocedures were documented in the sitespecific sampling plans, Sampling QAPP, and 2007 Sampling QAPP Addendum. For the data
review, verification, and validation, ERG will review the laboratory data packages to ensure that proper laboratory quality control procedures were followed. ERG will document the results of the laboratory QC review in the method-specific checklis ts and final data review narrative. Section 2.5 discusses the quality objectives and acceptan ce criteria for the data review project.

3.4 Element B.6: Instrument/Equipment Te sting, Inspection, and Maintenance



### The laboratories selected to analyze samples must perform preventive maintenance on all of their analytical equipm ent. Equipment maintenance log books must contain records of equipment usage, maintenance, modifications, cal ibrations, and repairs. If data on supplies acceptance testing or equipment maintenance is pr ovided in the laboratory documentation package, ERG will review the information to determine if any procedures would affect sample analysis data quality.

ERG will review the laboratory data packag es to determine if the laboratories used the appropriate equipment, preparation material, columns (if applicable), and detectors during the analysis of each sample. If so supplied, ERG will review the instrume nt/equipment maintenance records to ensure the equipment was properl y maintained throughout its operation including

### Section No. 3 Revision No. 0 March 2009

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verification that calibrations follow major changes in instrument configuration or maintenance

events.

3.5 Element B.7: Instrument/Equipment Calibration and Frequency



### The laboratories selected to analyze sa mples are responsible for performing all required instrument calibrations. Instrument calibration procedures, including frequency specifications and maintenance requirements, are sp ecified in the analytic al methods and in the laboratory contracts. Whenever changes are made to a system or a method, the laboratory must ensure that its equipment is opera ting properly by performing the a ppropriate QC tests. Analytical instruments requiring calibration must be uniquely identified to allow proper association of

calibration records.

To ensure that the calibration standard is met, the laboratory must analyze test samples that are either certified as to purity, c oncentration, and authenticity, or prepared from materials of known purity and composition. ERG w ill verify that calibration measurements were performed and/or verified with calibrated system s at the specified frequencies by reviewing the

criteria listed in Section E of the method-specific checklists.

3.6 Element B.10: Project Data Management



### ERG has received electronic data packages of the results of chemical analyses for Episodes 6542 and 6543 from EPA. For each epis ode and each analyte group listed in Table 2-2 (classicals, metals, organics, a nd other analytes), the data pack age contains a Microsoft® Excel spreadsheet containing the chemical analysis resu lts and a portable document format (PDF) file containing the supporting laborat ory documentation (e.g., traffic reports, laboratory checklists,
instrument calibration information). ERG will us e the electronic data package to conduct the analytical data review, veri fication, and validation.

### Section No. 3 Revision No. 0 March 2009

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ERG will document the results of the anal ytical data review using method-specific

checklists and a data revi ew narrative as follows:

 

### Method-specific checklists – ERG will provide a completed method-specific checklist for each sample number or range of sample numbers for each analyte; and

 

### Data review narrative – ERG will provide a data review narrative for each analyte group) which will summarize the results of the data review, verification, and validation. The data review narrative will also include a discussion of any data qualifiers and the reason for the qualifier. The data qualifiers that will be used in this project are discussed in Section 5.1.

After reviewing the data, ERG will post the analytical results including any data qualifiers on the EPA mainframe computer. Table 3-1 lists the elements in the analytical database. ERG will check that all data provided by the labora tory in Microsoft® Excel spreadsheet format is transferred to the EPA mainframe computer.

### Section No. 3 Revision No. 0 March 2009

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Table 3-1. Typical Database Structure

Field Description Field Name Source of Data
Analyte Concentration AMOUNT Laboratory , in same order as chemical name
Analyte Name ANALYTE Laboratory
CAS Registry Number CAS_NO Laboratory

Calculated Detection Limit DETLIMIT Labora tory, in same order as chemical name
Episode Number EPISODE Upper right corner of Traffic Report
Laboratory Name LABNAME Laboratory Column or Extraction Type PROCEDUR Laboratory
Reason for Qualification REASON Laboratory(a)
Sample Number SAMPLE Traffic report
Data Qualifier QUAL ERG Concentration Units UNIT Laboratory, in mg/L or as specified in method or laboratory contract
Laboratory Method Used METHOD Laboratory

CAS - Chemical Abstract Service. (a) A “greater than” sign (>) will be the qualifier (QUAL) when the corresponding reason (REASON) is “sample result is greater than the upper calibration range.”

### Section No. 4 Revision No. 0 March 2009

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4.0 A SSESSMENT AND 

### O VERSIGHT 

### E LEMENTS



### This section describes the methods ERG will use to assess the quality of the analytical data collected for Episode s 6542 and 6543 of the CCH sampling program.

4.1 Element C.1: Assessments and Response Actions



### This subsection describes the technical re view, audits, and corre ctive actions that will be performed on the CCH project. ERG will not conduct audits of laboratory systems and procedures during th is project.

4.1.1 Technical Support



### All work conducted by ERG on Work Assi gnment 5-18 for the analytical data review will be subject to tec hnical review. As discussed in Section 1.3.4 of the QMP (4),

technical review is a documented critical review of work that has been performed within the

“state of the art.” A senior chemist at ERG will complete method-specifi c checklists and create

review narratives to document the analytical data review, verifica tion, and validation. Dr. Ray

Merrill will review the final data review narrative. If incomplete data packages are received or if questions develop that impact ERG’s ability to perform the data review, ERG’s senior chemist will forward a request to the ERG WAM and QA coordinator, who will notify the EPA WAM

about the issue.

Ms. Betsy Bicknell will serve as the Pr oject QA Coordinator for this project. To assess the implementation of QA/QC pr ocedures on this project, she will:

 

### Review this QAPP for completeness and applicability.

 

### Audit project files to ensure project staff have developed QC procedures and are using these procedures.

### Section No. 4 Revision No. 0 March 2009

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At any time or at the end of the project or work assignment, Ms. Bicknell, or her designee, may inspect the project QA files.

4.1.2 Analytical Data Review



### At the completion of each data review, the ERG Project QA Coordinator will

review records of activities and wi ll evaluate the following elements:

 

### Overall level of organiza tion and professionalism;

 

### Compliance with all procedures outlined in this QAPP; and

 

### Completeness of documentation (i.e., method-specific checklists and data review narratives).

The ERG Project QA Coordinator will disc uss any deficiencies with the project team and identify any necessary co rrective actions. If any of thes e deficiencies may potentially affect the use of the analytical data for tech nical analyses, the ERG Pr oject QA Coordinator will immediately inform the EPA and ERG WAMs, so th at any corrective actions can be taken.

4.1.3 Corrective Action



### ERG will review all laboratory data generated from Sampling Episodes 6542 and 6543 for accuracy and precision, completeness, repr esentativeness, and comparability to ensure that the quality objectives and cr iteria discussed in Section 2.5 of this QAPP have been met. ERG will report any deficiencies in the laborat ory reports to the EPA WAM. ERG will not

contact the laboratories or take corrective acti on to modify or change the data. ERG will document any recommended data qua lifiers in the data review narrative and post the qualifiers to EPA’s computer mainframe as discussed in Section 5.1.

### Section No. 4 Revision No. 0 March 2009

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4.2 Element C.2: Reports to Management



### ERG will append this QAPP as required. ERG will inform the EPA WAM of the progress of all data review activities through the semimonthly and monthly written reports required under Work Assignment 5-18.

Any quality deficiencies detected by the ER G data review chemists or the Project
QA Coordinator will be communicated, in wri ting, to the EPA WAM. The ERG WAM is responsible for ensuring that appropriate correctiv e action is taken and re ported to the Project QA Coordinator. In addition, as required by Work Assignment 5-18, ERG will provide quality assurance updates to the EP A WAM on a quarterly basis.

### Section No. 5 Revision No. 0 March 2009

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5.0 D ATA 

### V ALIDATION AND 

### U SABILITY 

### E LEMENTS



### This section describes data review, verification, and valid ation. It also discusses

how EPA will evaluate data to determine if it is acceptable for use in answering the questions posed in Section 2.3.1.

5.1 Elements D.1 and D.2: Data Revi ew, Verification, and Validation



### This subsection discusses th e procedures used for the data review, verification, and validation. ERG will review sample anal ysis results for completeness, comparability, precision, accuracy, and sensitivity as outlined in Section 2.5. ERG will perform the following steps in conducting the data review:

1. Obtain laboratory data package from EPA.

2. Verify all required samples have an analytical result and were handled properly by the laboratory using me thod-specific checklist sections A through C.

3. Validate chemical analysis results us ing method-specific checklist sections D through H.

4. Complete method-specific checklists for all sample numbers.

5. Determine if any data qualifiers are required (see discussion below).

6. Summarize the results of the revi ew in a data review narrative.

7. Transfer method-specific checklists and data review narra tives to the EPA WAM.

8. Resolve EPA comments on the method-sp ecific checklists and data review narratives.

9. Upload the data to the EPA mainframe computer.

### Section No. 5 Revision No. 0 March 2009

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Data Qualifiers



### ERG will add qualifiers to the analytical da tabase to notify users of the data about particular data quality issues. Only two qualifiers will be added directly into the Data Qualifier field (QUAL) in the analytical database on EPA’s mainframe computer as appropriate:

1. Result represents a maximum (add ‘> ’) – Laboratory dilutions may be necessary when there are sample matrix interferences or when levels of an analyte in a sample exceed the calibra tion range. ERG will verify that all samples are within the method-specif ied calibration range. If not (a sample should have been diluted to br ing a result into the calibration range and the laboratory data package co ntains no documentation explaining the reason), ERG will consider these data as the upper limit of the calibration range and will enter a ‘>’ in the QUAL field for that analyte.

2. Result should be excluded (add ‘EXCLUDE’) – In some cases the data will be considered unusable due to gross QC deficiencies or failures. ERG will enter ‘EXCLUDE’ in the QUAL fi eld for that analyte. Some instances where data may be excluded are:

— QC is missing or grossly outside li mits (e.g., 0 percent recovery);

— Statements in the laboratory na rrative that indicate there were matrix problems that interfere w ith identification or quantitation;

— Statements in the laboratory narrative that indicate that the identification or quantitation of the data may be questionable;

— High levels of target analyte cont amination in the blank associated with the samples; and

— Analyte was not detected in any spiked samples (MS/MSD and OPR).

Any other qualification of the data will be discu ssed in the data review narratives and will not be flagged in the analytical database.

5.2 Element D.3: Reconciliation with User Requirements



### The data collected during the CCH sampling program can be used to answer the questions posed in Section 2.3.1 by clearly identifying the presen ce (concentrations of pollutants above the analytical method minimum level) or nonpresence (concentrations of pollutants below

### Section No. 5 Revision No. 0 March 2009

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the analytical method detection le vel) of analytes in the sample d wastewater. ERG will perform the analytical data review to en sure that the laboratory results meet the method-specified quality control objectives and are suitable for use in an swering the overall project key questions. For this data review project, ERG will provide a narr ative describing the quality of the data and their fit for use in developing effluent guide lines for the CCH manufacturing segment.

### Section No. 6 Revision No. 0 March 2009

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6.0 R EFERENCES



### 1. U.S. Environmental Protection Agency. EPA Requirements for Quality Assurance Project Plans QA/R-5 

### . EPA/240/B-01/003. Office of Environmental Information. March 2001.

2. Eastern Research Group, Inc. Final Quality Assurance Project Plan for the Chlorine and Chlorinated Hydrocarbon Sampling Program. 

### May 2006.

3. Eastern Research Group, Inc. Final Quality Assurance Project Plan for the Chlorine and Chlorinated Hydrocarbon Sampling Program 2007 Addendum



### . July 2007.

4. Eastern Research Group, Inc. Quality Management Plan 

### . April 2007.

5. Eastern Research Group, Inc. Security Plan for Handling Confidential Business Information Under the Clean Water Act 

### . Revision 1. March 5, 2004.

6. Eastern Research Group, Inc. Chlorine and Chlorinated Hydrocarbons Project File Management Plan 

### . May 2005.

### Attachment 1

DATA REVIEW PROCEDURES

# Data Review Procedures for Office of Water Effluent Guidelines Sampling Data

Prepared for:


# U.S. Environmental Protection Agency Engineering and Analysis Division Office of Water 1200 Pennsylvania Avenue, NW Washington, D.C. 20460

Prepared by:


## Eastern Research Group, Inc. 14555 Avion Parkway Suite 200 Chantilly, VA 20151-1102

March 2009

EPA Contract No. 68-C-02-095 Work Assignment 5-18

### ii TABLE OF CONTENTS

Page

1.0 B ACKGROUND 

### .......................................................................................................1-1

2.0 D ATA 

### Q UALITY 

### R EVIEW 

### G OALS 

### ...........................................................................2-1

3.0 D ATA 

### R EVIEW 

### P LAN 

### .............................................................................................3-1 3.1 General Review of Sample Identity and Handling ..................................3-2 3.2 Review of General QC Requirements......................................................3-2 3.3 Detailed Review of Method-Specific Parameters....................................3-3 3.3.1 Dioxins and Furans (Method 1613B) ..........................................3-4 3.3.2 Total Suspended Solids (TSS) (Method 160.1) ...........................3-5 3.3.3 Volatile and Semivolatile Organic Compounds (Methods 1624C and 1625C)...................................................................................3-7

4.0 D ATA 

### R EVIEW 

### S UMMARIES 

### ..................................................................................4-1

5.0 R ECOMMENDATIONS AND 

### B UDGET 

### .......................................................................5-1

Appendix A: DATA REVIEW CHECKLISTS

### iii LIST OF TABLES

Page

2-1 Data Package Detail Expect ed for Project Categories......................................... 2-3

5-1 Number of Samples by Method for CCH Analytical Data Review..................... 5-2

### 1-1 1.0 B ACKGROUND



### EPA is considering possible revision of the national effluent guidelines regulations for the chlorine and chlorina ted hydrocarbon (CCH) manuf acturing segments. Currently, wastewater discharges from chlorina ted hydrocarbon manufacturi ng are subject to the Organic Chemicals, Plastics, a nd Synthetic Fibers (OCPSF) Poin t Source Category (40 CFR Part 414) and wastewater discharges from chlor-alka li manufacturing of chlorine are subject to the Inorganic Chemicals Point Source Category (40 CFR Part 425). Bo th of these industries have been identified as discharging si gnificant quantities of toxics as represen ted by “toxic weighted pound equivalents” (TWPEs). Of particular conc ern is the quantity a nd toxicity of dioxin discharges in treated effluent.

EPA is collecting information and data regarding the sources and characteristics of discharges from CCH manufacturing. As part of the evaluation, EPA is conducting a sampling program to 1) obtain wastewater char acterization data and 2) obtain wastewater treatment technology and pollution prevention perf ormance data. EPA will use the analytical data from the sampling program in combination with other CCH data to evaluate possible pollution prevention and treatment op tions for these wastewaters.

In 2007, EPA conducted two, two-day samp ling episodes at CCH manufacturing facilities (Episodes 6542 and 6543). At each facili ty EPA collected samples at the influent to and effluent from the plant’s wastewater treatmen t system and several intermediate points within the system. The samples were collected as manual composites in which six aliquots were collected for each sampling point approximately four hours apart. The six samples were composited to create one sample representative of a 24-hour time period. Samples for dioxins and furans, polychlorinated biphenyls (PCBs), and volatile organic hydrocarbons (VOAs) were composited at the analytical laboratory.

ERG will document information and data collected during these episodes in sampling episode reports (SERs), which will be used by EPA and ERG in conducting additional technical analyses. Prior to usi ng the data in the SER and technical analyses, the analytical data received from the laboratories must undergo a quality control (QC) review to ensure the

### 1-2 completeness, representativeness, and accuracy of the laboratory results. This document outlines procedures that can be used by ERG’s measurem ents group to complete the laboratory quality review. ERG’s measurements group, located in Research Triangle Park, North Carolina, performs analytical data review for various media (e.g., air, wa ter, waste). This group has actively supported EPA’s measurements and data review needs since 1986.

### 2-1 2.0 D ATA 

### Q UALITY 

### R EVIEW 

### G OALS



### The Quality Assurance Project Plan for the Chlorine and Chlorinated Hydrocarbons Sampling Program dated May 4, 2006 lists the follo wing key questions that will be addressed by the CCH sampling program:

• 

### What pollutants are being di scharged by CCH operations?

y What are the sources of dioxin from CCH operations?

y What are the concentrations and quantities of pollutants currently being discharged (i.e., “baseline” concentration)?

y What is the performance/efficiency of pollution prevention and wastewater treatment technologies being used to reduce pollutants discharged from CCH operations?

All data collected must be reviewed to qualif y it for use in answering these questions. In addition, data collected may be reviewed by in terested stakeholders and compared to split samples collected by industry during each sampling episode.

The end use of the laboratory data de termines the extent of QC and quality assurance (QA) review. Implementation of a “one size fits all” approach to quality requirements is not appropriate. Implementation of the EPA Quality System 1 

### is based on the principle of a “graded approach” since this approach allows quality systems and quality plans for different programs to vary according to the specific objectives and needs of the organization or project. In

EPA’s Requirements for Quality Assurance Project Plans 2 

### , EPA recommends that QA and QC activities applied to a project be sufficient for:

y The purpose of the environmental data operation (e.g., enforcement, research and development, rulemaking);

y The type of work to be done (e.g., pollutant monitoring, site characterization, risk characterizatio n, bench level proof of concept experiments); and

1 For more information on EPA’s Quality System, see http://www.epa.gov/QUALITY/.
2 See EPA Requirements for Quality Assurance Project Plans (March 2001), available online at http://www.epa.gov/QUALITY/ qs-docs/r5-final.pdf.

### 2-2 y The intended end use of the resu lts (e.g., compliance determination, selection of remedial technology, development of environmental regulation).

EPA offices specify project categories ba sed on the intended end use of the data

collected. 3 

### The following describes typical QC requirements:

y Category 1: Projects defined as a study to generate data used for enforcement activities, litigation, or some research projects involving human subjects. The Quality Assuran ce Project Plan (QAPP) for category 1 projects must address all elements listed in EPA Requirements for Quality Assurance Project Plans

. 4



### y Category 2: Project defined as a study to ge nerate data used in support of the development of environmental re gulations or standards. The QAPP for category 2 must address all elements listed in EPA Requirements for Quality Assurance Project Plans

. 5



### y Category 3: An applied research project defined as a study to generate data to demonstrate the performance of accepted processes or technologies under defined conditions. These studies are often pilot- or field-scale.

y Category 4: A basic research project define d as a study to generate data used to evaluate unproven theories, processes, or technologies. These studies are often bench-scale.

QA/QC data supporting each of thes e categories is provided with di fferent levels of detail. Based on the key questions listed in the CCH QAPP, the CCH analytic al data would be classified as Category 2 data since EPA may use the data to develop regulations or characterize the performance of various treatment technologies. Table 2-1 shows the typical review steps included for each of the project categories. As shown in Tabl e 2-1, Category 2 projects should

receive a Level 3 data review.

3 See http://www.epa.gov/ORD/NRMRL/q a/guide/qadocsformsplanning.htm
4 See EPA Requirements for Quality Assurance Project Plans (March 2001), available online at http://www.epa.gov/QUALITY/ qs-docs/r5-final.pdf.

### 2-3 Table 2-1. Data Package Detail Expected for Project Categories

Quality Review Procedure Category 1 Projects Category 2 Projects Category 3 Projects Category 4 Projects Screening Level Data Review: Review of traffic reports, sample handling, and proper sample preparation 9 9 9 9

Level 2 Data Review: Screening level review plus a review of sample QA/QC results 9 9 9

Level 3 Data Review: Level 2 review plus review of instrument performance 9 9

Level 4 Data Review: Level 3 review plus analysis of raw data such as chromatograms or primary instrument output 9

### 3-1 3.0 D ATA 

### R EVIEW 

### P LAN



### The CCH project will use analytical data that must be of known quality for technical analyses. Prior to each sampling epis ode, EPA developed a detailed sampling plan that lists the number of samples collected for each sampling point and analyte, detailed sample collection procedures including preservation requirements, QA samples collected, and sample tracking and shipping procedures. Laboratories send detailed data packages to EPA which can include: an analytical narrative discussing exceptions or QC irregularities, a list of the samples, the traffic reports for the samples, and met hod-specific information such as initial method calibration, continuing quality cont rol results, other quality contro l measures, sample results, and

raw instrument data. This section outlines ERG’ s plan for reviewing the packages received from the laboratories to ensure they are of sufficien t quality for use in CCH technical analyses.

ERG uses standard review procedures and detailed method-speci fic checklists to review laboratory data packages. Appendix A contains the method-specific checklists. ERG will complete a detailed, method-specific checklis t for each sample set and provide specific information for individual samples, as neede d. For example, ERG will review all samples analyzed by the laboratory for a single calibratio n in a valid sequence that includes calibration and sample results.

Each data review consists of three major stages which are described in the following sections:

y Section 3.1 describes the general proce dures for verifying sample identity and traceability;

y Section 3.2 describes the general QC fo r sample handling and preparation; and

y Section 3.3 describes the met hod-specific QC requirements.

ERG will review data for each sample and summa rize the results. Section 4.0 of this plan describes the overall data review summaries that ERG will prepare.

### 3-2 3.1 General Review of Sample Identity and Handling

Sections A and B of the detailed revi ew forms are common to all analytical methods and are fundamental to the identity and traceability of the sample. These sections are

described below:

y SECTION A: Data Package Contents and Sample Identifiers. Each sampling episode data package need s to identify samples and include sufficient data for the data review to ensure the quality of the results can be determined. Items for this part of the check list include laboratory name, EPA project name, sampling epis ode number, sample identification number (SCC number), ERG data review er signature, and date. The data reviewer will perform an initial check to confirm that all the data required for the review is in the data package. Section A-2 provides a table of contents for the review checklist and notes which requirements are applicable for each of the review categories discussed in Section 2.0.

y SECTION B: Traffic reports . Traffic reports are the link between the field sampling information and the la boratory analysis. Traffic report forms are generated with every set of samples sent to a laboratory for analysis. The traffic report is the source of the data identifiers necessary to track the origin of the samples. Items for the check list include assuring completeness of the sample receipt records, receipt date, sample identification numbers, sample receipt temperature, and condition.

3.2 Review of General QC Requirements

Sections C and D of the review forms evaluate the common QC requirements in the methods. All methods include specifications for sample hold time and preparation/extraction of samples.

y SECTION C: Sample Handling Information. Sample shipments received by a laboratory are checked fo r proper container use, preservation and hold time. The initial hold time check ensures samples were not held in the field past their expiration date making the analysis results invalid. Hold time prior to extraction is determ ined from the day of collection to the day samples are processed by ex traction. ERG will determine if sample results are invalid due to im proper preservation or excessive hold time prior to extraction.

y SECTION D: Sample Preparation and Extract Handling Information

. ERG ensures that samples were stored at the appropriate temperature as

### 3-3 specified by the method. ERG also check s the validity of the analysis hold time. The analysis hold time is measured from the time of preparation/extraction of the samples by the laboratory to the time of sample analysis.

3.3 Detailed Review of Method-Specific Parameters

Sections E through I are reserved for th e detailed review of method-specific parameters. Method-specific QC involves reviewing the primar y instrument calibration and performance measures. At a minimum, these revi ews typically include verification of equipment calibration, blank prepara tion, spiking procedures, and assessm ent of field QA samples from the sampling episode. Classical parameters, such as total suspended solids (TSS), are measured following simple calibration, blank, and spike pr ocedures, and typically require only the minimum review components. Reviews for higher level instrumental techniques, such as toxic metals or specific organic compound methods, ty pically involve evaluatio n of the response and recovery of unique and/or labeled analytes as a key indicator of method performance. Several methods also require laboratories to provide da ta on initial precision and accuracy to demonstrate their ability to perform the requested anal ysis on a sample in a “clean” matrix.

For example, in Method 1613B, the is otopic dilution method for dioxins and furans, isotopically labeled carbon compounds are spik ed into all samples. The recovery of the labeled compounds must meet initial precision an d recovery (IPR) method specifications. ERG will also review ongoing precision and recovery (OPR) QC data from the data package to determine if the laboratory pe rformance met method requirement s during the sample analysis period. If OPR results do not meet method requireme nts, the data review for this sample series will indicate data quality for sample analysis could be compromised.

The following list presents the analytical methods used for CCH Sampling Episodes 6542 and 6543:

y Classical Parameters

— Total Suspended Solids (TSS) EPA Method 160.2 (Gravimetric)

— Total Dissolved Solids (TDS) EPA Method 160.1 (Gravimetric)

— Sulfate 300.0 EPA Method Rev 2.1 (Colorimetric, Gravimetric, or Turbidimetric)

### 3-4 — Chloride EPA Method 300.0 Rev 2.1 (Colorimetric or Titrimetric)

— Alkalinity SM2320B (Colorimetric or Titrimetric)

— Biochemical Oxygen Demand (BOD) SM5210B (5 day; DO Depletion)

— Chemical Oxygen Demand (COD) EPA Method 410.4, Rev 2 or HACH 8000 (Colorimetric or Titrimetric)

— Total Organic Carbon (TOC) SM5310B or SM5310C (Combustion or Oxidation)

y Total Metals Methods

— Total Metals – 27 Element Quantitation EPA Method 200.7 (ICP and GFAA)

— Mercury Method 245.1

y Major Organics Group Methods and Data Review

— Volatile Organic Compounds ( VOC) EPA Method 1624C (isotope dilution GC/MS)

— Semivolatile Organic Compounds EPA Method 1625C (isotope dilution GC/MS)

y Specific Organic Class Me thods and Data Review

— Chlorinated Biphenyls Congeners (PCBs) EPA Method 1668A (isotope dilution HRGC/MS)

— Tetra- Through Octa-Chlorinated Dioxins and Furans (D/F) EPA Method 1613B (isotope dilution HRGC/MS)

The following subsections summarize the method-sp ecific QC requirements for some of the high priority analytes for the CCH sa mpling program. These methods include analysis of dioxins and furans (Method 1613B), total suspended so lids (Method 160.1), and major organic group methods (1624C and 1625C). Appendix A cont ains the checklists for all methods.

3.3.1 Dioxins and Furans (Method 1613B)

This section summarizes the method- specific QC requirements for Method 1613B. Details are provided in Sections E throug h I of the attached detailed checklist (see Appendix A). Completion of Sections E through H correspond to a Level 3 data review and completion of Section I is included in a Level 4 data review (see Table 2- 1). The analysis of dioxin and furan congeners includes the following QC procedures:

y Instrument performance (Section E- 1) and calibration (Section E-2): Laboratories must provide documentati on of the instrument performance

### 3-5 and calibration. Data reviewers must ve rify that the instrument used for the analysis has a sufficient reso lution, measures the correct ion abundance ratios and retention times for labeled and unlabeled compounds in the calibration standard, that cal ibration standards were prepared correctly, and that the recovery of labeled co mpounds falls within the method-specified parameters.

y Method Blanks (Section E-3): Labora tories must provide information about the preparation of method blanks analyzed with the sample set. Reviewers must verify that the laborat ories used the correct procedures to prepare the blanks and spike the clea n matrix samples with the correct concentrations of surrogates. In addition, 1600 series methods require analysis of OPR samples spiked wi th labeled and unlabeled compounds.

y Recovery of Labeled Compounds (Secti on F) and Instrument Recovery of Internal Standards (Section G): The amount of labeled compounds recovered from spiked samples must be within the method-specified limit.

y Performance Evaluation (QA) Sample s (Section H): If QA samples (e.g., field duplicates or equipment field blanks) are submitted with the sample set, and the QAPP specifies requireme nts for QA sample results, then ERG will determine if results of QA samples meet the QAPP specifications.

y Detailed Raw Data Review – Co mpound Identification (Section I): Reviewers will verify that the rela tive retention times, signal-to-noise ratios, ion abundance ratios, and vall ey heights are within the methodspecified parameters for identifying a compound. This review is performed to identify interferen ces, errors in specific congener identification, and unusual tr eatment of the data.

3.3.2 Total Suspended Solids (TSS) (Method 160.1)

TSS is a measure of the retained materi al on a standard glas s fiber filter after filtration of a well-mixed sample. The determination is a gravimetric measurement of the

residue dried to a constant we ight at 103 to 105°C. This method is applicable to drinking,
surface, and saline waters as well as domestic and industrial wastes over a range of 4 to 20,000 mg/L. Samples high in filterable residues may be subject to pos itive interference.

The internal quality control procedur es for TSS by EPA Method 160.1 include:

y Verification of Equipment, Ca libration, and Lab Environment:

### 3-6 — Is the drying oven temperature recorded and between 103 to 105°C? Is the oven temperature recorded and correct for the method?

— Is a desiccator with active co lor indicator recorded ?

— Is the balance make and model r ecorded and capable of weighing to 0.1 mg? Does the report indicate the analytical balance been serviced and calibrated within th e last year? Is the balance checked with “S” class weights?

— Are suitable filter holders and filtering apparatus referenced and in use?

y Verification of Preparation Procedures:

— Is there a record of filters drie d at 103 to 105°C for 1 hour before use?

— Is the filter drying done until a c onstant weight is achieved?

— Are filters stored in a desiccator, after preparation until needed?

y Verification of Analytical Pr ocedure and Record Keeping:

— Are the filters weighed imme diately before use?

— Is the filter placed wrinkle side up in the filtering apparatus?

— Is the sample brought to room temperature before analysis?

— Are non representative particles (e.g. , leaves and sticks) excluded from the sample?

— How soon are samples analyzed after collection?

— Do sample volume or filter size selected to yield between 10 and 200 mg of total residue?

— Are temperature and humidity reco rded for the weighing facility?

— Is the start weight recorded on a bench sheet?

— Is the sample volume recorded on the bench sheet?

— Is the final weight of the crucible and dry sample recorded on the bench sheet?

— Are the oven times written on the bench sheets?

— Are calculations shown on the bench sheets?

— Are the analyst’s initials recorded?

— Are the sample date and the analysis date recorded?

— Does the analytical balance check agree within 0.5 mg of known weight?

y Verification of Performa nce Evaluation Samples:

— Are the method blanks (MBs) less than one tenth the sample results?

— Are the relative percent differenc e of duplicate sample (DUP) less than 20% for samples >5X the method detection limit?

— Have one set per of mineral refe rence samples been analyzed per batch of samples? Are the resu lts within ±15% from expected concentration?

### 3-7 3.3.3 Volatile and Semivolatile Organic Compounds (Methods 1624C and 1625C)

Methods 1624C and 1625C are used to determine the volatile and semivolatile toxic organic pollutants associ ated with the Clean Water Ac t (as amended 1987); the Resource Conservation and Recovery Act (as amended in 1986); the Comprehensive Environmental Response, Compensation, and Liability Act (as amended in 1986); and other compounds

amenable to either:

y Purge and trap gas chromatography/mass spectrometry (GCMS) for Method 1624C; or

y Extraction and analysis by capillary column gas chromatography-mass spectrometry (GCMS) for Method 1625C.

The chemical compounds may be determined in waters, soils, and municipal sludges by the

methods. The detection limits of the methods are usually dependent on the level of interferences

rather than instrumental limitations.

Each laboratory that uses Methods 16 24C and 1625C is required to operate a formal QA program. The minimum requirements of this program consist of an initial demonstration of laboratory capab ility, analysis of samples spik ed with labeled compounds to evaluate and document data quality, and analysis of standards and blanks as tests of continued performance. 5 

### Low resolution mass spectrometric anal ysis of organic co mpounds involves the addition of surrogate compounds that must be meas ured with acceptable recovery for analyses to be validated. Laboratory performance is comp ared to established performance criteria to

determine if the results of an alyses meet the performance characteristics of the method.

Detailed quality control and quality assura nce requirements are listed in Section 8

of Methods 1624C and 1625C. The checklist s for Methods 1624C and 1625C include:

5 If the method is to be applied routinely to samples contai ning high solids with very little moisture (e.g., soils, filter cake, compost), the high solids reference matrix is substitute d for the reagent water in all performance tests, and the high solids method is used for these tests. The CCH samples are not expected to have high levels of solids.

### 3-8 y Verification of initial precision and accuracy, including verification that recoveries of compounds in standard s fall within the method-specified
ranges;

y Verification of spiked compound recoveries;

y Verification that records maintained by the lab are adequate to define that quality of the data;

y Verification of method blanks incl uding method blank preparation and results of analysis;

y Verification of equipm ent calibration; and

y Analysis of field QA samples.

### 4-1 4.0 D ATA 

### R EVIEW 

### S UMMARIES



### The level of detail for the data quality review should be based on a graded approach that varies according to the intended end use of the data . The end use of the data is described in Section 2.0 of this report and is de fined during the planning and preparation of the QAPP. The amount and sophistica tion of data review should depend on the data available and the Category of the project (Table 2-1). If the data qualifiers fail at any stage of the data review, the reviewer may recommend not proceeding with th e next stage of data review. The levels of

data review are summarized belo w. As stated in Section 2.0 a nd shown in Table 2-1, CCH is a Category 2 project and Levels 1 through 3 are requi red. ERG will start with the Level 1 review and work through to Level 3.

y Level 1 – Perform Screening Re view of Sample Receipt and Condition. This level of review is appli cable for data that are intended for screening purposes (e.g., determining th e presence or abse nce of a target or surrogate).

y Level 2 – Evaluate Sample Receip t and Condition Plus Basic QA/QC Review. This level of review is appli cable to data that are used to characterize process performance and is used to determine if the data adequately represent the process. Ba sic QC at Level 2 includes findings about sample condition on receipt, stor age, stabilization, preparation and QC spiking requirements.

y Level 3 – Evaluate Instrument Performance and ongoing QC . This level of review is applicable for data that are intended for use in regulatory development or complian ce certification. Level 3 review includes review of the data for compliance with a ll sections of the method-specific checklist except raw data review.

y Level 4 – Evaluate Raw Data. This level of review is applicable for data used in enforcement and litigation activities or for research projects involving human subjects. Since CCH is a Category 2 project, this stage of review is not recommended and not described in this section. Level 4 review includes review of the data fo r compliance with all sections of the method specific checklist.

ERG’s data review reports will include a narrative summary and findings of all
areas where the QC does not meet the QAPP or met hod requirements. No data will be discarded,

rather each data review narrative will include a su fficient summary for data users to decide if the

### 4-2 data can be used for its design pur pose(s). At all levels of data review, the resulting report will summarize the findings and identify what qua lity criteria have not been met.

ERG will provide a narrative discussion describing potential limitations in the data quality. The narrative discussion will include all of the components of a Level 3 data review. If the data fail to meet requirement s at any level of review, ERG may recommend that EPA not proceed to the next level of data review and limit use of the data since the quality can not be established. However, ERG expects all data in the CCH program will undergo a Level 3

data review. Data review fi ndings that results in noncomplian ce with method requirements (i.e., a check list “No” is indicated) will be supporte d by comments regarding use of the data and the appropriate flag that should be ente red into the corresponding data base.

### 5-1 5.0 R ECOMMENDATIONS



### ERG recommends the following steps for the CCH analytical data review:

y Perform Level 1 and Level 2 data reviews for all samples from Episodes 6542 and 6543.

y The number of samples for the Level 3 review will be specified by EPA. Level 3 data review is not necessary for 100 percent of the samples because laboratories follow the same protocols during sample analysis, and as a result, typically will make the same QC mistakes or omissions for all samples. However, if data will be used in court hearings for legal decisions, EPA may decide that a more thorough review is necessary and request that the Level 3 re view include up to 100 percent of the samples.

y ERG does not recommend a review of the instrumental data or hand interpretation of the mass spectra si nce the procedures for analysis are documented and QA/QC for the procedures are well established (Level 4 review).

Table 5-1 lists the number of samples for the data quality review for the two episodes.

### 5-2 Table 5-1. Number of Samples by Metho d for CCH Analytical Data Review

Method and Parameters Number of Samples for Episode 6542 Number of Samples for Episode 6543
Classical Parameters Method 160.1 - Total Dissolved Solids (TDS) 13 + 1QC 15 + 1QC Method 160.2 - Total Suspended Solids (TSS) 13 + 1QC 15 + 1QC EPA Method 300.0 Rev 2.1 – Sulfate and Chloride 13 + 1QC 15 + 1QC SM 2320B - Alkalinity 13 + 1QC 15 + 1QC EPA Method 410.1, Rev2 – Chemical Oxygen Demand (COD) 13 + 1QC 11 + 1QC SM 5310B/C – Total Organic Carbon (TOC) 13 + 1QC 11 + 1QC SM 5210B – Biochemical Oxygen Demand (BOD5) 13 + 1QC 9 + 1QC
Total Metals EPA Methods 200.7, 200.8, and 200.9 – Total Metals 13 + 1QC 11 + 1QC EPA Method 245.1 - Mercury 13 + 1QC 11 + 1QC Major Organics Group Methods EPA Method 1624C – Volatile Organic Compounds (VOCs) 9 9 EPA Method 1625C – Semivolatile Organic Compounds 7 7 Specific Organic Class Methods EPA Method 1668A – Chlorinated Biphenyl Congeners (PCBs) 5 5 EPA Method 1613B – Dioxin and Furan Congeners 14 18

### Appendix A

DETAILED DATA REVIEW CHECKLISTS

### Laboratory Name:______________ CCH Episode #.: ___________ Method 160.1 – Page 1 of 3 

## OW Effluent Guidelines Data Review Checklist Total Dissolved Solids (TDS) Method 160.1

SECTION A-1. Sample Identifiers
CCH Effluent Guidelines Development

Sampling Episode: Laboratory Name:

Sample Number or Range: Data Reviewer signature: Date:

Instructions: Complete this checklist el ectronically or using a ballpoint pen. Record reviewer comments in the Reviewer Comment section. Record detailed information in the “Comments and Overal l Assessment” section for each criterion not (“N”) met.



## SECTION A-2. Overall Method Total Disso lved Solids Data Package Checklist General Comment Checklist

Deliverable Requirement Required for Category Present Comments Copies of Shipping Documents (Fed-Ex Airbills) 1, 2, 3 Case Narrative 1, 2, 3 Table of Contents 1 Cross reference of Field Sample No., Lab Sample No., and Analytical Batch 1, 2, 3

Traffic Report Form (inc luding Sample Receipt Checklist) 1, 2, 3

Sample Calculation (usually just a page copied from SOW) 1

Results Summary for Each Sample and Blank 1, 2, 3 Initial Calibration Data 1,2 Copies of Sample Preparation Work Sheets 1,2,3 Copies of Analysis Run Logs 1,2
1. COMPLIANCE SCREENING (ERG Sections A through D)-- Sample and QC results only; no instrument calibration or performance checks 2. SUMMARY VALIDATION (ERG Sections A through E)-- Sample, QC, calibration & instrument performance results; no raw data 3. FULL VALIDATION (ERG Sections A through E) -- Sample, QC, calibration & instrument pe rformance results; includes raw data transc ription checks & result recalculation checks.

### Laboratory Name:______________ CCH Episode #.: ___________ Method 160.1 – Page 2 of 3 Criterion Met 

## EPA METHOD for Total Dissolved Solids Reviewer Comment Y N 

## SECTION B. Sample Receipt, Traffic Report

1. Sample Receipt Record: Signatures Complete?

2. Receipt Date: Entered by Analysis Laboratory?

3. Receipt Temperature: Storage temperature <4°C but not frozen. Correct receipt temperature indicated?
4. Condition (Breakage?/Leakage?) 

## SECTION C. Sample Handling Information

1. Sample container: Was the correct sample container used? [Method specifies glass or plastic]
2. Maximum holding time: Were the samples held for 7 days or less? 

## SECTION D. Sample Preparations/F iltration and Drying Information

1. Were the samples stored at 6°C but not less then 0°C?

2. Was the drying oven operated at 180°C? (7.2)
3. Was desiccant type noted in report ? If so, was a desiccator with active color indicator used? Was desiccant active?
4. Were suitable filter holders and filtering apparatus in use? (7.1)
5. Were the filters prewashed three times with 20 mL of distilled water? (7.1)

6. Were evaporating dishes dried at 180 or 550°C for 1 hour before use? (7.2) 550°C is required when volatile residue is also to be determined. (TSA information may not be part of data pkg.)
7. Were the evaporating dishes stored in a desiccator, after drying until needed? (TSA information may not be part of data pkg.)
8. Was the sample well mixed prior to filtration?
9. Was the filter rinsed three times with 10 mL portions of distilled water? (TSA information may not be part of data pkg.)
10. Was the sample brought to room temperature before analysis? (TSA information may not be part of data pkg.)
11. Was the desicator drying cycle repeated until a constant weight is achieved or weight loss is less than 4% of the previous weight or less than 0.5 mg between successive weighing?
12. Was a sample volume selected to yield between 1.0 and 200 mg of total non-filterable residue? Sample Volume Effluent: Influent:

### Laboratory Name:______________ CCH Episode #.: ___________ Method 160.1 – Page 3 of 3 Criterion Met 

## EPA METHOD for Total Dissolved Solids Reviewer Comment Y N 

## SECTION E. Instru ment Parameter Review SECTION E-1. Analysis QC Information –

1. Were the analyst’s initials recorded with the data?

2. Was an example calculation shown in the narrative or supporting data sheets? Calculation performed correctly?

mg TDS/L = (weight of dried residue - weight of evaporating dish (g)) x 1000 L of sample used 3. Was the temperature and humidity of the laboratory or weighing room recorded?
4. Was the tare weight of the drying dish reported?
5. Was the sample volume recorded in the proper units?

6. Was the final weight of the drying dish dry sample recorded?
7. Were the oven-drying times reported? Was the evaporated residue dried for at least one hour at 180 ±2°C for at least 1 hour?
8. Was there a record that the analytical balance was zeroed and leveled prior to each weighing?
9. Was desiccant kept inside the balance to maintain humidity control in the balance?
10. Was the oven temperature checked for proper setting and stability and the temperature recorded?
11. Was the oven thermometer immersed in a sand bath or other suitable thermal mass?
12. Did the desiccator have a good seal? (vacuum or grease) 

## SECTION E-2. QC Informat ion – Instrument Calibration

13. Was the balance checked with “S” class weights? (100 mg, 1g, and 100g)
14. Has the analytical balance been serviced and calibrated within the last year? Date: _______________ 

## SECTION E-3. QC Information – Metho d Blanks, Duplicates, Reference Samples

15. Was a blank water (method blank) value reported? (One per batch or Sample Delivery Group, 1 per 20 samples minimum) Is the blank water value >0.5 mg.
16. Was a duplicate sample reported? (One per batch or Sample Delivery Group (1 per 20 Samples minimum) RPD <20% for samples > 5X required DL, ± required DL for samples <5X DL
17. Was a reference sample result reported? (One mineral reference sample per batch or delivery group, 1 per 20 samples minimum) (criteria ± 15% from expected value)

### Laboratory Name:______________ CCH Episode #.: ___________ Method 160.2 – Page 1 of 4 

## OW Effluent Guidelines Data Review Checklist Total Suspended Solid s (TSS) Method 160.2

SECTION A-1. Sample Identifiers
CCH Effluent Guidelines Development

Sampling Episode: Laboratory Name:

Sample Number or Range: Data Reviewer signature: Date:

Instructions: Complete this checklist el ectronically or using a ballpoint pen. Record reviewer comments in the Reviewer Comment section. Record detailed information in the “Comments and Overal l Assessment” section for each criterion not (“N”) met.



## SECTION A-2. Overall Method Total Sus pended Solid Data Package Checklist General Comment Checklist

Deliverable Requirement Required for Category Present Comments Copies of Shipping Documents (Fed-Ex Airbills) 1, 2, 3 Case Narrative 1, 2, 3 Table of Contents 1 Cross reference of Field Sample No., Lab Sample No., and Analytical Batch 1, 2, 3

Traffic Report Form (inc luding Sample Receipt Checklist) 1, 2, 3

Sample Calculation (usually just a page copied from SOW) 1

Results Summary for Each Sample and Blank 1, 2, 3 Initial Calibration Data 1,2 Copies of Sample Preparation Work Sheets 1,2,3 Copies of Analysis Run Logs 1,2
1. COMPLIANCE SCREENING (ERG Sections A through D) -- Sample and QC results only; no instrument calibration or performance checks 2. SUMMARY VALIDATION (ERG Sections A thr ough E) -- Sample, QC, calibration & instrume nt performance results; no raw data 3. FULL VALIDATION (ERG Sections A through E) -- Sample, QC, calibra tion & instrument performance results; includes raw data trans cription checks & result recalculation checks.

### Laboratory Name:______________ CCH Episode #.: ___________ Method 160.2 – Page 2 of 4 

## Criterion Met EPA METHOD for Tota l Suspended Solids Reviewer Comment Y N SECTION B. Sample Receipt, Traffic Report

1. Sample Receipt Record: Signatures Complete?

2. Receipt Date: Entered by Analysis Laboratory?

3. Receipt Temperature: Storage temperature <4°C but not frozen. Correct receipt temperature indicated?
4. Condition: Breakage?/Leakage? 

## SECTION C. Sample Handling Information

1. Sample container: Was the correct sample container used? [Method specifies glass or plastic]
2. Maximum holding time: Were the samples held for 7 days or less? 

## SECTION D. Sample Preparations/F iltration and Drying Information

1. Were the samples stored at 6°C but not less then 0°C?

2. Was the drying oven operated at 103 to 105°C? (2-54)
3. Was a desiccator with active co lor indicator used? (2-54) Was desiccant noted in report?
4. Were suitable filter holders and filtering apparatus in use? (2-55)
5. Were the filters prewashed three times with 20 mL of distilled water? (7.1)

6. Were the filters/Gooch filters dried at 103 to 105°C for 1 hour before use? (7.1)
7. Were filters/Gooch filters stored in a desiccator, after drying until needed? (6.2)
8. Was the filter placed wrinkle side up in the filtering apparatus? (7.1) (TSA information may not be part of data pkg.)
9. Were the filters seated with a small volume of distilled water to create a seal before filtering sample to avoid sample loss? (7.1) (TSA information may not be part of data pkg.)
10. Was the sample brought to room temperature before analysis? (Standard Methods 2-54)
11. Were non representative particles (e.g. leaves and sticks) excluded from the sample? (2-56)
12. Were samples analyzed as soon as possible after collection? (2-53). Method specifies 7 days. Were the sampling date and the analysis date recorded ? (Were the analysis times recorded?)
13. Was the sample well mixed prior to filtration? (7.4)

### Laboratory Name:______________ CCH Episode #.: ___________ Method 160.2 – Page 3 of 4 

## Criterion Met EPA METHOD for Tota l Suspended Solids Reviewer Comment Y N

14. Was a sample volume or filter size selected to yield between 1.0 and 200 mg of total non-filterable residue? (7.2) Sample Volume Effluent: Influent:
15. If the filtration time exceeds 5 to 10 minutes, was the filtration volume adjusted using the recommended method? (7.2)
16. Were filters (if Gooch not used) transferred to an aluminum or stainless steel planchet? (Standards Method requirement)
17. Were the graduated cylinders and filters/Gooch filters washed (after sampling) with three successive 10 ml volumes of distilled water? (7.5)
18. Were the filters/Gooch filters dried at least 1 hour and cooled in the desiccators befo re final weighing? (7.6) 

## SECTION E. Instru ment Parameter Review SECTION E-1. Analysis QC Information –

1. Were the analyst’s initials recorded with the data?

2. Was an example calculation shown in the narrative or supporting data sheets? Calculation performed correctly?

mg TSS/L = (weight of filter with resi due (g) - weight of filter tare(g)) x 1000 L of sample used

3. Was the temperature and humidity of the laboratory or weighing room recorded?
4. Was the tare weight of the crucible or filter reported?
5. Was the sample volume recorded?

6. Was the final weight of the crucible and dry sample recorded on the bench sheet?
7. Was the desicator drying cycle repeated until a constant weight is achieved or weight loss is less than 4% of the previous weight or less than 0.5 mg between successive weighing?
8. Were the oven-drying times reported? (Method requires 103 to 105 °C)
9. Was there a record that the analytical balance was zeroed and leveled prior to each weighing?
10. Was desiccant kept inside the balance to maintain humidity control in the balance?
11. Was the oven temperature checked for proper setting and stability and the temperature recorded?
12. Was the oven thermometer immersed in a sand bath? (TSA information may not be part of data pkg.)
13. Did the desiccator have a good seal? (vacuum or grease) (TSA information may not be part of data pkg.)

### Laboratory Name:______________ CCH Episode #.: ___________ Method 160.2 – Page 4 of 4 

## Criterion Met EPA METHOD for Tota l Suspended Solids Reviewer Comment Y N SECTION E-2. QC Informat ion – Instrument Calibration

14. Was the balance checked with “S” class weights? (100 mg, 1g, and 100g)
15. Has the analytical balance been serviced and calibrated within the last year? Date: _______________ 

## SECTION E-3. QC Information – Method Blanks

16. Was a blank water value reported? Was the blank water value >0.5 mg

## CCH Study Data Review Checklist Chloride and Sulfate EPA Method 300 (Ion Chromatography-Not for Disinfection Byproducts)

SECTION A-1. Sample Identifiers
CCH Effluent Guidelines Development

Sampling Episode: Laboratory Name:

Sample Number or Range: Data Reviewer signature: Date:

Instructions: Complete this checklist el ectronically or using a ballpoint pen. Record reviewer comments in the Reviewer Comment section. Record detailed information in the Comments in the “Overa ll Assessment” section for each criterion not (“N”) met.



## SECTION A-2. OVERAL L ASSESSMENT OF THE QUALITY OF THE DATA General Comment Checklist

Deliverable Requirement Required for Category Present Comments Copies of Shipping Documents (Fed-Ex Airbills) 1, 2, 3
Case Narrative 1, 2, 3
Table of Contents 3 Cross reference of Field Sample No., Lab Sample No., and Analytical Batch 1, 2, 3

Traffic Report Form (inc luding Sample Receipt Checklist) 1, 2, 3

Sample Calculation (usually just a page copied from SOW) 3

Results Summary for Each Sample and Blank 1, 2, 3 Laboratory Fortified Blank Spike Results 1, 2, 3 Laboratory Fortified Matrix (LFM) (Matrix Spike/Duplicate Matrix Sp ike Recovery Summaries 1, 2, 3

Field or Laboratory Duplicate Results 1,2,3 Instrument Performance Check (Resolution) 2, 3
Initial Calibration Data 2, 3 Continuing Calibration Data 2, 3 Windows Defining Mixture/Column Resolution Check 3

Selected Chromatograms for Each Sample, Blank, and Standard 3

Quantitation List 3 Copies of Sample Preparation Work Sheets 3 Copies of Run Logs 3
1. COMPLIANCE SCREENING (ERG Sections A through D) -- Sample and QC results only; no instrument calibration or performance checks 2. SUMMARY VALIDATION (ERG Sections A through F)-- Sample, QC, calibration & instrument performance results; no raw data 3. FULL VALIDATION (ERG Sections A through G-2)-- Sample, QC, calib ration & instrument performance results; includes raw data tran scription checks & result recalculation checks.



### Laboratory Name:________________ CCH Episode #.: _____________ Method 300 – Page 1 of 3

### Criterion met 

## EPA METHOD 300 REQUIREMENT Reviewer Comment Y N 

## SECTION B. SA MPLE RECEIPT
1. Sample Receipt Record: Signatures complete? 2. Receipt Date: Entered by analysis laboratory? 3. Receipt Temperature: Storage in the dark at a temperature ≤ 6  C. (40 CFR 136 Table II) Correct receipt and storage conditions indicated? 4. Sample Condition: Sample bottle breakage? Sample leakage? 

## SECTION C. SAMPLE INFORMATION
1. Sample container: Polyethylene, fluoropolymer, or glass. Correct sample container used? 

## SECTION D. SAMPLE PREP ARATION/EXTRACT HANDLING INFORMATION
1. Sample holding time prior to analysis: 28 days maximum recommended for Method A compounds. (300/8.3) Correct hold time indicated? 2. Sample holding time prior to analysis: Immediate analysis is recommended for Method B compounds. (300/8.3) Were Method B compounds analyzed immediately? 3. Storage conditions: Extract stored between 0 and 4  C. Correct storage conditions indicated? 

## SECTION E-1. QC INFORMATION – Instrument Performance

1. Initial Demonstration of Pe rformance, Quality Control Sample (QCS): Before sample analysis and on a quarterly basis QCS sample must be anal yzed. Was recovery of QCS targets within ± 15% of the stated values? (300/9.2.2) 

## SECTION E-2. QC INFORMATIO N – Instrument Calibration
2. Initial Calibration (ICAL): Was an initial calibration curve with at least three points performed for each analyte? (300/10.2.2) 3. Continuing Calibration Verification (CCV): was the CCV calibration standard analyzed prior to analyzing samples, blanks? (300/10.5) 

## SECTION E-3. QC INFORM ATION – Method Blanks
4. Laboratory Reagent Batch Blanks: Was a blank sample analyzed after with each an alysis batch? (300/9.3.1) Were any of the target compounds or interfering compounds found in the blank at > Method Detection Limit (MDL)? If so, was analysis stopped and contamination eliminated? 5. Laboratory Fortified Blank (LFB): Was an LFB analyzed with every sample batch or one for every 20 samples (if more than 20 samples were analyzed)? (300/10.8) 6. LFB Recovery: Was accuracy as percent recovery within the required control limits? (300/9.3.2, 9.4.1.3, 9.3.2.2) Were ongoing LFB results within control limits (x ± 3S)? (300/9.3.2.3) 7. Laboratory Fortified Sample Matrix (LFM) (MS/MSD): Were 10% of field samples per batch fortified at ≥ 5x the lowest calibration standard? Were LFM recoveries within the 75 to 125 % limit? (300/9.4.1.1) 8. Field or Laboratory Duplicates: Were a minimum of 10% of the field samples or at least one sample per analysis batch



### Laboratory Name:________________ CCH Episode #.: _____________ Method 300 – Page 2 of 3

### Laboratory Name:________________ CCH Episode #.: _____________ Method 300 – Page 3 of 3 Criterion met 

## EPA METHOD 300 REQUIREMENT Reviewer Comment Y N analyzed in dupli cate? (300/9.4.3) Do the duplicate analysis meet acceptance criteria (MRL to 10x MRL then %Diff limited to ±20%, 10% for 10xMRL or higher)? (300/9.4.3.2) 

## SECTION F. INSTRUMENT PERFORMANCE CHECKS
1. Continuing Calibration Verification (CCV): Was a CCV calibration standard analyzed after every 20 samples and whenever the anion eluent was changed? Did the retention time and response for each analyte agree withing 10% of the original calibration?(300/9.4) 2. Continuing Calibration Veri fication Control Limits: Did the continuing calibration results meet the method requirements? (MRL to 10xMRL 75 – 125% recovery, 10xMRL and above 85 – 115% recovery) (300/10.5) 3. Interference Check : Did target analyte peaks show distortion, shoulders or interference that would interfere with accurate calculation of target quantity? 

## SECTION G-2. DETAILED RAW DA TA REVIEW – Sample Results
1. Sample Results: Were the sample results less than five times the Method Blank results? 2. Sample Results: Were the sample results at least greater than ten times the Method Blank results? 3. Minimum Levels: Were the minimum levels reported by the lab comparable to those specified in the method? 4. Duplicate Samples: Were duplicate samples collected? Were the RPDs less than 20%? 5. Calculation Check: Was sufficient data provided to recalculate a sample result? Do es the hand calculated value agree with the reported value?

### Laboratory Name:________________ CCH Episode #.: _____________ Method 2320B – Page 1 of 3 

## CCH Study Data Review Checklist Alkalinity EPA Method 2320B (Titrimetric)

SECTION A-1. Sample Identifiers
CCH Effluent Guidelines Development

Sampling Episode: Laboratory Name:

Sample Number or Range: Data Reviewer signature: Date:

Instructions: Complete this checklist el ectronically or using a ballpoint pen. Record reviewer comments in the Reviewer Comment section. Record detailed information in the Comments in the “Overa ll Assessment” section for each criterion not (“N”) met.



## SECTION A-2. OVERAL L ASSESSMENT OF THE QUALITY OF THE DATA General Comment Checklist

Deliverable Requirement Required for Category Present Comments Copies of Shipping Documents (Fed-Ex Airbills) 1, 2, 3 Case Narrative 1, 2, 3
Table of Contents 3 Cross reference of Field Sample No., Lab Sample No., and Analytical Batch 1, 2, 3

Traffic Report Form (inc luding Sample Receipt Checklist) 1, 2, 3

Sample Calculation (usually just a page copied from SOW) 3

Results Summary for Each Sample and Blank 1, 2, 3 Laboratory Fortified Blank Spike Results 1, 2, 3 Laboratory Fortified Matrix (LFM) (Matrix Spike/Duplicate Matrix Sp ike Recovery Summaries 1, 2, 3

Field or Laboratory Duplicate Results 1,2,3 Instrument Performance Check (Resolution) 2, 3 Initial Calibration Data 2, 3 Continuing Calibration Data 2, 3 Windows Defining Mixture/Column Resolution Check 3

Selected Chromatograms for Each Sample, Blank, and Standard 3

Quantitation List 3 Copies of Sample Preparation Work Sheets 3 Copies of Run Logs 3
1. COMPLIANCE SCREENING (ERG Sections A through D) -- Sample and QC results only; no instrument calibration or performance checks 2. SUMMARY VALIDATION (ERG Sections A through F)-- Sample, QC, calibration & instrument performance results; no raw data 3. FULL VALIDATION (ERG Sections A through G) -- Sample, QC, calibration & instrument pe rformance results; includes raw data transc ription checks & result recalculation checks.

### Laboratory Name:________________ CCH Episode #.: _____________ Method 2320B – Page 2 of 3 Criterion met 

## EPA METHOD 2320B REQUIREMENT Reviewer Comment Y N 

## SECTION B. SA MPLE RECEIPT
1. Sample Receipt Record: Signatures complete? 2. Receipt Date: Entered by analysis laboratory? 3. Receipt Temperature: Storage at a temperature between 0 and 6  C. (40 CFR 136 Table II) Correct receipt and storage conditions indicated? 4. Sample Condition: Sample bottle breakage? Sample leakage? 

## SECTION C. SAMPLE INFORMATION

1. Sample container: Polyethylene, fluoropolymer, or glass. Correct sample container used? 

## SECTION D. SAMPLE H ANDLING INFORMATION
1. Sample holding time prior to analysis: Analysis within 14 days maximum. How soon after collection were samples analyzed? (40 CFR 136 Table II) 2. Temperature: Was the temperature documented during tritation? Was the temperature at 25 ± 2 oC (room temperature)? 3. Sample alteration: Was the sample filtered, diluted, concentrated, or altered in any way during the titration? 

## SECTION E-1. INSTRUMENT PERFORMANCE CHECKS

1. Reagents: If reagents were prepared by the laboratory, was a titration curve constructed for the standardization of the reagents? 2. Titration Equipment: Was a pH meter, color indicators, or an electrically operated titrator used for titration? 3. Initial Calibration: Was an initial calibration curve with at least three points performed for the pH meter? 4. Buffer Solutions: Were the buffer solutions used for the pH meter calibration certified solutions? 5. Calibration Verification: Was the calibration checked with a buffer solution routinel y while analyzing samples? 6. Sluggish response: If the pH meter exhibited a sluggish response, was the electrode allowed to reach equilibrium, or cleaned between samples (ex. oily samples can leave residue)? 

## SECTION E-2. QC INFORM ATION – Method Blanks

7. Indicator Blank: If using color indicators, was an indicator blank prepared for each batch of samples? 8. Blank Interference Check: Was any turbidity or interfering color in the indicator blank documented?

### Laboratory Name:________________ CCH Episode #.: _____________ Method 2320B – Page 3 of 3 

## SECTION G. DETAILED RAW DATA REVIEW
1. Low-alkalinity: Alkalinity less then 20 mg CaCO 3 /L must be determined by the low-alkalinity method. Was any alkalinity determined to be < 20 mg CaCO 3 /L. If so, was it determined by the low-alkalinity method? 2. Alkalinity Calculations: Were the alkalinity and total alkalinity calculated accordin g to Method SM 2320B Sections 5a and 5b? 3. Classifications: Was the phenolphthalein alkalinity not zero but less than total alkalinity? Then the alkalinity can be classified as carbonate alkalinity. 4. Classifications: Was the phenolphthalein alkalinity more than half total alkalinity? Then the alkalinity can be classified as hydroxide alkalinity. 5. Classifications: Was the phenolphthalein alkalinity less than half total alkalinity? Then the alkalinity can be classified as bicarbonate alkalinity. 6. Nomographic Calculations: Were the alkalinity relationships calculated nomographically (optional)? If so, were the relationships calcula ted according to Method SM 2320B Section 5c? 7. Phenolphthalein Alkalinity Calculation: Was the phenolphthalein alkalinity calculated nomographically (optional)? If so, was it calculated according to Method SM 2320B Section 5c? 8. Duplicate Samples: Were duplicate samples collected? Were the RPDs less than 20%? 9. Calculation Check: Was sufficient data provided to recalculate a sample result? Do es the hand calculated value agree with the reported value?

### Laboratory Name:________________ CCH Episode #.:__________ SM 5210B Page 1 of 3 

## CCH Study Data Review Checklist STANDARD METHOD 5210B BOD

SECTION A-1. Sample Identifiers
CCH Effluent Guidelines Development

Sampling Episode: Laboratory Name:

Sample Number or Range: Data Reviewer signature: Date:

Instructions: Complete this checklist el ectronically or using a ballpoint pen. Record reviewer comments in the Reviewer Comment section. Record detailed information in the Comments in the “Overa ll Assessment” section for each criterion not (“N”) met.



## SECTION A-2. OVERAL L ASSESSMENT OF THE QUALITY OF THE DATA General Comment Checklist

Deliverable Requirement Required for Category Present Comments Copies of Shipping Documents (Fed-Ex Airbills) 1, 2, 3 Case Narrative 1, 2, 3
Table of Contents 3 Cross reference of Field Sample No., Lab Sample No., and Analytical Batch 1, 2, 3

Traffic Report Form (inc luding Sample Receipt Checklist) 1, 2, 3

Sample Calculation (usually just a page copied from SOW) 3

Results Summary for Each Sample and Blank 1, 2, 3 Field or Laboratory Duplicate Results 1,2,3 Initial Calibration Data 2, 3 Calibration Check Data 2, 3 Copies of Sample Preparation Work Sheets 3 Copies of Run Logs 3
1. COMPLIANCE SCREENING (ERG Sections A through D) -- Sample and QC results only; no instrument calibration or performance checks 2. SUMMARY VALIDATION (ERG Sections A through F) -- Sample, QC , calibration & instrument performance results; no raw data 3. FULL VALIDATION (ERG Sections A through F) -- Sample, QC, calibration & instrument pe rformance results; includes raw data trans cription checks & result recalculation checks.



## Criterion met STANDARD METHOD 5210 B Reviewer Comment Y N SECTION B. SA MPLE RECEIPT
1. Sample Receipt Record: Signatures complete? 2. Receipt Date: Entered by analysis laboratory? 3. Receipt Temperature: Storage in the dark at a temperature ≤ 6  C. Correct receipt and storage conditions indicated? (40 CFR

### Laboratory Name:________________ CCH Episode #.:__________ SM 5210B Page 2 of 3 

## Criterion met STANDARD METHOD 5210 B Reviewer Comment Y N 136 Table II) 4. Sample Condition: Sample bottle breakage? Sample leakage? 

## SECTION C. SAMPLE INFORMATION
1. Sample container: Polyethylene, fluoropolymer, or glass. Correct sample container used? 2. Sample Bottle Volume: Recommended but not required, 100 mL (liquids). Sample bottle volume indicated?



## SECTION D. SAMPLE PREP ARATION/EXTRACT HANDLING INFORMATION
1. Sample holding time prior to analysis: Samples analyzed within 48 hours of collection? (40 CFR 136 Table II) 2. Storage conditions: Extract stored between 0 and 6  C. Correct storage conditions indicated? 3. Sample Stabilization : Are samples checked for chlorine? How? Are samples treated for chlorine with sodium sulfate? 4. Sample pH : Is sample pH adjusted to prior to analysis? What pH criteria is used? 5. Hydrogen peroxide: Was hydrogen peroxide present in the samples? How was hydrogen peroxide treated? 6. Analysis Temperature: Are samples equilibrated to 20 ±3 °C? 7. Seeding: Are samples seeded if required? 8. Seed Source: If seeded, was seed material source documented? 9. Seed Correction: Was the seed correction calculated based on average seed control sample results? 

## SECTION E-1. QC INFORMAT ION – Method Performance
1. Nitrification Inhibitor: Was nitrification inhibitor added to all samples and controls? (CBOD 5 ) 2. Nitrification Inhibitor Type: What nitrification inhibitor was used? 3. Seeding: Were all samples, seed controls, and glucoseglutamic acid (GGA) for CBOD seeded? 4. Initial Dissolved Oxygen: Was initial DO measured (within 30 min) of sample dilution preparation? (Should be between 7 and 9 mg/mL) 5. Dilution : Were samples out of calibration range diluted for analysis? Note: For dilutions >67% of sample, were extra nutrients added? 6. Incubation: Are samples incubated for 5 days ± 6 hours? 7. Are any final DO measurements below 1.0? 8. Have all samples shown a DO depletion of at least 2.0 mg/L? 9. Seed Correction: Were seed corrections properly subtracted from seeded samples? 10. Was the final BOD of the samples properly calculated? 

## SECTION E-2. QC INFORMATIO N – Instrument Calibration
11. Initial Calibration (ICAL): Was an initial calibration reported on day one (1) of analysis? 12. Continuing Calibration Check: Was the dissolved oxygen

### Laboratory Name:________________ CCH Episode #.:__________ SM 5210B Page 3 of 3 

## Criterion met STANDARD METHOD 5210 B Reviewer Comment Y N (DO) meter calibrated on day five of the procedure? 13. Calibration Drift Check: Was the DO meter calibration checked for drift during and at the end of the sample set? 14. Drift Test Requirements: Did the drift checks agree within ± 0.2 mg/L? 

## SECTION E-3. QC INFORM ATION –Reagent Blanks
15. Water Quality : Was water type or quality documented? Is water aged before use, if so how long? 16. Was water allowed to come to room temperature before usage? 17. Were nutrient and phosphate buffer prepared or purchased? 18. Was reagent quality verified and documented? 19. Phosphate Buffer pH: Was this buffer pH= 7.2? 20. Water Blank: Was a water blank analyzed in each analysis batch? Was it ≤ 0.20 mg/L? 21. Glucose-glutamic Acid: Was a glucose-glutamic acid standard analyzed with each analysis batch? 

## SECTION F-1. Method QC
1. Analysis Time: Was the analysis incubation start and end documented? Did it meet method required times? 2. Incubator temperature? Was incubator temperature documented? Was it within in specifications? 3. Duplicates: Were duplicates run at every 20 samples? (5%) Are duplicates within 30%?

### Laboratory Name:________________ CCH Episode #.:__________ HACH Method 8000 Page 1 of 3 

## CCH Study Data Review Checklist HACH METHOD 8000 COD

SECTION A-1. Sample Identifiers
CCH Effluent Guidelines Development

Sampling Episode: Laboratory Name:

Sample Number or Range: Data Reviewer signature: Date:

Instructions: Complete this checklist el ectronically or using a ballpoint pen. Record reviewer comments in the Reviewer Comment section. Record detailed information in the Comments in the “Overa ll Assessment” section for each criterion not (“N”) met.



## SECTION A-2. OVERAL L ASSESSMENT OF THE QUALITY OF THE DATA General Comment Checklist

Deliverable Requirement Required for Category Present Comments Copies of Shipping Documents (Fed-Ex Airbills) 1, 2, 3 Case Narrative 1, 2, 3
Table of Contents 3 Cross reference of Field Sample No., Lab Sample No., and Analytical Batch 1, 2, 3

Traffic Report Form (inc luding Sample Receipt Checklist) 1, 2, 3

Sample Calculation (usually just a page copied from SOW) 3

Results Summary for Each Sample and Blank 1, 2, 3 Field or Laboratory Duplicate Results 1,2,3 Initial Calibration Data 2, 3 Calibration Check Data 2, 3 Copies of Sample Preparation Work Sheets 3 Copies of Run Logs 3
1. COMPLIANCE SCREENING (ERG Sections A through D)-- Sample and QC results only; no instrument calibration or performance checks 2. SUMMARY VALIDATION (ERG Sections A through F)-- Sample, QC, calibration & instrument performance results; no raw data 3. FULL VALIDATION (ERG Sections A through F )-- Sample, QC, calibration & instrument pe rformance results; includes raw data transc ription checks & result recalculation checks.

### Laboratory Name:________________ CCH Episode #.:__________ HACH Method 8000 Page 2 of 3 Criterion Met 

## HACH METHOD 8000 Reviewer Comment Y N 

## SECTION B. SA MPLE RECEIPT
1. Sample Receipt Record: Signatures complete? 2. Receipt Date: Entered by analysis laboratory? 3. Receipt Temperature: Storage in the dark at a temperature ≤ 6  C. (40 CFR 136 Table II) Correct receipt and storage conditions indicated? 4. Sample Condition: Sample bottle breakage? Sample leakage? 

## SECTION C. SAMPLE INFORMATION
1. Sample container: Polyethylene, fluoropolymer, or glass. Correct sample container used? 2. Septum/liner/cap: Fluoropolymer lined. Correct septum/liner/cap indicated? 3. Sample Bottle Volume: Recommended but not required, 100 mL (liquids) Sample bottle volume indicated? 

## SECTION D. SAMPLE PREP ARATION/EXTRACT HANDLING INFORMATION
1. Sample Stabilization : Were samples stabilized with sulfuric acid to pH of less than 2? Were results corrected for the volume of sulfuric acid added? 2. Were sample vials used that contained Mercury Sulfate for chloride stabilization? 3. Was the level of chloride interference exceeded for the HACH sample vials used? (Table 1 in HACH DR4000 Procedure) 4. Sample holding time prior to analysis: Stabilized samples held up to 28 days maximum. Correct hold time indicated? 5. Storage conditions: Extract stored between 0 and 4  C. Correct storage conditions indicated? Maximum analysis holding time: 28 days from collection to analysis. Correct analysis time indicated? 6. Homogenization: Were the samples uniform or did samples contain solids requiring homogenizing? Was this procedure noted in the data? Were samples homogenized for 30 seconds in a blender? 7. Digestion: Was digestion performed on samples before analysis? 8. Was the COD reactor preheated to 150 °C? 

## SECTION E-1. QC INFORMAT ION – Method Performance

1. Initial Demonstration of Pe rformance, Quality Control Sample (QCS): Were multiple measurements of a known standard (e.g., 100 mg/L analyzed to determine method precision? Were the results within ±0.5% of the standard? 2. Detection Limit: Was the method detection limit determined and ≤ 1% of the calibration range? 

## SECTION E-2. QC INFORMATIO N – Instrument Calibration
3. Initial Calibration (ICAL): Was an initial zero reported for certified blank vial? 4. Low range: (0-150 mg/L) Was a minimum of 5 points used to prepare the initial calibration curve?

### Laboratory Name:________________ CCH Episode #.:__________ HACH Method 8000 Page 3 of 3 5. Continuing Calibration Verification (CCV) and Accuracy Check: Was the calibration accuracy checked with a zero (0) and high range potassium acid phthalate (KPH) standard? 

## SECTION E-3. QC IN FORMATION –Blanks
6. Colorimetric Blanks: Was a reagent (deionized water) used to zero the instrument in absorbance mode? 

## SECTION F. INSTRUME NT INTERFERENCE
1. Chloride Interference: Was chloride concentration above stabilizer limits for the method?

## CCH Study Data Review Checklist Trace Element Analysis of Wat er and Wastes EPA Method 200.7

(Inductively Coupled Plasma At omic Emission Spectrometry)

SECTION A-1. Sample Identifiers
CCH Effluent Guidelines Development

Sampling Episode: Laboratory Name:

Sample Number or Range: Data Reviewer signature: Date:

Instructions: Complete this checklist el ectronically or using a ballpoint pen. Record reviewer comments in the Reviewer Comment section. Record detailed information in the Comments in the “Overa ll Assessment” section for each criterion not (“N”) met.



## SECTION A-2. OVERAL L ASSESSMENT OF THE QUALITY OF THE DATA
General Comment Checklist

Deliverable Requirement Required for Category Present Comments Copies of Shipping Documents (Fed-Ex Airbills) 1, 2, 3
Case Narrative 1, 2, 3
Table of Contents 3 Cross reference of Field Sample No., Lab Sample No., and Analytical Batch 1, 2, 3

Traffic Report Form (inc luding Sample Receipt Checklist) 1, 2, 3

Sample Calculation (usually just a page copied from SOW) 3

Results Summary for Each Sample and Blank 1, 2, 3 Instrument Check Sample 1, 2, 3
Calibration Blank 1, 2, 3 Quality Control Sample 1, 2, 3
Initial Calibration Data 2, 3 Quantitation List 3 Copies of Sample Preparation Work Sheets 3 Copies of Run Logs 3
1. COMPLIANCE SCREENING (ERG Sections A through D) -- Sample and QC results only; no instrument calibration or performance checks 2. SUMMARY VALIDATION (ERG Sections A through F) -- Sample, QC , calibration & instrument performance results; no raw data 3. FULL VALIDATION (ERG Sections A through G) -- Sample, QC, calib ration & instrument performance results; includes raw data trans cription checks & result recalculation checks.



### Laboratory Name:________________ CCH Episode #.:_____________ Method 200.7 – Page 1 of 4

### Criterion met 

## EPA METHOD 200.7 REQUIREMENT Reviewer Comment Y N 

## SECTION B. SA MPLE RECEIPT
1. Sample Receipt Record: Signatures complete? 2. Receipt Date: Entered by analysis laboratory? 3. Sample Condition: Sample bottle breakage? Sample leakage?(200.7/8.1) 4. Sample Hold Time: Were samples analyzed within 180 days of collection? (CLP contract within 35 days for sample receipt?) 

## SECTION C. SAMPLE INFORMATION
1. Sample container: Polyethylene, fluoropolymer, or glass Correct sample container used? (40 CFR 136 Table II) 2. Septum/liner/cap: Fluoropolymer lined. Correct septum/liner/cap indicated? 3. Sample bottle volume: Typically 1L. Correct sample bottle volume indicated? 

## SECTION D. SAMPLE PREP ARATION/EXTRACT HANDLING INFORMATION
1. Data Type: Decisions about preservation and pretreatment of samples are made before collection. Was information provided designating the type of data as dissolved, suspended or total metals? (200.7/8.2) 2. Dissolved Elements: For dissolved elements was the sample filtered through a 0.45 um membrane filter soon after collection? Was the filtrate acidified with 1 to 1 nitric acid to a pH of 2 or less? 3. Suspended Elements: For determination of suspended elements was a known volume of unpreserved sample filtered through a 0.45 um membrane soon after sampling? Was the filter plus suspended material stored in a suitable container without preservation for shipment? (200.7/8.2.2) 4. Total Elements: For the determination of total or total recoverable elements was the sample acidified with 1 to 1 nitric acid to pH of 2 or less after sampling? 5. Dissolved Elements Analysis : Were dissolved elements analyzed directly as receive d or acidified to dissolve precipitate? (200.7/9.1) 6. Suspended Elements Analysis : Was the sample digested with nitric and hydrochloric acid and filtered prior to analysis? (2 00.7/9.2) 7. Total Elements Analysis: Was a well mixed volume of the sample digested with nitric acid and hydrochloric acid and filtered prior to analysis? (200.7/9.3) 

## SECTION E-1. QC INFORMATION – Instrument Performance
1. Instrument Check Sample: Were the results of the target analyte ICS analyzed at a freq uency of 10% and within 5% of expected value (or within established control)? (200.7/12.1.1/7.6.1) 2. Duplicate Sample (DUP): Was a duplicate sample analyzed once per analysis batch or SDG. Was the RPD of the duplicate <± 20 for samples > 5x



### Laboratory Name:________________ CCH Episode #.:_____________ Method 200.7 – Page 2 of 4

### Criterion met 

## EPA METHOD 200.7 REQUIREMENT Reviewer Comment Y N

CRDL; ±CRDL for samples <5X CRDL 3. Interference Check Sample: Was a check sample analyzed at the beginning, end, and at periodic intervals during a sample batch run? (7.6.2) Were results within control limits of 1.5 times the STD of the mean value? (200.7/12.1.1) 4. Serial Dilution Sample: Was one serial dilution sample run per batch or SDG? Was serial dilution sample ± 10% of the original results for analytes with concentration 50 X the IDL? 

## SECTION E-2. QC INFORMATION – Instru ment Calibration and Detection Limit
5. Detection Limit (Contract Required Detection Limit): Did reported detection limits meet contract required limits shown in Table 1 (below)? 6. Initial Calibration (ICAL): Was a minimum of one blank and one calibration standard analyzed (ICAL)? 7. Initial Calibration Verification (ICV): Was an ICV analyzed and did it meet requi red 90 – 100% of expected concentration? Was the ICV from a secondary source? 8. Continuing Calibration Verification (CCV) : Was CCV analyzed daily before samples, after every 10 samples and at end of the analysis run? Did CCV meet 90-110% of expected concentration requirement? 9. Contract Required Detection Limit Verification Standard (CRI): Was the CRI analyzed after initial Calibration Verification (ICV) but before sample analysis, and did the results meet 65 – 135% of expected concentration? 

## SECTION E-3. QC IN FORMATION –Blanks
10. Calibration Blank: Was a Calibration Blank prepared and used to flush the system between standards and samples? (200.7/7.5.1)

11. Reagent/Method Blank (MB): Was a blank containing all reagents prepared and used to evaluate contaminants in reagents?(200.7/7.5.2) 12. Calibration Blank: Was a calibration blan k (7.5.1) analyzed at a frequency of 10% and within control limits (2STD of mean)? (200.7/12.1.1) 

## SECTION F. RECOVERY OF INTERNAL STANDARDS
1. Instrument Check St andard (LCS): Was a standard containing compatible elements prepared at the midpoint of the calibration curve and used to assess continuing calibration and instrument performance once per batch or SDG? (200.7/12.1.1,7.6,3.7) Were LCS results within 80 – 120% of expected values? 2. Interference Check Sample (ICS): Was a representative sample spiked with the elements of interest at 100 ug/L or 5 times the MDL and used to test matrix interference and correction factors? (200.7/12.1.2, 7.6.2,3.8) Was the ICS run at the start and finish of daily sample runs or twice per 8 hours? Did ICS results meet 80 – 120% of expected concentration? 3. Matrix Spike Sample (MS): Was one MS analyzed per



### Laboratory Name:________________ CCH Episode #.:_____________ Method 200.7 – Page 3 of 4

### Laboratory Name:________________ CCH Episode #.:_____________ Method 200.7 – Page 4 of 4 Criterion met 

## EPA METHOD 200.7 REQUIREMENT Reviewer Comment Y N

batch or SDG? Did the results indicate 75 – 125% recovery of expected value? 4. Quality Control Sample: Was a secondary source calibration sample at 1 mg/L prepared and analyzed to confirm calibration accuracy? (200.7/7.6.3/3.9) 

## SECTION G. DETAILED SAMPLE RAW DATA REVIEW
1. Sample Results Reporting: Were results reported in units of micrograms per liter (ug/L) for water samples? 2. Sample Results: Were the sample results less than five times the Method Blank results? 3. Sample Results: Were the sample results at least greater than ten times the Method Blank results? 4. Minimum Levels: Were the minimum levels reported by the lab comparable to those specified in the method? 5. Duplicate Samples: Were duplicate samples collected? Were the RPDs less than 20%?

TABLE 1. Target Analyte List, CAS Numbers, and Contract Required Detection Limits (CRDL) for Metals by ICPAES ANALYTE CAS No. CRDL for Water ( μ g/L) CRDL for Soil (mg/Kg) Aluminum (Al) 7429-90-5 200 40 Antimony (Sb) 7440-36-0 60 12 Arsenic (As) 7440-38-2 10 2 Barium (Ba) 7440-39-3 200 40 Beryllium (Be) 7440-41-7 5 1 Cadmium (Cd) 7440-43-9 5 1 Calcium (Ca) 7440-70-2 5000 1000 Chromium (Cr) 7440-47-3 10 2 Cobalt (Co) 7440-48-4 50 10 Copper (Cu) 7440-50-8 25 5 Iron (Fe) 7439-89-6 100 20 Lead (Pb) 7439-92-1 3 1 Magnesium (Mg) 7439-95-4 5000 1000 Manganese (Mn) 7439-96-5 15 3 Molybdenum (Mo) 7439-97-6 20 4 Nickel (Ni) 7440-02-0 40 8 Potassium (K) 7723-14-0 5000 1000 Selenium (Se) 7782-49-2 5 1 Silver (Ag) 7440-22-4 10 2 Sodium (Na) 7440-23-5 5000 1000 Thallium (Tl) 7440-28-0 10 2 Vanadium (V) 7440-62-2 20 4 Zinc (Zn) 7440-66-6 10 2

### Laboratory Name:________________ CCH Episode #.:_____________ Method 245.7 – Page 1 of 5 

## CCH Study Data Review Checklist Total Mercury Analysis EPA Method 245.7 (Cold Vapor Atomic Fluorescence Spectroscopy)

SECTION A-1. Sample Identifiers
CCH Effluent Guidelines Development

Sampling Episode: Laboratory Name:

Sample Number or Range: Data Reviewer signature: Date:

Instructions: Complete this checklist el ectronically or using a ballpoint pen. Record reviewer comments in the Reviewer Comment section. Record detailed information in the Comments in the “Overa ll Assessment” section for each criterion not (“N”) met.



## SECTION A-2. OVERAL L ASSESSMENT OF THE QUALITY OF THE DATA General Comment Checklist

Deliverable Requirement Required for Category Present Comments Copies of Shipping Documents (Fed-Ex Airbills) 1, 2, 3 Case Narrative 1, 2, 3
Table of Contents 3 Cross reference of Field Sample No., Lab Sample No., and Analytical Batch 1, 2, 3

Traffic Report Form (inc luding Sample Receipt Checklist) 1, 2, 3

Sample Calculation (usually just a page copied from SOW) 3

Results Summary for Each Sample and Blank 1, 2, 3 Instrument Check Sample 1, 2, 3 Calibration Blank 1, 2, 3 Quality Control Sample 1, 2, 3 Initial Calibration Data 2, 3 Quantitation List 3 Copies of Sample Preparation Work Sheets 3 Copies of Run Logs 3
1. COMPLIANCE SCREENING (ERG Sections A through D) -- Sample and QC results only; no instrument calibration or performance checks 2. SUMMARY VALIDATION (ERG Sections A through F) -- Sample, QC , calibration & instrument performance results; no raw data 3. FULL VALIDATION (ERG Sections A through G) -- Sample, QC, calib ration & instrument performance results; includes raw data trans cription checks & result recalculation checks.

### Laboratory Name:________________ CCH Episode #.:_____________ Method 245.7 – Page 2 of 5 Criterion Met 

## EPA METHOD 245.7 REQUIREMENT Reviewer Comment Y N 

## SECTION B. SA MPLE RECEIPT
1. Sample Receipt Record: Signatures complete? 2. Receipt Date: Entered by analysis laboratory? 3. Sample Condition: Sample bottle breakage? Sample leakage? Bottles must be tightly sealed to avoid diffusion of atmospheric Hg through the cap threads. (245.7/8.2) 4. Sample Hold Time: Were samples analyzed within 90 days of collection? (40 CFR 136 Table II) (CLP contract within 35 days for sample receipt?) 

## SECTION C. SAMPLE INFORMATION
1. Sample container: Fluoropolymer bottles with fluoropolymer-lined caps. (Glass may be used if Hg is the only target analyte. Correct sample container used? 2. Septum/liner/cap: Fluoropolymer lined. Correct septum/liner/cap indicated? 3. Sample bottle volume: Typically 1L. Correct sample bottle volume indicated? 

## SECTION D. SAMPLE PREP ARATION/EXTRACT HANDLING INFORMATION
1. Data Type: Decisions about preservation and pretreatment of samples are made before collection. Was information provided designating the type of data as dissolved or total mercury? (8.4) 2. Dissolved Elements: For dissolved mercury, samples must be accompanied by a blank that was filtered under the same conditions. Was the sample filtered through a 0.45 um capsule filter soon after collection? 3. Preservation: Was the filtrate acidified with 5 mL/L pretested 12 N HCl within 48h of collection? (Or 5 mL/L BrCl) (245.7/8.5) (40 CFR 136 Table II) 4. Total Mercury: For the determination of total mercury was the sample acidified with 1-to-1 nitric acid to pH of 2 or less after sampling? 5. Dissolved Elements Analysis: Were dissolved elements analyzed directly as receive d or acidified to dissolve precipitate? Was KBrO3/KBr added to samples at least 24 hours before analysis? (245.7/8.5.2) 

## SECTION E-1. QC INFORMATION – Instrument Performance
1. Detection Limit (CRDL/MDL): Did reported detection limits meet contract required limits shown in Table 1 (below)? 2. Duplicate Sample (DUP): Was a duplicate sample analyzed once per analysis batch or SDG? Was the RPD of the duplicate <± 20 for samples > 5x CRDL; ±CRDL for samples <5 X CRDL or met the criteria in Table 2? 3. Quality Control Sample : Was a secondary source calibration sample at 1 mg/L pr epared, analyzed and reported to confirm calibration accuracy? ( 245.7/9.3) 4. Initial Precision and Recovery (IPR): Was an initial

### Laboratory Name:________________ CCH Episode #.:_____________ Method 245.7 – Page 3 of 5 Criterion Met 

## EPA METHOD 245.7 REQUIREMENT Reviewer Comment Y N

precision and recovery reported?

5. OPR: Was an ongoing precision and recovery performed and compared to the IPR? Does th e recovery of Hg in the OPR meet the requirements in Table 2 (below)? 

## SECTION E-2. QC INFORMATION – Instru ment Calibration and Detection Limit
6. Initial Calibration: Was a minimum of one blank and eight calibration standards analyzed with each analytical batch (ICAL)? Was the correlation coefficient, r ≥ 0.995? 7. Initial Calibration Verification (ICV): Was an ICV at the midpoint of the ICAL analyzed and did it meet required 80 – 120% of expected concentration? Was the ICV from a secondary source standard? Was the ICV analyzed daily, immediately following the ICAL and prior to sample analysis? 8. Continuing Calibration Verification (CCV): Was the CCV analyzed daily before samples, after every 10 samples and at end of the analysis run? Did CCV meet 80-120% of expected concentration requirement? 9. Contract Required Detection Limit Verification Standard (CRI): Was a CRI analyzed after initial calibration verification (ICV) but before sample analysis, and did the results meet 65 – 135% of expected concentration? 

## SECTION E-3. QC IN FORMATION –Blanks
10. Calibration Blank: Was a Calibration Blank prepared and analyzed after it was used to flush the system between standards and samples? (245.7/9.1.1.2) Was the ICB & CCB analyzed after the ICV & every CCV? Were the results less than the required detection limits? 11. Reagent/Method Blank (MB): Was a blank containing all reagents prepared and used to evaluate contaminants in reagents? Was the MB run once per batch or SDG and every 20 samples? (245.7/9.2.1) Was the MB result < Contract Required DL? 12. Field Blank/Bottle Blank: Was a field blank and/or bottle blank analyzed? Was the field blank data used to correct sample results?(245.7/12.4.2) 

## SECTION F. RECOVERY OF INTERNAL STANDARDS
1. Instrument Check St andard (LCS): Was a standard containing compatible elements prepared at the midpoint of the calibration curve and used to assess continuing calibration and instrument performance once per batch or SDG? (245.7/12.1.1,7.6,3.7) Were LCS results within 75 – 125% of expected values? 2. Matrix Spike Sample (MS/MSD): Was one MS/MSD pair analyzed for every 10 samples? Did the results indicate 75 – 125% (or Table 2) recovery of expected value? 

## SECTION G. DETAILED SAMPLE RAW DATA REVIEW
1. Sample Results Reporting: Were results reported in units of micrograms per liter (ug/L) for water samples? 2. Sample Results: Were the sample results less than five

### Laboratory Name:________________ CCH Episode #.:_____________ Method 245.7 – Page 4 of 5 Criterion Met 

## EPA METHOD 245.7 REQUIREMENT Reviewer Comment Y N

times the Method Blank results? 3. Sample Results: Were the sample results at least greater than ten times the Method Blank results? 4. Minimum Levels: Were the minimum levels reported by the lab comparable to those specified in the method? 5. Duplicate Samples: Were duplicate samples collected? Were the RPDs less than 20%?

### Laboratory Name:________________ CCH Episode #.:_____________ Method 245.7 – Page 5 of 5 TABLE 1. Target Analyte List, CAS Numbers, and Contract Required Detection Limits for Metals by ICP-AES ANALYTE Lowest Water Quality Criterion 1 Method Detection Limit 2 Minimum Level 3

Mercury (Hg) 1.3 ng/L 1.8 ng/L 5.0 ng/L

1 The lowest water quality criterion is for the Great Lakes Syst em (Table 4, 40 CFR 132). The lowest criterion that is applicable nationwide (e.g., outside of the Great Lakes) is 12 ng/L (40 CFR 131.36).

2 Method detection limit (MDL 40 CFR 136, Appendix B)

3 Minimum level (ML) of quantitation (see Glossary)



### Table 2. Quality Control Acceptan ce Criteria for Performance Tests Acceptance Criterion Performance Test Recovery (%) RSD (%) RPD (%)

Initial Precision and Recovery (IPR) 78 - 108 16

— Ongoing Precision and Recovery (OPR) 76 - 113

— — Matrix Spike/Matrix Spike Duplicate (MS/MSD) 63 – 111 — 18

## CCH Study Data Review Checklist Volatile Organic Compo unds EPA Method 1624C (Isotope Dilution GC/MS)

SECTION A-1. Sample Identifiers
CCH Effluent Guidelines Development

Sampling Episode: Laboratory Name:

Sample Number or Range: Data Reviewer signature: Date:

Instructions: Complete this checklist el ectronically or using a ballpoint pen. Record reviewer comments in the Reviewer Comment section. Record detailed information in the Comments in the “Overa ll Assessment” section for each criterion not (“N”) met.



## SECTION A. OVERALL ASSESSMEN T OF THE QUALITY OF THE DATA General Comment Checklist

Deliverable Requirement Required for Category Present Comments Copies of Shipping Documents (Fed-Ex Airbills) 1, 2, 3
Case Narrative 1, 2, 3
Table of Contents 3 Cross reference of Field Sample No., Lab Sample No., and Analytical Batch 1, 2, 3

Traffic Report Form (including Samp le Receipt Checklist) 1, 2, 3 Sample Calculation (usually just a page copied from SOW) 3

Results Summary fo r Each Sample and Blank (includes ion abundance ratios) 1, 2, 3

Blank Spike Results (OPR) 1, 2, 3 Labeled Compound Recovery Summary 1, 2, 3 Matrix Spike/Duplicate Matrix Spike Recovery Summaries 1, 2, 3

Instrument Performance Check (Resolution) 2, 3
Initial Calibration Data 2, 3 Continuing Calibration Data 2, 3 Windows Defining Mixture/Column Resolution Check 3 Selected Ion Chromatograms for Each Sample, Blank, and Standard 3

Quantitation List 3 Copies of Sample Preparation Work Sheets 3 Copies of Run Logs 3
1. COMPLIANCE SCREENING (ERG Sections A through D) -- Sample and QC results only; no instrument calibration or performance checks 2. SUMMARY VALIDATION (ERG Sections A through F)-- Sample, QC, calibration & instrument performance results; no raw data 3. FULL VALIDATION (ERG Sections A through G-2)-- Sample, QC, calib ration & instrument performance results; includes raw data tran scription checks & result recalculation checks.



### Laboratory Name:________________ CCH Episode #.: _____________ Method 1624C – Page 1 of 4

### Criterion met 

## EPA METHOD 1624C REQUIREMENT Reviewer Comment Y N 

## SECTION B. SA MPLE RECEIPT
1. Sample Receipt Record: Signatures complete? 2. Receipt Date: Entered by analysis laboratory? 3. Receipt Temperature: Storage in the dark at a temperature < 6  C. (40 CFR 136 Table II) Correct receipt conditions indicated? 4. Sample Condition: Sample bottle breakage? Sample leakage? Air bubbles noted in sample? (1624C/9.1) 

## SECTION C. SAMPLE INFORMATION
1. Sample container: Glass, hermetic seal. Correct sample container used? 2. Septum/liner/cap: Fluoropolymer lined. Correct septum/liner/cap indicated? 3. Sample bottle volume: 25 to 40 mL. Correct sample bottle volume indicated? 

## SECTION D. SAMPLE PREP ARATION/EXTRACT HANDLING INFORMATION
1. Aqueous sample residual chlorine: If an aqueous sample contains residual chlorine, 10 mg/40 mL of sodium thiosulfate preservative is added to the empty bottle. Was residual chlorine measured (Method 330.4, 330.5)? Was preservative added? 2. BTEX Sample Preservation: Were BTEX compounds found in the sample? If BTEX compounds were reported, was a separate sample collected, acidified, and anal yzed for these compounds? (1624C/9.3) 3. Sample holding time prior to analysis: 14 days recommended maximum. Correct hold time indicated? 4. Storage conditions: extract stored between 0 and 4  C. Correct storage conditions indicated? 5. Maximum analysis holding time: 14 days from collection to analysis. (1624C/9.4) Correct analysis time indicated? 

## SECTION E-1. QC INFORMATION – Instrument Performance
1. Mass Intensity: Did the analytical system meet the massintensity criteria in Table 4 of Method 1624C for 50 ng BFB?(1624C/7.1) 2. Initial Precision and Recovery (IPR): Were two sets of four 5-mL aliquots of the aqueous performance standard analyzed before blanks and samples? 3. Average Recovery of IPR: Did the average recovery and standard deviation of the recovery for the first set of analyses meet the requirements in Table 6 of Method 1624C? (If yes, Instrument Perf ormance Passes 1624C/8.2.3) 4. Additional Recovery for Failed IPR: Did the average recovery and standard deviation of the failed set of analytes meet the requirements in Table 6 of Method 1624C? (If yes, Instruments Perf ormance Passes 1624C/8.2.4) 5. Detection Limits: Did the analytical system meet the minimum levels in Table 3 of Method 1624C for the compounds analyzed? (1624C/7.1) 6. Continuing Calibration Verification (CCV)/Ongoing Precision and Accuracy (OPA): Was the CCV calibration



### Laboratory Name:________________ CCH Episode #.: _____________ Method 1624C – Page 2 of 4

### Criterion met 

## EPA METHOD 1624C REQUIREMENT Reviewer Comment Y N

standard analyzed prior to analyzing samples, blanks? (1624C/11.1) 7. CCV/OPA: Did Concentrations meet the corresponding limit for ongoing accuracy in Table 6 of Method 1624C before samples were analyzed? (1624C/11.5.1) 

## SECTION E-2. QC INFORMATIO N – Instrument Calibration
8. Initial Calibration (ICAL): Was an initial calibration curve with at least five points performed for each analyte? (1624C/7.4) 9. Isotope Dilution Calibration: Was calibration by isotope dilution used for compounds for which a labeled analog is available? (1624C/7.4) 10. Internal Standa rd Calibration: Was calibration by internal standard used for compounds fo r which a labeled analog is not available? (1624C/17.5) 11. ICAL RSD: Was the averaged response factor coefficient of variation less than 20% for analytes calculated by the isotope dilution method? For compounds that did not meet this RSD, was the complete calibration curve used? (1624C/7.4.) 12. ICAL RSD: Was the averaged response factor RSD less than 35% for compounds calculated by the internal standard method? For compounds that did not meet this RSD, was the complete calibration curve used? (1624C/ 7.5) 13. ICAL levels: Were the unlabeled compounds calibrated at the correct level as listed in Table 4 of Method of 1624C? (1624C/Table 4) 14. Labeled Compound Spiking Levels: Were the labeled compounds spiked at 20 μ g/L level (except acrolein, acrylonitrile, acetone, diethyl ether, p-dioxane, and MEK at 100 μ g/L). (1624C/6.6) 

## SECTION E-3. QC INFORM ATION – Method Blanks
15. Method blanks: Was the level at which the analytical system will carry greater than 5 μ g/L of pollutant into a succeeding blank determined and reported? (1624C/8.5.1)

16. Ongoing Laboratory Batch Blanks: Was a blank sample analyzed after every 8-hour shift? Were any of the target compounds or interfering compounds found in the blank at > 10 μ g/L? If so, was analysis stopped and contamination eliminated? 17. Field Blank: Reagent water or other reference Was the Field Blank reported? Was the Field Blank above the detection limit? 

## SECTION F. RECOVERY OF LABELED ISOTOP E DILUTION INTERNAL STANDARDS
1. Recovery of labeled compounds: The recovery criteria of each labeled compound are listed in Table 6 of Method 1624C. Did the average recovery % meet the criteria? (1624C/8.3.3) 2. Recovery of labeled compounds: If recovery criteria of the labeled compounds are not met, was sample dilution analyzed? (1624C/18.3.3) 3. Dilution of Samples: Have all samples where EICP area exceeds the calibration range been diluted until they are in the calibration range?



### Laboratory Name:________________ CCH Episode #.: _____________ Method 1624C – Page 3 of 4

### Laboratory Name:________________ CCH Episode #.: _____________ Method 1624C – Page 4 of 4 Criterion met 

## EPA METHOD 1624C REQUIREMENT Reviewer Comment Y N 4. Diluted Sample Reporting: Have diluted samples been reported at the least dilute level which is within the calibration range? (1624C/13.6.1) 

## SECTION G-1. DETAILED RAW DATA REVIEW – Compound Identification Quality Control The following criteria must be met for a GC peak to be identified as a volatile organic target: 1. The Signals: Did the GC peak contain at least five complete spectra across the upper half of the GC peak? (1624C/7/2/1) 2. Characteristic m/z: Did the characteristic m/z stored in the spectral library maximize within the same two consecutive mass scans? 3. Mass intensity: Did the corrected relative intensities of mass spectral peaks and the GC pe ak maximum agree within a factor of two for all masses stored in the spectral library? (1624C12.2.2) 4. Relative Retention Time Between Labeled analog and pollutant: Did the relative retention time between analog and pollutant meet the requirements in Table 3 of Method 1624C? 5. OPA/Aqueous Performance Standard: Was an aqueous performance standard (Section 6.7.2) analyzed prior to calibration? Were these results compared to the areas obtained by injection 1 μ L of the methanolic standard? Were water soluble compounds recovered at greater than 20% Were all other compounds recovered from 60 to 110% of expected? 6. Toluene Recovery: Did 100 η g toluene produce area at m/z 91 or 99 approximately one-tenth that required to exceed the linear range of the system? 7. Absolute Retention Times: The absolute retention times of the labeled compounds in the CCV must be within the limits given in Table 3 of Method 1624C. (1624C/11.3,12.1.3) 8. GC resolution: Was the valley height between toluene and toluenen-d 8 must be less than 10% of the taller of the two peaks? 

## SECTION G-2. DETAILED RAW DA TA REVIEW – Sample Results
9. Sample Results: were the sample results less than five times the Method Blank results? 10. Sample Results: were the sample results at least greater than ten times the Method Blank results? 11. Minimum Levels: were the minimum levels reported by the lab comparable to those specified in the method? 12. MS/MSD: if a MS/MSD was reported, were the recoveries within ± 50%? 13. Duplicate Samples: were duplicate samples collected? Were the RPDs less than 20%?

## CCH Data Review Checklist Semivolatile Organic Comp ounds EPA Method 1625C (Isotope Dilution GC/MS)

SECTION A-1. Sample Identifiers
CCH Effluent Guidelines Development

Sampling Episode: Laboratory Name:

Sample Number or Range: Data Reviewer signature: Date:

Instructions: Complete this checklist el ectronically or using a ballpoint pen. Record reviewer comments in the Reviewer Comment section. Record detailed information in the Comments in the “Overa ll Assessment” section for each criterion not (“N”) met.



## SECTION A-2. OVERAL L ASSESSMENT OF THE QUALITY OF THE DATA General Comment Checklist

Deliverable Requirement Required for Category Present Comments Copies of Shipping Documents (Fed-Ex Airbills) 1, 2, 3
Case Narrative 1, 2, 3
Table of Contents 3 Cross reference of Field Sample No., Lab Sample No., and Analytical Batch 1, 2, 3

Traffic Report Form (including Samp le Receipt Checklist) 1, 2, 3 Sample Calculation (usually just a page copied from SOW) 3

Results Summary fo r Each Sample and Blank (includes ion abundance ratios) 1, 2, 3

Blank Spike Results (OPR) 1, 2, 3 Labeled Compound Recovery Summary 1, 2, 3 Matrix Spike/Duplicate Matrix Spike Recovery Summaries 1, 2, 3 Instrument Performance Check (Resolution) 2, 3
Initial Calibration Data 2, 3 Continuing Calibration Data 2, 3 Windows Defining Mixture/Column Resolution Check 3 Selected Ion Chromatograms for Each Sample, Blank, and Standard 3

Quantitation List 3 Copies of Sample Preparation Work Sheets 3 Copies of Run Logs 3
1. COMPLIANCE SCREENING (ERG Sections A through D) -- Sample and QC results only; no instrument calibration or performance checks 2. SUMMARY VALIDATION (ERG Sections A through F) -- Sample, QC , calibration & instrument performance results; no raw data 3. FULL VALIDATION (ERG Sections A through G-2) -- Sample, QC, ca libration & instrument performance results; includes raw data tr anscription checks & result recalculation checks.



### Laboratory Name:________________ CCH Episode #.: _____________ Method 1625C – Page 1 of 4

### Criterion met 

## EPA METHOD 1625 REQUIREMENT Reviewer Comment Y N 

## SECTION B. SA MPLE RECEIPT
1. Sample Receipt Record: Signatures complete? 2. Receipt Date: Entered by analysis laboratory? 3. Receipt Temperature: Storage in the dark at a temperature 0 - 6  C. (40 CFR 136 Table II) Correct receipt conditions indicated? 4. Sample Condition: Sample bottle breakage? Sample leakage? (1625C/9.1) 

## SECTION C. SAMPLE INFORMATION
1. Sample container: Amber glass, or clear glass protected from the light. Correct sample container used? 2. Septum/liner/cap: Fluoropolymer lined. Correct septum/liner/cap indicated? 3. Sample bottle volume: > 1L (liquids), or >0.5 L (solids) Correct sample bottle volume indicated? 

## SECTION D. SAMPLE PREP ARATION/EXTRACT HANDLING INFORMATION
1. Aqueous sample residual chlorine: If an aqueous sample contains residual chlorine, 80 mg/L of sodium thiosulfate preservative is added to the empty bottle. Was residual chlorine measured (Method 330.4, 330.5)? Was preservative added? 2. Sample holding time prior to analysis: Extract samples within 7 days of collection. Correct hold time indicated? 3. Storage conditions: Extract stored between 0 and 4  C. Correct storage conditions indicated? 4. Maximum analysis holding time: 40 days from extraction . (1625C/9.3) Correct analysis time indicated? 

## SECTION E-1. QC INFORMATION – Instrument Performance
1. Mass Intensity: Did the analytical system meet the massintensity criteria in Table 7 of Method 1625C for DFTPP?(1625C/7.1) 2. Initial Precision and Accuracy (IPA): Were two sets of four 1-L aliquots of the aqueous performance standard analyzed before blanks an d samples? (1625C/8.2.1) 3. Average Recovery of IPA: Did the average recovery and standard deviation of the recovery for the first set of analyses meet the requirements in Table 10 of Method 1625C? (If yes, Instrument Perf ormance Passes 1625C/8.2.3) 4. Additional Recovery for Failed IPA: Did the average recovery and standard deviation of the failed set of analytes meet the requirements in Table 10 of Method 1625C?) (If yes, Instruments Perf ormance Passes 1625C/8.2.4) 5. Detection Limits: Did the analytical system meet the minimum levels in Table 5 of Method 1625C for the compounds analyzed? (1625C/7.3) 6. Continuing Calibration Verification (CCV): Was the CCV calibration standard analyzed prior to analyzing samples, blanks? (1625C/12.5) 7. Continuing Calibration Verification: Was the CCV used to verify calibration every 20 extracts or less? Was



### Laboratory Name:________________ CCH Episode #.: _____________ Method 1625C – Page 2 of 4

### Criterion met 

## EPA METHOD 1625 REQUIREMENT Reviewer Comment Y N

Pentachlorophenol recovered > 85%? (1625C/10.8.25) 8. CCV and Ongoing Precision and Accuracy: Did concentrations meet the corresponding limit for ongoing accuracy in Table 10 before samples were analyzed? (1625C/12.5.1, 12.7.3) 

## SECTION E-2. QC INFORMATIO N – Instrument Calibration
9. Initial Calibration (ICAL): Was an initial calibration curve with at least five points performed for each analyte? (1625C/7.4, 7.5) 10. Isotope Dilution Calibration: Was calibration by isotope dilution used for compounds for which a labeled analog is available? 11. Internal Standa rd Calibration: Was calibration by internal standard used for compounds fo r which a labeled analog is not available? (1625C/17.5) 12. ICAL RSD: Was the averaged response factor RSD less than 35% for compounds calculated by the internal standard method? For compounds that did not meet this RSD, was the complete calibration curve used? (1625C/ 7.5) 13. Labeled Compound Spiking Levels: Were the labeled compounds spiked at nominally 100 μ g/L level. (1625C/6.14) 

## SECTION E-3. QC INFORM ATION – Method Blanks
14. Method blanks: Was the level of the reagent blank greater than 10 μ g/L (aqueous) or 100 ug/kg (solids)? (1625C/8.5.2) If so, was analysis stopped and contamination eliminated? 15. Ongoing Laboratory Batch Blanks: Was a blank sample analyzed after every 8-hour shift or 20 samples? (1625C/8.5.1) 16. Field Blank: Reagent water or other reference. Was the Field Blank reported? Was the Field Blank above the detection limit? 

## SECTION F. RECOVERY OF LABELED ISOTOP E DILUTION INTERNAL STANDARDS
1. Recovery of labeled compounds: The recovery criteria of each labeled compound are listed in Table 10 of Method 1625. Did the average recovery % meet the criteria? (1625C/8.3.3) 2. Recovery of labeled compounds: If recovery criteria of the labeled compounds are not met, was sample dilution analyzed? (1625C/18.4) and guidelines followed for reporting? 3. Dilution of Samples: Have all samples where EICP area exceeds the calibration range been diluted until they are in the calibration range? (1625C/14.4) 4. Diluted Sample Reporting: Have diluted samples been reported at the least dilute level which is within the calibration range? (1625C/14.6)



### Laboratory Name:________________ CCH Episode #.: _____________ Method 1625C – Page 3 of 4

### Laboratory Name:________________ CCH Episode #.: _____________ Method 1625C – Page 4 of 4 

## SECTION G-1. DETAILED RAW DATA REVIEW – Compound Identification Quality Control The following criteria must be met for a GC peak to be identified as a semivolatile organic target: 1. The Signals: Did the GC peak contain at least five complete spectra across the upper half of the GC peak? (1625C/7.2.4) 2. Characteristic m/z: Did the characteristic m/z stored in the spectral library maximize within the same two consecutive mass scans? 3. Absolute Retention Times: Did the absolute retention time of 2,2’-difluorobiphenyl fall within 1078 and 1248 seconds? (1625C/12.3) 4. Relative Retention Time Between Labeled analog and pollutant: Did the relative retention time between analog and pollutant meet the requirements in Tables 5 and 6 of Method 1625C? (1625C/12.3) 5. GC resolution: Was the valley height between anthracene and phenanthrene at m/z 178 (o r the analogs at n/z 188) less than 10% of the taller of the two peaks? 6. Library Reverse Search: Was a library reverse search performed for the compounds of interest? (1625C/5.13.2, 7.2.5, T3, T4) 

## SECTION G-2. DETAILED RAW DA TA REVIEW – Sample Results

7. Sample Results: Were the sample results less than five times the Method Blank results? 8. Sample Results: Were the sample results at least greater than ten times the Method Blank results? 9. Minimum Levels: Were the minimum levels reported by the lab comparable to those specified in the method? 10. MS/MSD: If a MS/MSD was reported, were the recoveries within ± 50%? 11. Duplicate Samples: Were duplicate samples collected? Were the RPDs less than 20%?

### Laboratory Name:______________ CCH Episode #.:______ _____ Method 1613B – Page 1 of 7 

## OW Effluent Guidelines Data Review Checklist Tetra- Through Octa-Chlorinated Dioxins and Furans (D/F) EPA Method 1613B (Isotope dilution HRGC/MS)

SECTION A-1. Sample Identifiers
CCH Effluent Guidelines Development

Sampling Episode: Laboratory Name:

Sample Number or Range: Data Reviewer signature: Date:

Instructions: Complete this checklist el ectronically or using a ballpoint pen. Record reviewer comments in the Reviewer Comment section. Record detailed information in the “Comments and Overal l Assessment” section for each criterion not (“N”) met.



## SECTION A-2. Overall Method 16 13B Data Package Checklist General Comment Checklist

Deliverable Requirement Required for Category Present Comments Copies of Shipping Documents (Fed-Ex Airbills) 1, 2, 3 Case Narrative 1, 2, 3 Table of Contents 1 Cross reference of Field Sample No., Lab Sample No., and Analytical Batch 1, 2, 3

Chain-of-Custody Form (including Sample Receipt Checklist) 1, 2, 3

Sample Calculation (usually just a page copied from SOW) 1

Results Summary for E ach Sample and Blank (includes ion abundance ratios) 1, 2, 3

Blank Spike Results (OPR) 1, 2 Labeled Compound Recovery Summary 1, 2 Matrix Spike/Duplicate Matrix Spike Recovery Summaries 1, 2

Instrument Performance Check (Resolution) 1,2 Initial Calibration Data 1,2 Continuing Calibration Data 1,2 Resolution Check 1,2 Selected Ion Chromatograms for Each Sample, Blank, and Standard 1,2

Quantitation List 1,2 Copies of Sample Preparation Work Sheets 1,2,3 Copies of Run Logs 1,2
1. COMPLIANCE SCREENING (ERG Sections A through D) -- Sample and QC results only; no instrument calibration or performance checks 2. SUMMARY VALIDATION (ERG Sections A through H) -- Sample, QC, calibration & instrument performance results; no raw data 3. FULL VALIDATION (ERG Sections A through I) -- Sample, QC, calibration & instrument perf ormance results; includes raw data trans cription checks & result recalculation checks.

### Laboratory Name:______________ CCH Episode #.:______ _____ Method 1613B – Page 2 of 7 Criterion Met 

## EPA METHOD 1613B REQUIREMENT Reviewer Comment Y N 

## SECTION B. Sample Receipt, Traffic Report

1. Sample Receipt Record: Signatures Complete?

2. Receipt Date : Entered by Analysis Laboratory?

3. Samples Listed Correctly and Complete?

4. Receipt Temperature: Storage temperature <6°C but not frozen. Correct receipt temperature indicated?
5. Condition: Breakage?/Leakage? 

## SECTION C. Sample Handling Information

1. Sample container : Was the correct sample container used? [Method specifies amber or clear glass bottles wrapped in foil or stored in boxes that prevent exposure to light.]
2. Septum/liner/cap : Was the container cap PFTE lined?

3. Sample bottle volume : Was the correct sample bottle volume used (e.g., 1 liter, 1 quart, 1 pint, or 0.5 liter)?
4. Sample preservation : Were the samples preserved by neutralizing any chlorine residual with 0.008% sodium thiosulfate?
5. Maximum holding time : Were the samples held for 7 days or less? 

## SECTION D. Sample Preparatio ns/Extract Handling Information

1. Storage temperature - cooled to 6°C? Were the samples stored at 6°C (40 CFR 136 Table II) but not less then 0°C?
2. Maximum analysis time : Were the samples analyzed w ithin 40 days from day of extraction? 

## SECTION E. Instru ment Parameter Review SECTION E-1. QC Informat ion – Instrument Performance

1. Instrument Resolution: Was the PFK determined resolution greater than or equal to 10,000?
2. Instrument Mass Deviation: Was the deviation between the exact mass and the theoretical mass (Table 3 in 1613B) for each of the three to five ions monitored less than 5 ppm.
3. Mass Drift: Did the PFK lock-masses vary by less than +/-20% throughout each respective time window (1613B/7.2.1.2)?
4. Ion abundance ratios: Were all labeled and unlabeled PCDDs and PCDFs in the calibration standard (CS1) within the QC limits in 1613B Table 3A for their respective ion abundance ratios (1613B/7.2.2)? Do the ion abundance ratios fall within the

### Laboratory Name:______________ CCH Episode #.:______ _____ Method 1613B – Page 3 of 7 Criterion Met 

## EPA METHOD 1613B REQUIREMENT Reviewer Comment Y N

required limits (see reference table in Method)?
5. Signal to Noise ratio: Are all labeled and unlabeled analytes in the CS1 calibration standard detected with signal to noise ratios greater than or equal to 10.0? (1613B/7.2.3)

6. Retention Time: Does the absolute retention time of 13C labeled -1,2,3,4- TCDD exceed 25.0 minutes on the DB-5 column, and the retention time of 13C labele d 1,2,3,4-TCDD exceed 15.0 minutes on the DB-225 column? (1613B/7.2.4)
7. Resolution: Is the height of the valley between the most closely eluted isomers and the 2,3,7,8-substituted isomers less than 25% (1613B/7.4.2)? 

## SECTION E-2.(1613B/10.5) QC I nformation – Instrument Calibration

8. Was an initial five point calibration curve determined for each analyte?
9. Was the calibration curve determined less than 30 days prior to the time the first samples were analyzed?
10. Was the averaged response f actor RSD less than 20% for analytes calculated by the isotope dilution method?
11. Was the averaged response f actor RSD less than 35% for analytes calculated by the internal standard method?
12. Labeled Compound Spiking Levels (when all CDD/CDF compounds are analyzed): Were the labeled compounds spiked at the correct nominal level? 13C -2,3,7,8-TCDD 100 ng/mL 13C -2,3,7,8-TCDF 100 ng/mL 13C -1,2,3,7,8-PeCDD 100 ng/mL 13C -1,2,3,7,8-PeCDF 100 ng/mL 13C -2,3,4,7,8-PeCDF 100 ng/mL 13C -1,2,3,4,7,8-HxCDD 100 ng/mL 13C -1,2,3,6,7,8,-HxCDD 100 ng/mL 13C -1,2,3,4,7,8-HxCDF 100 ng/mL 13C -1,2,3,6,7,8-HxCDF 100 ng/mL 13C -1,2,3,7,8,9-HxCDF 100 ng/mL 13C -2,3,4,6,7,8,-HxCDF 100 ng/mL 13C -1,2,3,4,6,7,8-HpCDD 100 ng/mL 13C -1,2,3,4,6,7,8-HpCDF 100 ng/mL 13C -1,2,3,4,7,8,9-HpCDF 100 ng/mL 13C -OCDD 17-157 200 ng/mL 37Cl -2,3,7,8-TCDD 10 ng/mL
13. Labeled Compound Spiking Levels (when only TCDD/TCDF compounds are analyzed): Were the labeled compounds spiked at the correct level?
13 C -2,3,7,8-TCDD 100 ng/mL
13 C -2,3,7,8-TCDF 100 ng/mL
37 Cl -2,3,7,8-TCDD 10 ng/mL
14. Labeled Compound Recovery in Calibration Standards

### Laboratory Name:______________ CCH Episode #.:______ _____ Method 1613B – Page 4 of 7 Criterion Met 

## EPA METHOD 1613B REQUIREMENT Reviewer Comment Y N (when all CDD/CDF compounds are analyzed): Did the spiked 13C isotope recovery meet the following criteria?
13 C -2,3,7,8-TCDD 25–164%
13 C -2,3,7,8-TCDF 24–169%
13 C -1,2,3,7,8-PeCDD 25–181%
13 C -1,2,3,7,8-PeCDF 24–185%
13 C -2,3,4,7,8-PeCDF 21–178%
13 C -1,2,3,4,7,8-HxCDD 32–141%
13 C -1,2,3,6,7,8,-HxCDD 28–130%
13 C -1,2,3,4,7,8-HxCDF 26–152%
13 C -1,2,3,6,7,8-HxCDF 26–123%
13 C -1,2,3,7,8,9-HxCDF 29–147%
13 C -2,3,4,6,7,8,-HxCDF 28–136%
13 C -1,2,3,4,6,7,8-HpCDD 23–140%
13 C -1,2,3,4,6,7,8-HpCDF 28–143%
13 C -1,2,3,4,7,8,9-HpCDF 26–138%
13 C -OCDD 17-157%
37 Cl -2,3,7,8-TCDD 35-197%
15. Labeled Compound Recovery in Calibration Standards (when all only TCDD/TCDF compounds are analyzed): Did the spiked 13C isotope recovery meet the following criteria?
13 C -2,3,7,8-TCDD 31-137%
13 C -2,3,7,8-TCDF 29-140%
37 Cl -2,3,7,8-TCDD 42–164.% 

## SECTION E-3. (1613B/11.0) QC Information – Method Blanks

16. Were Reference matrix method blanks initially acceptable? Ongoing Laboratory Method/Batch Blanks acceptable? (Samples on a given 12-hour shift, to a maximum of 20 samples)?

Note any 2,3,7,8-substituted CDD/CDF found in the blank at greater than the minimum level listed below.

For Compounds using 13 C 12 -1,2,3,4-TCDD as the injection internal standard:

2,3,7,8-TCDF 13 C -2,3,7,8-TCDF 10 pg/L 2,3,7,8-TCDD 13 C -2,3,7,8-TCDD 10 pg/L 1,2,3,7,8-PeCDF 13 C -1,2,3,7,8-PeCDF 50 pg/L 2,3,4,7,8-PeCDF 13 C -2,3,4,7,8-PeCDF 50 pg/L 1,2,3,7,8-PeCDD 13 C -1,2,3,7,8-PeCDD 50 pg/L

Compounds using 13 C 12 -1,2,3,7,8,9-HxCDD as the injection internal standard:

1,2,3,4,7,8-HxCDF 13 C -1,2,3,4,7,8-HxCDF 50 pg/L 1,2,3,6,7,8-HxCDF 13 C -1,2,3,6,7,8-HxCDF 50 pg/L 1,2,3,7,8,9-HxCDF 13 C -1,2,3,7,8,9-HxCDF 50 pg/L 2,3,4,6,7,8-HxCDF 13 C -2,3,4,6,7,8,-HxCDF 50 pg/L 1,2,3,4,7,8-HxCDD 13 C -1,2,3,4,7,8-HxCDD 50 pg/L

### Laboratory Name:______________ CCH Episode #.:______ _____ Method 1613B – Page 5 of 7 Criterion Met 

## EPA METHOD 1613B REQUIREMENT Reviewer Comment Y N
1,2,3,6,7,8-HxCDD 13 C -1,2,3,6,7,8,-HxCDD 50 pg/L 1,2,3,4,6,7,8-HpCDF 13 C -1,2,3,4,6,7,8-HpCDF 50 pg/L 1,2,3,4,7,8,9-HpCDF 13 C -1,2,3,4,7,8,9-HpCDF 50 pg/L 1,2,3,4,6,7,8-HpCDD 13 C -1,2,3,4,6,7,8-HpCDD 50 pg/L OCDF 13 C -OCDD 100 pg/L OCDD 13C -OCDD 100 pg/L
17. Method Blank— Were required reagent water blanks prepared, and treated as a sample in all respects for the purpose of determining if the field or sample transporting procedures and environments have contaminated the sample? Was Field Blank reported? Was the Field Blank below the detection limit? 

## SECTION F. Recovery of C-13 Labeled Isotope Dilution Internal Standards

1. Labeled Standard Recovery: Was recovery of each C-13 labeled PCDD and PCDF isomer using Method 1613B within acceptable range defined in Table 6 of Method 1613B? 

## SECTION G. Instrument Recovery of Internal Standards

1. Internal Standard Recovery: Was the sum of the area counts of two masses for each of the two instrument recovery internal standards for samples, blanks, and standards within a factor of four (-25% to +400%) from the sum of the associated average areas from the five initial calibration standards? (EPA Region 10 SOP for Method 1613B Data Validation)

Note: When all CDDs/CDFs are analyzed the internal standard solution contains 13 C 12 -1,2,3,4-TCDD and 13 C 12 - 1,2,3,7,8,9-HxCDD.

When only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined, the standard solution contains 13 C 12 -1,2,3,4- TCDD only.

Was the Internal Standard Recovery Correct? (1613B/15.0) 

## SECTION H. Performance E valuation (QA) Samples

1. Field duplicates, transfer blanks , trip blanks, blind spikes, blind blanks, and performance evaluation (PE) samples should be reviewed during data evaluation. If QA samples are included among the field samples for measurement by the laboratory, then the data validator should refer to the applicable QAPP for any QA requirements regarding QA samples. Did the QA samples meet the required precision and bias limits? (1613B/9.6- 15.0)

Results from the measurement of project and regional QA samples will reflect upon the ability of the laboratory to report analytical results of known and documented quality

### Laboratory Name:______________ CCH Episode #.:______ _____ Method 1613B – Page 6 of 7 Criterion Met 

## EPA METHOD 1613B REQUIREMENT Reviewer Comment Y N
which meet the Precision, Accu racy, and Representativeness QA/QC requirements of the QAPP. (Reference, Region 10 SOP for Data Validation from Method 1613B) 

## SECTION I. Detailed Raw Data Review – Compound Identification Quality Control
The following criteria must be met for a GC peak to be identified as a PCDD or PCDF: 1. Were the signals for the two exact m/z's being monitored present, and maximized within plus or minus 2 seconds of one another (see 1613B/Section 15.1)?
2. The signal-to-noise ratio Was the signal to noise (S/N) of each of the two exact m/z's greater than or equal to 2.5 for a sample extract, and greater th an or equal to 10 for a calibration standard (see 1613B/Section 15.2)?
3. The ratio: Was the ratio of the integrated ion currents (EICPs) of both the exact m/z's monitored within the limits of the method (see 1613B/Section 15.3)?
4. Relative Retention Times: Was the relative retention time (RRT) of the peaks representing an unlabeled 2,3,7,8 substituted PCDD or PCDF within the limits given in the method? The retention time (RT) of peaks repres enting non-2,3,7,8-substituted PCDDs or PCDFs must be within the RT windows established in the method (see 1613B/Section 15.4)?
5. Confirmatory Column Analysis: Was the measurement of 2,3,7, 8-TCDF on the primary DB-5 GC column confirmed by analysis on a confirmatory column such as DB-225, SP-2330, DB-DIOXIN, or equivalent? Were all QC requirements of the method met on both the primary and secondary GC columns (see 1613B/Section 15.5)?

6. Non-PCDPE Interferences: If non-PCDPE interferences to the measurement of 2,3,7,8- TCDF on the secondary GC co lumn are present, did the laboratory measure 2,3,7,8-TCDF on a third dissimilar GC column in order to separate the 2,3,7,8-TCDF peak from the non-PCDPE interference peak? Did the measurement of 2,3,7,8-TCDF on a third dissimilar GC column include full calibration (both initial and calibration verification) on the third GC column? Did analysis resolve interference?
7. The identification of a GC peak: Was the identification of a GC peak (on either primar y or confirmatory GC column) as a PCDF made when no signal having a S/N 2.5 at the same retention time (± 2 seconds) in the corresponding polychlorinated diphenyl ether (PCDPE) channel? These criteria require that the laboratory document the EICP of all PCDPE m/z's which ar e scanned (see 1613B/15.3). Was EICP documented for all PCDPE m/z’s?

### Laboratory Name:______________ CCH Episode #.:______ _____ Method 1613B – Page 7 of 7 8. Retention Time Verification: Were the retention times of target compounds verified using reference standards before iden tifications were determined (see 1613B/15.4)? Were retention times verified and correct?
9. The valley height: Was the valley height between 2,3,7,8- TCDD and the other TCDD isomers at m/z 319.8965, and between 2,3,7,8-TCDF and the other TCDF isomers at m/z 303.9016 less than 25% on their respective columns (see 1613B/Section 14.4.2.2)?

### Laboratory Name:________________ CCH Episode #.: _____________ Method 1668A – Page 1 of 5 

## CCH Study Data Review Checklist Chlorinated Biphenyl Congeners in Water, Soil, Sediment, and Tissue (Isotope Dilution HRGC/HRMS Method 1668A)

SECTION A-1. Sample Identifiers
CCH Effluent Guidelines Development

Sampling Episode: Laboratory Name:

Sample Number or Range: Data Reviewer signature: Date:

Instructions: Complete this checklist el ectronically or using a ballpoint pen. Record reviewer comments in the Reviewer Comment section. Record detailed information in the Comments in the “Overa ll Assessment” section for each criterion not (“N”) met.



## SECTION A-2. OVERAL L ASSESSMENT OF THE QUALITY OF THE DATA General Comment Checklist

Deliverable Requirement Required for Category Present Comments Copies of Shipping Documents (Fed-Ex Airbills) 1, 2, 3 Case Narrative 1, 2, 3
Table of Contents 3 Cross reference of Field Sample No., Lab Sample No., and Analytical Batch 1, 2, 3

Traffic Report Form (inc luding Sample Receipt Checklist) 1, 2, 3

Sample Calculation (usually just a page copied from SOW) 3

Results Summary fo r Each Sample and Blank (includes ion abundance ratios) 1, 2, 3

Blank Spike Results (OPR) 1, 2, 3 Labeled Compound Recovery Summary 1, 2, 3 Matrix Spike/Duplicate Matrix Spike Recovery Summaries 1, 2, 3

Instrument Performance Check (Resolution) 2, 3 Initial Calibration Data 2, 3 Continuing Calibration Data 2, 3 Windows Defining Mixture/Column Resolution Check 3 Selected Ion Chromatograms for Each Sample, Blank, and Standard 3

Quantitation List 3 Copies of Sample Preparation Work Sheets 3 Copies of Run Logs 3
1. COMPLIANCE SCREENING (ERG Sections A thr ough D)--Sample and QC results only; no instrument calibration or performance checks 2. SUMMARY VALIDATION (ERG Sections A through F)--Sample, QC, calibration & instrument performance results; no raw data 3. FULL VALIDATION (ERG Sections A through G-2)--Sample, QC, calibration & instrument performance results; includes raw data tran scription checks & result recalculation checks.

### Laboratory Name:________________ CCH Episode #.: _____________ Method 1668A – Page 2 of 5 Criterion met 

## EPA METHOD 1668A REQUIREMENT Reviewer Comment Y N 

## SECTION B. SA MPLE RECEIPT
1. Sample Receipt Record: Signatures complete? 2. Receipt Date: entered by analysis laboratory? 3. Receipt Temperature: storage in the dark at a temperature < 6  C. (40 CFR 136 Table II) Correct receipt conditions indicated? 4. Sample Condition: sample bottle breakage? Sample leakage? 

## SECTION C. SAMPLE H ANDLING INFORMATION
1. Sample container: Amber or clear glass bottles – Clear glass wrapped in foil or stored in boxes that prevent exposure to light. Correct sample container used? 2. Spetum/liner/cap: Fluoropolymer lined. Correct septum/liner/cap indicated? 3. Sample bottle volume: 1 liter (liquids) or 0.5 liter (solids). Correct sample bottle volume indicated? 

## SECTION D. SAMPLE PREP ARATION/EXTRACT HANDLING INFORMATION

1. Hold time for aqueous, solid, semisolid, tissues, or other matrices: Extract and analyze within 1 year of collection. (1668A/8.5) Correct hold time indicated? 2. Sample holding time prior to extraction: Maximum of 1
year. Correct extraction time indicated? 3. Storage conditions: Extracts stored in the dark at <-10  C. Correct storage conditions indicated? 4. Maximum analysis holding time for aqueous extractions: one year at a pH< 9. Correct holding time indicated? 

## SECTION E-1. QC INFORMATION – Instrument Performance

1. Instrument Resolution: For the PFK molecular leak, the resolution must be greater than or equal to 10,000 at m/z 330.9792. Is the instrument resolution provided and sufficient? (1668A/10.2.1) 2. Instrument Mass Deviation: The deviation between the exact mass and the theoretical mass (Table 7 in Method 1668A) for each of the two ions monitored must be less than 5 ppm. (1668A/10.2.2) Is the mass deviation documented and acceptable? 3. Mass Drift: Using PFK to provide lock-masses. Each lockmass shall be monitored and shall not vary by more than ± 20% throughout each resp ective time window. (1668A/10.3.1.2) Is mass drift documented and acceptable? 4. Ion abundance ratios: All CB s and labeled compounds in the Calibration standard (CS-1) must be within the QC limits in Table 8 of Method 1668A for their respective ion abundance rations. (1668A/10.3.2). Do the ion abundance ratios fall within the required? 5. Continuing Performance and Calibration Verification

### Laboratory Name:________________ CCH Episode #.: _____________ Method 1668A – Page 3 of 5 Criterion met 

## EPA METHOD 1668A REQUIREMENT Reviewer Comment Y N

(CCV): Was the CCV (CS-3) and Diluted combined 209 congener soulution standard analyzed prior to analyzing samples, blanks, IPRs, and OPRs? (1668A/15.1 and Table 6 below) Do they meet performance criteria? 6. CCV Recovery: The CCV (CS-4) recovery limits are listed in Table 6 of Method 1668A (1668A/15.3.5) Do the recoveries meet acceptance criteria for CCV? 7. Signal to Noise ratio: All labeled and unlabeled analytes in the CCV calibration standard must have signal to noise ratios greater or equal to 10.0. (1668A/10.3.3) If the S/N ratio is indicated, is it greater than or equal to 10.0? 8. Absolute Retention Time: The absolute retention times of the labeled compounds in the CCV must be within ± 15 seconds of the respective reten tion times in the most recent CCV. (1668A/15.4.1.1) Are the retention times within specifications? 9. Absolute Retention Time: The absolute retention time of CB 209 must exceed 55 minutes. Are the retention times within specifications 10. Relative Retention Time: The relative retention time of the native and labeled compounds in the CCV must be within their respective RRT times listed in Table 2 of Method 1668A. (1668A/15.4.1.2) Are the absolute retention times within specifications? 11. Initial Precision and Recovery (IPR): Was an IPR performed prior to analyzing samples and blanks? (1668A/9.2.3) 12. IPR Recovery: The IPR recovery limits are listed in Table 6 of Method 1668A. (1668A/9.2.3) Do the recoveries meet acceptance criteria for IPR? 13. Ongoing Precision and Recovery (OPR): Is the OPR calibration standard analyzed pr ior to analyzing samples and blanks? (1668A/15.5.1) 14. OPR Recovery: The OPR recovery limits are listed in Table 6 of Method 1668A. (1668A/15.5.3) Do the recoveries meet acceptance criteria for OPR? 15. Sample Dilution: If the SICP area at the either quantitation m/z exceeds the calibration range, was the sample diluted tobring the concentration within the calibration range and reanalyzed? (1668A/17.5) 

## SECTION E-2. QC INFORMATIO N – Instrument Calibration
16. Initial Calibration (ICAL): Was an initial calibration curve with at least five points performed for each compound? (1668A/10.4.) 17. Isotope Dilution Calibration: Was calibration by isotope dilution used for compounds for which a labeled analog is available? (1668A/10.4) 18. ICAL RSD: Was the averaged response factor RSD less than 20% for compounds calculated by the isotope dilution method? For compounds that did not meet this RSD, was the complete calibration curve used? (1668A/10.4.4) 19. Internal Standa rd Calibration: Was calibration by internal standard used for compounds fo r which a labeled analog is not available? (1668A/10.5)

### Laboratory Name:________________ CCH Episode #.: _____________ Method 1668A – Page 4 of 5 Criterion met 

## EPA METHOD 1668A REQUIREMENT Reviewer Comment Y N
20. ICAL levels: Were the unlabeled compounds calibrated at the correct level as listed in Table 5 of Method of 1668A? 21. Labeled Compound Spiking Levels: Were the labeled compounds spiked at the acceptable level (conc. in extract) listed in Table 3 of Method 1668A? 

## SECTION E-3. QC INFORM ATION – Method Blanks
22. Blank: Was the Method blank extracted with each sample batch and analyzed immediately following the OPR? (1668A/15.6) 23. Methods blanks/ Ongoing Laboratory Batch Blanks: Note any compounds found in th e blank at greater than the minimum level listed in Table 2 of Method 1668A. (1668A/9.5.2) Analysis should not be performed if blank is above minimum level or within a factor of 3 of the regulatory limit, whichever is greater. – Were blank results less than the minimum level in1668A -Table 2? (1668A/9.5.2) 24. Field Blank: Reagent water or other reference matrix placed in a sample container in the laboratory or the field, and treated as a sample in all respects for the purpose of determining if the field or sample transporting procedures and environments have contaminated the sample. Was Field Blank reported? Was the Field Blank above the detection limit? 

## SECTION F. RECOVERY OF LABELED ISOTOP E DILUTION INTERNAL STANDARDS

1. Recovery of labeled compounds: The recovery criteria of each labeled compound are listed in Table 6 of Method 1668A. Did the average recovery % meet the criteria? (1668A/18.5.1) (Note: Background of IUPAC numbers 105, 114, 118, 123, 156 and 167 are common) 2. Recovery of labeled compounds: If recovery criteria of the labeled compounds are not met, was sample dilution analyzed? (1668A/18.5.1) 3. Recovery of labeled compounds: If recovery criteria of the labeled compounds are not met in the diluted sample, was the calibration verified with a CCV standard? (1668A/18.5.2) 4. Recovery of labeled compounds: If the calibration can not be verified, was another calibration performed and the sample re-analyzed? (1668A/18.5.3)

### Laboratory Name:________________ CCH Episode #.: _____________ Method 1668A – Page 5 of 5 

## SECTION G-1. DETAILED RAW DATA REVIEW – Compound Identification Quality Control The following criteria must be met for a GC peak to be identified as a CB: 1. The signals for the two exact m/zs being monitored (listed in Table 7 of Method 1668A) must be present, and must maximize within the same two scans. (1668A/16.1) 2. The signal-to-noise ratio (S/N) of each of the two exact m/zs must be greater than or equal to 2.5 for each compound in a sample. (1668A/16.2) If, through observation of the SICP, the S/N ratio looks questionable calculate an approximate S/N using the heights of the signals. Is the S/N ratio greater than or equal to 2.5? 3. The ratio of the integrated ion ar eas of the two exact m/zs monitored (listed in Table 7 of Method 1668A) must be within the limit in Table 8 of 1668A or ± 15% of the ratio in the CS-3 or CCV, if the CCV is more recent. (1668A/16.3). 4. Relative Retention Times: The relative retention time (RRT) of the peaks representin g a CB must be within the window specified in Table 2 of Method 1668A. (1668A/16.4) 

## SECTION G-2. DETAILED RAW DA TA REVIEW – Sample Results
5. Sample Results: Were the sample results less than five times the Method Blank results? 6. Sample Results: Were the sample results at least greater than ten times the Method Blank results? 7. Minimum Levels: Were the minimum levels reported by the lab comparable to those specified in the method? 8. MS/MSD: If a MS/MSD was reported, were the recoveries within ± 50%? 9. Duplicate Samples: Were duplicate samples collected? Were the RPDs less than 20%?