Quality Assurance Project Plan
for
Laboratory Sample Preparation and Analysis Activities in the
National Pilot Study of Pharmaceuticals and Personal Care
Products (PPCPs) in Fish Tissue
October 19, 2006
Prepared for
United States Environmental Protection Agency
Office of Water
Office of Science and Technology
Standards and Health Protection Division
Prepared jointly by
Computer Sciences Corporation (CSC) Environmental Programs Group
Prepared under
Office of Superfund Remediation and Technology Innovation (OSRTI) Sample Management Office
Contract No. EP-W-06-046
and
Tetra Tech, Inc.
Prepared under
Office of Science and Technology (OST)
Contract No. EP-C-04-030
EPA 820-F-23-004
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PPCP Fish Pilot Study Sample Preparation and Analysis QAPP
Revision 0
Dale: 19 October 2006
Page ii of vi
Quality Assurance Project Plan for
Laboratory Sample Preparation and Analysis Activities in the National Pilot Study of
Pharmaceuticals and Personal Care Products (PPCPs) in Fish Tissue
Approvals:
Tangda Cooler. SUPD Pjjoieet Officer, HP A
Wdmit krohL ...
.canne Stahl. Project Manager, EPA
Oil,
Wathen, Acting Chief, FSBOB, EPA
Robert Shippen, SHPD Quality Assurance Coordinator, EPA
Marion Kelly, OSf Quality Assurance Officer, EPA
0
Erin Salo, Project Manager, CSC
^
Leslie Braur, Quality Assurance Manager, CSC
lyder, Tetra T&gfi Projs
Blaine Snyder, Tetra T&gfi Project Manager
¦Sik r7.. /Mu
Esther Peicj^, Tetra Tech QuaJjjy .Assurance Officer
JdL
Kevin Chambliss, Baylor University Lab Project Manager
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1'IVI' Fish 1'ikH StuJv Sample l'lflvrjtutn and A:\ah UM'I1
Distribution List
I eslte Braun
Computer Sciences Corporation
15000 Conference Center Drhe
Chantilly, VA 20151
71)3-818-4022 (phone)
703-818-4601 (fax)
Bryan W. Brooks. Ph.D.
Department of Environmental Studies. Center for
Reservoir and Aquatic Systems Research
Baylor University
One Bear Place #97266
Waco IX 76798-7266
254/710-6553 (phone)
254/710-3409 (fax)
C. Kevin Chambliss
Department of Chemistn, & Biochemistry
Baylor University
One Bear Place *97348
Waco. IX 76798-7348
(254) 710-6849 phone
(254)710-4272 fax
fangela Cooper
USHPA'OST (4305T)
1200 Pennsylvania Ave., N.W.
Washington, DC 20460
202/5664)369 (phone!
202'566-0409 {fax)
Neai Jarmclle
Computer Sciences Corporation
6101 Stevenson Avenue
Alexandria. VA 22304
703-461-2145 (phone)
703-461-S056 (fax)
Marion Kelly
t)SI:PA/()ST (4303T)
1200 Perms) Ivania Avenue, N.W.
Washington, DC 20460
202-566-1045 (phone)
202/566-1053 (fax)
John O'Donnell
I'etra Tech, Inc.
10306 Hasten Place, Suite 340
Fairfax, VA 22030
703/3 85-W100 1 phone)
703'385-600™flax!
List her Peters
Tetra Tech. Inc.
10306 Easton Plaee, Suite 340
Fairfax, VA 22030
703/385-6000 (phone)
703'385-6007 (fax)
Jennifer Pitt
Tetra Tech. Inc.
400 Red Brook Bl\d„ Suite 200
Owings Mills. V1D 2111"
410/350-8993 (phone l
410/356-^005 (faxl
Julie Rest
Computer Sciences Corporation
6101 Stevenson Avenue
Alexandria, VA 223n4
703-461-2369(phone)
703-461-8056 (fax)
lirin Salo
Computer Sciences Corporation
0101 Ste\enson Avenue
Alexandria. VA 22304
703-461-2350 (phone!
703-461-8056 (fax)
Robert Shippen
USEPA OS] (430514
1200 Penns) Ivania A\e., N.W,
Washington. DC 2046(1
202/566-0301 (phone!
202''566-0409 (tax)
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Blaine Snvder
Tetra Tech, Inc.
4IH) Red Brook Blvd.. Suite 200
Owings Mills. Ml) 21117
410 356-XW3 (phone)
41U/356-WHI5 (fax)
Leanne Stall!
USHPA/OST (43(15 Ft
1200 Pennsylvania Ave., WW.
Washington, DC 20460
202'566-()4()4 (phone i
202/566-0409 |fax)
Lynn Wallers
Computer Sciences Corporation
hi01 Sievenson Avenue
Alexandria, VA 22304
703 '461-2060 i phone)
703; 461 -St)56 j fax)
John Wat lien
CSEPA'OST H305T)
1200 Pennsylvania Ave., N.W.
Washington, DC 20460
2o2'5t'i&-l)367 tphone)
202/566-040') (tax)
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m P 1 j.sh Pslot Suiiiv Sample Preparation and An.ilv ms o \ PP
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Tablf of Contents
1.0 Project Background
2Ji Project Description
3.0 Project Organization
3.1 LPA Management and Stuff
3.1.1 OST Director
3.1.2 OST Quality Assurance Officer and SHPD QA Coordinator
3.1.3 1'. PA Project Manager
3.2 Computer Sciences Corporation (CSC) Staff
3.2.1 CSC Project Manager
3.2.2 CSC QA Manager
3.3 Tctra Tech Staff
3.3.1 TetraTech Project .Manager .
3.3.2 Tctra l ech Quality Assurance Officer <
3.4 Contract Laboratory f
3.4.1 Laboratory Project Manager (
3.4.2 Laboratory QA Manager.
4.0 Quality Objectives
4.1 Project Quality Objectives
4.2 Measurement Quality Objectives
4.2.1 Precision
4.2.2 Bias
4.2.3 Accuracy
4.2.4 Sensitiv ity
4.2.5 Representativeness
4.2.6 Completeness
4.2.7 Comparability Js
5.0 Special Training Requirements
6.0 Documentation and Records
6.1 Sample Preparation Records
6.2 Analytical Records
6.3 Data Compilation, Review and Validation Records
7.1) Sampling Process Design
7.1 Sample Ty pe
7.2 Sampling Period
".3 Sample frame
7.4 Selection of Sampling Sites
8.0 Sampling Method Requirements
8.1 Target Species
8.2 Composite Sampling
8.3 Sample Collection
9.0 Sample Handling and Custody Requirements
9.1 Field Requirements
9.2 Laboratory Requirements
10.0 Analytical Methods Requirements
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PPCP Fish Pilot Study Sample Preparation and Analysts QAPP
KCV 'Mk>? 1
DjU" I" * K. U. JIPLC-MS Ms I T
10.1.1 Reference Tissue Specimens i
10.1.2 Sample ['reparation !7
1(1.1,3 niM.C-MS.-MS Ami!>sis IS
10.2 PPCPs hy <;C-MS SIM ". 18
Hi.2.1 Sitnipie Preparation iu
10.2.2 <;C-MS Analysis 20
10.3 Lipids in fish tissues 20
11.0 Quality Control Requirements 21
12.0 Instrument/Equipment Testing, Inspection, and Maintenance Requirements
13.0 Instrument Calibration and frequency 2f>
14.0 Inspection/Acceptance Requirements for Supplies and Consumables 2<>
15.0 Requirements for Acquisition of Non-direct Measurement Data 2:6
16.0 Data Management 2(>
16.1 Laboratory Data Management -7
16.2 CSC Data Management ^7
1~.(l Assessments and Response Actions 2K
17.1 Surveillance 24>
17.2 Peer Review M
17.3 Quality Systems Audit M
17.4 Readiness Rexieu 3 I
1",? Technical Sxstems Audi! --2
! 7.6 Data Quality Audits i2
17.7 Data Quality Assessment ^2
18.0 Reports to Management v
19.0 Data Review. Validation, and Verification *3
20.(1 References ............ 34
Appendix A - Method/Chemical Acceptance Criteria
Appendix B — Sampling Locations
Appendix C - Baylor's LniversitCs Laboratory Corrective Action Plan
Appendix D - CSC Data Review Form
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Tabic I. PPCP Pilot Slutly Target Chemicals anil Corresponding Analysis Methods. .. "
Table 2. Retention Times :in
Tabic 3. Retention "l imes and Ions Specified for Selected Ion Mi>nitorin» of PP( Ps by
GC'-MS SIM - Uuylor I Diversity 2"
Table 4. Method Performance Criteria
Table 5. .Assessment and Response Actions •()
Figure i.
Project Organization and Relat ion ships
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P.PCP Fish Pilot Study Sample jnJ \t,uv m, i.t \I'P
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This Quality Assurance Project Plan (QAPP) presents performance and acceptance criteria and
measurement ^ualit\ objectives (MQOs) established for the anal) sis of environmental samples collected during
the Xulintkil Pilot Study of Phurmaeeutiedls jnd Personal ('are Products tPPl "Ps i in Fish Tissue (hereafter
referred lo as either the "PPt'P Fish Pilot Study," or more simply "the study") This QAPP also describes the
methods and procedures that will be followed to ensure these criteria and VlQOs are met. This document
addresses onh the sample analysis effort; performance criteria and procedures related lo sample collection are
described in PP.Vs Ijthility. Issuntnee Project Plan tor Sample ('olleetiim Activities for a Pilot Study in
Investiture the Occurrence nf Phurmaceuticids and Personal Cure Products tPf'i "Psi in Fish Tissue 11 j.
This document was prepared in accordance with and contains each of the elements described in the most
recent version of EPA QA/R-5. EPA Requirements for (Jaality Asstirance Pnijeci Plans [2], 'lo improve clarity,
the order of certain elements in this QAPP has been modi lied slightly from the order presented in EPA QA/R-5.
For example, in this QAPP the Project Organization section (element "A4" in QAR-5) follows the Project
Background and Project Description sections (elements "A5" and "A6" in QA/R-5>.
In accordance with the instructions provided in LPA QA K-5. this QAPP is considered to be a d\ riamic
document that is subject to change as sample collection and anal) sis progresses. All changes to procedures
described in this Q \PP w ill he rev tewed b\ the I;PA Stud) Manager and the EPA Quality Assurance Manager lo
determine if the changes significantly impact the technical and quality objectives of the project. If changes are
deemed to he significant, the QAPP will be tevised according!), circulated for approval, and provided to all
project participants listed in the QAPP distribution list.
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PPCP Fish Pilot Study Sample Preparation and Analysis QAPP
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1.0 Project Background
F.PA's Office of Science and Technology (OST) within the Office of Water (OW) is initiating a pilot
study to investigate the occurrence of pharmaceutical and personal care product (PPCP) chemicals in fish tissue
called the National Pilot Study of Pharmaceuticals and Personal Care Products in Fish Tissue (hereafter referred
to as the "PPCP Fish Pilot Stud}1"), Increasing evidence indicates widespread occurrence of PPCP chemicals in
surface water, sediments, and municipal effluent, but data on the accumulation of PPCP chemicals in fish tissue
are scarce. This study was planned lo respond to HPA's new priority of obtaining environmental data on
emerging contaminants and to increase lite data available on the occurrence of PPCP chemicals in fish. The
proposed targeted study design calls for collecting ftsh samples from five diluent-dominated streams in the
vicinity of wastewater treatment plant {WWI'P) discharges and one reference site. Tissue fractions front each fish
sample (fillets and livers) will lie analyzed for 39 PPCP chemicals, 1 hese analyses will provide data to determine
the potential of the target chemicals to survive the wastewater treatment process and to bioaccumulate in the
tissue offish,
Tctra Tech has been tasked with planning, implementing, and managing sample collection, preparation
and analysis, and forwarding pilot project results to Computer Sciences Corporation (CSC) for data review and
database development, Tcira Tech will collect all samples and will subcontract with Baylor University "s Center
for Reservoir and Aquatic Systems Research (hereafter referred to as Bay lor") for the preparation and analysis of
fish samples. Baylor will be subcontracted to analyze PPCP Fish Pilot Study samples for the target chemicals
using analytical methods, such as high performance liquid chromatography-tandem mass spectrometry (HPf.C-
MS MS), gas chromatography .''mass spectrometry selective ion monitoring tCiC'MS-SIM), or other methods that
can achieve the method detection limits specified by EPA.
2.0 Project Description
The study design reflects the study goal and objectives defined by \ fSKPA. The stud} goal can he stated
simply — to investigate the t sccurrence of a broad suite /; f'PPCPs (39 chemicals i in the tissue oj adult /rcyfneater
fish that are typically cons timed by humans and or wildlife. Performance and acceptance criteria and
measurement quality objectives (MQOs) established for the analysis of environmental samples collected during
this study are addressed in this document: those methods and procedures used to collect and ship fish tissue
samples for the PPCP Fish Pilot Study are documented in a separate QAPP {Quality Assurance Project Plan for
Sample ('ollection Activities for a Pilot Study to Investigate the Occurrence oj Pharmaceuticals and Personal
Cure Products fPPC 'Ps) in Fish Tissue/1 J).
In consultation with the USHPA Office of Science and Technology. letra lech will coordinate with
t !8EPA headquarters and regional staff to collect fish tissue samples from targeted effluent-dominated streams.
Field teams will sample five sites where waters are dominated by wastewater treatment plant tWAVTP) effluent,
along with one reference quality site (Appendix B). The samples will be collected between August and
November of 2006. The fish tissue samples will be collected based on a targeted design to provide information
on the occurrence of PPCP contaminants in fish. Upon collection, fish samples will be shipped to the laboratory
where they will be weighed, composited, sub-sampled into liver tissue and muscle tissue (fillets fractions,
homogenized, and divided into aliquois for analysis and archiving, if sufficient tissue is available. The aliquots
for each tissue fraction will then be analyzed for the PPCP chemicals listed hi Table 1. Details regarding the study-
design. including how streams are to be sampled, how they were selected, etc., can be found in reference [1]
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PPCP fish Pilot Study Sample Preparation and Analysis QAPP
RcViNi'H
Date I^cVtobrr
PjL't' » ul Vi
T:il)h- I. I'I'CP Pilot Smth 1 -ii < tii-HiiiaK :in;i ( 'i)ri-cs|nit»liii!: Ah:iKms MeUmds
Analysis Method
Chemical (CAS Number)
t'hurmuccdticals unJ Personal Cure Products (PPl'IN) h\
High i'crfurnuikv Liquid t'hromjingraphj - 1 jnticm \la.ss
Spectrometry (Method tlPIJ '-MS MS)
I J-Himethyhunthme (hi l-5'i-fi)
Acciominnpbcti 1103-'>O-2)
Atenolol <21>I 22-68-71
Caffeine (5K-I1K-2)
Carbanwepiiu.' i 29X- lfi-4 i
Cisneudine (5l4XI-ftt-sh
Ciullhric Acid 1882-111)-7)
Codeine (76-57-3)
Hillu/em H2 WM1-71
hrytliromjcm 1114-07-Kt
riint\clme (5 l<)|(i-XV-3!
C remftbro/ii 125 Ri 2 -3l t-u j
Ibuprutin (15 l
Miconazole |22*'l(i-47-X)
Nortluoxetim.' IX3X') 1 -03-61
Proprjutilol (525-(>6-(t)
Sertraline t7-f>)
lhia!vnJa/i'le i 148-7'J.N)
1 rimelhoprmi 1738-70-51
(1401-69-0)
w'arlann ifil-8l-2i
Pharmaceutical-. ,mJ PctMinul t'.iie Products jl'Pt P>| b> (ius
Chromatography Mass Spectrometry - Selective loti
\intiitorinii iMi'ihua"(il' MS-SIM,<
4-Mclhj Ihtii/) lidinc camphor nr 4-MISC 13fiXo 1 -17-9j
Rett/ophenone j 1 l'i-(>l -•>)
Celcstolide 113I7M1II-I t
GaUixuIidc 11222-1)5-5)
m- loluamide (61K-47-3I
Musk ketone (SI-14-I)
\htsk \\ kite iN 1-15-21
Non\ Iphenol inonucthosy late, homer 1 (27*)S6-3ft-3A)
No)s> Iphenol rnoruxlliox) lale. isomer 2 (279R6-36-3R)
Non; 1 phenyl mtmovllum laic, isomer 3 1279Xt>-36-3C1
1 Iciiierylene ((>197-30-4)
/j-Xtmj {phenol 11114-4(1-5)
f-Uc!} IphennS (1 SU6-2(>-41
Tonalkk- (13DM)2-I in 21145-77-7)
triclosan (3 3X0-34-5)
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PPCP Ftsti Pilot Study Sample Preparation and Analysis QAPP
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3.0 Project Organization
The Office of Science and Technology's (GST's) Standards and Health Protection Division f SI IPD) is
responsible tor overall management of the PPCP Fish Pilot Study, including day-to-day responsibility for
managing various aspects of"the study, SHPD is responsible for managing ail sample collection, data and
laboratory analyses, and data verification (data review) activities. SUPI) is also responsible for day-to-da\
interaction with contractors arid with other federal, state, and local authorities involved in the project.
SHPD has contracted Tetra Tech to provide support for project planning, sample collection, and
procurement and oversight of all laboratory sen ices necessary for this study. SI IPD has also contracted with
CSt" for general technical support, data verification and validation, and data management. To minimize
variability that could arise from sample preparation and anal} sis. SHPD requested that all laboratory activities be
conducted in a single laboratory for the duration of the project. This laboratory must verily the absence of
laboratory contamination for target chemicals during sample preparation, have sufficient capacity to receive and
process all fish collected during the stud}. and be capable of anal) zing each sample while adhering to all quality
assurance/quality control (QA/QC) procedures in an environment that is free from detectable levels of all target
chemicals.
Figure 1 illustrates the project organization and relationships between groups participating in the major
activities to be conducted under this study. Sections 3.1 through 3.4 describe the roles and responsibilities of the
indh iduals involved in stud} activities related to sample preparation and anal} sis. Details regarding roles of
individuals involved in sample collection and handling can be found in the Quality Assurance Project Plan for
Sample Collection Activities for a Pilot Stiulv to Investigate the ()ccnrrenee nj Pharmaceuticals and Personal
Care Products fPPCPs> in Fish Tissue. Section 3.1 of this QAPP describes the responsibilities of EPA staff:
Section 3.2 describes the responsibilities of the Computer Sciences Corporation (CSC) staff: Section 3,3 describes
the responsibilities of Tetra Tech staff; and Section 3.4 describes the responsibilities of staff at the contract
laboratory that will support this stud).
3.1 EPA A fanagement and Staff
3.1.1 OST Director
The OST Director, hphraim King, is responsible for providing financial and staff resources necessary to
meet study objectives and implement study requirements described in this QAPP.
3.1.2 OST Quality Assurance Officer and SI IPD QA Coordinator
The OST Quality Assurance Officer is Marion Kelh. who will be responsible for reviewing ami
approving all Quality Assurance Project Plans (QAPPs). The SHPD Qua!it> Assurance Coordinator is Robert
Shippen, who will be responsible for reviewing and recommending approval of all QAPPs, Additional OST QA
Officer and SHPD QA Coordinator responsibilities include the following:
reviewing and evaluating field procedures.
• conducting external performance and s) stem audits of the procedures, and
participating in Agency QA reviews of the study.
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PPCP Fish Pilot Study Sample Preparation and Analysis QAPP
Revision 0
Date, 19 October 2006
Page 4 of 3 6
Ephraim King
OST Director
Esther Peters
Tetra Tech QA Officer
Leanne Stahl
EPA Project Manager
£
Marion Kelly
OST QA Officer
Robert Shipperr
SHPD QA Coordinator
Leslie Braun
CSC QA Officer
Tetra Tech, Inc. Project Manager
Blaine Snyder
Sample
Collection
Computer Sciences Corporation
(CSC) Project Manager
(TBD)
Data
Review
Database
Development
s
s
Baylor University Co-Laboratory
Project Managers
Bryan Brooks and Kevin Chambliss
Sample
Preparation
i
Sample
Analysis
Sample Collection Team and
Preparation/Analysis Team
Data Review and
Database Development Team
Figure 1. Project Organization and Relationships
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PPCP Hsh Pilot Study Sample Preparation and Analysis QAPP
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Date 14 October 20"! Jf*
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3.1.3 EPA Project Manager
I he EPA Project Manager, Leanne Stahl. reports to the OST Director and is responsible for providing
overall direction concerning the study to the Tetra Tech and Computer Sciences Corporation Project Managers
shown in Figure 1. The EPA Project Manager also is responsible for:
Overseeing the development, approval, and implementation ot'QAPPs for all phases of the PPCP Fish
Pilot Study.
• Communicating study objectives to the contract Project Managers shown in Figure 1.
• Reviewing and approving all major work products associated with the study.
• Providing oversight of all contractor activities related to collection and analysis of samples for this study.
Participating in meetings with the contract Project Managers, other EPA staff, and staff from other
organizations and contractors concerning the study.
• Working with QA staff to identify corrective actions necessary to ensure that study objectives are met.
Reviewing and approving major deliverables related to the analysis of samples collected in this study.
3.2 Computer Sciences Corporation (CSC) Staff
3.2.1 CSC Project Manager
CSC's Project Manager, Erin Salo, is responsible for applying resources needed to ensure that CSC
project deliverables are completed on time, within budget and to client satisfaction. Other responsibilities of the
CSC Project Manager include;
• Working with the EPA Project Manager to address project requirements in this QAPP.
« Communicating project objectives to CSC staff.
Ensuring that all QA procedures described in this QAPP related to data review and database development
are followed during the study.
Monitoring performance of CSC staff participating in this study to ensure the quality, timeliness, and
responsiveness of work performed.
• Reviewing and approving CSC study deliverables for the analytical activities.
Participating in meetings with EPA and/or CSC staff concerning study objectives, schedules, and
concerns.
Providing day-to-day oversight of technical activities performed by CSC staff participating in the study.
Ensuring that all necessary corrective action procedures are documented and implemented in a timely
manner.
3.2.: CSC QA Manager
CSC's QA Manager, Leslie Braun. is independent of the PPCP Study. Ms. Braun is responsible for:
• Assisting CSC's Project Manager with the development and review of this QAPP.
Overseeing the implementation of QA procedures related to CSC tasks that are described in this QAPP.
• Reporting deviations from this QAPP to the CSC Project Manager and assisting in implementing
corrective actions to resolve these deviations.
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1 v 1 Tetra Tech Project Manager
Tetra Tech's Project Manager, Blaine Snyder. is responsible for applying resources needed to ensure that
Tetra lech project deliverables are completed on time, within budget ami to client satisfaction. Other
responsibilities of the Tetra Tech Project Manager include-
• Working with the F.PA Project Manager to address project objectives and develop a project schedule.
• Communicating project objectives to '1 etra Tech staff.
I understanding and implementing the requirements described in the Laboratory Sample Preparation and
Analysis Activities QAIT and the Sample Collection Activ ities QAPP.
Monitoring performance of Tetra Tech staff participating in this study to ensure the quality, timeliness,
and responsiveness of work performed.
» Monitoring performance of the contract laboratory participating in this study to ensure the quality.
timeliness, and responsiveness of work performed.
Participating in meetings with F.PA and/or Tetra Tech staff concerning study objectives, schedules, and
concerns.
• Providing dav -lo-dav oversight of technical acti\ ities performed b\ Tetra lech staff participating in the
PPCP Fish Pilot Study.
Ensuring that all necessary corrective action procedures are documented and implemented in a timely
manner.
3.3.2 Ten a "lech Quality Assurance Officer
Tetra lech's Quality Assurance Officer. Hsther Peters, is responsible for:
• Implementing the QAPP describing the analytical activities for the PPCP Fish Pilot Study.
• Participating in meetings with HPA and/or Tetra 1 ech staff concerning study objectives, schedules, and
concerns.
• Pnn iding oversight of technical activ ities performed by the analytical laboiatory or delegating litis
responsibility to a qualified Tetra Tech professional.
• Ensuring that all necessary corrective action procedures are documented and implemented in a timely
manner.
3.4 ("ontrua Luh> trutnry
All sample preparation and chemical analyses in this study will be performed by an academic research
team at Bay lor University 's Center for Reservoir and Aquatic Systems Research (Hay lor). Detailed requirements
for sample preparation, tissue analy sis. and data management are described in Sections 10.0 and 16.0. Due to the
complexity of this study, a Laboratory Project Manager will be available and dedicated to the project. Sections
3.4.1 and 3.4.2 below describe the responsibilities of each of these staff members.
3.4.1 Laboratory Project Manager
Bryan Brooks ami Kevin Chambliss will assume the roles of co-Project Managers for Baylor I 'niversity.
t'hey will be responsible for the overall technical laboratory activities under subcontract to 1 etra Tech. 1 hesc
individuals will be responsible for planning, conducting, and supervising all laboraton activities to support the
PPCP Fish Pilot Study.
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PPCt* Fish Pilot Study Sample Preparation and Analysis QAH»
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3,4.2 Laboratory QA Manager
Kevin Chain bliss will he responsible fur quality assurance I QA) of all sample preparation and analysis
activities performed under the laboratory subcontract. He will review progress, evaluate results, report problems,
and implement corrective actions approved by Tetra Tech and L1PA.
4.0 Quality Objectives
4J Project Quality Objectives
The PPCP Fish Pilot Study will allow HPA to obtain data on the occurrence of certain pharmaceuticals
and personal care products in fish tissue. Hcn\e\er. there are sources of uncertainty associated with the study,
including the compositing and subsampling offish samples ant! variability in the laboratory analysis process. The
combined variability introduced by compositing fish samples, sub-sampling the composites for analysis, and
laboratory analy sis can be considered the "index" variability. Rather than prescribing a tolerable limit to "index"
variability, the approach for this study is to:
(1 i Prescribe sample collection procedures that would minimize "index" variability (e.g., through properly
trained sampling crews and standardization of collection methods).
(2) Employ a sample compositing and sub-sampling scheme that will ensure low levels of variability.
131 Select analytical methods capable of providing the best measurement performance {e.g.. highly sensitive
measurement systems with relatively low bias and acceptable precision).
(4 i Require the analytical laboratory to satisfy certain performance criteria for the [imposed analytical
methods.
4.2 Measurement Quality Objectives
As mentioned in the previous section, "index" variability can be minimized by selecting analytical
methods that provide the best available measurement performance, as gauged by standard data quality indicators
(DQls), The methods to be used in the PPCT Fish Pilot Study reflect state-of-the-art technology that should be
able to meet certain performance criteria demonstrated to be attainable in well-operated, controlled laboratory
environments. These criteria meet HPA's needs for data quality. Therefore, the general measurement quality
objective for this study is to satisfy method-specific performance criteria. The DQls in this plan are estimates
based on available data during method demonstration, and Baylor's methods have been under continued
refinement throughout the planning period, Therefore, it may be required {following analy sis of actual study
samples of fillet and liver tissues) to assess performance through development of control charts developed during
the study period to gain a better understanding of measurement system performance. This assessment measure is
included in the laboratory procedures to preserve data usability in the event of frequent outliers. The following
subsections and Section 11 of this QAPP provide details on how standard DQls will be monitored and controlled
in this study,
4.2.1 Precision
Precision is the degree of agreement among replicate measurements of the same property, under
prescribed similar conditions |3|. It can be expressed either as a range, a standard deviation, or a percentage of
the mean of the measurements (e.g.. relative range or relative standard deviation),
ideally, precision is measured by subdividing samples in the field, preserving and numbering each split
separately, and sending the aliquots to the analysis laboratory as "blind" duplicates. In this study, however,
samples must be homogenized, and composited in a strictly controlled, clean laboratory1 environment. 1 herefore.
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FRCP Fish ViUi'i Stud> Sample Pn-pdwuon »snJ AujInn^ i^APP
RcMnVn u
H.tU* N October 2w<,">
P u;' S of
she laboratory w ill prepare ami analy /e duplicate or duplicate spike samples to assess the index variability
associated with the subsampiing. extraction, and analytical portions of the measurement sy Mem, The stud)
measurement quality objective (MQO) for analytical precision is that results from 90% of these duplicates agree
within 50% for values greater than 5.\ the project quantitation limit (PQI.i and that Wi of those duplicates agree
within 11)0% for values less than 5s the PQ1..
In addition to the use of these duplicates, the laboratory will employ a series of hPA Office of Water
lOW ) laboratory QC measures (e.g.. MDL studies. laboratory control samples, and matrix spiked samples) that
provide information about the precision associated with various components of the analytical process. For
example, duplicate or spiked duplicate pairs will be prepared and analyzed to assess analytical precision front the
sample measurement process. 1 hese QC elements and associated requirements are described in more detail in
Section 1 I (Quality Control Requirements) of this QAPP. It should be noted that performance criteria for this
stud} are based on overall data quality. and failure to meet am single laboratory precision measure does not
automatically imply the data are unacceptable for use in this study. Laboratory QC measures are used to monitor
and control precision in real time so that overall precision goals are met. Details regarding the data quality
assessment process governing use of data in this study are given in Sections 16, 17, and Ul.
4.2.2 Bias
Bias is the sy stematie distortion ofa measurement process that causes errors in one direction [ 3 J. In (his
study, bias from the analytical process will be measured by preparing and analyzing laboratory-spiked field
samples with 1»the chemicals of interest (i.e. matrix spike samples), 2) internal standards, and 5) surrogate
chemicals that are expected to behave in a manner similar to the target chemicals. 1 lie measurement quality
objectiv e for overall analytical accuracy in this study is for 80% of the laboratory-spiked Held sample results to
fall within the acceptance criteria specified for each method.
In addition to the use of laboratory -spiked field samples, the laboratory will employ OW's laboratory QC
measures (e.g.. instrument calibration standards, method blanks, and laboratory1 control samples) that provide
information about the bias associated with various components of the analytical process. These QC measures and
associated requirements are described in more detail in Section 11 (Quality Control Requirements) of this QAPP.
It should be noted that performance criteria for this study aie based on overall data quality, and failure to meet any
single measure of bias does not automatically imply the data arc unacceptable for use in litis study. Laboratory
QC measures are used to monitor and control bias in real time so that overall precision goals are met. Details
about the data quality assessment process governing use of data in this study are given in Sections 16, 17. and I4).
4.2.3 Accuracy
Accuracy is a measure of the closeness of an individual measurement or the average of a number of
measurements to the true value. Accuracy includes a combination of random error (precision) and systematic
error (bias) components that result from sampling and analytical operations. Accuracy is determined by analyzing
a reference material of known pollutant concentrations or by reanalyzing a sample spiked with a known amount of
pollutant. |3j
In this study, certified reference materials (CRMs). h7ich iiiw/Aift/e, will be sent to the laboratory annually
to assess bias. CRM results will be pooled at the end of this study to determine overall study accuracy.
4.2.4 Sensitivity
Analytical sensitivity is defined as the minimum concentration ofa chemical above which a data user can
be reasonably confident that the chemical was reliably detected and quantified. For this study, the method
detection limit i MDL i and the PQI, will be used to define the sensitivity of each measurement process for
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PPCP Fish Pilot Study Simple Prepanttion mi Analysis QAPP
lies njoi 1
Date N < * o! ^
qualification purposes. Since both measurement methods employ mass spectral determinations, am positive
sample result that yields identifiable spectra will be reported.
The MDL in defined as the minimum concentration of a substance that can be measured and reported with
99% confidence thai the chemical concentration is greater than zero. Hie EPA procedures that will be used for
determining the MDI. are described in 40 CFR 136. Appendix B. [4|
The PQL is defined as tlte lowest concentration at which the entire analytical system must give a
recognizable signal and acceptable calibration point tor a chemical. It is often equivalent to the concentrations of
the lowest calibration standard analyzed by a specific analytical procedure, assuming that all the method-specified
sample weights, volumes, and processing steps have been employed, for this study, additional calibration
standards below the PQL will he included in the instrument calibration, however since spectral identification will
be used in the analysis of the sample data, ail positive sample results will be reported. The calibration standard
range will only define the required qualification and the reporting limits lbr non-detected sample values.
Idealh. the stnah tical methods to be used in this study will have MDl.s that are below all levels of
concern for the target chemicals. The measurement quality1 objective (MQOt for detectabilin is that |0(t% of the
samples be analyzed h\ the laboratory and reported down to the MDL-levd, Again, since both measurement
methods employ mass spectral determinations, any positive sample results will be reported, regardless of their
relationship to the MDf or the PQL.
4.2.5 Representativeness
Representativeness is a measure of the degree to which data accurately and precisely represent a
characteristic of a population parameter at a sampling point ot for an environmental condition. It is a qualitativ e
term that is evaluated to determine whether data appropriately reflect the media and phenomenon measured or
studied [3]. This study was designed to provide general information on the occurrence of certain pharmaceuticals
and personal care products in fish tissue. A description of this design is given in reference [11.
4.2.ft Completeness
Completeness is defined in terms of the percentage of data that are collected and deemed to be acceptable
for use in the study. Three measures of completeness can be defined, as follows:
Sampling Completeness: The number of valid samples collected relative to the number of samples
planned for collection:
Analytical Completeness: The number of valid sample measurements relative to the number of valid
samples collected; and
Overall Completeness: The number of valid sample measurements relative to the number of samples
planned for collection.
The analytical completeness goal in this study is to obtain valid measurements from 95"o of the valid
samples collected. In theory, however, a lower level of completeness can still lead to a valid study. The effects of
insufficient completeness will be evaluated during the data analysis phase of this study.
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I'K't' 1 ;nIi film SUaK SampL* I'rcparaiinn ami Vn.ilvM-. t.> VII'
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4.2.7 Comparability
Comparability expresses the confidence thai two data sets can contribute to a common analysis and
interpolation 13], The study will require the collection and analysis of numerous samples from various parts of the
country. To ensure comparability of data generated during this study, EPA will:
• limpkn standard operating procedures for sample collection j 1|.
• Maintain a consistent field sampling team leader j 1 ],
• Use one laboratory for the preparation (weighing, compositing, homogenizing, and dividing tissue into
aliquotsj and analysis of samples t i.e.. Ba\ lor L'niversit}t.
• I Sse one method for all analyses of a specific target chemical (Table 1 h
• Specif) method detection limits and QC acceptance criteria thai must be met throughout the study
(Appendix A}.
• Specify data reporting units and analytical procedures that must he used throughout the studs
(Section 10.0), and
• Use a standardized data qua I in assessment process (Section 19,0),
5,0 Special Training Requirements
Each Meld Sampling Team is required to ha\e the neeessar) know ledge and experience to perform all
Held activities. This includes both knowledge and experience in the collection and identification of fishes and in
the use of fisheries sampling gear specified for the study. It also includes training in project-specific sample
collection and handling procedures. The field sampling crews will be composed of contracted biologists with a
strong technical background in fisheries sampling activities. Each Meld Sampling Team will consist of one
experienced fisheries biologist (that must have experience with the array of fisheries sampling gear types to be
used) and field staff to assist with sample collection and processing. At some sites, the contracted biologists may
enlist the aid of VAVTP staff, state fisheries biologists, or other local personnel to provide logistical support and
assist with sample collection. In these cases, each participant will attend an on«Mte training session led by the
Tetra Tech Task Leader (an experienced fisheries biologist).
Hie laboratory project team will be comprised of senior research associates, complimented with enough
technical staff to ensure sufficient oversight and supervision, as well as adequate skills to maintain consistent
measurement s\ stem performance throughout the stud}. Required "skills" will include education and experience
in using the procedures and instruments employed in this study.
Because the 1 PA National Lake Fish Tissue Stud) (NLF I'SJ standard data review approach will be
implemented during this stud) (and customized to meet stud) needs), all CSC staff responsible for reviewing data
must be experienced in performing data rexiews. trained to review data in accordance with XL! TS's general data
review guidelines, experienced in reviewing data generated with the instrumentation that will be used in this
stud}, and familiar with the performance ctiteria and MQOs established for this stud}. f.ach reviewer also must
have read and understood the performance criteria and MlJOs applicable to this stud}.
6.0 Documentation and Records
On!) documentation and records relevant to sample preparation, analysis and data rev iew are discussed in
this section. Documentation and records related to sample collection can be found in reference j 1).
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{'K'P l-ish Ihln", Stikh Sample Prirp,nation and An.ih sis n,\PP
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6.1 Sample Preparation Records
The laboratory will document sample preparation information in notebooks maintained by laboratory
staff. Documentation related to sample preparation includes:
» Copies of the Chain-of-Custody Form-* documenting shipment of samples from the field. (Chain-of-
Custody forms are standardized, EPA-generated sample tracking forms.) (11
• I>(H;umentation of sample storage conditions (daily temperature records for sub-zero storage).
» Documentation of daily balance verification.
Documentation of standard and reagent preparation, including material suppliers, lots, and purity; amount
used (mass or volume) and final volume; indemnification of solvent or diluent; final concentration (where
applicable for standards); expiration date (considering the shelf life of all intermediate and precursor
solutions); and the preparer's initials and date of preparation.
• Standard operating procedure [5J for sample preparation, compositing, homogenization and sub-sampling.
Sample preparation records documenting the following information for each composite sample prepared;
* Identification (initials'date) of the person preparing composite samples l filleting, dissecting,
homogenizing, and preparing aliquots);
~ Verification of information about individual fish included in samples used to prepare the
composite (i.e.. weight and length):
~ Nine-digit liPA composite number (as assigned by 1'etra 1 cell, see Section 6.3. Data
Compilation. Review, and Validation Records)
for each analytical fraction (l.C \!S/\tS, GC. MS. and lipids), documentation of the following sample
preparation procedures:
« Sample mass used in anah sis.
• l:\traction date.
Surrogate and matrix spiking solution identification and volumes used.
• Reagent identification and volumes (minimally initial and final volumes, unless the laboratory identifies
reasonable benchmarks or procedural increments which ma} assist in troubleshooting in the event of
measurement system failure), and
• Relevant observation made during sample preparation.
ft J Analytical Records
Bay lor will at a minimum be required to do the following with respect to documentation and record
keeping:
Maintain daily records of storage condition for samples from the pilot study I-2U C! throughout sample
analysis and storage.
« Submit summary reports of all analytical results. These summary reports must be provided in both hard
copy and electronic format.
• Submit hard copies of all raw data. Raw data will include items such as quantitation reports, strip charts,
spectra, bench sheets, and laboratory notebooks showing tare and sample weights, and sample volumes.
Raw data also will include any other information that would allow an independent reviewer to verify the
calculations performed and trace the final results to the raw data. The laboratory will be required to
clearly identify each data element in their data package.
» Submit a written report that details any problems encountered during analysis of the samples. The written
report also should include comments on the performance of any pari of a method.
• Obtain pre-approval of any modifications to the analytical techniques specified and submit detailed
explanations of the changes implemented.
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i'Ps'P I'aIi i'llo: StuJ', Somi-L' I'rcparafwti and Analysis QAPP
Kt*\ 1M,C '
D.ac I'1 Octohe!
Page ! 2 ot >-
• Report results consistently in the reporting units (e.g., ng'kg or percent I specified in the method
(Section 10.1)),
» Submit chain-nt-cusiody and other sample tracking information,
6.3 Dutu CimipHalioti, /u-riVtc unit Valhiilii')} Rcj>>i\h
Tetra Tech and CSC will create and maintain study files that document data compilation and review,
which will include separate files for each "episode" (sampling event, site). The field sampling teams will be using
a nine-digit field-assigned composite sample ID number to uniquely identity each composite, l etra Tech will
pro\ ide the laboratory with a series of five-digit HPA sample numbers that will be assigned to each simple after
compositing and aliquotting. The nine-digit fish composite sample identification code will include:
State of collection 12 character abbreviation)
Year of collection (2 number abbreviation)
• Site identification (3 character code from Appendix B)
Composite number (1 through 6)
• Tissue fraction to be completed by laboratory ("I." for liver or "1" for fillet)
letra Tech will prepare and maintain the following PPCP Fish Pilot Study records:
• A cop) of this QAPP and the sample collection activity OAPP;
• A copy of the laboratory" statement of work:
• A summary page that documents the Episode Number, [he sample numbers assigned to the hpisode, and
the date of sample collection and shipment;
fhe name, address, phone number and primary contact of the laboratory preparing and analyzing samples
in the episode;
• A copy of each Chain-of-Custody form prepared and sent with each sample;
• A list that cross-references the composite sample identification number assigned to each sample by the
sample collection team against the live-digit HPA sample numbers assigned by the laboratory after
compositing, homogenizing, and aliquotting;
• A log of ail verbal communication with laboratory staff, sampling personnel, and EPA staff regarding the
staturs or problems with the particular Episode'1 samples:
Copies of all written correspondence with laboratory staff, sampling personnel, and f.PA staff regarding
the status or problems w ith the particular f.pisode/,samples: and
• All records submitted by the laboratory.
CSC will develop and maintain the following PPCP Fish Pilot Study records;
• Complete records regarding the data review process, including a final copy of any written data review
assessments and the final data submission from each laboratory; and
A database of final analytical results associated w ith each field sample,
CSC will provide copies of am data review assessment < if necessary1 i and a copy of the final database to
HPA Sand other appropriate stakeholders) after the data reviews are complete. 1 etra Tech will retain the master
file containing each episode tile, complete copies of each laboratory data submission (including the final
laboratory summary reports), and other records listed above, Tetra Tech will provide copies of these materials on
an as-needed basis to HPA upon request.
All documents and records prepared for this project will be maintained by Tetra Tech and CSC during the project
and retained for a period of three years following completion of the project, HPA will follow federal requirements
for ret en lion of project records described online at w w w ,epa,go%, records'.
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PPCP Pish Pilot Study Sample PieparalxM and Analysis QAPP
Res ".ten i I
I)j*,c I'H Mntvr Jiiito
7.0 Sampling Process Design
1 he objective of She PPCP Fish Pilot Study is to imestigate the occurrence oi'a broad suite of PPCPs t.W
chemicals) in the tissue of harvestablc sized adult freshwater fish that are typically consumed by wildlife and
humans, In so doing, the studs w ill provide the follow ing t\ pes of information;
• the potential for the target PPCP chemicals to bioaceumulate in fish muscle and Iher tissue, and
data lo answer questions concerning the occurrence of these chemicals in fish and the potential
for human exposure through fish consumption.
for the purposes of this study design, the target population will he effluent-dominated streams associated
with WW TPs within the contiguous I Suited States. I he streams in this study must have a viable llsh population
of a resident species which will spend most of its life stages within the effluent-dominated waters. A total of Use
locations will be sampled, plus one reference site.
7.1 Sample Type
To meet the study objectives, the PPCP Fish Pilot Study will include composite sampling of fish fillets
and llsh livers from each sample site. Six composite samples will be collected at each site. At least three adult
individuals will be collected per composite such that the combined bioinass of the specimens will be adequate to
provide sufficient tissue for analysis of the group of target chemicals. It has been determined that at least 30
grams of edible fillet tissue and 10 grants of liver tissue will be required front the composites to allow for anahsis
of all target chemicals. Based on the recommendations of i 'SHPA's Guidance for Assessing Chemical
("tmtamiihinf Data for Use in Fish Advisories. Volume 1: Fish Sampling ami Analysis Third Edition f t 'SHPA
2000) [5], fish used in a composite sample must meet the follow ing criteria:
• all be of the same species.
• satisfy any legal requirements of harvestablc size or weight, or at least be of consumable size if
no legal harvest requirements are in effect.
• be of similar si/e so that the smallest indiv idual in a composite is no less than 75% of the total
length ot the largest individual.
• be collected at the same time (i.e.. collected as close to the same time as possible but no more
than I week apart) (Note: 'This assumes that a sampling crew was unable lo collect all llsh needed
to prepare the composite sample on the same day. If organisms used in the same composite aic
collected on different da\s (no more than 1 week apart), individual fish will be frozen until all the
llsh to he included in the composite are available for deliver} to the laboratory.), and
• be collected in sufficient numbers (at least 3 per composite) and of adequate si/e (at least 3
harvestable si/e adult specimens that collective!} will provide greater than 30 grams of edible
tissue and 10 grams of liver tissue) to allow analysis of recommended target chemicals.
Individual organisms used in composite samples must be of the same species because of notable
differences in the species-specific bioaecumulation potential. Accurate taxonomic identification is essential in
preventing the mixing of close!) related species with the target species. I aider no circumstance should
individuals from different species be used in a composite sample.
Pish for this project are being sampled from wastewater treatment plant effluent-dominated streams.
Reconnaissance may indicate that appropriate llsh are available at a site, hut it is possible that inadequate numbers
of target species meeting the sample criteria will be found when the site is sampled. If this situation were to
occur, the Field Sampling Leader will contact the USHPA Project Manager to discuss possible options, which
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PK ? Ftvii 1'iliv, Su:d\ Sjn.pk' Prt-p.iMtioii ,tnj Ar^Kss fJ\PP
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IKux 14 ^
include collecting a different si/e or species of fish, sampling a site farther downstream, or sampling an alternate
location.
~ J* Sampling Perinci
Field sampling will be conducted during the period when water and weather conditions are conducive to
safe and efficient field sampling. For this study, the sampling period is from summer to early fall, since lipid
content is usually highest and water levels are usual!) lowest at that time. Where possible, sampling should not
occur during the spawning period of the particular target species heing sought. With these recommendations in
mind, and considering the geographic extent of the study area (i.e.. range of latitudes and longitudes) the field
sampling period will begin in August and last through November. Am adjustments to this schedule must be
approved by the USF.PA Project Manager.
~ J Sample Frame
for the purposes of this stud)', the target population will he effluent-dominated streams which serve as
receiving waters for WW IPs within the contiguous United States. WW I Ps using primary. secondary. and
tertiary treatment methods and discharging to a stream or river are included in the sample frame. The streams in
this study must also have a \ iable llsh population of a resident species that is subject to effluent exposure tor most
of its life cycle.
~ •/ Si'Lvtitm of Sampling Sites
Sites were targeted I Appendix B) in mid- to large-si/ed cities representing diverse geographic regions of
the country. Information on WWII* design capacity, a\erage discharge, and in-stream waste concentration was
collected for each candidate site through research of publicly accessible data (i.e.. NPDF.S permits, WW IP
websites, and L'SCiS How datai and through phone calls to state officials and permitting agencies. Once this
information was compiled, the list of candidate sites w as used by the EPA project team to select a group of
priority sites. The site selection criteria that were used are:
High effluent (low versus ambient flow
High population density
Large fraction of elderly residents
Large volume of PPC P sales/consumption (higher income brackets as surrogate)
Fish availability
In addition, fisheries information was compiled for each candidate site. This was accomplished by
rev iewing published fisheries reports and obtaining first-hand information from state fisheries personnel. The site
list was further narrowed down to 12 priority sites which could potentially support (via availability of resident
species and tissue biomassj the intended sampling. The five top priority sites were selected from the 12 priority
candidates to icpresent diverse geographic regions of the country.
8.0 Sampling Method Requirements
Sampling method procedures and requirements are detailed in the Sample Collection Acti\ ities QAPP [ 1 j,
Some of the key requirements are summarized below,
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PPCP Fish Pilot Study Sample Preparation and Analysis QAPP lsl(l„ t!
Date I ^ October 20J">
Page 15 of
8.1 Targes Species
A single species of fish will be collected from each site. Suggested target species are listed in the Sample
Collection Activities QAPP (Table 3) in order of preference (adapted from [5]). Additional target species may be
added to the list of preferred targets on an as-needed basis, following discussion with the USEPA Project
Manager and/or the Tetra Tech Project Manager. For a detailed description of target species criteria, refer to the
Sample Collection Activities QAPP | I j.
8.2 Composite Sampling
The PPCP Fish Pilot Study will involve composite sampling offish. Composite samples are cost-
effective for estimating average tissue concentrations of target chemicals in target species populations, and
compositing ensures adequate sample mass for analysis of all target chemicals. Six single-species composites
will be collected front each target stream, bach composite will consist of at least three fish of adequate size (i.e.,
adult specimens that collectively will provide at least 30 grams of edible tissue and 10 grams of liver tissue) to
allow analysis of the target chemicals. Fish retained for a composite sample must meet the criteria listed in
Section 7,1, For a more detailed description of composite samples, refer to the Sample Collection Activities
QAPP [I].
8.3 Sample Collection
The field objective is for sampling teams to obtain six representative composite samples from each stream
selected lor the PPCP Fish Pilot Study. Prior to sampling, field teams will determine habitats suitable for target
species, then sample those habitats in the stream reach located downstream from the WWTP outfall. Sampling
teams will be equipped with an array of both active and passive gears to ensure the collection of the desired target
numbers and species of fish. Selection of the most appropriate gear tvpe(s) for a particular target stream will be at
the discretion of the experienced on-site fisheries biologist. For a detailed description of sample collection
methods, refer to the Sample Collection Activities QAPP [1],
9.0 Sample Handling and Custody Requirements
Chain-of-Custody Forms will be used for sample documentation and tracking from the field to the sample
preparation and analysis laboratory. Detailed sample handling and custody requirements are described in
Sections 9.1 and V.2.
Field personnel are responsible for properly identifying and handling the samples as described in
Section 9.1. Laboratory personnel are responsible for receiving and preparing the samples as described in
Section 0.2. All parties involved in sample handling and preparation are responsible for using protocols designed
to preclude contamination.
(/ / Field Requirements
A more comprehensive description of field sample handling requirements can be found in the Sample
Collection Activities QAPP [1], Key requirements are summarized below.
Species should be identified by experienced personnel as soon as fish are removed from the collection
device. Non-target species or specimens of target species that do not meet size requirements will be returned to
the water. Individuals of the selected target species will be rinsed in distilled water to remove anv foreign material
from the external surface. Each fish within the selected target species will be measured and weighed to determine
total body length (mm) and total body mass (g). After initial processing, each fish found to be suitable for the
composite sample will be assigned a specimen number that can range from one to three (or four). This number
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PFCP Fish Pilot Study Sample Preparation and Vuk <•!« y\W
Kci ixion 0
EXr.c i-'n, :->txT :*Ki
Face If- >•:,»
will identify each fish within its respective composite. A nine-character composite sample identification number
consisting of the two-character state abbreviation, two-number \ ear abbre\ iation. three-letter site identification
code, composite number (i -6). and tissue t\ pe l*"F" or "I." for fillet or iiverj will be assigned b\ the field learns
for each composite collected. The composite sample identification number and information about individual fish
specimens will be recorded on field Record Forms.
Each llsh selected for the composite sample will be individually wrapped in cleaned (rinsed in
methylene chloride and dried at 45t)r'C for a minimum of one hour) extra heavy duty aluminum foil. Kach
individual!} wrapped fish will be placed into lood-grade plastic tubing and sealed on each end with a m ion cable
tie. I'he llsh sample identification label containing, the specimen number, composite sample identification number,
stream or river, and date of collection will be attached to the outside of each sample using one of the nylon cable
ties used to seal the plastic tubing. All of the foil-wrapped and plastic tubing-sealed specimens intended for a
composite sample will he kept together when possible in a large plastic bag in the same shipping container (ice
chest) for transport.
Once packaged, samples should be placed on dry ice for shipment. I he sampling personnel must ship the
samples with enough dry ice to ensure temperatures of *-20°C during shipment. Dry ice sublimes at a rate of
approximate!} ''1- lb per hour. Therefore, a minimum of ifi lbs of dry ice is recommended to ensure that the fish
remain fro/en for at least a 48-hour period, in case of shipping problems. If space, funds, and logistics permit,
50 lbs of dry ice is preferred,
Samples will be shipped \ia Federal Express. using priority o\ernight ser\ice. In addition, a member of
the field staff should telephone the laboratory to alert them about the anticipated delivery time of the samples.
Field collection staff should avoid shipping samples for weekend delivery to the laboratory unless prior plans for
such a delivery have been agreed upon with the laboratory. The Held sampling team will ship one copy of the
Field Record Form to the laboratory. I pen arrival of the samples, the laboratory will contact Tctra Tech to
confirm that the samples are in good condition.
y.J Liibuntltny Rcijaiivmems
Upon receipt of the llsh samples, the laboratory will record the arrival time on the Chain-of-Custody
Form, I'he laboratory will document any observations regarding the shipment te.g., torn or damaged packaging
and'or evidence of spoilage) on the Chain-of-Custody Form, as well as on the sample preparation records.
The laboratory will decontaminate any filleting instruments and surfaces as appropriate. Laboratory staff
will measure and weigh each fish, rinse the fish with distilled water, remove scales, fillet (including skin and belly
flap), remove (and weigh) the liver from each specimen, composite tissue from all specimens for each tissue
fraction, and homogenize the tissue following the procedures specified in f \V. Emiwtmwniul Protection Agency
tl'SEP.i 2>)tKh (iiiUiitk-c fttr Assessing Chemkui ('onummunt Ihihitui ! >c m Fish Advisories, Volume I Fish
Sampling and Analysis, Third Edition. (FPA 823-B-IKMI07! [5|, All samples will be composited using the
"batch" method, in which like tissue from ail of the individual specimens that comprise a sample are
homogenized together, regardless of each individual's proportion to one another (as opposed to the "individual"
method, in which equal weights of each specimen are added together).
After compositing, the laboratory will prepare the number of aliquots from each composite sample as
needed and appropriate for PPCP f ish Pilot Stud} anah tieal methods and QA procedures. Each aliquot will be
placed in an appropriately pre-c leaned glass jar with a FEP-lined cap. The laboratory will label each sample
container with the nine-digit composite number and the five-digit FPA sample number (both assigned by Tetra
Tech) and appropriately store the samples at -20' C until analysis. The laboratory will store am leftover
composite sample in a solvent-rinsed glass jar labeled with the nine-digit composite number and sealed with a
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PP(T f'lsh PiU't ^UkK Sample Prvjw.nion arid An.ih sis QAPP
Kcv ivon ''
Udte f° October 20i^
IVjX ' 7 of fa
foil-lined plastic cap labeled with the nine-digit composite number. 1 he sample must be maintained at -20 C
until archival in a sample repository designated by EPA.
10.0 Analytical Methods Requirements
As indicated in Table 1, the target chemicals can be measured using HPI .C-MS'MS and C1C-MS
methodologies. Since no established 1-PA methods exist tor the target cheniieals. they will be measured using
current literature techniques modified to include many of the KPA 600-sertes and SW846 QA/QC elements (see
Section 11.0). Sections 10.1 and 10.2 summarize the methodologies that F.PA expects to use in the PFCP Fish
Pilot Study.
1(11 PP( 7\ by HPI ('-MS MS
Baylor's current method for determination of"select pharmaceuticals in fish tissue by High Performance
Liquid Chromatography -Tandem Mass Spectrometry (HPI.C-MS VIS) includes sample extraction and
concentration, followed by analysis by reverse phase HPI.C-MS'MS lor detection and quantitative measurement
of target chemicals. Due to significant matrix effects for a number of chemicals, external calibration is not
appropriate for quantitative determinations using this method. Instead, standards are prepared by spiking known
concentrations of the target chemicals into "clean" fish tissue, and all standards are subjected to the entire sample
preparation procedure prior to analysis, Baylor's method was developed and has been used to support aquatic
systems and resources research and investigations however, the method continues to evolve in its use and
practical application. During the course of this pilot investigation, Baylor will be developing a detailed method
SOP that will follow the basic requirements described in Guide lines ami Formal for ,\A'{hods i<> he Pn>/v>.W at
41) i "FR Parts 136 or Pari 14!. EPA XJi July 1996 and the description in EPJ's (riddance tor
Preparing Shindtird Operating Procedures fSOP.s) EPA {J.l Xi-6, EPA 24(1 B-01 01)4, March 2001, The final
method SOPs will include any requirements for specialized equipment maintenance or corrective action beyond
those described in the laboratory's routine procedures and instrument manufacturers' instructions which may arise
due to the unique analy te and matrix combination measurements being performed.
10.1.1 Reference Tissue Specimens
L'ntil such time as the PPCP fish Pilot Stud} sampling program is able to supplement supplies. Bay lor
will continue to use their own control matrix supply. Fish from the genus Lepomis were collected from Clear
Creek (Denton, FX. USA) to serve as control samples in previous work, and remain Baylor's source of control
matrix. Clear Creek is not impacted by effluent discharges and is routinely used as a local reference stream by the
City of Denton. Texas Watershed Protection program.
10.1 2 Sample Preparation
All tissue specimens are prepaied and extracted using the following procedures. Muscle and liver tissues
are dissected, composited, and homogenized using standard procedures described in I'SEPA's Guidancejar
Assessing Chemical Contaminant Data for I 'se in Fish Advisories, J 'of tone f: Fish Sampling and Analysis. Third
Edition (I'SLPA 2000). Care must be taken during homogeni/ation to ensure the sample is uniformly mixed and
to ensure minima! loss of tissue mass, follow ing homogeni/ation. approximately 1 J) g of control tissue
homogenate is prepared for each calibration standard, blank and blank spike, along w ith 1.0 g of fish sample
homogenate (breach of the samples and sample QC (duplicates and spikes). Calibration standards are spiked
with multiple le\els of target chemicals and surrogates to facilitate multipoint calibration for each of the target
chemicals and for the laboratory" QC spikes. Liach sample and QC aliquot is also spiked with a known amount of
surrogate spike, and laboratory" blank spikes and spiked samples are further fortified with target chemicals. The
spiked blank is at the project quantitation limit, while the spiked sample is equivalent to the upper third of the
calibration range. Internal standards 7-aminoflunitrazapam-D? fESM, fluoxetine-!)6 (ESI-! and ibuprofen-
-------
'l} F;sh 1'ikii S:uJ\ V/urie Prep„.:,iL*>rt ^rJ, %^.isv s> \i \pfv
liv\
D.i'.v hM
Page IK iw
propionic 13C3 (HS1-) are added to each field. QC. and calibration sample. Calibration samples and matrix
spikes are also prepared by spiking she mixture with variable ainounis of pharmaceutical standards.
Samples and standards are then combined with 4 ml. extraction solvent (1:1 mixture of 0.1 M aqueous
acetic acid and methanol) in 20 ml horosilicate glass vials, shaken vigorously, and mixed on a rotan extractor for
five minutes. Following extraction, -1 ml. extraction solvent is used to quantitatively transfer residues (with
rinsing) into individual 50 mL centrifuge tubes. The samples, caiibiation standards, and QC samples are then
centrifuged at 16.000 rpm lor 40 min at 4 l,C. the supernatant transferred into clean glass culture tubes, and the
solvent is evaporated to drv ness under a stream of nitrogen at 45 CC. Samples are reconstituted in 0.5ml. of water,
sonicated for I min, and filtered prior to analysis.
10.1.3 1IPI .C-MS'MS Allah sis
Baylor uses a Varum ProStar Model 210 binarv pump system and a Model 410 autosampler for all
analyses. For each calibration standard. QC sample, and field sample. 10 ul are injected onto an Extend-CIS
(Agilent leehnologies, Palo Alto, C'A) guard cartridge measuring 12.5 mm ,\ 2.1 mm (5 (im. 80 A), which is
serially connected to a 15 cm 2.1 nun (5 um. 80 A) Kxtend-C 18 column for separation using a non-linear
gradient program of 0.1% {vwi formic acid in water and 100% methanol at 350 ,uL*'min and 30 °C. The gradient
profile yields chromatographic conditions suitable for separation of the 24 target chemicals in approximate!) 50
minutes. ! Muted chemicals are monitored by VIS'MS using a Varian model 1200L iriplequadrupole mass analy/er
equipped with an electrosprav interlace (LSI i.
To determine the best ionization mode (ESI t or -) and optimal MS/MS parameters for target analytes,
each drug was independently infused into the mass spectrometer as a 1 fig ml. solution in U.1% t v\) formic acid
at a How rate of 10 jaL/min. All analytes were initially tested using both positive and negative ionization modes
while the first quadrupole was scanned from m. r 50 to [M * 100], This enabled identilkalion of the optimal
source polarity and most intense precursor ion for each compound. Once these parameters were defined, the
collision energy at the second quadrupole was varied, while the third quadrupole was scanned to identify and
optimize the most efficient MS MS transition for each compound. Additional instrumental parameters held
constant for all anal) tes were as follows: nebulizing gas, ]y at (i u psi; drying gas. V at 19 psi; temperature,
300 °C; needle voltage. 5000 V: declusiering potential, 40 V; collision gas. argon at 2.0 mTorr.
The resultant retention time profile and identification of precursor and quantitation ions are indicated in
Table 2, Quantitation and qualifier ions were selected based on full-scan analyses of commercial standards and
t) pically represent the most abundant fragment ions for each compound. Sample anal) ses are evaluated using an
internal standard quantitation method. Internal standard calibration assesses the response of a target chemical in
the reference material against the response of an internal standard solution added prior to analysis.
10,2 PPCPs by (ii '-MS SfM
Ba\ ior's Deierminaiitm of Select Pcr.snnui1 'ure Products in Fish Tissue hy (his Chr,iniuto^rupln•- Xktss
Spectrometry (G( '-MS) provides procedures for sample extraction, clean-up, and concentration, as well as gas
chromatographic conditions for detection and quantitative measurement of target chemicals. While matrix effects
are commonly encountered in the analysis of fish tissues, experimental!) deriv ed data did not demonstrate a clear
advantage toward the extraction of standards. Therefore, this method includes application of more conventional
calibration and quantitation techniques than does the I.C-MS'MS method. However, the preparation for the GC-
MS method includes silica gel clean-up and deriv iti/ation to facilitate analyses. Ba> Ior's method was developed
and has been used to support aquatic systems and resources research and investigations; however, the method
continues to evolve in its use and practical application. During the course of this pilot investigation. Baylor will
be developing a detailed method SOP that will follow the basic requirements described in Guidelines und Forma!
for Methods to he Proposed ut 40 < 'FR Purls 136 or Purl 14!, EPA S31 -D~96-()(I3, Jul) 1996 and the description
-------
PPCP Fish Pilot Study Sample Preparaliert and Analysis QAPP
Rt?\ s.su»n''
Ite I^P.iopcr
IVsjie 1 ^ o' Vi
in EPA '.v liiikAmci'/or Preparing Standard Operating I'mcednres (SOPsl EPA OA <}-6, EPA-240
March 21)01. The final method SGPs will include am requirement?, for specialized equipment maintenance or
corrective action beyond those described in the laboratory's routine procedures and instrument manufacturers*
instructions which may arise due to the unique analyte and matrix combination measurements being performed.
10,2,1 Sample Preparation
All tissue specimens are prepared and extracted using the following procedures. Muscle and liver tissues
are dissected, composited, and homogenized using standard procedures described in I rSEPA's Outdance Jor
Assessing Chemical Contaminant Dattt for Use in Fish Advisories, ! 'ohune /. fi.s/t Sampling and Analysis, Third
Edition (USEPA 2000). Care must be taken during homogenization to ensure the sample is uniformly mixed and
to ensure minimal loss of tissue mass. Following homogenization. approximately 1.0 g of control tissue
homogenate is prepared for blank and blank spike, along with 1.0 g of fish sample homogenate for each of the
samples and sample QC (duplicates and spikes). Each sample and QC aliquot is then spiked with a known
amount of surrogate spike solution, containing 2 deuterated target chemicals (henzophenone and p-\-
nonylphenol ) and three other chemicals which distribute throughout the retention time profile, and laboratory
blank spikes and spiked samples are further fortified with target chemicals. The spiked blank is at the project
quantitation limit, while the spiked sample is equivalent to the upper third of the calibration range.
Samples are subsequently combined with a 10 ml. aliquot of acetone and shaken vigorously for 5
minutes. The sample residues are then quantitatively transferred (with rinsing) to a 50 mL centrifuge tube and
centrifuged at IfiJKIO rpm lor 40 minutes at 4 "i'C. Each of the sample supernatants arc then transferred into a
clean culture tube, and evaporated to dryness under a stream of dry nitrogen at 35 I.vaporated samples are
reconstituted in ca, 200 |il. acetone and loaded onto a silica gel column that has been preconditioned w ith 8 ml
he.\ane:acetone (65.35), The target chemicals are .subsequently eluted from the column with 10 ml, of the
hexane acetone mixture, and the volume of the collected eluate is reduced to ea. 200 j.iL under nitrogen. At this
point. KM) pi. of derivatizing agent (.V-methyl-,V(trimeth\ !siIyl)-trilluoroacetamide) is added tu each Held sample,
blank, and QC extract, and the mixture is heated at 60 "C for 45 minutes. Samples are evaporated to dryness and
100 ng Mirex is added as an internal standard. Samples are reconstituted in ISO pi. hexane and 20 }iL acetone and
immediately analyzed.
! able 2 - kfietuitin 1 imei ;un! Ion* Spedfk-il fur Selected Inn
Monitoring of PPf fs by HPL< -MS.'MS - Bjnim- I niyersil)
Chemical
RT (min)
Precursor ion
Quantification ion
Acetaminophen
5 4
152
1 10
Atenolol
6,1
2d 7
145
Cimetidine
i j
i i
25!
159
Codeine
7.9
3110
165
1,7-dimeth\ (xanthine
9.5
18!
124
Lirieomycin
11.2
4(17
35')
Trimethoprim
12.5
2«H
2ft 1
Thiahed azoic
12.5
202
Ps
Caffeine
14.6
) qs
I -x
Sullamethoxa/ole
18.4
254
i 5<*i
Mutoprolol
19.5
268
P>1
Propranolol
24 0
2m
1 H»
Diltiazent
2(i.<>
* H -
4 Is
178
Carbama/.epine
29 b
237
ll)4
T\ tosin
.>1.4
916
4
Fluoxetine
32.7
*10
148
Norfluoxetirie
32.9
134
-------
PPCP Fish Pilot Study Sample Preparation and Analysis QAPP
Rci wun '»
I talc I1' <\U'bt'I ?" 'I-
Ki^l' -i i ttl Vi
Sertraline
34,7
306
275
Erythronncin
37.2
71ft
55 S
Clofihrie Acid
38,6
-309
163
Warfarin
140.4
417 ! 161
Miconazole
41.7
213 | 127
lbuprofen
44,1
-205 I 161
Gemfibrozil
46.7
-240 ! 121
10.2.2 Gt-MS Analvsis
Chemicals arc separated and measured using a Varian Model CP3800 gas chromatograph interlaced with
a Varian Model 1200 triple-quadrupole ma>s spectrometer. Chemicals are separated on a 30 m • 0,25 mm -1 0.25
urn X I1-5 capillary column using a temperature gradient from 100-180 °C at 15 cC/min. The temperature is then
raised to 2WC at 6 X'min. and the llnal teniperalnrc is held for 6 miti with helium as the carrier gas at
approximately 1.0 ml./min. The spectrometer is operated in selected ion monitoring (SIM) mode, and all
chemicals are ionized at 250 "C with an electron impact source operated at a potential of 70 eV, The
chromatographic conditions result in the following retention lime profile, with the identification and quantitation
ions identified in fable 3. Quantitation and qualifier ions were selected based on full-scan analyses of
commercial standards and typically represent the most abundant fragment tons for each compound. Additional
instrumental parameters held constant for all anal) les are as follows: mobile phase/flow rate. 1 ic at 1.0 niL'min;
injector temperature. 275 ;C; injection volume, 1 )iL; split ratio, 20:1: transfer line temperature, 280 "'C; and
source temperature, 25(1 °C.
l ahie 3 - Retention Times inui Ittm Specified for Selected Ion
Monilorine of t'i'O's by CX-MS SIM - iia\lor_l imersit\
Chemical
K I (mini
(.htalifier ions
Quantification ion
m-Toluamide
6.7»>
91, I'M)
1 10
Ben/.oplienone
7.59
77, 105
182
p-OcH Iphenol
10.74
165, 1KU
278
Galautlide
11 m
213, 25 X
243
Tonalide
113)3
201
243
Musk xvlcne
11.94
297
282
p-\om Iphenol
123)2
149, 179
1 J
<
t-J
Musk ketone
16.32
217, 265
261
TrieIos;m
17.09
345, 362
20
Octoci \ lene
253)5
177, 24')
361
Nonylphenol
15.07
120.207
265
monoetho.wluU" isomer 1
\om Iphenol
16.53
207, 2(>5
251
monoethoxvlate isomer 2
\'on\ Iphenol
16.73
149. 221
265
monoethow late isomer 3
Celestolide
173,244
229
4-MBt"
is 7r,
115.211
25
11). 3 IJpitls in fish lissiws
Baylor's method for determination of lipids follows those specific procedures described in reference [ 11
for the gravimetric determination of lipids in llsh tissue. The procedure includes extraction of a known mass of
fish tissue (fillet or liverl w ith meths lene chloride, nitration of the solvent/tissue mixture, and drying of the
-------
PPt'P Fish Pilot Study Sa«nple Preparation and Analysis QAPP IMon y
Date 1M October
Page 2! of 5(t
solvent in a tared vessel to determine the mass of lipid residue remaining. The amount of residue divided by the
initial sample mass is the percent lipid.
110 Quality Control Requirements
Data quality is addressed, in part, by consistent performance of valid procedures established in laboratory-
methods (Section 10.0). It is enhanced by the training and experience of project staff (Section 5.0) and
documentation of project activities (Section 6.0). This QAPP and other supporting materials will be distributed to
all project personnel. The Laboratory QC Gfficer(s) will ensure that all analytical"data and sample results are
reviewed, calculations verified, and that report compilations are free from transcription errors. The laboratory
manager shall certify results in the analytical narrative along with descriptions of any areas of departure from the
laboratory methods or the requirements of the project QAPP.
In preparation for use of Baylor University methods. Baylor defined and Tetra Tech approved a minimum
set of standard QC elements, including development of experimentally derived MDLs. initial and continuing
calibration acceptance criteria, spiking levels and acceptance criteria (percent recovery) for laboratory -spiked
control samples (LCS) and field samples (MS/'MSD). precision acceptance criteria for duplicate or laboratory-
spiked duplicate (MS/MSD) samples, and surrogate spikes and acceptance criteria based on the requirements in
EPA 600 series methods, and those presented in SW846 guidance. These QC elements will be used as the basis
for assessment of all contaminant analyses performed in this study, and they include the following:
Procedural requirements:
Use of pure and traceable reference standards.
Demonstration of instrument calibration and system performance. For this study, a minimum of five
concentrations of calibration standards will be prepared (extracted for LC-MS/MS) and analyzed in
advance of sample analyses. Internal standard calibration will be used in both methods. Internal standard
calibration assesses the response of a target chemical in the reference material against the response of an
internal standard added just prior to analysis. Internal standard calibrations are used to generate relative
response factors (RRf s) which are used to evaluate calibration curve linearity and subsequently, to
calculate sample concentrations. Following is the formula to be employed in internal standard calibration
evaluations and in evaluation of continuing calibration results.
Relative Response l-'actor (RKl-'i
R A
RRF = ' a—
where R, is the response of the target chemical and R,, is the response of the internal standard, and is
the amount (or concentration) of the internal standard andis the concentration of the target chemical in
the calibration standard.
Calibration curve RRFs are then be plotted to assess linearity. Linearity of calibration is expressed in
percent relative standard deviation.
-------
WCP Rsh Pilot SluJv Sample Preparation rind Analysis QAPP
Ke\ is ion (~
Dale 1 ^ I )wU>her 2! h
Rjf?c 22 it) 3**
Percent Relative Standard Deviation (%RSD)
%RSD - -- 100
X
vv here .* is the standard deviation. and / is the average concentration of the replicate samples, and
standard deviation is defined through the following:
Standard Deviation
i n * \..
"11/ -A
SD = V-~ —
1 ?? -1
where is the measured value of the replicate, / is the mean of the measured \ allies, and n is the
number of replicates. In most anal} tical methods, an acceptable ° oRSI) qualifies the curve for use of the
average response, calibration, or relative response factors, depending on the method of quantitation.
Alternatively a curve must be plotted, and results generated against the calibration plot. For this study
<30%R5D will constitute a linear response, and the a\erage RRF can be used for sample calculations.
Alternatively, a plot of the linear regression curie can be used for sample analyses.
• Periodic calibration verification. Calibration verification criteria are generally expressed as an acceptable
percent difference (%Dt, which is calculated front either concentration, calibration, or response factors, or
from the relative response factor (RRF). It is calculated as follows:
%/J..., =
,4,..,
where is the amount observed and ,is the nominal (known) amount of the standard,
calculated as a direct percent difference in concentration. Results of < 25% difference will demonstrate
acceptable calibration for continued sample anah sis.
Sensitivity requirement
Verification that the laboratory can achieve required MDL.s and PQLs. With each anah tical batch, the
laboratory will provide evidence of method performance at the project quantitation limit. Data
qualification will be based on performance of the 1 C'S and on the sample concentrations observed relative
to the calibrated linear range. The pilot study will include calibration below the PQI . hence results
reported to approximately 2.5 times below the PQi, can be reported front within the linear range without
qualification for calibration.
Precision timl accuracy ihiast requirements¦
• Development of initial acceptance criteria for the PPCP Fish Pilot Study. Available data were not
adequate to fulfill the requirements for the initial precision and recovery (1 PR) established in many
-------
PPCP Fish Pilot Study Sample Prcpatatton and Analysis QAPP
1 >
Dati !'»I >cwbcr 2', <-i-
methods. Ralher. the initial acceptance windows were developed from MDL study data, most of which
were spiked at 2-10 times the Project Quantitation Limit (PQL). As very little work has been conducted
with these chemicals in edible fish or in livers, the initial effort was deemed sufficient to establish initial
acceptance criteria for the pilot program: however, haieh-specifie laboraton control samples (LCS) arid
surrogate recoveries will be collected and plotted into control charts for ongoing assessment of
performance and potential trend analysis.
Analysis of laboraton control samples to demonstrate the laboratory can achieve precise and accurate
results with the method prior to use on field samples, for this studv. Ba\ lor will include analysis of LCS
prepared bv adding known amounts o! all target chemicals to control tissue matrix at the PQL, Unlike
standard LCS analyses, this modification reinforces report limits with each analytical hatch. The purpose
of the studv is to cleark demonstrate whether or not there is a statistical difference in the concentrations
of PPCPs in fish from effluent-dominated streams when compared to those from a reference stream
representing a control condition. Therefore, LSC results will be evaluated as a range of acceptable
recover) and will be calculated as follows:
% Recovery (surrogates and 1 .('Si:
where amilriicahvsult is the observed concentration, and iruemlue is the amount added during sample
preparation. Recover} limit> of60% to 150% have been proposed as acceptable performance until such
time as control charts indicate revised limits are necessary (See Section 4).
Recovery of surrogate or labeled chemicals, where available, spiked into the sample to assess the effect of
matrix interferences on compound identification and quantitation. Surrogate recoveries will be assessed
using the same equation presented above for I ,CS evaluation. Recover) limits of 60% to 150% have been
proposed as acceptable performance until such lime as control charts indicate revised limits are necessity .
Duplicate matrix spike analyses {MS/MSD. where sample mass is sufficient) to assess the effect of matrix
interferences on sample quantitation, and to assess precision of the entire measurement s\ stent, including
sample homogenization and extraction. Matrix spikes will he prepared at concentrations in the upper
third of the calibration range, at concentrations corresponding to those presented in Appendix A.
MS'MSD recoveries must take into account the target chemical results native to the unspiked sample, if
any. Therefore, the calculation of MS/MSD recoveries is performed as follows:
% Recovery < MS/MSD):
where spiked spiki'tis.mipleix-Mtii is the ohscrv cd concentration of target chemical in the MS or MSD
analysis, the samplcivsuli is amount of target chemical in the unspiked sample analysis, and
anv wntspikiii is the amount of target chemical spiked into the VIS or MSI) aliquot. Reeo\ ery limits of
60% to 150% have been proposed as acceptable performance until such time as control charts or trend
analyses indicate revised limits are necessary.
imevitlue
~ % 100%
-------
IT* 'P I ssh V\Un Studs Sample Preparation mi A:uiv.:* UAW
Rju»\ t*-.
Daw i1' < ^ctdbcf
I'aiie M
Precision, whether on laboratory duplicates or on MS/MSI) pairs, i.s assessed through calculation of
relative percent difference. Larger sets of replicates are assessed using the %RSD equation, while the
following represents a duplicate precision evaluation'
Relative Percent Difference (RPI)l
KPD-^ -LC(i-.vlO()%
CC-VC\)
where (\ is the first of two measurements and (is the second of 2 measurements. The absolute
difference of the two values is divided h\ the mean.
Or
/?/»/) = ^-~---^-.vino%
(i , t- C , }: 2
where CI is the first of twu measurements and C2 is the second of 2 measurements.
If tissue mass is limited, the laboratory uill analyze one spiked sample, and one laboratory duplicate,
rather than MS MSI) to proerve mass. Duplicate RPDs should be less than 40 percent; however, for
values less than 5 times the PQI.. a broader acceptance of 100% RPD will apply,
Analysis of blanks to demonstrate freedom from contamination. Blanks should be free of" target
chemicals above the PQL, Sample results '-* 5x the blank values will be reported without qualification.
Results greater than the PQI,, but less than 5x the blank value will be qualified as maximum quantities
while any sample values at or below the blank concentration will he reported as non-detected at the
reported level.
Method performance statistics will be calculated for both of the methods to be used in this study, Tabl
summarizes the method performance statistics and criteria and information on how the) will be t^ed to control
data quality for this study. Appendix A indicates the method'chemical acceptance criteria.
-------
PPCP FMi Pilot Study Sample Preparation aid Analysis QAPP
Rcvismn u
Date I" Hctohcr
!\uc 2^
I nJ>Ic 4 - Method Pes Ln numet' ( rilcrin
Statistic
fh'wriptuui
Required/requeue}-
Method Detection Limit
(MDI.i and Project
Quantitation Limit (PQL)
MDL to be obtained following
procedures described in 40 CFR
part 136 Appendix IV
The laboratory participating in the sitklv will be
required to do one MI>L study prior to the
analysis of actual field samples. The resulting
MDL must support the PQL, The lowest
standard used to calibrate the instrument must
be below the l'(,)L.
Labeled or surrogate
compound reccn ery
Recover}' ol"labeled and
surrogate chemicals spiked into
all samples.
Labeled and surrogate standards arc spiked into
ever) sample anal)/ed. Recoveries must be
within the acceptable range given in the
method.
ICS recovery
Measured concentration nr
recovery of a laboratory control
sample (an aliquot of control
matrix spiked at the Project
Quantitation Limit)
One typically required per analytical batch
(specific frequency provided in the methods)
Recovery must be within the acceptable range
given in the method (M)%-150% at the PQL).
Matrix spike (MS)
recovery
Recovery from spiked samples
(MSI and or spiked duplicate
samples (MS MS!)).
The laboratory will be required to spike one
sample per batch (possibly in duplicate,
depending on sampling success) of samples
received for analysis, t he laboratory will
determine specific samples to spike.
Calculated spike recoveries (60%-150%) and
RPDs (40%t must be wiihin the acceptable
range given in the method.
Matrix spike (MSI
precision
RPD between measured
concentrations in duplicate
spiked field samples (MSMSDl.
Analytical precision
(includes sample
compositing,
homogeni/ation. and
aliquotting)
RPD between duplicate analyses
of a composite sample.
Alternatively, if only one sample is selected for
matrix spiking, the laboratory will be required
to analyze in duplicate 5% ol the composite
samples (to be specified by Tetra Lech). The
RPD of the duplicate measurements nui.it be
less than 40% lor values greater than 5 times
the MDL, and must be less than 100% for
values less than 5 times the MDL.
12.0 instrument/Equipment Testing, Inspection, and Maintenance Requirements
The laboratory contracted in this study will he responsible for testing and inspecting the equipment used
in this stud). The laboratory also will be responsible tor implementing preventative and corrective maintenance
necessary to produce precise and accurate data that meets the measurement quality objectives listed in this QAPP
Specific requirements for maintaining the equipment at the laboratory will be documented in the laboratory QA
plan, Bavlor-CRASR QMP 2005. Quality Management Plan for the Center for Re>er\oir and Aquatic S\stems
Research (CRASR) Baylor University, September 2005. and in the method SOPs being developed during the
course ol this study. Specific records of preventative maintenance, problems, and corrective actions will be
documented by the laboratory in instrument logbooks maintained on-site in the laboratory. These logbooks will
-------
PPCP Fish Pilot Sludv Sample Preparation and Analysis QAPP
Revision if
Date i ^ ( ^'"."hcr 2i> > *y '<
be periodical h reviewed by a laboratory manager'super*,isor and will be available to an external audi! team upon
request
13.0 Instrument Calibration and Frequency
The laboratory supporting litis studv will be required to calibrate instruments used in the study prior to
analysis of field samples and to periodically verify calibration during the course of the study. Calibration
standard.-, used by the laboratory will need lo be certified as to purity, concentration, and authenticity, or prepared
from materials of known purity and composition. Detailed instrument calibration procedures will be specified in
the laboratory's anal} tical method S( >Ps, which are being developed during the course of this study.
The methods employed in this study require a multi-point calibration prior to use of the instrument for
analysis of field and QC samples. 1 he frequency of this initial, multi-point calibration varies between methods
due to variations in instrument stability and calibration procedures. 1'he methods require the laboratory to verify
instrument calibration against a valid multi-point calibration cunc. or valid N1ST class "S" weights for lipids, at
least once per working shift during which samples are analysed.
14.0 Inspection/Acceptance Requirements for Supplies and Consumables
The laboratory" participating in this stud)1 will not be prov iding supplies or consumables to HPA, 1 he
laboratory will be required to adhere to the inspection and acceptance requirements outlined in Section 4.0 of their
approved quality management plan. /Savior ¦(. R.ISR OMP 2t>05, Quality Management Plan for the Center for
Reservoir anJ Aquatic Systems Reseitrch (l^RASRt Baylor I 'isiwrstlv, September 2(tt)y which reliably meets or
surpasses the measurement performance requirements of this study. Section 4.0 describes Baylor's purchasing
process in general terms, and identifies the person initiating a procurement request as being responsible for its
acceptance. Further the QMP indicates that "laboratory personnel assess all items required for specific activities
prior to data collection." The laboratory must have a comprehensive OA program in place and operating at all
times during the performance of the contract. In performing work for this study, the laboratory shall adhere to the
requirements in the analytical methods described in this QAPP, to EPA Heqiiirement\ for Qualm Assurance
l'ni/eet Plans for Environmental Data Operations, and to the general laboratory procedures specified in the
fiiinJfrookjor . inalytical Quality Control in Hater and Wastewater t EPA-fitHM-TO-OJQ). Cumulatively, these
sources provide guidelines concerning laboratory inspection and acceptance of chemical standards.
15.0 Requirements for Acquisition of Non-direct Measurement Data
The analytical phase of this study will not involve the collection of data obtained from non-measurement
sources such as computer databases, spreadsheets and programs, and literature files.
16.0 Data Management
Data management practices employed in this study will be based on standard data management practices
used for the National Study of Chemical Residues in Lake Fish Tissue. These practices (i.e.. sample tracking,
data tracking, data inspection, data quality assessment, database development) are described in I 'SLP.Vs Quality
Assurance Report Jar the Xational Study of Chemical Residues in lake Fish Tissue: Analytical Data for Yet trs I
through 4 (I'ShPA 2005 s [7]. The data management procedures to be implemented for the PPCP Fish Pilot Studv
are effective and efficient, and auditors conducting internal and external reviews have evaluated them and found
them to be successful. 1 lies are summarized below.
-------
PPCP Fish hint Siudv Sample Preparation anJ AnaKs^ QAPP
Revision i*
Date 1 October
Papr 27 of 3'*
16.1 Laboratory Data Management
Laboratory data management procedures will include the following:
• The laboratory will be required to maintain all records and documentation associated with the preparation
and analysis of samples for a minimum period of five years after completion of the study.
• To facilitate data tracking, the laboratory will be required to use EPA-assigned episode and sample
numbers when reporting results.
• All results of sample analyses, labeled and native standards, surrogate chemicals, spike chemicals, and
blanks must be reported on hard copy and on electronic media,
• All required reports and documentation, including ehromatograms and mass spectra, must be sequentially
paginated and clearly labeled with the laboratory name, contract number, episode number, and associated
EPA sample numbers. Any diskettes, or other electronic media submitted must be similarly labeled.
16.2 i 'Si' Data Management
Data management procedures employed by CSC w ill include the use of 1) an automated tracking system
to effectively manage data review and database development activities. 2) standardized data review guidelines to
promote consistency in data quality audits across reviewers and ov er time. 3) a multi-stage data review process
designed to maximize the amount of useable data generated during the study, and 4) a standardized database
development process that facilitates rapid development of a database with at least 99.9% accuracy.
The automated sample tracking system will facilitate development of up-to-date information concerning
work in progress, projected delivery dates, and notice of any problems encountered with laboratory analyses or
data turnaround times. To ensure that this information is as complete and accurate as possible, entries will be
made into the tracking system at each stage of the sample-to-data sequence.
Standardized data review guidelines will be used in this stud}' to facilitate rapid, consistent, accurate, and
thorough data quality audits. Data review guidelines already have been developed and are in use for a varietv of
analyses performed under EPA OST programs. These guidelines are described in CSC's General Data Review
Guidelines for Use with 1600 Scries Methods and Other Classical. Metals, and Organic Methods (Draft, January
1999) [8], They detail method-specific data review procedures for commonly used methods and more general
procedures that can be applied to less frequently used methods. Where appropriate. CSC will modify existing
data review guidelines as necessary to reflect the methods, method modifications, and data quality objectives for
the PPCP Pish Pilot Study. Any modifications deemed to be necessary will be made in accordance with the CSC
Quality Management Plan {Version 5, June 2006. or subsequent updates, if applicable).
Although each guideline will be written for a specific method, technique, or group of chemicals, all
guidelines will specify a general five-stage review process that will ensure data are in proper format, are
complete, are contractually compliant, and are usable. CSC chemists will use this multi-stage process to verify1
the quality of each laboratory submission under the study. If an error is detected in any stage of the review, CSC
staff will initiate corrective action procedures to obtain the maximum amount of usable data front the study.
These actions may serve to obtain missing data, correct typographical or transcription errors on data reporting
forms, or initiate reanalysis of Held or QC samples that do not meet the performance criteria for this study.
Concurrent with the performance of data quality audits, CSC staff will develop a database of combined
field and analytical results. This database will be formatted in a manner that is consistent with EPA's National
Lake Fish Tissue Study database, with modifications in the format necessary to integrate field data. The database
also will be compatible with STORET: data will be stored locally in a Microsoft Access database during the studv
and delivered to EPA upon study completion or at requested intervals. Each record in the database will contain
-------
PPCP Pish Pilot Stuth .Sample Pa-par.iinin and Analysts (JAM1
Rev ision U
DjIl i1' October 2(!Ch
Page 2S ot *t>
information pertaining to both a "field sample" and to an "analytical sample. At a minimum, each record should
include fields containing the following information:
• Five-digit EPA sample number assigned by Tetra l ech;
• 9-digit composite sample identification number assigned by field teams;
¦ Sample type (indicates the type of sample - liver or fillet tissue);
• Fish species;
• Length of each fish;
• Weight of each fish;
• Method of collection (active or passive);
• Sample collection date;
• Sample collection time;
« State and county;
• WWTP facility name:
• Stream (receiving water) name;
• Site coordinates (latitude and longitude) for the start and end of the sampling reach;
• Estimated stream width and depth;
• Average stream flow;
• Chemical concentrations; and
• Lipid content measurements.
The data structure listed above for the integrated field and analytical database and the field database
{Section 16.1) will allow data users and reviewers to:
(1) Look up individual fish sample data in the database for a given composite sample number.
(2) Extract analytical data from a gi\ en sampling location from the database.
(3) Extract fish sample data from a given sampling location from the database.
As with the data quality audits, a multi-stage process of inspections and corrective actions will be used to
facilitate timely, efficient construction of databases that are least 99.9% accurate. The database development
process will begin with a completeness check to verity the laboratory has submitted all data in an appropriate
format. If deficiencies are found, the CSC Project Manger will notify the Tetra Tech Project Manger, who will in
turn contact the Baylor Laboratory Manager to obtain information to address the deficiencies. After problems
have been identified and resolved, the CSC Database Administrator will prepare a "QC Check Report" that
displays the results submitted by the laboratory. The CSC chemist responsible for performing the data quality-
audit will review this QC Check Report to verify that the electronic data accurately reflect the hard copy
submission. Accuracy will be confirmed by spot checking at least 10% of all results that were downloaded
directly from an analytical instrument in the laboratory and by performing a 100% QC check of data that were
manually entered by the laboratory or CSC. If errors are identified during spot checking ot electronic data, the
CSC Project Manager will notify the Tetra Tech Project Manager, who will in turn contact the Baylor Laboratory-
Manager, to specify errors that require correction. If errors are identified during the 100% QC check of manually
entered data. CSC will correct the errors in the database. Following completion of the data quality audit, the CSC
chemist and the Database Administrator will modify the database to reflect data usability determinations. A
report, generated to reflect the modified database, will then be reviewed by the CSC chemist to verify database
accuracy before submission to EPA.
17.0 Assessments and Response Actions
'l he laboratory is required to have a comprehensive QA program in place and operating at all times during
the performance of their contract. Baylor's QA Program is described in Baylor-CRASR QMP 2005, Quality
Management Plan for the Center for Reservoir and Aquatic Systems Research (CRASR) Baylor University.
-------
I'I't'P Fish Pilot SHuls Sample I'rcjsiuiSiim .md Atulws
Kmvon li
Dale I'l'K-vK-r v->
Ptr(K' of -V'
September 2005. In performing laboratory work for this study. they shall adhere to the requirements of their
QMP, the requirements of the analytical methods described in this QAPP. in the laboratory SOPs being developed
during the course of this study, and the genera! laboratory procedures spec! lied in the Hamibonk Jor Analytical
£Juulity Confrul in Hater and tl'aMcwtiwr (HPA-6(lO-4-79-Oll>>. as well as the data management principle* set
forth in EPA 21*5- Guml.4ut
-------
PPCT Fish Ptlol Sludy Sample Preparation and Analysis QAPP
Rci Hhin«'
I hue ll> OL'tuhci
J'aiTC in
Assessment
Measure
Definition
FnNjucno
Ucs|innsj|ilc r»rl>
Ralmimk
Uoc»mcnl»tlinn
Sutvcillanec
Continual or frequent monitoring and verification of the
status of an enniy and the analyst* of recordi to ensure
thai specified requirements arc bem$ hi filled
"l"hrouglioiil ''.iniipte 1^^^,11.1111136. l.d'^T^Ian
analysis, and d.ua u ibev j'nvohu'v
U"rT«s 1 cvh tJA < MlK't't or
de*if IH'C ;uid * 'M
i'i>'|Cwt \!nn !"ci
tdcnlif) ,iud (.'CTCvt ^uaKhi.-d prnlilu'iti. ft. simts iiv
tlio o.k,ui u> siiiunnn/c dv,"l,H t. ;t pplcnn.-.l d(>,^ > f *f!v ,i> p >-.sdi?r
Identitu ii'mn oud t,ucn.\ ti<^t ot .tu.d\ tiw.d pt^bk-m . en
dcluicfK ir\ *\i!l lie »IikufTicntcd ilnt^nt'h
vr(nniii!ni.alir>ri re> uhese < uI^ivm^
d if.i p.'.i «i,;cs u iU miti lied and f-1 ued uah i,ut,Uiui
mdi^iitrni1 that tliry h;u r brcn rev iewed and .i;ipn>\ cd
IVet Review
A documented aitic&l review of work lhai i* conducted
by qualified individuals who a« ihvtcxKsutari. tnei
technical !>¦ equivalent of those wh© jwsf femtKd the work
Pcrfomwd wt at least 2 aftheiiiia mktge
audiu €m%4ucterf by CSC daia icvicweri.
and I06?i©fdata review nmraU\€i
prepmed Ippii'v«, A
I'toctduraJ
Review
Oil >lit,i'i\ v a ,C« « l/C r llu* ^1'ipiUt k'I dJi.lk.nUC- 1 '
iin»('ra «.nfctu"it >< ami iiptmu/e .\,i!u] dL»u u tk».ii> 5'2 Ci jtdu. led .t\ lUc ir.ifHn
i v.'!r i 1 c.h \\ \ i ?Mi^r
ti? iL'^f/urc
I hi |Tv>i,t\iu idcr.ttpw^ .i'i,f 1-' tlsc cxrsj*i1
M-iicood finnitdi.ifcK *"¦ mi^itc un-isicm >
ilu^rndfi-m ibr J sia 1.idk'v. 1h'3i (iihi.'1.shi { i 1 src»-1j<. c
a, i'i'n> ik ir'ijdvisuMi'.i-'J r.M( 1 hi1"!? Vu* _vv'i itf
ij*l dsi\-'»tia.!vd d.ti! 3 V V »ilt,1 ^ '?,(
\ fc|8-"!!i ni ftii'liiis1 v ,%Hn| v">rrv%rise .(.(jnu-
in 1 uni.J/'cJ dill'"(< Tx «. j : ..c,Kii,'! rc . k a Viiit hi,
f«ftiiij'cd with j!ic pr->K\t rec.ud'. tuid 1l!>^nhiard ih^
MmmIwa nrki 11
Readiness
Revievv
A sv .loin tiu dm iimcnicd tc% n * >r C'Ci'tfiivJ «s-.c a h.shiV p h»a.tn sis
th(.p ix upiw.dlv oiri.UMcd K»1-»"e |'rt>v\cdiiir bevmd
psopu mil,;'-tune iUhI ptmi i.i uniuticn t nt ?lic
stwdv
1 j|tt 1 VlM i CviSl < ^ V
1 UJKcr d^1 jtui
i S.C Is- l.wcfi,
\\miv «ii] br .'tti'ulcd a pt'rhtd 0! titnt* lt> ru^p-ni
!¦> Ok^c t null nt' v ui in 1uHifcn1.nl iippropn.itt
corrvjrvr 1 •. dibi.^ vmnu, mh xiu i-ji:,«,tit,ihs.«. .mdn •¦>:
t.uiliiics, L-quipuH ni, per-snirml, pnH.ed.tfe->,
Kv.>-' d \ ccpiri,!' diil.i1 iti 1 itn n i! if. m m. u imcnl ami
rep '!1uh< ;»«,pnT s' vth. r .1 >*,*
,11s1 • -vM 1 ,'f|" ,s.t?ii likek
It i S As .»TC dcv'.Sl.'vi
ilscs udl i>.-
{H'TtlUIIK-d b, df.1 1 !' \
' it
i vtf.» U'Ji iJ \
ui th«' K?H s'.tMjv ,i L-qiufb.-l'i, iii^is ?c »M'd
K-|iju diit.i Vvill bf ;s-csv.-d pjsnr tu iiiuKsi-. ami
¦.onlnui.dU dtiiuipltuiEi kMhil'isc- ia utlrii UA ij(
Jc" .uiif'-.d ifi th"- < J MJP
11.IM ijn.ilifif?' ^ill S-c n*;d nh-rc .ippr^prhik 1
ldL-imt\ linilMtSnil' »il thu d.-Uo HI ibi' pr»ijr<= t d,u-lhj^c
t^i 'blu.thon mil |.'ll'>vv st.iti.ljird u»m esilMri'., ii Jit\
Sv sleinntic and smlcptndesi) I'Siimuiainm determine i!
H'j :Jin n.nuUi.--. .>rui rohteJ u vilt. cumph vuih pl.^nntJ
1 lx.il fif1. J 1 Abuih.T Shf-C MT.Ui/f'lHfit1. -itfC
nupLTii-'fited tH'.'lv ,'inJ .'tc muLihlr n» ,ufnt\c
o-bjeclivcs.
tUiirM ot l"'«ur.itoi\ j>uV.ij'c--
subniiiied
1 SC Kvi ictvf»1 iejs'3l u( d,»Ui ijUidilv will bv prepared )iu n tli * Ji«,> >ct
o:icJ tike U s\i
^sJkvth'n dciii'i! ,md K'n[. ,hi»! «.¦ d^tennrm. tiu-
.td^i.tuv df the d, is^-h
v 1 'Hitiiiifcicr».viip{>. ujn.ir 1 centred t
kIm \ p,i,ki\i7Cv Will lv uun.dtd and d.ited with not.kiipji
indicating tei ilwy Have been rev •
30
-------
PPCP Fish Pilot Study Sample Preparation and Analysis QAPP
KclKti-;-, . the CSC Project Manager will monitor the progress of the data quality audits (data rev iews) and
database development to ensure that each laboratory data submission is reviewed in a timely manner, in the event
that dedicated staff is not able to meet l.'PA schedules, the CSC Project Manager will work to identify additional
resources that are qualified and capable of reviewing the data in a timely manner. If such resources cannot be
identified, and if training new employees is not feasible, the CSC Project Manager will meet with the EPA Project
Manager to discuss an appropriate solution.
J~ 2 Peer Review
All laboratory results and calculations will be reviewed by the laboratory manager prior to data
submission. Any errors identified during this peer review will be returned to the analyst for correction prior to
submission of the data package. Following correction of the errors (See Appendix C for Bay lor's Corrective
Action Procedures), the Laboratory Manager will verifv that the final package is complete and compliant with the
contract, and will sign each data submission to certify that s/hc has reviewed the package and determined it to be
in compliance with the terms and conditions of the contract.
Peer reviews also will be performed within CSC to verily that the data quality audits are being performed
consistently over time and across peer rev iewers, that the audit findings are technically correct, and that the audits
arc being performed in accordance w ith this QAPP, "I hese peer review s of the CSC data quality audit process
will be performed on at leas! one data deliver}' package from each method/matrix combination submitted as part
of this study (i.e.. at least one data package for I CMS1 MS determination of pharmaceuticals in liver, one data
package for UC7MS determination of personal care products in fillets, etc.). B\ addressing data validation and
review processes on a method/tissue fraction basis, the laboratory will have greater flexibility in its report
preparation process, and validation will be conducted on an analytical batch basis. This approach will facilitate a
more expeditious review and release process lor interim reports and technical discussions. Peer reviewers will be
charged with evaluating the completeness of the original data review, the technical accuracy of the review er's
findings, and the technical accuracy of the analytical database developed to store results associated with the data
package. They will use a standard data review form that thev complete, sign, and date to document review of the
data quality audit process (Appendix D). The CSC Project Manager will be responsible for identifying and
assigning qualified peer reviewers and for selecting packages lo he peer reviewed. Qualified peer reviewers will
include any staff members who have been trained in CSC data review procedures, are experienced in rev iewing
data similar to those being reviewed, and are familiar with the requirements of the PPCP l-'ish Pilot Study and this
QAPP. To the extent possible, these peer rex iews will he performed after the primary data reviewer has drafted a
written nan alive describing the results of his/her audit, but before this narrative is submitted to HPA.
To ensure the findings of each data quality audit are documented in a consistent and technically accurate
manner. CSC staff will conduct a peer review ol 100% of the data review summaries (narratives) prepared for this
stud). Each data rev iew summary will he subjected to at least two levels of peer ret iew, and each peer res iew or
will he charged with evaluating the clarity, technical accuracy, and the grammatical quality of the data review
summary.
17.3 OitLilit) Systems Aitiiu
A quality systems audit will not he performed during this study (see "I able 51.
17.4 Readiness Review
A readiness review- of the laboratory's capability to produce precise ami accurate results with the methods
specified in this study will be performed before the laboratory is allowed to analyze field samples collected during
the study, As part of the readiness review, the laboratory will submit data demonstrating that it is capable of
analyzing a known, reference matrix with the methods to be used in this study. In most cases, laboratories meet
-------
I'lVP 1 ish 1'iiLt: Stwiv Suuifk" I'lfp.ii.sHim and AimK-ss \i'l' Re. is mi ¦<
D.sU' !'H IcUiin':
'2 nf ?'»
this requirement by performing I PR tests. I PR tests consist of preparing four replicate aliquots thai contain the
target pollutants, analyzing these replicate aliquots with the specified method, and calculating the average percent
recover) and standard deviation of the measured aliquots. I f the av erage percent reco\ cry and standard deviation
meet pre-defined acceptance criteria, (he laboratory is considered to be qualified (or ready) to perform the
analyses,
< >n a case-by-case basis. EPA. Tetra Tech, and CSC max decide to accept alternate data in lieu of IPR
data for the readiness reviews. In such cases, the alternate data must prov ide a> much information about
laboratory readiness as would the IPR samples, I/xampIes of acceptable non-1 PR data that might be used for a
readiness review include performance evaluation (PI") sample data, ongoing QC data gathered o\ er a period of
time, or VJDL study data. For this study, due to the highly specialized nature of the target chemicals and matrices.
I'.PA. Tetra Tech. and CSC have accepted alternative method demonstration data developed during method
refinement (which has been underway at Bay lor since the project planning phase}.
Readiness rev tews w ill be performed by CM* data rev iewers and Tetra lech's QA Officer or designee,
who will document and forward their findings to the Tetra 'lech Project Manager. If problems are identified
during these reviews, the Tetra Tech QA Officer (or designee) and CSC Project Manager will work with the
laboratory (to the extent possible) to resolve the problem. If the problem cannot he resolved within the time
frame required by FPA or within the scope of the laboratory's existing contract, the EPA Project Manager will be
contacted immediately.
/ " 5 Tcclmu-ul Systems . ludii
The laboratory must be prepared for an on-site (or technical systems) audit of its facilities, equipment,
staff, and procedures for sample analysis, training, record keeping, data validation, data management, and data
reporting. Laboratory audits w ill be conducted only if the results of the readiness reviews, data quality audits, and
surveillance suggest serious or chronic laboratory problems that warrant on-site examinations and discussions
with laboratory personnel. If Mich an audit is determined to be necessary, a standardized audit checklist will he
used to facilitate an audit walkthrough and to document audit findings. Audit participants may include the HP A
Quality Assurance Officer tor a qualified KPA staff member designated by the I'.PA QAO) and a Tetra Tech staff
member (assigned by the Tetra Tech QA Officer) experienced in conducting laboratory audits. One audit team
member will be responsible for leading the audit and conducting a post-audit debriefing to convey significant
findings to laboratory staff at the conclusion of the audit. 'I he other audit team member will be responsible for
gathering nre-audit documentation of problems that necessitated the audit, customizing the audit checklist as
necessary to ensure that those problems are addre.s-.ed during the audit, documenting audit findings on the audit
checklist during the audit, and drafting a forma! report of audit finding?, for review by F PA,
17.6 Data Quality A adits
Lvery laboratory data package submitted under thi> study will be subjected to a data quality1 audit. These
data quality audits will be performed by qualified CSC data review staff who have been trained in procedures for
performing data quality audits and who are familiar with the laboratory methods used to prepare the data
packages. These data quality audits will be performed using a multi-stage review process designed to identify and
correct data deficiencies as early as possible in order to maximize the amount of usable data generated during this
study.
l~ " Duh/ (Jaaliiy Assessment
Upon completion of each data quality audit, the CSC Data Rev iewer will work with CSC's database
development staff to create an analytical database that contains all field sample results from the PPCP Fish Pilot
Study (see Section 1ft,2).
32
-------
WCP Fwfc Ktot Study Samp/be Preparation and Analysis QAPP
Re.'sum •
Dale I'' (Vtobv'i 2'H'f,
!'a-c35 nt K
At selected intervals and upon completion of the study. C'SC's database development stuff will perform
statistical analyses to verify the accuracy of the database. The statistical procedures will he directed at evaluating
the overall quality of the database against data quality objectives established for the study and in identify ing
trends in field and QC results obtained during the stud). CSC staff will document their findings and
recommendations concerning this data quality assessment in a written report to HP A.
18.0 Reports to Management
Following the completion of sample analyses and data quality audit and assessment. CSC chemists will
prepare a Quality Assurance Report, in narrative formal, that describes data quality limitations and CSC
recommendations concerning data use.
Upon request, CSC can also provide a weekly report that describes the status of ail current data review
activities and prepare periodic database status reports that provide up-to-date information concerning database
activities that occurred since distribution of previous reports.
19.0 Data Review, Validation, and Verification
Criteria for acceptance"
A multi-stage data review process, as summarized in Section lb (and detailed below) will he used to
evaluate the quality of ail data submitted in the I'PCP fish Pilot Studs. Acceptance criteria against which data
will be evaluated include I) stud) performance criteria and \iQOs detailed in this and affiliated QAPPs,
2) applicable QC acceptance criteria, and 3} best professional judgment (BPJ) of CSC chemists responsible for
performing data quality assessments. The goal of this data review process will be to maximize the amount of
useable data gathered in the study. "I bis will be accomplished by 11 performing data reviews promptly so that
corrective actions may be taken wherever possible and 2i considering data quality failures in light of the entire
analytical sequence rather than as isolated events.
Process:
In the first stage of the data review process. CSC chemists will perform a "Data Completeness Check" in
which all elements in each laboratory submission will be evaluated to verify that results for all specified samples
are provided, that data are reported in the correct format, and that all relevant information (such as preparation and
anal; sis logs) are included in the data package. Corrective action procedures will be initiated if deficiencies are
noted.
The second stage of the data review process will focus on an "Instrument Performance Check" in which
the CSC chemists will verify that calibrations, calibration verifications, standards, and calibration blanks were
analyzed at the appropriate frequency and met method or stud} performance specifications, It'errors are noted at
this stage, corrective action procedures will be initiated immediately.
Stage three of the data review process will focus on a "Laboratory Performance Check" in which CSC
staff will verify that the laboratory correctly performed the required analytical procedures and was able to
demonstrate a high level of precision and accuracy. This stage includes evaluation of QC elements such as the
preparation and laboratory blank* and laboratory control samples, Corrective action procedures will be initiated
with the laboratories to resolve any deficiencies identified.
In stage four of the data review process, the CSC,' chemist will perform a "Method/Matrix Performance
Check" to discern whether any l)C failures are a result of laboratory performance or difficulties with the method
-------
I'PtT I ish hloi Studv Sample Pu-jMraikHi kinJ AiuKm* i^AIM'
hriOH i»
\XiW W 2H'ih
Pj,jc „*i *<:
or sample matrix. Data evaluated in this stage will include matrix spike, matrix spike duplicate, duplicate sample,
and surrogate spike results. "I he CSC chemist also will verity that proper sample dilutions wore performed and
that necessary sample cleanup steps were taken. If problems are encountered, the CSC chemist will immediately
notify the 1'etra Tech Project Manager to implement correcthe actions.
Reconciliation with user requirements;
Finalh, CSC will perform a "Data Quality and I lability Assessment" in which the o\crall quality of data
is evaluated against the performance criteria and MQOs detailed in this QAPP, As noted above, this assessment
will strive to maximize use of data gathered in this stud)' based on performance criteria established for this study.
This will be accomplished by evaluating the overall quality of a particular data set rather than focusing on
individual QC failures. Results of this assessment will he documented in a written (,14 Report that CSC will
submit to EPA. To expedite the process, this report will follow a standardized format developed for hl'A's
National Lake Fish Tissue Studs- and. wherever possible, utilize standardized language to communicate data
limitations and CSC recommendations concerning data quality.
20.0 References
(1) U.S. Bin ironmentai Protection Agency 11 SEP \ t. 20t!6, Quality Assurance Project Plan for Sample
Collection Activities for a Pilot Study to Investigate the (kemrenee of Pharmaceuticals and Personal
Cure Products t PP( 7\ i in Fish Tissue. EPA Office of Water, Office of Science and Technology.
Washington, DC.
(2) U. S. Hnvironmental Protection Agency ft SEPAl. 2001. EPA Reiiuircmentsf'r Quality Assurance
Project Plans, EPA OA'R-5. I'PA Office of Environmental Information, Washington, DC. EPA/240/B-
01/003.
13} U.S. Environmental lYotection Agency fUSFPA). 2002. £7VI Guidance for Quality Assurance Project
Plaits. EPA OA, Ii~5. HPA Office of Environmental Information. Washington. DC. EPA«'24O'R-02'OO9.
(4) Appendix B, 40 CFR part 13ft
15} U.S. Em ironmentai Protection Agency (USEPA). 2000. Guidance for Assessing Chemical Cuiiiaminant
Data for I 'se in Fish Advisories. I 'olume I ¦ Fish Sampling and Analysis, Third Edition. EPA Office of
Water, Washington. DC. F.PA 823-B-00-OU7.
16] U.S. Environmental Protection Agency (USEPA). 19%. Guide to Method Flexibility and Approval of
EPA Water Methods. EPA Office of Water, Engineering and Analysis Division 8,4303), Washington DC.
EPA-82 i-D-%-004.
171 U.S. Environmental Protection Agency (USEPA). 2005. Quality Assurance Report for the National Study
of ( hemical Residues in Lake Fish Tissue Analytical Data }<>r Year\ ! through -l. EPA Office of Water,
Office of Science and Technology, Washington DC. EPA-823-R-U5-005
(8) Computer Sciences Corporation. General Pat a Review Guidelines for I "se with 1600 Series Methods and
Other Classical a. Meiiils, and Organic Methods (Draft, January I'KM)
34
-------
Appendix A
Method/Chemical Acceptance Criteria
-------
Appendix A — Method/Chemical Acceptance Criteria
PRELIMINARY ACCEPTANCE CRITERIA LC-iViS Analysis of PPCPs in fish tissue
MDL
0.5
(ng/g)
Calibration Standards {
Acceptance Criteria
Chemical
PQL
Oig'g)
CC1
CC2
CC3
CC4
(CCV)
CCS
CC6
CC7
cca
ICV
CCV
LCS/MS/MSD
PQULCS
Spike/MS
(optional)
%RSD
%D
UCL
LCL
propranolol
0,01
0.05
0.02
0.05
0.125
0.25
0.5
1.0
2.0
4.0
30%
25%
60%
150%
carbamazepine
0.02
0.05
0.02
0.05
0.125
0.25
0.5
1.0
2.0
4.0
30%
25%
60%
150%
clofibric acid
0.06
0.50
0.20
0.50 ^
1.25
2.5
5,0
10
20
40
30%
25%
60%
150%
miconazole
0.10
0.50
0.20
0.50
1.25
2 5
5.0
10
20
40
30%
25%
60%
150%
diltiazem
0.10
0.50
0.20
0.50
125
2.5
5.0
10
20
40
30%
25%
60%
150%
warfarin
0.13
0.80
0.20
0.50
1.25
2.5
5.0
10
20
40
30%
25%
60%
150%
1,7-
dimethylxanthine
0.19
1.0
0.40
1.0
2.5
5.0
10
20
40
80
30%
25%
60%
150%
gemfibrozil
0.19
1,0
0.40
1.0
2.5
5.0
10
20
40
80
30%
25%
60%
150%
codeine
0.20
1.0
0.40
1.0
2.5
5,0
10
20
40
80
30%
25%
60%
150%
metoprolol
0.33
1.0
0.40
1.0
2.5
5.0
10
20
40
80
30%
25%
60%
150%
sulfamethoxazole
0.36
1.0
2.0
5.0
12.5
25
50
100
200
400
30%
25%
60%
150%
cimetidine
0.88
5.0
2.0
5.0
12.5
25
50
100
200
400
30%
25%
60%
150%
erythromycin
0.90
5.0
2.0
5.0
12.5
25
50
100
200
400
30%
25%
60%
150%
lincomycin
1.18
8.0
2.0
5.0
12.5
25
50
100
200
400
30%
25%
60%
150%
thiabendazole
1,38
5.0
2.0
5.0
12.5
25
50
100
200
400
30%
25%
60%
150%
acetominophen
1.44
5.0
2.0
5.0
12.5
25
50
100
200
400
30%
25%
60%
150%
sertraline
1.83
10
4.0
10
25
50
100
200
400
800
30%
25%
60%
150%
atenolol
2.18
10
4.0
10
25
50
100
200
400
800
30%
25%
60%
150%
norfluoxetine
2.20
10
4.0
10
25
50
100
200
400
800
30%
25%
60%
150%
caffeine
2.96
10
4.0
10
25
50
100
200
400
800
30%
25%
60%
150%
tylosin
3.73
20
8.0
20
50
100
200
400
800
1800
30%
25%
60%
150%
ibuprofen
4.57
20
8.0
20
50
100
200
400
800
1600
30%
25%
60%
150%
trimethoprim
4.99
20
8.0
20
50
100
200
400
800
1600
30%
25%
60%
150%
fluoxetine
8.01
20
8.0
20
50
100
200
400
800
1600
30%
25%
60%
150%
MDL 0.5 represents projected values using 1.0 g tissue and reconstitution in 0.5 mL solvent prior to analysis
-------
PRELIMINARY ACCEPTANCE CRITERIA GC-MS analysis of PPCPs in fish tissue
MDL
0.5
(ng'g)
Calibration Standards (ng/g)
Acceptance Criteria
Chemical
PQL
(ng/g)
CC1
CC2
CC3
CC4
(CCV)
CCS
CC6
CC7
ICV
CCV
LCS/MS/MSD
Precision
(%RPD)
PQULCS
Spike/MS
%RSD
%D
UCL
LCL
p-nonylphenol
2.81
10
4.0
10
25
50
100
200
400
30%
25%
60%
150%
40%
p-octylphenol
2.92
10
4,0
10
25
50
100
200
400
30%
25%
60%
150%
40%
m-toluamide
3.48
10
4.0
10
25
50
100
200
400
30%
25%
60%
150%
40%
celestolide
4.03
20
8.0
20
50
100
200
400
800
30%
25%
60%
150%
40%
tonaiide
4.81
20
8.0
20
50
100
200
400
800
30%
25%
60%
150%
40%
NPE #3
4.95
20
8.0
20
50
100
200
400
800
30%
25%
60%
150%
40%
triclosan
5.33
20
8.0
20
50
100
200
400
800
30%
25%
60%
150%
40%
4-MBC
5.34
20
8.0
20
50
100
200
400
800
30%
25%
60%
150%
40%
NPE#2
6.30
20
8.0
20
50
100
200
400
800
30%
25%
80%
150%
40%
NPE#1
10.59
20
8.0
20
50
100
200
400
800
30%
25%
60%
150%
40%
musk xylene
7.29
30
12
30
75
150
300
600
1200
30%
25%
60%
150%
40%
benzophenone
7.46
30
12
30
75
150
300
600
1200
30%
25%
60%
150%
40%
galaxolide
9.05
30
12
30
75
150
300
600
1200
30%
25%
60%
150%
40%
octocrylene
16.58
50
20
50
I 125
250
500
1000
2000
30%
25%
60%
150%
40%
musk ketone
16.89
50
20
50
125
250
500
1000
2000
30%
25%
60%
150%
40%
-------
Appendix B
Sampling Locations
-------
Appendix B - Sampling Locations
St.
City
Facility Name
Treatment
Receiving Water
Name
County
Name
Pop
PCS
Design
Capacity
Existing
Flow
MGD
%
Effluent
% 6S&
older
Median
Income
A2
Phoenix (PHX)
91st Avenue WWTP
secondary
Salt River
Maricopa
1,418,041
165
153
100%'
8.1
541,207
IL
Chicago (CHI)
Northside WRD
Advanced secondary
North Shore Channel
Cook
5,376,741
333
234
100%3
10.3
$38,625
TX
Dallas (DAL)
Dallas WWTP
tertiary
Trinity Rivert
Dallas
3,500,000
150
100%3
8.1
$43,324
FL
Orlando (ORL)
Orlando-Iron Br Fac
Advanced Treatment 1
Little Econlockhatchee
Seminole
442,542
40.00
36
64%2
11.3
535,732
PA
West Chester (WCH)
Taylor Run WWTP
secondary
Taylor Run
Chester
17,701
1,5
36 - 86%*
9.0
537,803
NM
Santa Fe (SAF)
Santa Fe WWTP
secondary
Santa Fe River
Santa Fe
68,041
9
8,5
100%
13.9
549,705
NV
Las Vegas (LAV)
City of Las Vegas WPCF
primary & secondary,
removes ammonia
Las Veqas Washt
Clark
575,000
110
84
100%®
11.6
544,046
TX
San Antonio (SAN)
Dos Rios WRC
Advanced treatment &
disinfection
Medina & San Antonio
Rivers
Bexar
1,236,249
125
56.5
100%
10.4
536,214
VA
Lorton (LOR)
Noman M. Cole, Jr.
Pollution Control Plant
tertiary
Pohick Creek
Fairfax
17,786
54
>40
no gauge
data
7.9
581,050
TX
Denton (DNT)
Pecan Creek Water
Reclamation Plant
secondary
Pecan Creek
Denton
98.288
21
100%'
7.9
535.422
NC
Raleigh (RAL)
Neuse River WWTP
tertiary
Neuse River
Wake
326.653
60
36.67
48 - 78%
8.3
546.612
DC
Washington DC (WDC)
Biue Plains STP
tertiary
Potomac River
DC
553,523
370
335
no gauge
data ?
12.2
540,127
L—J = Priority
I | •• Secondary
* Instream waste concentration from Tcira Tech's WERF field sampling data
0 Gauge is upstream of the Potomac's confluence with the Anacostia River; Blue Plains STP is downstream of this confluence, so Potomac's discharge will be much greater
than the gauge shows,
1 Information from Debra Daniel, AZ DFQ
2 Calculation based on data provided by Alex Trounov, Tt Fairfax
3 Flow is primarily made up of effluent discharged from multiple facilities (http://ndep.nv.gov/docs_04/bwpc_nv0000060_fs.pdf &
www.epa.gov/osp/regions/emerpoll/howe.ppt).
4 During non-storm conditions, flows are comprised almost entirely of effluent; during summer months, water in Pecan Cr. is exclusively effluent (Brooks et. al., 2005).
% Natural drainage in the Las Vegas Valley and the receiving stream for all area surface water dischargers. The water in the wash is primarily treated wastewater from the
Clark County Water Reclamation District, City of Las Vegas, & City of I lenderson.
t Recommendation from Scott Dyer, PGI
-------
Appendix C
Baylor University's Laboratory
Corrective Action Plan
-------
Appendix C - Baylor University's laboratory1 Corrective Action Plan
General QA/QC Details
Here wc include typical QA/QC information, including requested corrective action procedures'.
Laboratory Measurement Quality Control Requirements ami Acceptability Criteria
Detailed laboratory QC requirements are contained within each individual method and laboratory quality
assurance manuals (QAMs), The minimum requirements that all participants abide by are stated below. Lab QC
sample results are reported with the laboratory data report.
Lab QC samples are prepared and analyzed in batches, which are defined as follows:
Batches are environmental samples that are prepared and/or analyzed together with the same process and
personnel, using the same lot(s) of reagents. A preparation batch is composed of one to 2ft environmental samples
of the same matrix, meeting the above mentioned criteria and with a maximum time between the start of
processing of the first and last sample in the batch to be 24 hours. An analytical batch is composed of prepared
environmental samples (extracts, digestates or concentrates) that are analyzed together as a group. An analytical
batch can include prepared samples originating from various environmental matrices and can exceed 20 samples.
Laboratory duplicate - Laboratory duplicates are used to assess precision. A laboratory duplicate is prepared b>
splitting aliquots of a single sample (or a matrix spike or a laboratory control standard) in the laboratory. Both
samples are carried through the entire preparation and analytical process. Laboratory duplicates are run at a rate of
one per preparatory (if applicable) and analytical batch.
Precision is calculated by the relative percent difference (RPD) of duplicate results as defined by 100 times the
difference (range) of each duplicate set. divided by the average value (mean) of the set. For duplicate results, X]
and X;, the RPD is calculated from the following equation:
RPD = { (X, - X;)/ (X,+X:)/2r UK)
Performance limits and control charts are used to determine the acceptability of duplicate analyses.
1 .aboratorv Control Standard (LCS)/[.aboratorv Control Standard Duplicate tLCSD) - I.CS'LCSD pairs are
analyte-free tissue matrix samples spiked with the analyte of interest prepared from standardized reference
material. The LCS'LCSD pairs are generally spiked into analyte-free tissue matrix at a level less than or equal to
the mid-point of the calibration curve for each analyte. They are carried through the complete preparation and
analytical process. The LCS/l.CSD pairs are used to document the bias of the method due to the analytical
process. Bias can be assessed by measuring the percent recovery of l.CSs and LCSDs, and precision can be
assessed by comparing the results of LCS/l.CSD pairs. LCS/l.CSD pairs are run at a rate of one each per
preparatory (if applicable} and analytical batch. Laboratory-specific control limits and charts are calculated and
maintained by laboratory staff on a periodic basis.
Bias of l.CSs and LCSDs is expressed by percent recover}- (%R) where SR is the observed spiked sample
concentration, and SA is the spike added:
1 References to analyses of metals and field Wank samples do not apply to the PPCP Fish Pilot Study.
-------
%R = SR/SA * 100
! he mean bias of LCSi C SO pairs is expressed hy %R.„,vt, where "uR; is the percent recovery of the I.C'S and
%Ru-sn is the percent recover} of the i.CSD:
%R«c„ = (%Ri < s - %Ri« so)/2
Precision betw een LCS/I.CSD pairs is expressed by relative percent difference (RIM)). For 1 t'S'LCSD results. Xs
and X>. the RPD is calculated from the following equation;
RIM) - St\i-\; !,¦--(
Matrix spikes (MS) - A matrix spike is an aliquot of sample spiked with a known concentration of the anulyte of
interest. Percent recover) of the known concentration of added anahte is used to assess accuracy of the analytical
process. The spiking occurs prior to sample preparation and analvsis, Matrix spike samples are routine!} prepared
and analyzed at a rate of 10% of samples processed or one per preparatory (if applicable) and analytical batch
whichever is greater. The MS is spiked at a level less than or equal to the midpoint of the calibration or anal) sis
range for each analyte. The MS is used to document the accuracy of a method due to sample matrix and not to
control the analytical process. Percent Recovers (%R"> is defined as Hit) times the observed concentration, minus
the sample concentration, divided by the true concentration of the spike. MS recoveries are indicativ e of matrix-
specific biases arid are plotted on control charts maintained hy the laboratory. Measurement performance
specifications for matrix spikes are not specified in this document, and MS data should be evaluated on a ease-by-
case basis.
The formula used to calculate percent recovery, where %R is percent recovers; SSR is the observed spiked
sample concentration: SR is the sample concentration: and SA is the spike added, is:
U-:,R - (SSR -SRiSA ' 1 Oil
Method Blank- A method blank is an anahte-frec matrix to which all reagents are added in the same volumes or
proportions as used in the sample processing ami analyzed with each preparatory (if applicable) and analytical
batch. The method blank is carried through the complete sample preparation and analytical procedure. The
method blank is used to document contamination from the analytical process. The analysis of method blanks
should yield values less than the laboratory's reporting limit. For very high level analyses, blank value should be
less then 5% of the lowest value of the preparatory t if applicable! and anai\ tical hatch or corrective action will be
implemented,
Additional method specific OC requirements - Additional QC samples are run (e.g.. surrogates, internal standards,
continuing calibration samples, interference check samples) and will he specified in the method SOPs being
developed during the course of this stud}'. The requirements for these samples, their acceptance criteria, and
corrective action are method-specilie.
Failures in Oualitv Control and ("m'tecth e \ciion
Sampling QC excursions are ev aluated bv the Baylor I "niv ersity Project Manager, in consultation with the Bay lor
I 'niversitj QAO. In that differences in sample results are used to assess the entire sampling process, including
environmental variability, the arbitrary rejection of results based on pre-determined limits is not practical,
therefore, the professional judgment of the Baylor University Project Manager and QAO will be relied upon in
evaluating results. Rejecting sample results based on wide variabilis is a possibility. Field blanks for trace
elements and trace organics are scrutinized very closelv, Field blank values exceeding the acceptability criteria
-------
may automatically invalidate the sample, especially in cases where high blank values may be indicative of
contamination which may be causal in putting a value above the standard. Notations of field split excursions and
blank contamination are noted in the quarterly report and the final QC Report. Equipment blanks for metals
analysis are also scrutinized very closely.
Corrective action will involve identification of the cause of the failure where possible. Response actions will
typically include re-analysis of questionable samples. In some cases, a site may have to be re-sampled to achieve
project goals.
Laboratory measurement quality control failures are evaluated by the laboratory staff. The disposition of such
failures and conveyance to the project sponsor are discussed below under Failures in Measurement Systems and
Corrective Actions.
Failures in .Measurement Systems and Corrective Actions
Failures in field measurement systems involve, bill are not limited to such things as instrument malfunctions, failures
in calibration, contamination, and quality control samples outside defined limits. In many cases, the field technician
will be able to correct the problem. If the problem is resolvable, then the technician will document the problem on the
field data sheet and complete the analysis. If the problem is not resolvable, then it is conveyed to the Baylor
University Field Supervisor, who will make the determination and notify the Baylor University QAO. If the
analytical system failure may compromise the sample results, the resulting data will not be submitted for loading and
storage in the SWQM portion of the I'RACS database, if data is collected in Texas. The nature and disposition of the
problem is reported on the data report which is sent to the Baylor University Project Manager. The Baylor University
Project Manager will include this information in the CAR and submit with the Progress Report which is sent quarterly
to the sponsoring organization's Project Manager.
-------
Appendix D
CSC Data Review Form
-------
FISH STUDY PEER REVIEW
SAMPLE NO?.: CLASS
Original Reviewer
Second Reviewer
Was the eatire data package renewed? _
I: not what parameters were renewed"
This review '.vai the revolt of (check one > C da:a rtv.r.v isummez:
D fesbase investigation14
O cites: request (please explain below^
0 other (plertse explain below)
Issues noted dunng re-revlew nod resQlutisiK:
RECORD
INSTRUMENT:
SieuMure:
Ccmpletioa Dare:
------- |