&EPA
United States
Environmental Protection
Agency
Office of Acid Deposition,
Environmental Monitoring and
Quality Assurance
Washington DC 20460
EPA/600/8-88/083
June 1988
Research and Development
National Surface
Water Survey
Eastern Lake Survey
(Phase IITemporal
Variability)
Quality Assurance Plan
*j££fc
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EPA 600/8-88/083
June 1988
NATIONAL SURFACE WATER SURVEY
EASTERN LAKE SURVEY (PHASE II TEMPORAL VARIABILITY)
QUALITY ASSURANCE PLAN
by
J. L. Engels, T. E. Mitchell-Hall, S. K. Drouse',
M. D. Best, and D. C. McDonald
Lockheed Engineering and Management Services Company, Inc.
Las Vegas, Nevada 89119
Contract No. 68-03-3249
Project Officer
Robert D. Schonbrod
Exposure Assessment Research Division
Environmental Monitoring Systems Laboratory
Las Vegas, Nevada 89193-3478
ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
:ICE OF RESEARCH AND DEVELOPM
, ENVIRONMENTAL PROTECTION AG
LAS VEGAS, NEVADA 89193-3478
OFFICE OF RESEARCH AND DEVELOPMENT^, ., , f.,.
U.S. ENVIRONMENTAL PROTECTION AGENCY ' ''"
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NOTICE
The information in this document has been funded wholly or in part by the
United States Environmental Protection Agency under contract number 68-03-3249
to Lockheed Engineering and Management Services Company, Inc. It has been
subject to the Agency's peer and administrative review, and it has been
approved for publication as an EPA document.
Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
ii
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ABSTRACT
The National Surface Water Survey is part of the National Acid Precipi-
tation Assessment Program. This survey has been undertaken to evaluate the
current water chemistry of lakes and streams and to select regionally repre-
sentative surface waters for a long-term monitoring program to study changes
in aquatic resources. A synoptic survey of lakes in the eastern United States
was included in the first phase of the National Surface Water Survey. The
Eastern Lake Survey-Phase II involves an evaluation of within-lake chemical
variability for a subset of lakes sampled during Phase I. This manual delin-
eates the quality assurance plan for the Eastern Lake Survey-Phase II.
To ensure that procedures are performed consistently and that the quality
of the data generated can be determined, the Quality Assurance Project Plan for
the Eastern Lake Survey-Phase II specifies the following measures:
° Provide detailed, written sampling methodology.
Train all personnel participating in field activities.
e Conduct site visits to each field base and to the processing laboratory
during the sampling period to ensure that all methods are performed
properly.
Perform extensive evaluation of analytical laboratories before their
selection and throughout their participation.
Assess variability introduced at each level of activity in field and
analytical laboratories by processing audit samples (synthetic samples
and natural lake samples), duplicates, and blanks as well as routine
samples.
Provide detailed, written analytical methodology.
Use internal quality control procedures at the processing and analyt-
ical laboratories to detect potential contamination and to verify
established detection limits.
Enforce the requirements for maximum allowable sample holding times.
Use protocols in the field and in the processing and analytical
laboratories to confirm that the reported data are correct.
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° Enter data manually into the data base twice and scan for outlying
values to eliminate the effects of transcription errors.
c Verify data by means of range checks, internal consistency checks,
quality assurance evaluations.
and
Validate verified data by analysis of the reasonableness of data; base
the analysis on the values expected for the particular region or
subregion involved.
A final report providing results and discussion of quality control and
quality assurance issues will be prepared following completion of survey
activities.
This report was submitted in partia. fulfillment of Contract No. 68-03-3249
by Lockheed Engineering and Management Services Company, Inc., under the spon-
sorship of the U.S. Environmental Protection Agency. This report covers a
period from February, 1986, to June, 1987, and work was completed as of October,
1987.
IV
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CONTENTS
Section Page Revision
Abstract iii 2
Figures viii 2
Tables ix 2
Abbreviations xi
Acknowledgment xiii 2
1.0 Introduction 1 of 4 2
2.0 Project Description 1 of 4 2
2.1 Objectives 1 of 4 2
2.2 Subsurvey* 1 of 4 2
2.3 Purpose of the Quality Assurance Plan 3 of 4 2
3.0 Project Organization 1 of 3 2
4.0 Quality Assurance Objectives 1 of 5 2
4.1 Detectability, Precision, and Accuracy 1 of 5 2
4.2 Completeness 5 of 5 2
4.3 Representativeness 5 of 5 2
4.4 Comparability 5 of 5 2
5.0 Sampling Strategy 1 of 6 2
5.1 Lake Selection 1 of 6 2
5.2 Sampling Design 3 of 6 2
6.0 Field Operations 1 of 18 2
6.1 Activities of the Sampling Crews 1 of 18 2
6.2 Processing Laboratory Operations 8 of 18 2
6.3 Training 18 of 18 2
7.0 Field Measurement Quality Control Checks 1 of 7 2
7.1 Lake Site Measurements 1 of 7 2
7.2 Processing Laboratory Measurements 2 of 7 2
8.0 Analytical Procedures 1 of 2 2
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CONTENTS (Continued)
Section Page Revision
9.0
10.0
11.0
12.0
13.0
14.0
15.0
Analytical Laboratory Internal Quality Control
9.1 Sample Receipt
9.2 Sample Analysis
9.3 Analytical Laboratory Documentation for Quality
Control
9.4 Internal Quality Control Within Each Method. . . .
9.5 Overall Internal Quality Control
9.6 Instrumental Detection Limits
9.7 Data Reporting
9.8 Daily Evaluation of Quality Control Data
Performance and System Audits
10.1 Performance Audit Samples
10.2 Quality Assurance System Audits (On-Site
Evaluations)
Acceptance Criteria
11.1 Acceptance Criteria for Audit Samples
11.2 Acceptance Criteria for Duplicate Measurements . .
11.3 Acceptance Criteria for Blank Samples
11.4 Corrective Action
Data Management System
12.1 Data Set 1 - The Raw Data Set
12.2 Data Set 2 - The Verified Data Set
12.3 Data Set 3 - The Validated Data Set
12.4 Data Set 4 - The Enhanced Data Set
Data Evaluation and Verification
13.1 Field Data Review
13.2 Analytical Data Review
Data Validation
14.1 Overview
14.2 Detection of Outliers
14.3 Detection of Systematic Error
14.4 Treatment of Outliers and Systematic Differences .
Preparation of An Enhanced Data Set
15.1 Substi tuuon of Values
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I
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CONTENTS (Continued)
Section Page Revision
15.2 Averaging of Field Duplicate Pairs 1 of 3 2
115.3 Treatment of Negative Values 1 of 3 2
15.4 The Enhanced Data Set 3 of 3 2
16.0 References 1 of 4 2
Appendixes
I A. Field and Processing Laboratory Data Forms
anrl I ahpl <;
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and Labels 1 of 13
B. Analytical Laboratory and Quality Assurance
Data Forms 1 of 28
C. Field Operations and Processing Laboratory
On-Site Evaluation Questionnaire 1 of 18
D. Analytical Laboratory On-Site Evaluation
I Questionnaire 1 of 53
E. Eastern Lake Survey - Phase II Preaward Audit
Sample Sw^i ing Sh^t 1 of 3
F. Eastern Lake Survey - Phase II
_ Verification Report 1 of 34
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FIGURES
Number
1-1
3-1
4-1
5-1
5-2
6-1
6-2
6-3
12-1
13-1
14-1
15-1
Structure and timetable of the National Surface
Water Survey
Operational Management Diagram for the Eastern Lake
Survey - Phase II
Flow of quality assurance and quality control samples,
Eastern Lake Survey - Phase II
Flowchart of the lake selection process for the Eastern
Lake Survey - Phase II seasonal surveys
Alkalinity map classes in the Eastern Lake Survey -
Phase II study area
Flowchart of sampling crew activities for the
Eastern Lake Survey - Phase II
Flowchart of processing laboratory activities for the
Eastern Lake Survey - Phase II
Eastern Lake Survey - Phase II field data flow scheme . . .
Data management for the Eastern Lake Survey - Phase II. . .
Flowchart of the data verification process, Eastern
Lake Survey - Phase II
Flowchart of the data validation process, Eastern Lake
Survey - Phase II
Flowchart of the development of the enhanced data set,
Eastern Lake Survey - Phase II
Page
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TABLES
Number
1-1 Sections in This Report and in the Analytical Methods
Manual that Address Quality Assurance Subjects
4-1 Data Quality Objectives for Detectability, Precision,
and Accuracy
5-1 Variables used in Cluster Analyses for ELS-II
Lake Selection . . ....
6-1 Data Forms and Labels used in the Field and in the
Processing Laboratory during the Eastern Lake
Survey - Phase II
6-2 Sample Codes used for the Eastern Lake Survey - Phase II . .
6-3 Aliquots, Containers, Preservatives, and Corresponding
Parameters for the Eastern Lake Survey - Phase II
6-4 Samples for Special Studies Conducted During the Eastern
Lake Survey - Phase II
8-1 Measurements Made by the Analytical Laboratories for the
Eastern Lake Survey - Phase II
9-1 Maximum Allowable Sample Holding Times for the
Eastern Lake Survey - Phase II . .
9-2 Maximum Control Limits for Quality Control Check Samples . .
9-3 Summary of Internal Quality Control Checks
9-4 Data Forms Used by the Analytical Laboratory
9-5 Factors to Convert mg/L to ueq/L
9-6 Chemical Reanalysis Criteria
9-7 Factors for Determining the Conductance of Ions
9-8 Decimal Place Reporting Requirements
ix
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CONTENTS
Section Page Revision
Abstract
Figures
Tables
Abbreviations
Acknowledgment
1.0 Introduction
2.0 Project Description
2.1 Objectives ' .' .-
2.2 Subsurveys
2.3 Purpose of the Quality Assurance Plan. . . .
3.0 Project Organization
4.0 Quality Assurance Objectives
4.1 Detectability, Precision, and Accuracy . . .
4.2 Completeness
4.3 Representativeness
4.4 Comparability
5.0 Sampling Strategy
5.1 Lake Selection
5.2 Sampling Design
6.0 Field Operations
6.1 Activities of the Sampling Crews
6.2 Processing Laboratory Operations
6.3 Training
7.0 Field Measurement Quality Control Checks
7.1 Lake Site Measurements
7.2 Processing Laboratory Measurements
8.0 Analytical Procedures
... iii
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TABLES (Continued)
Number Page
9-9 National Surface Water Survey Laboratory and Field
Data Qualifiers (Tags) 16 of 16
10-1 Theoretical Composition of Field and Laboratory Synthetic
Audit Samples for the Eastern Lake Survey - Phase II ... 2 of 6
10-2 Audit Sample Schedule for the Eastern Lake Survey -
Phase II 4 of 6
12-1 Data Qualifiers (Flags) for the Raw Data Set 3 of 8
13-1 Exception-Identification and Data Review Programs 4 of 8
14-1 Physical Variables Subject to Validation 2 of 8
14-2 Pairs of Variables Used to Check for Random
and Systematic Errors 4 of 8
14-3 Related Groups of Variables Used in
Multivariate Analyses 6 of 8
15-1 Data Qualifiers (Flags) for Validated Data Set 2 of 3
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ABBREVIATIONS3
AAS
ANC
APHA
AQUARIUS III
ASTM
BNC
CD
CE
CI
CRDL
D
DBMS
DIG
DL
DO
DOC
DQO
ELS-I
ELS-II
EMSL-LV
EPA
ERL-C
FIA
HPLC
IBD
ICP
ID
IDL
IFB
IR
LDR
LMD
Lockheed-EMSCO
MIBK
NAPAP
NBS
NCC
NLS
atomic absorption spectroscopy
acid-neutralizing capacity
American Public Health Association
Automated Quality Assurance Review, Interactive Users
System
American Society for Testing and Materials
base-neutralizing capacity
conductance difference
column efficiency
confidence interval
contract-required detection limit
difference
data base management system
dissolved inorganic carbon
detection limit
dissolved oxygen
dissolved organic carbon
data quality objective
Eastern Lake Survey - Phase I
Eastern Lake Survey - Phase II
Environmental Monitoring Systems Laboratory-Las Vegas
(Nevada)
Environmental Protection Agency
Environmental Research Laboratory-Corvallis (Oregon)
flow injection analysis (or analyzer)
high-performance liquid chromotography
ion balance difference
inductively coupled plasma atomic emission spectroscopy
identification
instrumental detection limit
Invitation for Bid
infrared
linear dynamic range
local master data base
Lockheed Engineering and Management Services Company, Inc
methyl isobutyl ketone
National Acid Precipitation Assessment Program
National Bureau of Standards
National Computer Center
National Lake Survey
dThis list does not include units of measurement or chemical symbols.
xi
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ABBREVIATIONS (Continued)
NSS National Stream Survey
NSWS National Surface Water Survey
NTU -- nephelometric turbidity units
p95 -- 95th percent!le
PCA principal component analysis
PCD platinum-cobalt units
PCV -- pyrocatechol violet
PE performance evaluation
QA -- quality assurance
QC -- quality control
QCCS quality control check sample
RSD relative standard deviation
RTP -- Research Triangle Park (North Carolina)
RW simulated rainwater audit sample
SAS -- Statistical Analysis System
SMO Sample Management Office
SOP standard operating procedure
WLS-I Western Lake Survey - Phase I
xi
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ACKNOWLEDGMENT
Contributions essential to the completion of this quality assurance document
were provided by the following: Bill Bardswick (Ontario Air Resources Branch),
Jacqueline Lockard (Illinois State Water Survey, now of Hazardous Waste Research
and Information Center), Kenneth Steele (University of Arkansas), Penelope
Kellar (Kilkelly Environmental Associates), Deb Chaloud, Donna Sutton, Annalisa
Hall, David Peck, Henry Kerfoot, Marianne Faber, Kit Howe, John Nicholson, and
Lynn Stanley (Lockheed Engineering and Management Services Company, Inc.),
Susan Christie, Deborah Coffey, and Robert Cusimano (Northrop Services, Inc.),
and the Computer Sciences Corporation word processing staff at EMSL-LV.
Their assistance is greatly appreciated.
xm
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Section 1.0
Revision 2
Date: 11/87
Page 1 of 4
1.0 INTRODUCTION
Published evidence from site-specific studies is consistent with the
hypothesis that certain surface waters within the United States have decreased
in pH, acid-neutralizing capacity (ANC), or both over time; acidic deposition
possibly contributes to such decreases. Attempts have been made to extrapolate
these local studies to a regional or national scale to estimate quantitatively
the risk to aquatic resources from acidic deposition. These endeavors have
achieved limited success because of problems associated with (1) the compar-
ability of the sampling and analytical methodologies used, (2) the possibility
of biased or nonrepresentative sampling sites, and (3) a small and incomplete
data base. (Linthurst et al., 1986).
To overcome these deficiencies, the U.^ Environmental Protection Agency
(EPA) implemented the Aquatic Effects Research Program (AERP) within its Office
of Research and Development. The AERP is also a major component of the National
Acid Precipitation Assessment Program (NAPAP) Task Group 6 (Aquatic Effects), a
cooperative effort of nine federal agencies. One segment of AERP activities is
the National Surface Water Survey (NSWS). NSWS is designed to evaluate the
present water chemistry of lakes and streams in regions of the United States
potentially susceptible to acidic deposition and to select regionally represen-
tative surface waters for long-term study.
Figure 1-1 shows how NSWS activities relate to each other. The first NSWS
lake study was the Eastern Lake Survey - Phase I (ELS-I), a synoptic survey of
selected lakes in the Northeastern, Upper Midwestern, and Southeastern
United States (Linthurst et al., 1986). ELS-I and the corresponding Western
Lake Survey - Phase I (WLS-I) provided a chemical characterization of lakes
based on a single sample collected from each lake during fall overturn. The
National Stream Survey (NSS) provided a chemical characterization of streams
from samples collected during spring overturn. Phase II of the Eastern Lake
Survey (ELS-II) evaluates within-lake temporal and spatial variability of
physical and chemical characteristics for a subset of lakes sampled during
ELS-I. The information obtained from Phase II sampling will be important in
planning the Temporally Integrated Monitoring of Ecosystems (TIME) project, a
long-term study designed to quantify changes in surface-water chemistry that
result from changes in the level of acidic deposition.
This quality assurance (QA) plan is the final version of the working
drafts and supplementary documentation that have been used during ELS-II
operations to define QA activities. The QA policy of the EPA requires every
monitoring and measurement project to have a written and approved QA project
plan (Costle, 1979a and 1979b). This requirement applies to all environmental
monitoring and measurement efforts authorized or supported by EPA through
regulations, grants, contracts, or other formal means. The QA plan should
specify the policies, organization, objectives, functional activities, QA acti-
vities, and quality control (QC) activities designed to achieve the data quality
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Section 1.0
Revision 2
Date: 11/87
Page 2 of 4
National Surface Water Survey
(NSWS)
National Lake Survey (NLS)
Phase I-Synoptic Survey
Eastern Lake (1934)
Western Lake (1985)
Phase II - Temporal Variability Survey
Eastern Lake (1986)
Snowpack Pilot
Spring Variability Pilot
Spring Seasonal
Summer Seasonal
Fall Seasonal
National Stream Survey (NSS)
Phase I-Synoptic Survey
Pilot Survey (1985)
Synoptic Survey (1986)
Southeast Screening (1986!
Episodes Pilot (1986)
Figure 1-1. Structure and timetable of the National Surface Water Survey.
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Section 1.0
Revision 2
Date: 11/87
Page 3 of 4
goals of the project. All project personnel should be familiar with the
policies and objectives outlined in the QA plan.
EPA guidance states that the 16 items shown in Table 1-1 should be
addressed in the QA project plan (U.S. EPA, 1980). Some of these items are
presented in the methods manuals (Kerfoot et al., in final preparation;
Hillman et al., 1986) for this project. Method-specific discussions are not
repeated in this document.
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Section 1.0
Revision 2
Date: 11/87
Page 4 of 4
TABLE 1-1. SECTIONS IN THIS REPORT AND IN THE ANALYTICAL METHODS
MANUAL THAT ADDRESS QUALITY ASSURANCE SUBJECTS3
Subject
Title Page
Table of Contents
Project Description
Project Organization
and Responsibility
Quality Assurance Objectives
Sampling Procedures
Sample Custody
Calibration Procedures
Analytical Procedures
Data Analysis, Validation,
and Reporting
Internal Quality Control Checks
Performance and System Audits
Preventive Maintenance
Assessment of Precision, Accuracy,
and Completeness
Corrective Actions
Quality Assurance Reports to
Management
This Report
T of C
2
3
4
6
6
6
8
6. 9, 12,
13, 14
7,9
10
6
4, 11
9, 11
9, 10
Analytical
Methods Manual
1
2
2, 3
2
4-13
3
3
2, 3
3
aThese 16 QA subjects must be addressed in every EPA QA Project Plan
(U.S. EPA, 1980).
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Section 2.0
Revision 2
Date: 11/87
Page 1 of 4
2.0 PROJECT DESCRIPTION
In ELS-II, a subset of Northeastern lakes sampled in Region 1 of ELS-I
is resampled to assess the within-lake temporal and spatial variability of
physical and chemical characteristics. ELS-II focuses on lakes that are
considered most susceptible to acid deposition, those with an acid-neutralizing
capacity (ANC) of less than 400 ueq/L.
2.1 OBJECTIVES
Primary objectives to be addressed in ELS-II are:
° Assess the temporal and spatial variability in the fall index sample.
(The fall index sample is the sample that was collected from each
lake during ELS-I. The fall index site is the site in the lake from
which the fall index sample was collected, normally the deepest part of
the lake and normally the center of the lake.)
° Estimate the number of low-ANC lakes (potentially susceptible to
acidic deposition) not acidic in the fall that are acidic in other
seasons, emphasizing spring episodes.
° Establish a baseline for seasonal patterns in lake water chemical
characteristics.
Other objectives include:
Relate the fall index sample to seasonal and annual variability in
water chemistry patterns.
c Relate the lake water chemical characteristics with major watershed,
hydrologic, bathymetric, and autochthonous variables (in cooperation
with other EPA and NAPAP projects).
2.2 SUBSURYEYS
For ELS-II, lake chemistry is measured at least once during each of three
consecutive seasons (spring, summer, and fall seasonal surveys). Additional
sampling is conducted during the spring snowmelt period to permit an evaluation
of the severity of episodes, or acidic releases, into the lakes (spring variability
pilot study). The snowpack of some of the associated watersheds also is sampled
to determine the relationship between snowpack conditions and acidic episodes
in the lakes (snowpack pilot study). In all, then, five subsurveys are contained
in ELS-II: (1) spring variability, (2) snowpack, (3) spring seasonal, (4)
summer seasonal, and (5) fall seasonal. This QA plan pertains to all the
ELS-II subsurveys except the snowpack survey, which has its own QA plan (DeWalle,
1986).
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Section 2.0
Revision 2
Date: 11/87
Page 2 of 4
2.2.1 Spring Variability Pilot
The spring variability pilot study is designed to provide experience in
winter sampling techniques and to obtain data describing the spatial and
temporal variability of lake chemistry during snowmelt. Because of the
intensive sampling required and the difficult sampling conditions, only a few
lakes are included in this survey. For the same reasons, and because the goals
are specific and not directly related to the objectives of the other ELS-II
surveys, lake selection was strongly based on logistical considerations and the
desire to evaluate a range of lake characteristics ana was not random.
The spring variability study includes four experiments: (1) comparing
the data obtained from two different types of in situ monitoring devices,
(2) collecting samples and taking measurements from sites on transects and from
random sites to determine spatial variability In the littoral zone, (3) comparing
two sampling protocols for lakes that are thermally stratified, and (4) evaluating
whether assistance from a diaphragm pump improves the efficiency of sample
collection with a Van Dorn unit.
All the chemical variables that were measured during ELS-I are measured
during the spring variability study. At each lake, samples are collected from
a site by the inlet, a site by the outlet, the fall index site from immediately
below the ice and from mid-hypolimnion, the littoral station with the lowest
pH, and the pelagic station with the lowest pH.
2.2.2 Seasonal Surveys
The three seasonal surveys are conducted to identify annual and seasonal
variations and patterns in lake water chemical characteristics. All the
seasonal samples undergo the same analyses as samples from ELS-I, plus analysis
for pyrocatechol violet (PCV)-reactive aluminum. For each individual seasonal
survey, additional goals and concerns may apply and additional analyses may be
required; these survey-specific goals and analyses are described in the
following paragraphs. The samples are collected from the fall index site.
2.2.2.1 Spring Seasonal Survey
For the spring seasonal survey, samples are collected immediately following
ice-out to provide an index of the lake chemical characteristics during the
spring overturn period before the onset of summer stratification.
2.2.2.2 Summer Seasonal Survey
The summer seasonal survey takes place during the period expected to be
of greatest spatial and temporal variability and of highest pH in the lakes.
In addition to the standard set of analyses, dissolved oxygen is measured in
situ; total nitrogen and chlorophyll a^ are determined in the laboratory; a
second total phosphorus determination is made; tows are taken for zooplankton
counts; and special sample portions are collected from the hypolimnion to deter-
mine if low levels of dissolved oxygen affect the valencies and compounds of
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Section 2.0
Revision 2
Date: 11/87
Page 3 of 4
metals that are present (anoxics study). A laboratory bias study is performed
in conjunction with the summer survey; the two contract analytical laboratories
participating in the survey analyze splits of the same sample so that any
inter!aboratory bias can be identified.
2.2.2.3 Fall Seasonal Survey-
Besides its role as a component seasonal survey, the fall survey serves
as a means to assess the variability, or sampling error, associated with the
fall index sample taken during ELS-I. The degree of sampling error will indicate
the representativeness of the single ELS-I sample as a measure of conditions in
the lake during the fall overturn period.
2.3 PURPOSE OF THE QUALITY ASSURANCE PLAN
The purpose of the QA project plan for ELS-II is to specify measures to
ensure that the procedures are performed consistently and that the data collected
are of known and documented quality. These measures are the following:
° Provide detailed, written sampling methodology (see the ELS-II
field operations report [Merritt and Sheppe, in preparation], which
summarizes the protocols in the unpublished field operations manuals:
Bonoff et al., 1985; Groeger et al., 1985; Drewes et al., 1986; and
Todechiney et al., 1986).
Train all personnel participating in field and sample processing
activities.
Conduct site visits to each field base and to the processing
laboratory to ensure that all methods are performed properly.
Perform extensive evaluation of the performance of analytical
laboratories before their selection and throughout their participation.
° Assess the amount of overall variability introduced in the field, the
processing laboratory, and the analytical laboratories by processing
audit samples (synthetic and natural lake samples), duplicates, and
blanks as well as routine samples. (The processing laboratory is the
laboratory in Las Vegas, Nevada, that performs preliminary analyses; an
analytical laboratory is an off-site contract laboratory that performs
the more detailed chemical analyses.)
Provide detailed, written analytical methodology (see the analytical
methods manuals, Kerfoot et al., in final preparation, and Hillman et al.,
1986).
Use internal QC procedures at the analytical laboratory to detect poten-
tial contamination and to verify the established detection limits.
e Enforce the requirements for maximum allowable sample holding times.
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Section 2.0
Revision 2
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Page 4 of 4
Use protocols in the field, in the processing laboratory, and in the
analytical laboratory to confirm that the reported data are correct.
« Enter data manually into the data base twice, and scan for outlying
values to eliminate effects of transcription errors. (For the summer
and fall surveys, only data from the field forms are entered twice;
data from the analytical laboratories are entered directly onto floppy
disks at the laboratory and are uploaded electronically into the data
base, so double entry is unnecessary.)
Verify the raw data set by means of range checks, internal consistency
checks, and other QA evaluations.
Validate the verified data set by analyzing the scientific reasonable-
ness of the data, based on the values expected for the particular
region or subregion involved.
Following completion of ELS-II activities, a final report will be prepared
that will present and discuss QA and QC analyses and studies.
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Section 3.0
Revision 2
Date: 11/87
Page 1 of 3
3.0 PROJECT ORGANIZATION
Figure 3-1 illustrates the ELS-II operational management structure. The
program director has overall responsibility for the program. The program
managers and technical director have the following responsibilities:
Program Managers. The program managers serve as liaisons between the
headquarters staff, the laboratory directors, and NAPAP personnel.
Questions regarding general management and resources should be forwarded
to the program managers through the technical director.
Technical Director. The technical director sees that the program objectives
are satisfied, that the components of the program are well-integrated, and
that the deadlines are met. The technical director coordinates and inte-
grates the activities of the Environmental Research Laboratory at Corvallis,
Oregon (ERL-C), the Environmental Monitoring Systems Laboratory at Las
Vegas, Nevada (EMSL-LV), and the contractors. The technical director also
coordinates peer reviews and resolves issues of responsibility. The
office of the technical director is the focal point for general public
inquiry and distribution of report information. The technical director
represents the program managers as necessary and keeps the program managers
informed of EPA laboratory activities, progress, and performance.
The following describes the roles of the laboratories at Corvallis and
Las Vegas.
ERL-C is a focal point for ELS-II. Its responsibilities include:
Developing the sampling design.
Selecting the sampling sites.
Preparing the sampling protocols (jointly with EMSL-LV).
Collecting supplemental historical and other available data on each
sampling site (aquatic and terrestrial components).
Analyzing the data (jointly with EMSL-LV).
Interpreting and mapping the data.
Preparing reports (progress and final reports, with contributions from
the other participants relative to their responsibilities).
° Assessing and resolving all science-related issues other than QA/QC
(jointly with other participants as necessary).
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Program Director
Program Managers
Peer Reviewers >|
ERL-C
Sampling Design
Site Selection
Site Description
Data Validation
Data Interpretation
Reporting Routine
Data
Technical Director
EMSL-LV
Field Operations
and Logistics
Special Processing
Operations
Analytical Methods
Data Verification
QA and QC Operations
and Reporting
(including QA
Manager)
Data Management
(with data base
manager)
Figure 3-1. Operational Management Diagram for the
Eastern Lake Survey - Phase II.
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Coordinating activities of survey participants.
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« Independently assessing the variability (accuracy and precision of
I field measurements and laboratory data).
Assessing and resolving all problems pertaining to QA and QC, logistics,
and analytical services.
Coordinating the development and maintenance of a data management
I system, including (1) entry of all field, laboratory, and support data
into the data base and simultaneous assessment of data quality and (2)
preparation of computer-generated summary tables, statistics, and
graphics for reports. Systems Applications, Inc. (SAI), the firm
(contracted to be the data base manager for ELS-II, performs a sub-
stantial part of these activities.
EMSL-LV has particular expertise in matters relating to quality assurance
(QA) and quality control (QC), logistics, analytical services, and sampling
protocols. The responsibilities of this laboratory for ELS-II include:
« Developing the QA and QC procedures for all components of the program.
o Preparing the sampling protocols (jointly with ERL-C).
Preparing methods manuals for the processing and analytical
laboratories.
« Preparing field training and operations manuals.
Preparing and implementing the QA project plan.
Coordinating the logistical support and equipment needs for all field
operations.
« Training the sampling personnel.
Distributing all samples to the analytical laboratories.
Developing and implementing the QA and QC procedures for verification
of field measurements and processing and analytical laboratory data.
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4.0 QUALITY ASSURANCE OBJECTIVES
4.1 DETECTABILITY, PRECISION, AND ACCURACY
The QA objectives for detectability, precision, and accuracy of the
parameters being measured are outlined in Table 4-1. Precision and accuracy
are determined by analyzing data from QA and QC samples. These QA and QC
samples are incorporated into the overall sample flow as indicated in Figure 4-1
External QA samples include:
e Field blank. A field blank is a deionized water sample that meets the
specifications for the American Society for the Testing of Materials
(ASTM) Type 1 reagent water (ASTM, 1984). The field blank is carried
to the lake, passed through the Van Dorn sampler, and processed as
though it were a routine sample. One field blank is collected at two
field sites on each operating day. Only one field blank is analyzed
per sample batch (see Section 6.2.2.1); the other blank (called the
secondary blank) is collected as a precaution in case the first field
blank is contaminated, lost, or destroyed. Field blank data are used
to estimate the system detection limit, the system decision limit, and
the quantitation limit for each type of analysis. For data interpreta-
tion, a data point above the system detection limit is the data point
above which a response is considered positive. The system decision
limit represents the lowest instrument signal that can be distinguished
from background at a = 0.05. The quantitation limit is based on the
variability of blank sample measurements and is used in evaluating the
precision of routine sample measurements (see Best et a!., 1987).
° Field duplicate. A field duplicate is a second sample collected
immediately after the routine sample is collected. Field duplicate
data are used to estimate the overall within-batch precision for sample
collection, processing, and analysis. One field duplicate is collected
by each of two sampling crews each operating day. Only one field
duplicate sample is analyzed each operating day; the other one (called
the secondary duplicate) is collected as a precaution in case anything
happens to the first field duplicate.
° Audit sample. An audit sample is a sample with known characteristics
that TS used in determining the precision and the accuracy of the
measurement system. Two types of audit samples serve as QA checks for
ELS-II: field audit and laboratory audit samples. Field audit samples
(natural and synthetic) are used in checking the overall system (field
and laboratory) performance; laboratory audit samples (natural and
synthetic) are used in checking the performance of the analytical
laboratory. Audit samples are discussed in greater detail in Section
10.0.
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Page
TABLE 4-1. DATA QUALITY OBJECTIVES FOR DETECTABILITY,
PRECISION, AND ACCURACY
Detectability Precision
Required Relative Standard
2 Of 5
Accuracy
Expected Detection Deviation (RSD) Maximum Absolute
Parameter8 Units Range" Limit Upper Limit (S)C
Acid-neutralizing
capacity (ANC) ueq/L -30 - +400 1 10 10
Aluminum, non-
exchangeable
PCV-reactive mg/L 0.0 - 0.3e 0.01 10 10
Aluminum, total mg/L 0.008 - 0.75 0.005 10 (Al>0.01 mg/L)f 10
20 (AK0.01 mg/L)f 20
Aluminum, total mg/L 0.0 - 0.3 0.005 10 (Al>0.01 mg/L)f 10
extractable 20 (Al<0.01 mg/L)f 20
Aluminum, total
PCV-reactive mg/L 0.0 - 0.3e 0.01 10 10
Ammonium mg/L 0.03 - 0.5 0.01 5 10
Base-neutralizing
capacity (BNC) ueq/L +7.0 - +150 °" 10 10
Calcium mg/L 0.4 - 9 0.01 5 10
Carbon, dissolved
inorganic (DIC) mg/L 0.3 - 5.0 0.05 10 10
Carbon, dissolved mg/L 0.4 - 12.5 0.1 5 (DOC>5 mg/L)f 10
organic (DOC) 10 (DOC^5 mg/L)f 10
Chloride ng/L 0.3 - 25 0.01 5 10
Chlorophyll t ug/L 0.5 - 50* 0.1 9 9
Conductance uS/cm 11 - 103 n 2 5
Dissolved ions and metals are determined, except where noted.
bUnless otherwise noted, these are the ranges observed during ELS-1 in the 150 lakes
the ELS-II seasonal surveys; values have been rounded off.
cUn1ess otherwise noted, this is the SRSD at concentrations greater than 10 times the
detection limit.
^Absolute value of blank must be <10 ueq/L.
Bias (1)
(Al>0.01 mg/L)f
IAK0.01 mg/L)f
(Al>"0.01 mg/L)f
(AU0.01 mg/L)f
(DOC>5 mg/L)f
(DOC<5 mg/Lr
(continued)
designated for
required
eAnalysis was not performed during ELS-1; range of expected values was derived from other NSWS
studies when possible.
^Concentration expressed is the mean concentration of the routine/duplicate pairs.
9Not yet available.
"The mean of six nonconsecutive blank measurements must not exceed 0.9 uS/cm.
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TABLE 4-1. (Continued)
Parameter*
Fluoride, total
dissolved
Iron
Magnesium
Manganese
Nitrate
Nitrogen, total
Oxygen, dissolved
(DO)
pH, processing
laboratory
(closed system)
pH, analytical
laboratory
Phosphorus, total
Potassium
Silica
Sodium
Sulfate
True color
Turbidity
Units
g/L
ng/L
mg/L
mg/L
mg/L
mg/L
mg/L
PH
PH
g/L
mg/L
»g/L
mg/L
mg/L
PCUJ
NTUk
Detectability
Required
Expected Detection
Range'1 Limits
0.01
0.0
0.15
0.0
0.0
0.01
7
4.4
4.4
0.0
0.06
0.0
0.1
1.6
0.0
0.0
- 0.33 0.005
- 0.6 0.01
- 2.75 0.01
- 0.3 0.01
- 1.2 0.005
- 20* 0.004
- 12
- 7.6
- 7.6
- 0.1 0.002
- 1.7 0.01
- 7.0 0.05
- 14 0.01
- 15 0.05
- 200 0
- 5 2
Precision
Relative Standard
Deviation (RSD)
Upper Limit (J)c
5
10
5
10
10
6
5
0.1*
0.1*
10(P>0.01 iig/L)f
20(P_<0.01 mg/L)f
5
5
5
5
5<
10
Accuracy
Maximum Absolute
Bias (X)
10
10
10
10
10
5
5
0.1*
0.1*
10(P>0.01 mg/L)
20(P<0.01 mg/L)
10
10
10
10
10
Dissolved ions and metals are determined, except where noted.
''Unless otherwise noted, these are the ranges observed during ELS-J in the 150 lakes designated for
the ELS-II seasonal surveys; values have been rounded off.
cunless otherwise noted, this is the JRSD at concentrations greater than 10 times the required
detection limit.
^Absolute value of blank must be £10 ueq/L.
'Analysis was not performed during ELS-I; range of expected values was derived from other NSWS
studies when possible.
fConcentration expressed is the mean concentration of the routine/duplicate pairs.
9Not yet available.
"The mean of six nonconsecutive blank Measurements oust not exceed 0.9 uS/cm.
^Absolute goal u, applicable units.
JPCU « platinum-cobalt units.
kNTU nephelometrU turbidity units.
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Internal field QC samples are used primarily by the sampling crews and
processing laboratory staff to check the accuracy of the measurement systems
in the field and the processing laboratory. Internal field QC samples
include the following: Hydrolab quality control check sample (QCCS) for
pH and conductance, processing laboratory QCCS for pH, DIC, and turbidity,
trailer duplicate, and trailer (calibration) blank. These are described in
greater detail in Sections 6.0 and 7.0.
Internal analytical laboratory QC samples include the following:
calibration blank, reagent blank, QCCS, detection limit QCCS, and analytical
laboratory duplicate. These are described in Section 9.0.
4.2 COMPLETENESS
Data completeness refers to the amount of valid data obtained from
a measurement system compared to the amount expected to be obtained under
normal operating conditions. Data completeness is assessed for each subsurvey
and is a function of sample collection and analytical systems. The objective
for completeness of data for the ELS-II verified data set is 90 percent or
better for all parameters. This figure is based on experience gained during
previous studies.
4.3 REPRESENTATIVENESS
Representativeness refers to the degree to which the sample data accurately
represent the population of interest. ELS-II, like ELS-I, is not intended to
perfectly characterize a single lake, but to represent the stratum (alkalinity map
class within the geographic subregion) to which the lake belongs. Furthermore,
for ELS-II, only lakes with ANC of less than 400 ueq/L are being studied, so
the population does not include all lakes in a particular region or subregion.
However, the purpose of determining the temporal and spatial variability in the
ELS-II lakes is, in fact, to evaluate the representativeness of the ELS-I fall
index sample. (See Section 9.5.1 for a comparison of the terms "alkalinity"
and "ANC.")
4.4 COMPARABILITY
Data comparability is ensured by using a uniform set of procedures for
all sampling crews and laboratories and a uniform set of units for reporting
the data. The QA procedures described in succeeding sections allow for the
determination of accuracy (bias) for each analytical laboratory so that their
results can be compared. Because of the use of uniform procedures and reporting
units, results are comparable from one NSWS survey to another and to any similar
surveys that use the same procedures and units.
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5.0 SAMPLING STRATEGY
5.1 LAKE SELECTION
This section describes the lake selection process for the three seasonal
surveys. As explained in Section 2.0, the lakes sampled during the spring
variability study were selected based on logistical considerations.
Lakes were selected for the three ELS-II seasonal surveys principally on
the basis of results from the ELS-I synoptic chemical survey. The sampling
strategy for ELS-I was based on a stratified random design with equal alloca-
tion of samples among alkalinity map classes (Linthurst et al., 1986). To
retain the statistical goal of extrapolating the ELS-II results to the popula-
tion of lakes described in ELS-I and to meet funding and logistical constraints,
approximately 50 lakes were chosen for sampling within each stratum in the
Northeast (NLS Region 1). In brief, ELS-II lake selection involved four primary
steps (see Figure 5-1):
Step 1. Examine data to identify lakes of low interest that are not to be
sampled for ELS-II.
Step 2. Examine relationships among the physical and chemical variables
that were studied for the ELS-I lakes and identify clusters of lakes that
have similar characteristics (see Table 5-1). From this process, define
three groups by ANC (as measured in ELS-I): ANC less than 25 ueq/L, ANC
between 25 and 100 ueq/L, and ANC between 100 and 400 peq/L. Figure 5-2
is a map of the alkalinity classes in the study area; it also shows the
five subregions into which the study area is divided.
Step 3. Order the lakes in each group by subregion and site depth to
increase the likelihood for good spatial coverage of lakes throughout the
region.
Step 4. Select specific lakes (designated as "regular" lakes) within each
alkalinity map class (within a probability sampling frame) to be sampled
during ELS-II.
Lakes that have the following characteristics were excluded from considera-
tion for ELS-II:
Lakes with ANC greater than 400 ueq/L.
Large lakes (greater than 2000 ha) (Note: lakes less than about 4 ha
were not sampled in ELS-I and thus are not included in ELS-II).
Shallow lakes (less than 1.5 m in depth).
Lakes highly enriched by nutrients (total phosphorus concentration
greater than 90 ueq/L, nitrate greater than 50 ueq/L, ammonium greater
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RESERVED
LAKES
n»260
7
2. CLUSTER
ANALYSIS
>
1
Figure 5-1. Flowchart of the lake selection process for Eastern Lake
Survey - Phase II seasonal surveys (adapted from unpublished
research plan).
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TABLE 5-1. VARIABLES USED IN CLUSTER ANALYSES FOR ELS-II
LAKE SELECTION
Lake depth Dissolved organic carbon
Watershed area ANC
Lake elevation Sodium chloride
Lake area Aluminum
Lake stratification Calcium and magnesium
pH Nitrate
Color Ammonium
Base cations Total phosphorus
Sodium Turbidity
Sulfate Secchi disk transparency
Silica
than 30 pg/L, turbidity greater than 7 NTU, or Secchi disk transparency
less than 0.5 m).
° Lakes modified significantly by anthropogenic disturbances or in-lake
management practices (e.g., sewage treatment plants, liming operations).
After lakes with these characteristics were excluded, some remaining lakes
were selected as alternates in case a regular lake could not be sampled. Some
special interest lakes, which were not selected according to the probability
frame, were sampled as part of ELS-II; however, these lakes were not included
in population estimates.
5.2 SAMPLING DESIGN
The sampling design for each component study of ELS-II is discussed below.
For every component study, one 4-L Cubitainer and four 60-cc syringes are filled
for each routine sample.
5.2.1 Spring Variability Pilot Study
Spring snowmelt represents the dominant episodic event affecting the
chemical characteristics of Northeastern lakes and streams. Depressions in
lake pH during snowmelt can be highly variable in space and time, and they
cannot be adequately characterized by a single sample or a small number of
samples. Therefore, each lake is sampled at multiple sites on multiple dates.
Because of the sampling intensity, the constraints of manpower, time, and
sample volume, and the design uncertainty, it is not feasible to characterize
the spring snowmelt episodes for a large number of lakes; therefore, the spring
variability study involves only six lakes.
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ALKALINITY CLASSES
U»q/L)
< 100
100 to 200
> 200
STATE BOUNDARY
SUBREGION BOUNDARY)
PENNSYLVANIA
NEW HAMPSHIRE
MASSACHUSETTS
NEW YORK
RHODE ISLAND
CONNECTICUT
NEW JERSEY
Figure 5-2. Alkalinity map classes in the Eastern Lake Survey - Phase II
study area. Adapted from Omernik and Powers (1983)
and Omernik and Kinney (1935).
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On each lake, locations for in situ measurements and sample collection are
situated along transects perpendicular to the lake inlet(s). This maximizes
the probability of detecting acidic contributions from inflowing tributaries
and from direct watershed runoff. The in situ measurements are made and samples
are collected at weekly intervals for about 6 weeks. The first visit to the
lake precedes the initiation of snowmelt.
At each lake, in situ profiles of the temperature, conductance, and pH of
the water column are made at the following sites:
Five stations on each of two transects across each lake, including
sites near tributary inlets, in the littoral (shallower) zone away from
inlets, and in the pelagic (deeper) zone.
° Two tributaries and one lake outlet.
° The fall index site.
Samples are collected each week for a full set of chemical measurements
from the following sites.
The two stations (one littoral and one pelagic) with the lowest
in situ pH values, from immediately below the ice.
° The fall index site; one sample is collected from immediately beneath
the ice and one from 60 percent of the maximum depth (mid-hypolimnion).
The bottom of the tributary reaches immediately above the backwater
of the lake.
The lake outlet.
In addition, instrumentation capable of recording data is placed in the
lake's major inlet to monitor changes in water chemistry continuously.
5.2.2 Spring Seasonal Survey
For the spring seasonal survey, the 150 lakes are sampled one time,
during lake overturn. A sample is collected from each lake at the same
location (fall index site) and depth (1.5 m below the water surface), following
the same sampling procedure used during ELS-I. This minimizes the effect of
spatial variability and improves the evaluation of among-season chemical varia-
bility and patterns. For the seasonal surveys, sampling crews reach the lakes
either by ground and boat access or by helicopter.
5.2.3 Summer Seasonal Survey
Samples for the summer seasonal survey are collected at the same site
in each lake as the ELS-I fall index sample was collected. Samples are
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collected routinely from a depth of 1.5 m from the surface. If the lake is
deeper than 3 m, another sample is collected at either the mid-hypolimnion (if
the lake is stratified) or 1.5 m off the bottom of the lake, as determined from
temperature profile data. In addition to the routine, duplicate, and blank
samples collected in the other seasonal surveys, several other kinds of samples
are taken. A bottle of sample for chlorophyll ^analysis is filled from the
Van Dorn sampling unit. For the anoxics study, additional samples are taken
in syringes for iron and manganese determinations, avoiding air contact.
Three vertical tows with a plankton net are made at each sampling site to
collect zooplankton samples. For the laboratory bias study, a triplicate
sample is collected from near the surface and near the bottom of each lake
from which duplicate samples are collected.
5.2.4 Fall Seasonal Survey
For the fall seasonal survey, 147 lakes are sampled once, following the
same procedures outlined for the spring seasonal survey. The fall survey also
includes a variability study, for which 50 of the 147 lakes are sampled two
additional times to allow the variance component of the fall index sample to be
determi ned.
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TABLE 12-1. (Continued)
C9 Percent conductance difference (%CD) is outside criteria because of
possible analytical error - cation concentration too high (flag suspect
cation).
FLAGS GENERATED BY DUPLICATE PRECISION EXCEPTION PROGRAM:
DO External (field) duplicate precision exceeded the maximum expected percent
relative standard deviation (£RSD), but either the routine or the duplicate
concentrations were <10 x CRDL.
D2 External (field) duplicate precision exceeded the maximum expected percent
relative standard deviation URSD), and both the routine and duplicate
sample concentrations were >1Q x CRDL.
D3 Internal (lab) duplicate precision exceeded the maximum contract-required
percent relative standard deviation (ZRSD), and both the routine and
duplicate sample concentrations were _>10 x CRDL.
FLAGS USED WHEN FIELD DATA ARE OUTSIDE CRITERIA:
FO Percent conductance difference UCD) exceeded criteria when Hydrolab
conductance value was substituted.
Fl Hillman/Kramer protolyte analysis program indicates processing laboratory
pH problem when Hydrolab pH value is substituted.
F2 Hillman/Kramer protolyte analysis program indicates unexplained problem
with field (Hydrolab) pH or processing laboratory DIG value when Hydrolab
pH value is substituted for processing laboratory pH.
F3 Hillman/Kramer protolyte analysis program indicates field problem -
processing laboratory pH.
F4 Hillman/Kramer protolyte analysis program indicates field problem -
processing laboratory PIC.
F5 Hillman/Kramer protolyte analysis program indicates unexplained problem
with processing laboratory pH or DIG values when processing laboratory pH
value is "substituted.
FLAGS GENERATED BY HOLDING TIME EXCEPTION PROGRAM:
HO The maximum holding time criteria were not met.
(continued)
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TABLE 12-1. (Continued)
HI No "Date Analyzed" data were submitted for reanalysis data.
FLAG GENERATED BY DETECTION LIMIT EXCEPTION PROGRAM:
LI Instrumental Detection Limit (IDL) exceeded CRDL and sample concentration
was <10 x IDL.
MISCELLANEOUS FLAG:
MO Value obtained using a method which is unacceptable as specified by the
Invitation for Bid (IFB) contract.
FLAGS GENERATED BY AUDIT CHECK PROGRAM:
NO Audit sample value exceeded upper control limit.
Nl Audit sample value was below control limit.
FLAGS GENERATED BY HILLMAN/KRAMER PROTOLYTE ANALYSIS PROGRAM:
PO Protolyte analysis program indicates lab problem - initial pH from ANC
titration.
PI Protolyte analysis program indicate" lab problem - initial pH from BNC
titration.
P2 Protolyte analysis program indicates lab problem - unexplained - initial pH
from ANC or BNC titration.
P3 Protolyte analysis program indicates lab problem - initial PIC.
P4 Protolyte analysis program indicates lab problem - air-equilibrated pH or
PIC.
P5 Protolyte analysis program indicates lab problem - unexplained - initial pH
from ANC or BNC titration or initial PIC.
P6 Protolyte analysis program indicates lab problem - ANC determination.
P7 Protolyte analysis program indicates lab problem - BNC determination.
(continued)
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TABLE 12-1. (Continued)
FLAGS GENERATED BY QCCS EXCEPTION PROGRAM(S):
Ql QCCS was above contractual criteria.
Q2 QCCS was below contractual criteria.
Q3 Insufficient number of QCCS were measured.
Q4 No QCCS analysis was performed.
EXCLUSION FLAG:
X... Values for X flags should not be included in any statistical analysis.
MISSING VALUE CODE
"." Value never reported. (Note: This code appears in numeric fields only.)
12.2 DATA SET 2 - THE VERIFIED DATA SET
The raw field and laboratory data are transmitted on magnetic tapes from
SAI to the EMSL-LV QA group. All data are then evaluated and verified, and
appropriate flags (see Table 12-1) are applied to the raw data as described in
Section 13.0. The data are processed using the "Automated Quality Assurance
Review, Interactive Users System" (AQUARIUS III), computer-assisted QA system
developed by the EMSL-LV QA staff. Reports generated by AQUARIUS III range in
subject from complex protolyte analysis to simple external and internal blank
checks for QA purposes (see Table 13-1).
The AQUARIUS III aquatics analysis system generates data changes in the
form of transaction records from exception programs and from manually edited
records copied from a local master data base (LMD). These transaction records
are used by the EMSL-LV QA group to update the LMD. Results of verification by
the EMSL-LV QA group consist of a copy of the updated LMD and a history file that
contains the transaction records that were used to update the LMD. The updated
LMD and the history file are sent to SAI. There, the history file is applied to
a copy of the official raw data set and the result is checked against the
updated LMD. When the two data sets agree, the result is the official verified
data set.
In addition to the standard QA analyses, AQUARIUS III is used to generate
various printouts supplied to the QA manager to point out intralaboratory,
inter!aboratory, and interfield bias, as well as discrepancies in blanks,
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audits, or other QA samples. The overall outcome is a verified data set in
which all questionable values are qualified. The QA personnel coordinate
with the field bases, the processing laboratory, and the analytical labora-
tories to make all appropriate corrections in the data.
12.3 DATA SET 3 - THE VALIDATED DATA SET
The validation process begins in tandem with the verification process.
When a computerized version of the verified data set is provided by SAI
through Research Triangle Park (RTP) to the ERL-C staff, validation can be
completed. The validation process increases the overall integrity of the
data base by evaluating all data for internal and regional consistency using
all the QA and QC information available.
The validation process compares data for a set of variables against a
much narrower range utilizing knowledge of relationships in aquatic chemistry
and limnology to identify intrasite sample inconsistencies. Intersite valida-
tion consists of comparing single site values with adjacent sites within a
region. Data for groups of sites are compared and mapped to check for con-
sistency. The validation process is discussed further in Section 14.0. After
undergoing this review process, the data, lake by lake, are transferred to the
validated data base.
12.4 DATA SET 4 - THE ENHANCED DATA SET
Computer calculations of population estimates cannot be performed if values
are missing from the data set. An enhanced data set (Data Set 4) is prepared
to resolve such problems by inserting reliable values where ones are missing in
the validated data set (Data Set 3). Data Set 4 also is modified from Data Set
3 by averaging field duplicate values (if QA precision criteria are met) and by
replacing analytical values determined during validation to be erroneous.
These refinements are described in Section 15. For other applications, use of
the verified or validated data sets may be more appropriate.
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13.0 DATA EVALUATION AND VERIFICATION
Data review begins with daily calls made to the processing laboratory and
each analytical laboratory (1) to ensure that QA/QC guidelines are being fol-
lowed, (2) to ensure that samples are being handled and analyzed properly, (3)
to obtain current sample data, and (4) to discuss problems that may occur
during analyses. The primary objective of these calls is to identify and
resolve issues quickly, before they affect data quality or interfere with the
completion of the survey.
Preliminary sample data are obtained by verbal or computer communication,
by floppy disks sent by overnight courier, or by TELEFAX, depending on the
analytical laboratory. The preliminary data are evaluated by comparing the QA
sample data against acceptance criteria.
Responsible parties are notified of problems and all interactions are
recorded in bound notebooks.
As the processing and analytical laboratory data are received by the
EMSL-LV QA staff, all data are evaluated based on the available QA and QC
information, using the established and organized review process described here.
The objective of the data verification process is to identify and correct,
flag, or eliminate data of unacceptable quality. Computer programs have been
developed to automate this process as much as possible. Each batch of data is
evaluated on a sample-by-sample basis, as described in the following sections.
Figure 13-1 is a summary of the verification process.
13.1 FIELD DATA REVIEW
Each field data form is reviewed to check for the following items:
1. Lake ID. The lake ID recorded on the lake data form is compared to
the lake ID recorded on the batch form to identify and correct trans-
cription errors.
2. Processing Laboratory (Trailer) Duplicate. On the batch form, the
lake ID for the trailer duplicate should match the lake ID for a
routine sample.
3. Hydrolab Calibration Data. The pH and conductance calibration data on
the lake data form are compared to data on the Hydrolab calibration
forms to ensure that initial calibration criteria are met; if the
criteria are not met, correct data qualifiers are noted.
4. Hydrolab pH. The pH reading at 1.5 m, recorded on the lake data form,
is compared to the processing laboratory pH reading on the batch form.
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C>«. »... L-. \
M AMrM U» /
Q" ^X
Figure 13-1. Flowchart of the data verification process,
Eastern Lake Survey - Phase II.
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5. Processing Laboratory (Trailer) pH and DIC. Batch form measurements
for field audit samples are evaluated in accordance with the associated
acceptance criteria. Routine/duplicate pairs and trailer duplicate
pairs are evaluated for precision.
6. Data Qualifiers. Comments and data qualifiers are reviewed for
correct use and consistency.
Data anomalies are reported to the processing laboratory coordinator for
review, and data reporting errors are reported to SAI to be corrected before
entry into the raw data set. All telephone communications are recorded in
bound notebooks and data corrections are annotated on the appropriate forms.
13.2 ANALYTICAL DATA REVIEW
13.2.1 Preliminary Review of Sample Data Package
When the sample data packages are received by the EMSL-LV QA staff, they
are reviewed for completeness, internal QC compliance, and appropriate use of
data qualifiers. The first part of the ELS-II Verification Report (given in
Appendix F) is used to assure consistency in the review of all data packages.
Any discrepancies related to analytical data are reported to the appropriate
analytical laboratory manager for corrective action. If discrepancies affect
billing or data entry, then SMO or SAI is notified. Comments provided in the
cover letter are also reviewed to determine their impact on data quality and
the need for any follow-up action by the laboratory. This data review process
is also important in verifying that the contractual requirements are met for
the purpose of payment.
13.2.2 Review of Quality Assurance and Quality Control Data
The spring variability and spring seasonal analytical data are taken from
the data forms and are entered into the raw data set by SAI as the data packages
are received; the analytical laboratory data from the summer and fall surveys,
which are made available to SAI on floppy disks, are uploaded into the raw data
set. A magnetic tape containing raw data is sent to the EPA IBM 3081 at the
National Computer Center (NCC), Research Triangle Park, North Carolina. Each
tape received by the NCC tape library is given a volume serial number and a BIN
number that indicates the physical location of the tape. The tape is loaded
remotely by the EMSL-LV QA staff, and exception programs, listed in Table 13-1,
are generated by AQUARIUS III.
The remainder of the verification report is completed with the use of
outputs from exception reports (along with the original data and field note-
books). The verification report is a worksheet that systematically guides the
auditor through the verification process: it explains how to flag data, tracks
data resubmissions, tracks reanalysis and confirmation requests, lists the
steps to help explain the QA exceptions, summarizes all modifications to the
raw data base, and lists all flagged sample data.
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TABLE 13-1. EXCEPTION-IDENTIFICATION AND DATA REVIEW PROGRAMS
Program Type
Exception-Generating Programs:
1 = Audit Sample Summary (Lh,LL,FH,FL,FN,FS)
2 = Laboratory/Field Blank Summary (B.LB.FB)
3 = Field Duplicate Precision Summary (R/D Pairs)
4 = Instrumental Detection Limit Summary (All Species)
5 = Holding Time Summary (All Species)
6 = % Conductance Difference Calculations (All Species)
7 = Anion/Cation Balance Calculations (All Species)
8 = Internal Laboratory Duplicates
9 = Protolyte Analysis (DIC, DOC, pH, ANC, and
BNC Data Evaluation)
10 = Reagent/Calibration Blanks and QCCS
Data Review Programs:
1 = Raw Data Listing - Format for QA Manager
2 = Complete Raw Data Listing - Format for Audit Staff
3 = Comparison of Form 1 and Form 2 (pH and DIC)
4 = Comparison of Form 2 and Form 11 (pH and DIC)
5 = QA and QC Flag Summary
6 = Modified Gran Analysis Program
One hundred percent of the analytical data are verified, sample by sample.
A routine lake sample has to meet both the anion/cation ZIBD and JCD criteria
in order to be verified, unless the discrepancy can be explained by either the
presence of organic species (as indicated by the protolyte analysis program) or
an obvious correctable reporting error.
Values for a given analyte are flagged for every sample in a batch, even
though the verification is on a "per sample" basis, when the batch QA sample
data do not meet the acceptance criteria for QA samples such as field blanks,
field duplicates, or audit samples. Each analyte value is also flagged if
internal QC checks such as calibration and reagent blank analytical results,
internal duplicate precision, instrumental detection limits, QCCS analytical
results, and required holding times do not meet specifications. The final
source of flags is the protolyte analysis program. A description of the eval-
uation of DIC, DOC, pH, ANC, and BNC data by the protolyte analysis program
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is given in Section 13.2.3. In all cases, the flags that are generated by
the computer programs are reviewed by the auditor for reasonableness and
consistency before they are entered into the verified data set.
13.2.3 Computer Evaluation of PIC. DOC, pH, ANC, and BNC Data
An evaluative computer program performs data checks and uses carbonate
equilibria and DOC data to identify analytical error and the source of
protolytes (acidic or basic species) in tne sample. The DIG, pH, ANC, and
BNC data are rigorously evaluated in light of known characteristics of
carbonate equilibria. DOC data are introduced to the evaluation with the
use of a theoretical model (the Oliver model - see Section 13.2.3.2) to
predict characteristics of the more complex system. The overall process of
data evaluation based on carbonate equilibria is summarized below.
13.2.3.1 Redundant Alkalinity Checks for pH and DIC
Evaluations of carbonate equilibria indicate that alkalinity is not
affected by changes in dissolved C02 concentration. Furthermore, alkalinity
can be calculated from carbonate equilibria if the DIC and pH are known. A
theoretical alkalinity, C, is calculated from each of the three pH/DIC pairs:
Ci = pH/DIC of "closed system" syringe samples (processing laboratory)
C£ = pH/DIC of "open system" samples (analytical laboratory)
C3 = pH/DIC of "air-equilibrated system" samples (analytical
laboratory)
The third data pair (C3) is obtained from an aliquot that has been
equilibrated with standard air (300 ppm C02). If there is no analytical error,
the three calculated alkalinities should agree within experimental error. The
precision for calculated alkalinity values less than or equal to 100 ueq/L
should be within 10 ueq/L and within 10 percent for calculated alkalinity
values greater than 100 peq/L. The precision windows are based on the
estimated precision of the pH and DIC measurements used in the calculations.
If this comparison indicates a potential analytical error (i.e., the precision
limit is exceeded), the redundant pH and DIC values are compared to identify
the source of error. Further evaluation of the QA and QC information for tne
individual data pairs usually identifies one of the pH or DIC measurements
within the outlier pair as the source of error. Because of the redundancy in
measurement, an acceptable pH or DIC value from one of the data pairs should be
available to the data user for every sample that is analyzed.
13.2.3.2 Verification of Measured ANC
The measured ANC is evaluated by comparing it to the average of the accept-
able calculated values for alkalinity determined during the evaluation of
pH and DIC.
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Carbonate Systems. For a true carbonate system, the measured ANC should
equal (within experimental error) the calculated alkalinity. The measured
value for ANC and the calculated alkalinity should be within 15 ueq/L of each
other for calculated alkalinities less than or equal to 100 ueq/L, and within
10 percent for larger values. If the measured ANC differs from the calculated
alkalinity, an analytical error is indicated in either the titration or in the
pH or DIG measurements.
Mixed Systems. Mixed systems are those represented by samples that have
significant concentrations of other protolytes in addition to the carbonate
species. In natural waters, organic bases derived from humic and fulvic acids
are often present and make a significant contribution to the ANC. The acidic
functional groups of natural humic substances contribute to the BNC of natural
waters as well. The Oliver model is an empirical method of relating DOC, pH,
and organic protolytes in two ways (Oliver et al., 1983). The first way
relates the total organic protolyte content to DOC, and tne second relates the
mass action quotient (pK0) of the organics present to the sample pH.
DOC and pH are measured in each sample. The empirical relationships
(defined by the Oliver model) and the measured pH and DOC values are used to
estimate the contribution of organic protolytes to the measured ANC. The
measured ANC should equal, within experimental error, the sum of the calculated
alkalinity and the estimated organic protolyte contribution, assuming that
significant concentrations of other non-organic protolytes are not present and
there is no analytical error. The precision should be within 15 ueq/L for
calculated ANC less than or equal to 100 ueq/L and within 10 percent for larger
values.
13.2.3.3 Verification of Measured BNC
BNC, unlike ANC, is affected by changes in dissolved C02 concentration.
Therefore, evaluation and verification of those data cannot utilize as much
redundancy as that of ANC data. Only the initial pH and DIC values determined
in the analytical laboratory (data pair Cg) can be used to calculate BNC for
comparison with the measured value. As with ANC, other protolytes can contri-
bute to the measured BNC. An estimate of C02~acidity is calculated from data
pairs and carbonate equilibria. The calculated acidity should equal, within
experimental error, the measured BNC, if no other protolytes are present.
Precision for calculated acidity values less than or equal to 100 ueq/L should
be within 10 ueq/L and within 10 percent for larger values. If the calculated
acidity is greater than the measured BNC, an analytical error in the pH, DIC,
or BNC determination is indicated.
The pH and DIC measurements are verified by the previous tests (QA/QC
redundancy and alkalinity checks). If the calculated acidity is less than the
measured BNC, the difference may be due to the presence of other protolytes or
to an analytical measurement error. The Oliver model is used to evaluate the
contribution from organic protolytes.
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13.2.3.4 System Check for Total Carbonate
For a carbonate system, it can be shown that the sum of alkalinity and
acidity equals total carbonate concentration in the sample. For a mixed
system, it can be shown that the sum of ANC and BNC equals the total protolyte
concentration in the sample. Thus, the calculated values of alkalinity and
acidity can be combined and compared to the sum of the measured ANC and BNC,
as an additional check of the data. For a carbonate system, the sum of ANC and
BNC should equal, within experimental error, the total carbonate concentration
or the sum of calculated acidity and alkalinity. If this sum is less than the
calculated total carbonate, an analytical error is indicated because the two
titrations must account for all carbonate species present in the sample. Other
protolytes or analytical error is indicated if the sum of ANC and BNC exceeds
the calculated total carbonate. Again, the Oliver model is used to evaluate
the data.
The precision of the total carbonate results should be within 15 umole/L
for total carbonate concentrations less than or equal to 100 umole/L, and
within 10 percent for higher concentrations.
The protolyte analysis program generates flags (Table 12-1) based on the
data checks described above to indicate the source of problems.
13.2.4 Follow-up with Analytical Laboratories
After the review of all data has been completed, the analytical labora-
tories are requested to submit completed copies of data reporting forms that
were incomplete when previously submitted, to submit corrections of previously
reported data, to confirm previous results, and to reanalyze certain samples
that do not meet QA/QC criteria. In certain cases, the EMSL-LV QA staff may
request that the analytical laboratory submit the raw data for a particular
sample or batch. These raw data are used (1) to evaluate data anomalies not
easily explained or corrected during the data review process and (2) to support
requests for sample reanalysis or value confirmation. The analytical labora-
tories are required to submit confirmation and reanalysis data on Form 26 (see
Appendix B). The analytical laboratories are directed to respond within a
reasonable time so that the results can be evaluated in time for them to be
useful to the survey.
13.2.5 Evaluation of Outliers Identified by Corvallis Staff
During the verification process, outliers, observations that are not
typical of the population from which the sample is drawn, that have been identi-
fied by the ERL-C staff (see Section 14.2) are examined further by the EMSL-LV
QA staff. For any of these outliers not identified previously, confirmation of
the value is requested from the contract analytical laboratory. Any value
changes are incorporated into the changed data set before it is sent to SAI.
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6.0 FIELD OPERATIONS
Field operations are conducted from field bases under the supervision of
a base coordinator. Each ground crew samples one or two lakes per day; if
helicopters are being used, each helicopter crew samples four to eight lakes
each day. The processing laboratory is considered to be a part of field opera-
tions. The Las Vegas communications center monitors field activities and
tracks sample shipment from the field to the processing laboratory and from
the processing laboratory to the analytical laboratories.
The activities of the sampling crews and the processing laboratory are
discussed in the following sections. More detailed descriptions of field
operations are given in the field operations report (Merritt and Sheppe, in
preparation) and the processing laboratory report (Arent et al., in preparation),
6.1 ACTIVITIES OF THE SAMPLING CREWS
Helicopter and ground crews perform the same sampling activities. The
helicopter crew consists of a pilot, an observer, and a sampler. The sampler
takes all the required measurements and collects the samples. The observer's
responsibilities are to direct the pilot to the correct sampling location, to
ensure that all measurements and sampling operations are performed correctly
and that the data are accurately recorded, and to make technical decisions.
Each ground crew consists of a crew leader and a sampler. The crew leader is
responsible for accurate data transcription and for technical decisions. The
activities of each sampling crew are divided into (1) activities at the field
base and (2) activities en route to or at the lake site. A flow chart of the
sampling crew activities is shown in Figure 6-1.
6.1.1 Base Site Activities
Prior to leaving the field base, the sampling crews perform the following
tasks:
Helicopter crews prepare a detailed navigation sheet that gives courses
and distances for the excursion as well as the navigational coordinates
of each lake to be sampled. A flight plan is filed with the field base
coordinator (and the Federal Aviation Administration) in order to
predict sample arrival times and as a safety precaution. Ground crews
fill out a daily itinerary form that gives directions to the lake(s),
lists predicted call-in and return times, and describes clothing worn
by each member of the crew on that sampling day. Preliminary informa-
tion about a lake, including latitude, longitude, name, and status
(regular, alternate, or special interest) is supplied by ERL-C, local
authorities, or the communications center in Las Vegas. The location
of the fall index site is indicated on a map as the preferred sampling
site.
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ACTIVITIES CONDUCTED AT
FIELD BASE
BEFORE DEPARTURE
1. PREPARE SITE DESCRIPTION.
2. CALIBRATE HYDROLAB.
3. CHECK SUPPLIES FOR DAY'S SAMPLING.
4. LOAD EQUIPMENT.
5. FILE FLIGHT PLAN OR ITINERARY WITH
FIELD BASE COORDINATOR.
ACTIVITIES CONDUCTED AT
FIELD BASE
AFTER SAMPLING EXCURSION
1. UNLOAD SAMPLES.
2. FILE LAKE DATA FORMS WITH
FIELD BASE COORDINATOR.
3. SHIP SAMPLES TO PROCESSWG
LABORATORY.
4. CHECK HYDROLAB CALIBRATION
AND PERFORM REQUIRED
EQUIPMENT MAINTENANCE.
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ACTIVITIES CONDUCTED AT
LAKE SITE
1. TAKE AERIAL PHOTOGRAPHS Of LAKE
(HELICOPTER CREWS ONLY).
2. VERIFY LAKE IDENTITY.
LAST LAKE
TO BE
SAMPLED?
SAMPLING AND MEASUREMENT
ACTIVITIES
1. MEASURE SITE DEPTH.
2. PROFILE CONDUCTANCE. pH AND
TEMPERATURE. DETERMINE
STRATIFICATION STATUS.
3. DETERMINE SECH1 DISK
TRANSPARENCY.
4. PREPARE BLANK (AT FIRST LAKE ONLY).
5. COLLECT WATER SAMPLE IN
VAN DORN BOTTLE
-WITHDRAW SYRMGE SAMPLES.
-TRANSFER REMAINING SAMPLE TO A
4-t CUBITAINER.
6. IF NECESSARY. OBTAIN A DUPLICATE
SAMPLE, A TRIPLICATE SAMPLE. AND ANY
ADDITIONAL SAMPLES THAT ARE NEEDED.
7. VERIFY THAT FORM AND LABELS ARE
CORRECTLY FIUED OUT.
Figure 6-1. Flowchart of sampling crew activities for the
Eastern Lake Survey - Phase II.
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A member of each sampling crew calibrates a Hydrolab unit, which
is used to obtain pH, conductance, DO, and temperature profiles of each
lake. The Hydrolab QC procedures, including calibration, are described
in Section 7.0. Hydrolab calibration data are recorded on the Hydrolab
calibration form (see Appendix A).
The sampling crews then proceed to the first lake to collect samples.
6.1.2 Lake Site Activities
As the helicopter approaches the lake, a member of the helicopter crew
takes photographs of the area. A photograph of a card showing the date and the
lak. identification (ID) number precedes each set of lake photographs taken.
The photograph numbers are entered on the lake data form (Form ID). (Table 6-1
lists the data forms and labels used in the field, and they are shown in
Appendix A.) The observer notes watershed characteristics that can be deter-
mined from the air. The pilot lands the helicopter at or near the deepest part
of the lake. This point is determined by using a combination of visual obser-
vations from the air and a depth recorder.
The ground crews do not photograph the lake sites. The lake data form
contains an outline of the lake, sketched previously from topographic maps.
The sampling location is marked on the sketch with an X. The ground crew
navigates a boat to the indicated sampling location and locates the exact
sampling site (the deepest spot) by using a weighted sounding line.
NOTE: When the sampling crew arrives at the given coordinates, the
members may find conditions that require special handling. No
sample is taken if there is found to be: (1) no lake, (2) more
than one lake, (3) a stream or flowing water, (4) a lake too
shallow to allow collection of a debris-free water sample (less
than 0.75 to 1.5 m deep), (5) an inaccessible lake (usually ice-
covered), (6) a lake with high conductance (greater than 1500
uS/cm), (7) a small lake (less than 4 ha), (8) an urban or
industrial site, (9) a stock pond (i.e., an agricultural watering
pond), or (10) no permission for access. For a multilobed or
dendritic lake, the observer determines the location of the best
sampling site, following specific guidelines.
The following operations are performed in the order given. The helicopter
pilot maintains position by visual reference to landmarks or an anchored buoy,
as conditions dictate. The ground crew drops anchor well upwind of the sampling
site, permits the boat to drift over the site, and secures the anchor line.
Step 1 - Depth Determination. The lake depth at the sampling site is
determined by using an electronic depth finder (from the helicopter) or
a calibrated sounding line (from a boat). The result is recorded on the
lake data form.
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TABLE 6-1. DATA FORMS AND LABELS USED IN THE FIELD AND IN THE
PROCESSING LABORATORY DURING THE EASTERN LAKE SURVEY - PHASE IIa
Meteorological Form 1A
Sample Collection Form IB Spring Variability Study
Profile Data Form 1C
Lake Data Form ID Seasonal Surveys'3
Batch/QC Field Data Form 2
Shipping Form 3 All Surveys
Hydro!ab Form
Field Sample Label
Field Audit Sample Label
Laboratory Audit Sample Label
Sample Aliquot Labels (7)
Trace Metals Sample Label All Surveys
Summer Survey
Anoxics Study Sample Label
Chlorophyll Sample Label
EMSL Split Label
Zooplankton Sample Label
aForms and labels are shown in Appendix A.
bA different modification of the form was used for each of the three seasonal
surveys.
Step 2 - Parameter Profile. For spring seasonal and fall sampling, the pH,
conductance, DO, and temperature measurements are taken with the Hydro!ab
at 1.5 m below the lake surface and at 1.5 m above the lake bottom. DO is
measured at 1.5 m below the lake surface only, if the temperature difference
is !ess than or equal to 4 °C, the lake is considered unstratified. If the
temperature difference exceeds 4 °C, a third measurement is obtained at 60
percent of the site depth. If the temperature difference between measure-
ments at 1.5 m and at the 60 percent depth is less than 4 °C, the lake is
classified as weakly stratified. If the temperature difference exceeds
4 °C, the lake is considered to be strongly stratified. In a strongly
stratified lake, a temperature and conductance profile is obtained from
measurements taken at 5-m intervals for lakes more than 20 m deep and at
2-m intervals for lakes 20 m deep or less. The results are recorded on
the lake data form.
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During summer sampling, lake profiles are obtained in two stages, descend-
ing and ascending. Care must be used not to cause mixing of the water
near boundaries, especially for stratified shallow lakes.
Descending Stage. Temperature, conductance, pH, and DO are measured at
0.5 m and 1.5 m below the lake surface. Only temperature and conductance
are measured at depths below 1.5 m. Measurements are taken at 1-m
intervals, beginning at 0.5 m below the lake surface, for the first 10.5 m
of the water column. Below 10.5 m, readings are taken at 2-m intervals
until a depth of 1.5 m above the lake bottom is reached. To avoid damage
to the instrument and possible sediment disturbance, the Hydrolab sonde
unit is not lowered deeper than 1.5 m above the bottom.
NOTE: The sonde mu?t be allowed to equilibrate in the lake water for
5 minutes prior to recording the initial reading at 0.5 m below
the surface.
The profile obtained during the descending stage provides the
temperature data necessary for determining the approximate depths of
various thermal zones. First, the top of the hypolimnion is determined.
For the purposes of the summer study, the top of the hypolimnion is
defined as that depth which is approximately 2 °C warmer than the
temperature recorded at 1.5 m above the lake bottom. The depth of the
midpoint of the hypolimnion is then calculated by taking the average
of the depth at the top of the hypolimnion and at 1.5 m above the lake
bottom. The metalimnion (or thermocline) is defined as the layer of
water between 1.5 m below the surface and the top of the hypolimnion.
The midpoint of the metalimnion is that depth calculated as the average
of 1.5 m below the surface and the depth defined as the top of the
hypoliminion.
Ascending Stage. Once the thermal zones have been defined from the
temperature profile, a full Hydrolab profile (temperature, conductance,
DO, and pH) is recorded on the ascending stage for each remaining depth
of interest (i.e., 1.5 m above the lake bottom, mid-hypolimnion, top of
the hypolimnion, and mid-metalimnion).
For the spring variability pilot study, lake profiling consists of
temperature, pH, and conductance measurements taken at each sampling
station. The measurements are taken immediately below the ice, then at
0.5-m intervals to the depth at which the water temperature reaches 4 CC.
Two measurements are made below this depth: one at 1.5 m above the lake
bottom and one at the mid-hypolimnion. For the purposes of the spring
variability pilot study, the top of the hypolimnion is defined as the
depth in the water column where the temperature is 1 °C different than the
temperature measured at 1.5 m above the lake bottom. (For the compar-
ability study mentioned ir, Section 2.1, the ELS-I protocol and the protocol
described above are both followed at the same site. The ELS-I protocol
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calls for measurements to be taken every 0.2 m until the temperature nears
4 °C; below that depth, measurements are taken every 2 m if the site depth
is less than 20 m, or every 5 m if the site depth is greater than 20 m.)
Field data obtained during the spring variability pilot study are recorded
on a set of forms specific to that survey (Meteorological Form 1A, Sample
Collection Form IB, and Profile Data Form 1C - see Appendix A).
Step 3 - Determination of Secchi Disk Transparency. A Secchi disk secured
on a calibrated line is lowered on the shady side of the helicopter or
boat until the disk disappears from view. The disk is then raised until
it reappears. The depths at which the Secchi disk disappears and re-
appears are recorded on the lake data form. Their average is the Secchi
disk transparency. The observer must not wear sunglasses.
Step 4 - Sample Collection. Water samples are collected in a 6.2-L Van
Dorn bottle that has been rinsed with lake water. For spring seasonal and
fall sampling, the Van Dorn bottle is lowered to 1.5 m below the lake
surface. It is triggered to collect the sample, then is raised. During
summer samp". in3, an additional sample is collected either from the mid-
hypolimnion (in stratified lakes) or from 1.5 m above the bottom (in
isothermal lakes). It is imperative that air not be introduced into
the Van Dorn bottle before steps 5 and 6 are performed.
NOTE: Sample collection is performed on the upwind side of the
helicopter or boat to minimize the possibility of contamination.
For the spring variability pilot study, the Van Dorn bottle is not
immersed. Instead, water is pumped to the surface into a modified Van
Dorn by means of a diaphragm pump and Tygon tubing. The equipment is
rinsed, and water samples are collected from just below the ice cover at
the littoral and pelagic stations with the lowest pH values, at the lake
outlet, and at one or two lake inlets. Two additional samples are collected
at the fall index site: one from immediately below the ice cover and one
from mid-hypolimnion.
Step 5 - Collection of Syringe Samples. A 20-mL aliquot is withdrawn
from the Luer-Lok syringe port on the Van Dorn bottle by means of a 60-mL
syringe equipped with a valve. The syringe is rinsed with this aliquot
and the rinse water is discarded. The rinse procedure is repeated at
least two more times. A 60-mL sample aliquot is withdrawn from the Van
Dorn bottle and the syringe is sealed. Three more syringe samples are
obtained similarly. (For the summer survey, a fifth syringe of sample
is taken; no syringes are filled with the triplicate sample collected
for the laboratory bias study.) A field sample label (shown in Appendix
A) is completed and attached to each syringe. Batch ID and sample ID
numbers are assigned at the processing laboratory. After the syringes
are labeled, they are placed in a plastic bag and are stored in a
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cooler (maintained at 4 CC). Of the four syringes normally filled for
each routine and duplicate sample, two are for pH and DIG measurements
at the processing laboratory, one is for the PCV-reactive aluminum
measurement at the processing laboratory, and one is for the extract-
able aluminum measurement at the analytical laboratory. The filled
fifth syringe from summer sample collection is for the anoxics study
iron and manganese determinations.
Step 6 - Sample Transfer. A clean 4-L Cubita^er is rinsed with three
500-mL portions of sample. The Cubitainer is filled with sample, is
compressed to remove all headspace, and is capped securely. The field
sample label is completed and attached. After the- rubitainer is labeled
(and identification is written on the Cubitainer wall itself), it is
stored in the cooler.
Step 7 - Duplicate Sample Collection. At an assigned lake each day, one
crew from each field base site (as assigned by the field base coordinator)
collects a duplicate sample by repeating steps 4 through 6. On the label
(see Appendix A), sample type "Duplicate" is checked.
Step 8 - Collection of Field Blank Samples. One field blank is prepared
at the first lake visited each day by one crew from each of two field
bases. In place of step 4, the Van Dorn sampler is rinsed with three
200-mL portions of deionized water and is filled with deionized water.
Step 6 is performed as for a routine lake water sample. The sample type
"Blank" is checked on the field sample label. Two syringes are filled
with sample for the aluminum determinations before the Cubitainer is
filled.
Step 9 - Collection of Additional Samples for the Summer Survey. A
triplicate sample is collected for the laboratory bias study from 1.5 m
below the surface during the summer sampling. Summer sampling also
includes collection of samples for chlorophyll and zooplankton determi-
nations, and, as mentioned in step 5, samples for the anoxics study.
The chlorophyll sample is drawn from the residual sample collected in the
Van Dorn from 1.5 m below the surface. Anoxics study samples are taken
from the lake water collected in the Van Dorn bottle from mid-hypolimnion
or from 1.5 m above the bottom. In addition, three zooplankton tows are
taken.
Step 10 - Equipment and Sample Storage. Upon completion of steps 1 through
9, the Hydrolab sonde and the Van Dorn bottle are rinsed with deionized
water and are stored securely in the boat or helicopter. The observer or
crew leader verifies that the data form or forms are properly completed
and that all containers are sealed tightly and are correctly labeled.
Step 11 - Sampling at Subsequent Lake Sites. The helicopter or ground
crew proceeds to the next lake where the sampling and measurement
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activities are repeated. The helicopter is refueled, when necessary,
at remote airports or by fuel truck.
Step 12 - Return to Field Base. When there is insufficient time remaining
to sample another lake, the helicopter and ground crews return to the
field base. The Hydrolab calibration is checked at the end of each day,
and results are noted on the calibration form. The manufacturer's
instructions for care and maintenance of the pH electrodes are followed.
The rechargeable batteries are charged overnight, and the probes are
stored in tap water except for the pH reference electrode, which is stored
in 3M KC1.
6.2 PROCESSING LABORATORY OPERATIONS
This section descrioes the processing laboratory activities outlined in
Figure 6-2. Samples are shipped after each day of sampling from the field
bases to the processing laboratory in Las Vegas, Nevada. The processing lab-
oratory is staffed by a laboratory coordinator, a laboratory supervisor, and
analysts. The laboratory coordinator is responsible for the overall operation
of the processing laboratory (including sample tracking and logistics, data
management, and safety). The laboratory supervisor, with the aid of the
analysts, is responsible for analytical measurements and sample processing.
Six work stations are arranged for these operations: pH and DIG determina-
tions, flow injection analyses (FIA), methyl isobutyl ketone (MIBK) extrac-
tions, sample filtration, sample preservation, and logistics. Depending on
the sample load, one individual may fill more than one position, or more than
one analyst may be assigned to a particular position. When possible, the
laboratory coordinator also assists with sample processing.
Processing laboratory operations are described in detail in Hillman et al.
(1986) and in Arent et al. (in preparation), which summarizes the protocols
in the unpublished processing laboratory manual (Chaloud et al., 1986); the
procedure for determining PCV-reactive aluminum species also is presented in
Kerfoot et al. (in final preparation).
6.2.1 Reagent Preparation
Reagents for aluminum extraction and DIG, pH, and PCV-reactive aluminum
determination are prepared daily prior to sample arrival.
6.2.2 Sample Processing
The following steps describe the sample processing operations. They are
performed in the order given. Unless otherwise stated, these treatments and
analyses apply to all routine, duplicate, field blank, and field audit samples.
For all determinations (see Sections 6.2.2.2, 6.2.2.5, 6.2.2.6, 6.2.2.7, and
6.2.2.8) results are recorded on the Batch/QC Field Data Form, Form 2 (see
Appendix A). Copies of all raw data are sent to the QA manager when requested
or at the completion of survey operations.
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PREPARATION Of REAGENTS
FOR PROCESSING
LABORATORY OPERATIONS
INSTRUMENT
WARM-UP
AND CALIBRATION
RECEIPT OF FIELD
SAMPLES BY LABORATORY
COORDINATOR,
ORGANIZATION OF
SAMPLE BATCHES
BULK SAMPLES
TO ANALYSTS
1 SYRINGE TO
ANALYTICAL
CHEMIST
TURBIDITY
DETERMINATION
ALIQUOT
PREPARATION
AND PRESERVATION
DATA TRANSFER
FORM 2
PREPARATION
OF SOLUTIONS
FOR FIELD CREWS
SHIPMENT OF FORMS
(SAME DAY OR NEXT DAY)
SHIPMENT
OF SAMPLE
ALIOUOTS
Figure 6-2.
Flowchart of processing laboratory activities for the
Eastern Lake Survey - Phase II.
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6.2.2.1 Sample Description and Identification
Samples are organized into batches. Each batch contains 20 to 30 routine,
duplicate, blank, and audit samples collected on a given day for a single
survey, the samples in a batch are processed together. Each batch is assigned
a unique batch ID number, which is recorded on the labels of all samples (and
of corresponding aliquots). Then, each sample is randomly assigned a sample ID
number. The sample ID numbers run consecutively from 1 to the total number of
samples in the batch. The audit samples must not always be assigned the same
sample ID number. The batch and sample ID numbers and the sample types (indi-
cated by the codes given in Table 6-2) are recorded on the batch form. Descrip-
tions of each sample type and of the procedures used for apportioning and
identifying each sample type are given below.
6.2.2.1.1 Routine SamplesOne sample ID number is assigned to all th
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TABLE 6-2. SAMPLE CODES USED FOR THE EASTERN LAKE SURVEY - PHASE II
Sample Type Code Description
Routine lake sample R
Duplicate lake sample D
Field blank sample B
Processing laboratory (trailer) blank TB
Processing laboratory (trailer) duplicate TD
Triplicate lake sample S
Audit F L 1-1
| ID number of audit sample
preparation laboratory
Concentrate lot number
Concentration level/audit type
L - low
H « high
N natural
S synthetic
Type of audit sample
F - field audit sample
L « laboratory audit
sample
RW * simulated rainwater
audit sample
Anoxics study sample sent to
the University of Indiana.
(Anoxics study sample sent
to Las Vegas does not
receive this code).
Chlorophyll sample
Trace metals sample
Zooplankton sample
Total nitrogen and
total phosphorus
sample
G
H
Z
P
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TABLE 6-3. ALIQUOTS, CONTAINERS, PRESERVATIVES, AND CORRESPONDING ANALYSES,
EASTERN LAKE SURVEY - PHASE IIa
Aliquot
(Container Volume)
Preservative
and
Description
Analyses
(250 ml)
2
(15 ml)
3
(250 ml)
4
(125 ml)
(500 ml)
(125 ml)
Filtered, preserved with
HN03 to pH <2
Filtered, extracted with
MIBK-HQ
Ca, Mg, K, Na, Mn,
Fe
Extractable AT
Filtered, no preservative Cl~, total dissolved
F~. S042', N03',
Si02
Filtered, preserved with DOC, NH4+
H2S04 to pH <2
Unfiltered, no preservative pH, BNC, ANC
conductance, DIC
Unfiltered, preserved with Total P
H2S04 to pH <2
Unfiltered, preserved with Total Al
HN03 to pH <2
(125 mL)
aAliquots 2, 3, 4, 5, and 6 must be stored at 4 °C in the dark.
sample ID numbers are recorded on each of the seven aliquot labels and on the
split sample labels. The date and amount of preservative also are recorded on
the label.
After the batch and sample ID numbers are assigned and are recorded on
each sample label, the same information is entered on the batch form. The lake
ID and the appropriate code for each sample (from Table 6-2) also are entered
on the batch form. Then the temporary labels on the laboratory audit sample
aliquots, including portions for special studies, are placed in the laboratory
audit logbook.
6.2.2.1.5 Chlorophyll Audit SamplesA referee chlorophyll sample, which is
the material trapped on a 45-um filter after passing 250 mL of Lake Mead water
through the filter, is added to each batch of chlorophyll samples. Therefore,
about three referee samples are included in the weekly shipment of chlorophyll
samples to the laboratory that analyzes them. The same number of referee
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TABLE 6-4. SAMPLES FOR SPECIAL STUDIES CONDUCTED DURING THE
EASTERN LAKE SURVEY - PHASE II
Destination
Volume
Number
Processing; Analytes
University of
Indiana
University of
10-15 mL
10-15 mL
All samples
Anoxics study
Filtered, pH <2 w/HN03;
Pb, Cd, Ni, Mn, and Cu
Syringe-filtered, pH <2
Indiana
Freshwater
Institute
(Canada)
Oak Ridge
National
Laboratory
(Tennessee)
Academy of
Natural
Sciences
(Philadelphia)
EMSL-LV
EMSL-LV
filter
filter
3x250 mL
125 mL
(in HC1-
washed
bottle)
60-125 mL
samples
Chlorophyll routine,
duplicate, audit,
and referee
samples
Chlorophyll
audit and referee
samples only
Zooplankton samples
(3 tows per lake)
no true duplicates,
no blanks or audits
All samples
(summer survey
only)
Anoxics study
samples
w/HN03; Pb, Cd, Ni, Mn,
and Cu
250 mL unpreserved sample
filtered, filter stored at
-20 °C in dark; chlorophyll
250 mL unpreserved sample
filtered, filter stored at
-20 °C in dark; chlorophyll
Filtered (net tow),
preserved with 4 percent
formalin/sucrose;
zooplankton
Unfiltered, pH <2 w/H2S04;
total N and total P
Syringe-filtered, pH <2
w/HN03; Fe and Mn
samples is shipped to a second laboratory for analysis. A standard chlorophyll
extract, obtained from EMSL-Cincinnati, is analyzed by both laboratories after
all of the survey samples have been analyzed.
6.2.2.1.6 Rainwater Audit SamplesFor the fall seasonal survey, simulated
rainwater samples are included in the audit sample schedule so that the amount
of absolute bias, if any, can be assessed. Two formulations of rainwater audit
samples are used, and the compositions are certified by the National Bureau of
Standar'4: (NBS). To avoid contaminating the NBS samples, the containers are
not opened at the processing laboratory; the labels are changed and the samples
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are sent to the analytical laboratory in the same containers in which they were
received.
6.2.2.2 DIG Determination--
Immediate ly after assignment of batch and sample ID numbers, one analyst
begins the DIG analyses. The routine and duplicate samples for DIC determina-
tion are contained in sealed syringes that were filled at the lake site. For
field audit samples, a syringe sample is taken from the 2-L sample. The QC
procedures for DIC analysis are discussed in Section 7.2.1.
6.2.2.3 Sample Filtration, Preservation, and Aliquot Preparation-
All manipulations are performed under a laminar flow hood by analysts
wearing gloves. Sample filtration and preservation are described in the
processing laboratory report (Arent et a!., in preparation) and Hillman et al.
(1986). Seven aliquots and any required additional sample portions are prepared
from each bulk sample as specified in Table 6-3.
Several types of special samples are collected or prepared for specific
purposes. The types of special samples and the destinations to which they are
sent are given in Table 6-4. For all surveys, 10-to-15-mL splits of all samples
are shipped to the University of Indiana for determination of lead, cadmium,
nickel, manganese, and copper. These splits are processed in the same manner
as aliquot 1.
For the summer survey only, additional samples are needed for four special
studies:
c Concern exists that the oxidation of iron and manganese in anoxic
hypolimnetic samples could result in the formation of large colloids
that would be removed from the sample during filtration; a study is
included in the summer survey to determine if hypolimnetic samples are
anoxic, if large colloids are formed, and how to avoid the problems
these occurrences would present. This study requires collecting
hypolimnetic samples in syringes through 0.45 pm filters without exposing
the samples to the atmosphere, then immediately preserving them. The
samples are preserved with nitric acid that has been placed in the
125-mL aliquot bottles into which the anoxic samples are transferred.
A 15-mL portion of the sample is taken from each bottle and is shipped
to the University of Indiana for analysis. The remaining sample is
analyzed at EMSL-LV.
e At the processing laboratory, the chlorophyll a samples collected at
the lake site are placed in a freezer at -20 T, assigned identification
numbers, and put in batches. Additional QA samples are assigned to
each batch as described in Section 6.2.2.1.
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° A 125-mL split of each routine, duplicate, audit, and blank sample is
processed for analysis of total nitrogen and total phosphorus. The
splits are preserved with sulfuric acid and are shipped daily under
refrigeration to EMSL-LV for analysis.
Zooplankton tows are treated with a sucrose/formalin preservative in
the field; at the processing laboratory they are logged in and are stored
at room temperature until the end of the survey, when they are shipped
for analysis to the Academy of Natural Sciences in Philadelphia.
6.2.2.4 Preparation of Aliquots for Determination of Extractable Aluminum-
One or two analysts begin this procedure at the same time that the DIG
measurements are begun. The aluminum in a filtered (0.45-um pore size) sample
is complexed with 8-OH quinoline, and the complex is extracted from the sample
into an methyl issbatyl ketone (MIBK) layer. The MIBK extract is transferred
to a 15-mL centrifuge tube, which is capped tightly. An aliquot label is
attached to the tube. This is aliquot 2 in Table 6-3. The aliquot is stored
at 4 "C in the dark until shipment.
6.2.2.5 pH Determination
The pH of a sample is determined on a sample portion drawn from one of the
syringes, after the sample reaches room temperature. Portions of the sample
from the other syringes are needed only if the process must be repeated or
instrument stabilization is extremely slow. The QC procedures for pH deter-
mination are discussed in Section 7.2.2.
NOTE: pH is also measured in situ with the Hydrolab during field
operations.
6.2.2.6 Turbidity Determination--
A Monitek Model 21 laboratory nephelometer is used to determine the
turbidity of the samples. The nephelometer is calibrated directly in
nephelometric turbidity units (NTU). The QC procedures for turbidity
determination are discussed in Section 7.2.3.
6.2.2.7 True Color Determination--
After centr ifugation of the sample to remove turbidity, the color is
determined using the Hach Model CO-1 Color Test Kit, following the manufac-
turer's instructions. The QC procedures for true color determination are
discussed in Section 7.2.4.
6.2.2.8 Determination of PCV-Reactive Aluminum--
Two dissolved aluminum fractions in the routine, duplicate, blank, and
field audit samples are measured simultaneously with a Lachat automated flow
injection analyzer (FIA). One fraction is the aluminum in the sample that
reacts with PCV. The other fraction, isolated by passing a portion of sample
through a cation-exchange column to remove inorganic monomeric a".uii-.^tiir,, is the
relatively nontoxic, nonexchangeable PCV-reactive organoaluminum fraction. If
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desired, the amount of aluminum toxic to fish, the inorganic monomeric fraction,
then can be determined indirectly by subtraction.
In the FIA procedure, hydroxylamine hydrochloride is added to the carrier
stream of deionized water to bind any iron present that would interfere with
the determination of PCV-reactive aluminum. PCV is added to complex the
aluminum, and the stream is buffered to maximize the formation of the complex.
As the sample passes through the flow cell of a colorimeter, the intensity of
the complex color is measured. The complete procedure used for determination
of PCV-reactive aluminum is given in Chaloud et al. (1986) and in Kerfoot et
al. (in final preparation). The QC procedures for PCV-reactive aluminum deter-
mination are discussed in Section 7.2.5.
6.2.2.9 Sample Shipment--
When a batch has been processed completely and is ready for shipment, the
samples are assembled into groups according to tneir shipping destination.
Special samples (see Section 6.2.2.3.1) are shipped to: EMSL-LV (daily);
Oak Ridge National Laboratory, Tennessee (biweekly); Freshwater Institute,
Canada (biweekly); University of Indiana (last day of survey); Academy of
Natural Sciences, Philadelphia (last day of survey). All other samples
are shipped daily to the contract analytical laboratories.
Prior to shipping, six of the aliquots from each sample are individually
taped and bagged and then are put together in a Ziploc bag, which is placed in
a Styrofoam-lined shipping carton. Eight to twelve frozen freeze-gel packs are
placed in the cooler as well, in order to maintain the aliquots at 4 °C. The
MIBK aliquots are shipped in a separate cooler. One set of the shipping form
(Form 3, Appendix A) is completed for each batch, and two of the copies (sealed
in a Ziploc bag) are enclosed in the carton. The carton is sealed and is
shipped by overnight delivery service to its destination.
Upon receiving the shipment, the analytical laboratory personnel check the
temperature and condition of the containers and verify that all the sample
aliquots listed on the shipping form are included in the shipment. If any
discrepancies exist, the processing laboratory coordinator must be notified
immediately.
6.2.2.10 Data Distribution--
One copy of each of the field forms (except shipping forms from the spring
surveys) is kept at the processing laboratory. Other copies are sent to the
locations indicated in Figure 6-3.
One copy of each shipping form is sent to the EPA Sample Management Office
(SMO), which is responsible for disbursements to the analytical laboratories
and levying of penalties when appropriate. Two copies of the shipping form are
sent with the samples to the analytical laboratory. Upon receipt of the samples
by the analytical ".-.^.rdtory, the condition of the samples is noted on the
shipping forms, one copy of which is forwarded immediately to SMO. The original
shipping form is sent to the QA manager.
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ANALYTICAL
LABORATORY
Form 3 (one copy)
Form 3
(one copy)
Form 3
(one copy)
SAMPLE
MANAGEMENT
OFFICE
QA
MANAGER
PROCESSING
LABORATORY
(Keeps one copy of
Forms 1 and 3
[summer and fall
surveys only] and
Form 2
[all surveys])
Form 3
Forms 1 and 2
(originals and one
copy of each);
Form 3 (one copy)
Forms 1 and 2 (originals)
DATA
BASE
Figure 6-3. Eastern Lake Survey - Phase II field data flow scheme.
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After the laboratory analyses have been completed, the results are sent to
the data base manager (SAI) via the QA staff. QA procedures related to the
transfer of data into the data base are discussed in Section 12.0.
6.3 TRAINING
All personnel are trained prior to each survey. Safety procedures and
regulations, field base operations, and processing laboratory analytical proce-
dures are the chief subjects of instruction. Training includes classes and
realistic simulations of actual activities to be performed. These simulations
include helicopter and boat sampling on a lake and sample preparation in the
processing laboratory. Cardiopulmonary resuscitation training and first aid
certification are provided as well.
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7.0 FIELD MEASUREMENT QUALITY CONTROL CHECKS
Field measurements are made by the field crews at the lake sites and are
described in the field operations manuals. The QC checks for these measurements
are presented in Section 7.1. Section 7.2 delineates the QC checks for the
measurements made in the processing laboratory.
7.1 LAKE SITE MEASUREMENTS
The lake site measurements consist of three Hydrolab determinations (lake-
water temperature, pH, and conductance), Secchi disk transparency, ai- tempera-
ture, and site depth. During sampling for the seasonal surveys, DO also is
measured with the Hydrolab. All measurements are recorded on the lake data
form.
7.1.1 Hydrolab
The Hydrolab is used to measure in situ lake-water temperature, pH, and
conductance. Seasonal sampling includes an in situ DO measurement.
The QC protocol for Hydrolab measurements consists of two steps: (1)
calibrating the Hydrolab before each sampling trip and (2) measuring quality
control check samples (QCCS) for pH and conductance at the field base and at
the lake site to verify that no drift is occurring in the instrumental response.
0 Calibration. The calibration procedures are performed in a controlled-
temperature environment so that the calibration solutions are at thermal
equilibrium. Standard buffer solutions of pH 4.00 and 7.00 are used to
calibrate the potentiometer of the Hydrolab; for conductance, a standard
solution of 147 uS/cm is used to calibrate the conductivity cell; for
DO, the calibration standard is water-saturated air. The calibration
for the temperature function is set at the factory to ±0.2 °C, and no
daily calibration is needed. The accuracy is checked each day against
a thermometer that meets tolerances set by the National Bureau of
Standards (NBS); if an error of 1 °C or more is found, the manufacturer
shou^ be consulted. An error of this siz^ usually indicates a malfunc-
tion of the instrument. Back-up Hydrolabs are available so that a unit
that does not meet the calibration criteria need not be used.
Quality Control Checks. Three kinds of QCCS solutions are used to
check the stability of the Hydrolab response. Immediately after the
calibration has been completed and again at the end of the day's
sampling, a QCCS of C02~saturated water is analyzed for pH and
conductance in a controlled-temperature environment. The observed
values for the two measurements are recorded and compared to the
theoretical values ai the given temperature and pressure. (The
theoretical pH and conductance values are given in the field operations
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manuals.) If the observed values differ from the theoretical values by
more than ±0.15 pH units or ±20 uS/cm, the instrument is cleaned and
inspected, the calibration is repeated, and the QCCS is reanalyzed. If
the results are still unsatisfactory, the troubleshooting guide and the
instrument manual are consulted, and the day's data are flagged with a
data qualifier.
In the field, a dilute sulfuric acid solution with a pH of 4.00 is used
for the pH QCCS, and a potassium chloride solution of 147 uS/cm ii used
for the conductance QCCS. The QCCS results are recorded, but the
instrument is not adjusted in response to field QCCS measurements. If
the pH differs by more than ±0.20 pH unit or the conductance differs by
more than ±20 uS/cm from the expected value, the discrepancy is noted
on the lake data form. No QCCS solutions for DO are analyzed in the
field.
7.1.2 Secchi Disk Transparency
Secchi disk transparency measurements are taken on the shady side of the
helicopter or boat. The observer must not wear sunglasses. Care must be taken
to leave the sediment on the lake bottom undisturbed.
7.1.3 Air Temperature. Site Depth, and Elevation
Helicopter crews measure air temperature with a thermistor mounted on the
outside of the helicopter. An electronic depth sounder mounted inside the
helicopter is used to determine the deepest part of the lake. The depth
recorder is checked daily against a calibrated sounding line.
The helicopter altimeter reading is used to confirm the map reading of
site elevation; if a discrepancy occurs, it is recorded on the lake data form.
The pilot checks the calibration of the altimeter against the value reported at
a local airport. The frequency of this check is based on the pilot's discretion
and his experience with the aircraft.
Ground crews measure the air temperature with a hand-held thermometer.
The sampling site is located with a weighted sounding line. Elevation is
determined from topographic maps and local sources.
7.2 PROCESSING LABORATORY MEASUREMENTS
DIC, pH, turbidity, PCV-reactive aluminum, and true color are measured at
the processing laboratory. The data are recorded on the batch form. The QC'
procedures are described in detail in Hillman et al. (1986), Kerfoot et al. (in
final preparation), and Chaloud et al. (1986) and are summarized below.
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7.2.1 Determination of Dissolved Inorganic Carbon
DIG is measured in routine, duplicate, and field audit samples using the
Dohrman Model DC-80 carbon analyzer. QC steps are incorporated into the
measurement sequence as follows:
Step 1. Initial calibration is performed by measuring the DIC
calibration standard (10.00 mg/L C).
Step 2. Two QCCS solutions (2.00 mg/L C and 20.00 mg/L C) are measured
to verify the initial calibration.
Step 3. If the measured values of both QCCS solutions are within 10
percent of the theoretical concentrations, the values are entered in the
DIC logbook and analysis proceeds. If the standards are not within 10
percent of the theoretical concentrations, then steps 1 and 2 are
repeated.
Step 4. A calibration tPank is measured.
Step 5. If the measured value of the calibration blank is less than 0.1
mg/L C, the value is recorded and sample analysis continues. If the
measured value of the calibration blank is 0.1 mg/L C or greater, then (1)
the laboratory supervisor is informed, (2) corrective action is taken, and
(3) steps 1 through 5 are repeated. Normally, one calibration blank is
analyzed per batch.
Step 6. DIC is measured for 10 samples.
Step 7. A 2.0 mg/L C QCCS is analyzed to check the calibration.
Step 8. If the QCCS is within 10 percent of theoretical concentration,
the value is recorded in the logbook and sample analysis proceeds. If the
QCCS is not within 10 percent of the theoretical concentration, it should
be determined whether sufficient volume remains of the samples associated
with the unacceptable QCCS to reanalyze them. If enough sample is
available, steps 1 through 7 are repeated, including reanalysis of all
samples since the last acceptable QCCS. If the sample volume is in-
sufficient for reanalysis, the unacceptable QCCS value is recorded in the
DIC logbook and the sample ID numbers associated with the unacceptable
QCCS are noted on the batch form with a data qualifier ("tag"). The use
of NSWS data qualifiers is described in Section 9.7. Sample analysis must
not continue until acceptable QCCS values are obtained.
Step 9. One sample per batch is measured in duplicate. These duplicates
are called trailer duplicates. If the difference between the two measure-
ments is greater thai. 1C percent, another sample is measured in duplicate.
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Section 7.0
Revision 2
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Page 4 of 7
If the difference is still greater than 10 percent, the laboratory
supervisor must be notified, and the problem is noted on the batch form.
Step 10. When sample analysis is complete, a final QCCS is analyzed, and
the relevant QC information is recorded on the batch form.
7.2.2 Determination of pH
pH is determined in routine, duplicate, and field audit samples with an
Orion Model 611 pH meter and an Orion Ross epoxy-body combination pH electrode.
The QC steps are incorporated into the measurement sequence as follows:
Step 1. A one-point temperature check is performed daily; once a week,
a two-point temperature check is performed.
Step 2. The instrument is standardized according to the manufacturer's
instructions.
Step 3. The pH of the NBS-traceable pH 4.00 and pH 7.00 buffers is
measured, and the results are recorded in the logbook. If either
measurement differs from the certified value by more than 0.02 pH unit,
steps 2 and 3 are repeated. If acceptable results cannot be obtained,
the electrode is replaced and the above procedure is repeated.
NOTE: Two pH meters are used when the number of samples in a batch exceeds
20. In this instance, a dilute buffer check is performed to assure that
results are comparable. The dilute buffer check is described in detail in
Chaloud et al. (1986).
Step 4. When satisfactory results have been obtained for the buffers, the
pH of a pH 4.00 QCCS is measured and the result is recorded in the logbook.
If the reading differs from 4.0 by more than 0.1 pH unit, steps 2 and 3
are repeated, and the pH of a fresh QCCS is measured. If acceptable
results still are not obtained, the laboratory supervisor is consulted.
Lake samples are not analyzed until an acceptable value for the QCCS has
been obtained.
Step 5. Samples are measured for pH. A pH 4.00 QCCS is measured after
every five samples. During the summer survey, a pH 4.00 QCCS is measured
after every 10 samples or at the midpoint of each batch, whichever is the
fewer number of samples. The results are recorded in the logbook. If the
measured pH of the QCCS is 4.0 ± 0.1, measurement of samples proceeds.
Step 6. If the QCCS is not acceptable, it should be determined whether
sufficient sample volume remains in any syringes to repeat the analysis.
If so, steps 2 through 4 are repeated and all samples analyzed since the
last acceptable QCCS are reanalyzed. If insufficient sample remains,
the sample ID numbers associated with the unacceptable QCCS are recorded
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Section 7.0
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Page 5 of 7
in the logbook. Steps 2 through 4 are repeated before proceeding with
sample analysis.
Step 7. If two pH meters are being used, a dilute buffer check is
performed after each QCCS analysis.
Step 8. One sample per batch is measured in duplicate. If the difference
between the two measurements is greater than 0.1 pH unit, another sample
is measured in duplicate. If the difference is still greater than 0.1 pH
unit, the laboratory supervisor must be notified, and the problem is noted
on the batch form by means of a data qualifier (see Section 9.7).
Step 9. Each processing laboratory measurement must be within 0.5 pH unit
of the measurement on the same sample taken in the field. If the mea-
surement is outside this range, the processing laboratory measurement is
repeated. If the reanalysis is within 0.1 pH unit of the first measure-
ment, the value is recorded and qualified and the field crew is notified
of a potential problem with the field pH meter. If the reanalysis is not
within 0.1 pH unit of the first measurement, the analysis is repeated a
third time.
Step 10. After the last sample in a batch has been analyzed, a final
QCCS is analyzed, a dilute buffer check is performed if two meters are
being used, and the values are recorded in a logbook.
Step 11. When the pH measurements are completed, the relevant QC infor-
mation is recorded on the batch form.
7.2.3 Determination of Turbidity
Turbidity is determined in routine, duplicate, blank, and field audit
samples with a Monitek Model 21 laboratory nephelometer. The QC steps are
incorporated into the measurement sequence as follows:
Step 1. The nephelometer is zeroed while set on range 2 and then is
calibrated on range 20 with a suspended polymeric standard of 10.0
nepnelometric turbidity units (NTU), following the manufacturer's
recommendations.
Step 2. Calibration linearity is verified by analyzing 2.0, 5.0, and 20.0
NTU QCCS. (The 20.0 NTU QCCS is measured on range 200.) The measured
values must be 2.0 ± 0.2, 5.0 ± 0.5, and 20.0 ± 2.0 NTU. If the measured
values are unacceptable, step 1 is repeated. Acceptable results must be
obtained prior to sample analysis. Acceptable results for the 5.0 NTU
QCCS are recorded on the batch form.
Step 3. After every 10 samples, a 5.0 NTU QCCS is measured. If the
measured value is 5.0 ± 0.5 NTU, the QCCS and sample results are recorded
on the batch form. During the summer survey, a 5.0 NTU QCCS is measured
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Section 7.0
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Page 6 of 7
after every 10 samples or at the midpoint of each batch, whichever is
the fewer number of samples.
Step 4. If the QCCS measurement is unacceptable, the instrument must be
recalibrated and the previous 10 samples must be reanalyzed. Acceptable QC
values are recorded on the batch form along with the associated sample
results. All measurements are reported for range 20. Samples with low
turbidity are measured on range 2; results for range 2 are recorded in
the laboratory notebook but not on the batch form.
Step 5. A trailer duplicate sample is analyzed. The duplicate result
must be within 10 percent of the result for the associated routine
sample. If the results are not within 10 percent of each other, another
sample is analyzed in duplicate. If acceptable results still are not
obtained, the laboratory supervisor is notified and a data qualifier (see
Section 9.7) is recorded on the batch form with the results.
7.2.4 Determination of True Color
True color is determined with a color comparator (Hack Model CO-1 Color
Test Kit). The only QC check on true color measurements is that one sample per
batch is measured in duplicate. If the two measurements differ by more than 10
PCU, another sample is measured in duplicate. If acceptable results still are
not obtained, the laboratory supervisor must be notified and a data qualifier
(see Section 9.7) must be recorded on the batch form with the results. Acceptable
results also are recorded on the batch form.
7.2.5 Determination of PCV-Reactive Aluminum
QC steps are incorporated into the PCV-reactive aluminum procedure for
measurement as follows:
Step 1. The FIA is calibrated with a set of standards with aluminum
concentrations of 0 (an acidified blank), 25, 100, 200, and 350 ug/L.
Starting with the lowest concentration standard, each standard is analyzed
twice in succession. The observed values must be within 10 percent of the
theoretical values, and the correlation coefficient must be at least
0.995, or the instrument must be recalibrated.
Step 2. A QCCS of 75 ug/L aluminum is analyzed. The observed value
must be within 10 percent of the theoretical value (within the range of
67.5 to 82.5 ug/L). If the results for this or any later QCCS do not meet
the criteria, the instrument must be recalibrated.
Step 3. If high concentrations of aluminum are anticipated in the
samples, a second calibration is needed. The standards used for the
high-range calibration have aluminum concentrations of 300, 500, 750,
100U, and 6000 ug/L. The analytical procedure for the high-range
calibration is the same as for the normal calibration. After the
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Section 7.0
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Page 7 of 7
high-range calibration is completed, a 75 ug/L QCCS and a 600 ug/L QCCS
are analyzed. Results for both QCCSs must be within 10 percent of the
theoretical values.
Step 4. A natural audit sample with a known level of nonexchangeable
aluminum is analyzed to check the performance of the exchange column.
The measured value for nonexchangeable aluminum must be within 20
percent of the known value. If the measured value is not within the
required range, the column must be replaced or repacked.
Step 5. Ten samples are analyzed. If the aluminum concentration of any
sample exceeds 350 ug/L, a 600 ug/L QCCS must be analyzed with the next
75 ug/L QCCS routine check.
Step 6. After every ±0 samples and after the last sample, a 75 ug/L QCCS
is analyzed with and without the exchange column. If the observed value
is within the range of 67.5 to 82.5 ug/L, the value is recorded in the
logbook and analysis continues. If the range is not met, the QCCS is
reanalyzed; if the range still is not met, a fresh QCCS is prepared and
analyzed. If a problem still exists, the instrument must be recalibrated,
and all samples analyzed since the last acceptable QCCS result must be
reanalyzed.
Step 7. After the final 75 ug/L QCCS analysis, a natural audit sample
is analyzed to assure that the performance of the exchange column remains
acceptable.
Step 8. A 20 ug/L detection limit QCU is analyzed.
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8.0 ANALYTICAL PROCEDURES
Table 8-1 lists the procedures used by the analytical laboratories to
measure each analyte. A detailed description of these procedures is given in the
methods manuals (Kerfoot et a!., in final preparation, and Hillman et al., 1986).
Internal QC checks on the analytical procedures are discussed in Section 9.0.
TABLE 8-1. MEASUREMENTS MADE
FOR THE EASTERN LAKE
Parameter
1. Acid-neutralizing capacity (ANC)
2. Aluminum, total
3. Aluminum, total extractable
4. Ammonium, dissolved
5. Base-neutralizing capacity (BNC)
6. Calcium, dissolved
7. Carbon, dissolved inorganic (DIC)
8. Carbon, dissolved organic (DOC)
9. Chloride, dissolved
10. Chlorophyll £
Footnotes at end of table.
BY THE ANALYTICAL LABORATORIES
SURVEY - PHASE IIa
Method
Titration and Gran analysis
AASb (furnace)
Extraction with 8-hydroxyquinoline
into MIBK followed by AAS (furnace)
Automated colorimetry (phenate)
Titration and Gran analysis
AASb or ICPESb»c
Instrumental (acidification, C02
generation, infrared [IR] detection)
Instrumental (ultraviolet-promoted
oxidation, C0£ generation, IR
detection)
Ion chromatography
Extraction into methanol followed by
fluorometry and HPLCb
(continued)
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Page 2 of 2
TABLE 8-1. (Continued)
Parameter Method
11. Conductance Conductivity cell and meter
12. Fluoride, total dissolved Ion-selective electrode ana ,n-2ter
13. Iron, dissolved AAS or ICPESb»c
14. Magnesium, dissolved AAS or ICPESb»c
15. Manganese, dissolved AAS or ICPESb»c
16. Nitrogen, total Persulfate oxidation, FIAb with
automated colorimetry
17. Nitrate, dissolved Ion chromatography
18. pH pH electrode and meter
19. Phosphorus, total Persulfate oxidation, FIAb with
automated colorimetry
20. Potassium, dissolved AASb
21. Silica, dissolved Automated colorimetry
(molybdate blue)
22. Sodium, dissolved AASb
23. Sulfate, dissolved Ion chromatography
Analytical laboratories are those contracted to analyze either regular or
special samples.
bAAS = atomic absorption spectroscopy; ICPES = inductively coupled plasma
emission spectroscopy; HPLC - high performance liquid chromatography;
FIA = flow injection analysis.
CICPES may be used for determining calcium, iron, magnesium, and manganese if
the required detection limits can be met. If the ICPES instrumentation is not
able to meet the required detection limits, it may still be used to analyze
samples which contain the analytes at concentrations greater than 10 times the
ICPES detection limit. Other samples must be analyzed by furnace or flame AAS.
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9.0 ANALYTICAL LABORATORY INTERNAL QUALITY CONTROL
9.1 SAMPLE RECEIPT
All samples received by the analytical laboratory are checked in by a
receiving clerk who (1) records the date received on the shipping form,
(2) checks the samples to identify discrepancies with the shipping form,
(3) fills out the "sample condition" column of the shipping form, and (4) mails
a copy of the completed shipping form to the Sample Management Office (SMO).
The "sample condition" column should note such information as leakage in
shipping, insufficient sample volume, noticeable suspended particulates,
partially frozen samples, and the temperature inside the shipping container.
If there are any discrepancies, the processing laboratory coordinator must
be notified immediately. These data are kept in a computer file by the SMO and
are available to interested parties. The laboratory retains a copy of the
completed shipping form for the laboratory records. The samples are
refrigerated as soon as possible.
Samples are received already preserved and ready for chemical analysis.
Sample aliquots 2, 3, 4, 5, and 6 must be kept refrigerated at 4 °C and in the
dark while not in use. When an analysis is to be performed, the analyst
removes a portion of the sample and returns the remaining sample to the
refrigerator as soon as possible.
Even after all analyses have been completed and the results have been
checked, samples remain stored in a refrigerator at 4 °C, in case reanalysis
is necessary.
9.2 SAMPLE ANALYSIS
Procedures given in the methods manual (Kerfoot et al., in final prepara-
tion, or Hillman et al., 1986} are to be followed exactly for each parameter
whose value must be measured. Table 8-1 lists all required measurements and
the associated analytical methods. Table 4-1 lists the required precision and
accuracy, expected ranges, and required detection limits for each parameter.
All analyses for each parameter must be performed within the holding times
specified in Table 9-1.
9.3 ANALYTICAL LABORATORY DOCUMENTATION FOR QUALITY CONTROL
The following documents and information must be updated constantly and
must be available to the analyst and to the supervisor involved in the
project:
« Laboratory standard operating procedures (SOPs) - detailed instruc-
tions about the laboratory and instrument operations.
» Laboratory QA plan - clearly defined laboratory protocol that
specifies personnel responsibilities and the use of QC samples.
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Section 9.0
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TABLE 9-1. MAXIMUM ALLOWABLE SAMPLE HOLDING TIMES
FOR THE EASTERN LAKE SURVEY - PHASE II
Holding
Time
7 days
14 days
28 days
28 days(a)
Parameter
ANC
BNC
Total extract-
able Al
Conductance
DIC
DOC
Chlorophyll a
Total p
NH4+
ci-
SO
2-
Total
dissolved
Si02
Total N
Ca
Mg
K
Na
Total Al
Mn
Fe
EPA (U.S. EPA, 1983) recommends a maximum holding time of 6
months for these metals. This study requires that all of the metals be
determined within 28 days to ensure that significant changes do not
occur and to obtain the data in a timely manner.
(b)Although the EPA (U.S. EPA, 1983) recommends that nitrate in unpreserved
(un-acidified) samples be determined within 48 hours of collection,
evidence exists (Peden, 1981; APHA et al . , 1985) that nitrate is stable
for 2 to 4 weeks if stored In the dark at 4 °C.
(c)Although the EPA (U.S. EPA, 1983) recommends that pH be measured immediately
after sample collection, evidence exists (McQuaker et al . , 1983) that pH is
stable for up to 15 days if stored at 4 °C and sealed from the atmosphere.
The pH is also measured in a sealed sample at the processing laboratory
within 48 hours of sample collection.
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List of in-house samples - including projected dates for completion
of analyses; allows analyst to schedule further analyses.
° Instrument performance study information - information on baseline
noise, calibration standard response, precision as a function of
concentration, and detection limits; used by analyst and supervisor
to evaluate daily instrument performance.
« QC charts - plots of the measured values of the analytes in the QCCS
against the theoretical valje over time. The purpose of the QC charts
is to ensure that the 99 percent control limits for the measured values
do not differ from the theoretical values by more than the limits
given in Table 9-2. At least once a week, the QC charts are updated
by plotting the latest observed concentrations of the QCCS. Then, the
cumulative means, the 99 percei" control limits, and the 95 percent
warning limits are calculated. To ensure the continuity of the QC
charts, a QCCS of the same theoretical concentration must be used
throughout the plotting process. The 99 percent control limit must
not differ from the theoretical value by more than the limits given
in Table 9-2. If it does, the QA manager must be consulted. Bias for
a given analysis is indicated if there are seven or rpore successive
points on one side of the cumulative mean. Current control charts
must be available to the analyst and available during on-site
evaluations.
° Data sheet QC report - report by the laboratory manager reviewing the
QC results for each analysis and flagging for reanalysis those results
that are outside the statistically established QC limits.
9.4 INTERNAL QUALITY CONTROL WITHIN EACH METHOD
Internal QC must be an integral part of any measurement procedure to
ensure that the results are reliable. A summary of the internal QC procedures
for each method is given in Table 9-3.
9.4.1 Initial Calibration
An initial calibration is performed as required for each analytical method.
Next, the linear dynamic range li-DR) is determined for the initial calibrai.uii.
The concentrations of the calibration standards must bracket the expected
sample concentrations. (Occasionally, the standards suggested by a method must
be adjusted to meet this requirement.) The lowest concentration standard should
not be greater than 10 times the required detection limit. If during the
analysis the concentration of the sample i.f outside the LDR, two options are
available. One option is to dilute and reanalyze the sample. In this case,
the diluent should have a matrix similar to the sample matrix with respect to
all preservatives (acid type and concentration) used. Alternatively, two sets
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Section 9.0
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Page 4 of 16
TABLE 9-2. MAXIMUM CONTROL LIMITS FOR QUALITY CONTROL CHECK SAMPLES
Maximum Control Limit for QCCS
(% Difference from Theoretical
Parameter Concentration of QCCS)
Aluminum, extractable ±20
Aluminum, total ±20
Ammoni urn ±10
Calcium ±5
Carbon, dissolved inorganic (DIC) ±10
Carbon, dissolved organic (DOC) ±10
Chloride ±5
Chlorophyll £ No QCCS analyzed
Conductance ±2
Fluoride, total dissolved ±5
Iron ±10
Magnesium ±5
Manganese ±10
Nitrate ±10
Nitrogen, total ±10
Phosphorus, total ±20
Potassium ±5
Si 1i ca ±5
Sodi urn ±5
Sulfate ±5
of calibration standards may be prepared, one to encompass a range of low analyte
concentrations and one to encompass a range of higher concentrations. Samples
are first analyzed with the assumption that the analyte concentration will be
within the LDR of the lower concentration calibration. Each sample whose
concentration exceeds the upper end of that LDR is then reanalyzed using the
higher calibration. The use of the higher concentration calibration must be
noted on Form 21, Dilution Factors, shown in Appendix B. A listing of all
analytical data forms is given in Table 9-4.
9.4.2 Calibration Blank
A calibration blank must be analyzed once per batch, immediately after the
initial calibration, to check for baseline drift and low-level calibration-curve
bias (y-intercept). The instrument is rezeroed if necessary. The calibration
blank is defined as a "0" mg/L standard and contains only the matrix of the
calibration standards. The observed concentration of the calibration blank
must be less than or equal to twice the required detection limit. If it is
not, the instrument must be rezeroed and the calibration must be rechecked.
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Section 9.0
Revision 2
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Page 5 of 16
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Section 9.0
Revision 2
Date: 11/87
Page 6 of 16
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Section 9.0
Revision 2
Date: 11/87
Page 7 of 16
9.4.3 Quality Control Check Sample
Immediately after standardization of the instruments, a QCCS containing
the analyte of interest at a concentration in the middle of the calibration
range must be analyzed. The QCCS may be obtained commercially or it may be
prepared by the analyst from a source that is independent of the calibration
standards (i.e., the QCCS cannot be made by diluting the same stock solution
used to make the calibration standards). The QCCS must be analyzed (and its
measured concentration calcj'aied to verify the calibration curve) prior to
sample analysis, after every 10 samples, and after the last sample analysis.
The observed value for the QCCS must not differ from the theoretical value by
more than the limits given in Table 9-2. When an unacceptable value for the
QCCS is obtained, the instrument must be recalibrated and all samples that were
analyzed after the last acceptable QCCS must be reanalyzed. The observed
concentrations for the QCCS must be plotted on a QC chart as described in
Section 9.3. If bias is indicated (see Section 9.3) analysis must be stopped
and an explanation must be sought.
9.4.4 Detection Limit Quality Control Check Sample
The detection limit (DL) QCCS is a low-level concentration QCCS containing
the analyte of interest at a concentration two to three times the required
detection limit. This QCCS must be analyzed once per batch for extractable Al,
total Al, dissolved metals (Ca, Fe, K, Mg, Mn, Na), total P, and total N. The
results are reported on Form 20, Blanks and QCCS Results (see Appendix B). The
measured value of the analyte in the DL QCCS must be within 20 percent of the
theoretical concentration. If it is not, the problem must be identified and
corrected, and an acceptable result mus* be obtained prior to sample analysis.
The purpose of analyzing the DL QCCS is to eliminate the necessity of formally
determining the detection limit on a daily basis.
9.4.5 Reagent Blank
For methods requiring sample preparation (dissolved Si02, total N, total P,
and total Al), a reagent blank must be prepared and analyzed for each batch of
samples. A reagent blank is defined as a sample composed of all the reagents
(in the same quantities) used in preparing an actual lake sample for analysis.
The reagent blank also is carried through the same digestion and extraction
procedure as an actual sample. The concentration of the reagent blank must be
less than or equal to twice the required detection limit. If the concentration
exceeds this limit, the source of contamination must be investigated and elimi-
nated. A new reagent blank must then be prepared and analyzed for any sample
in which the high concentration reagent blank value contributed significantly
(more than 10 percent) to the value of the analyte in question. If a high
reagent blank problem cannot be corrected, then the QA manager must be contacted,
Reagent blank results are reported on Form 20 but are not subtracted from the
sample results.
-------
TABLE 9-4. DATA FORMS USED BY THE ANAL
Data Form
I
I
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11 Summary of m
llA(b)
13 ANC and BNO|
14
-------
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Section 9.U
Revision 2
Date: 11/87
Page 9 of 16
precision levels given in Table 4-1. The control limits should not exceed
these values. If they do, the QA manager must be notified immediately. If the
duplicate values fall outside the control limits, an explanation must be sought
(such as instrument malfunction or calibration drift). A second, different
sample must then be analyzed in duplicate. No further samples may be analyzed
until the duplicate sample results are within the control limits, unless
approval is given by the QA manager. The percent relative standard deviation
(SRSD) is calculated as described below:
s
ZRSD = x 100
y
n - 1
where: s is the standard deviation
X is an observed value
Y is the mean of the data (observed values)
n is the population of the routine (or other sample)/duplicate
pair (n - 2)
9.4.7 Ion Chromatography Resolution Test
An ion chromatography (1C) resolution test must be performed once per
analytical run (day) by analyzing a standard containing approximately 1 mg/L
each of sulfate and nitrate. If the resolution does not excee-1 60 percent, the
column should be replaced and the resolution test should be repeated.
9.4.8 Column Efficiency Test
A column efficiency test must be performed once per day on the reduction
column of the flow-injection analyzer. A column efficiency (CE) standard is
analyzed; if the result indicates that the column is less than 95 percent
efficient, the column must be reactivated or replaced and the test must be
repeated. After the requirement of 95 percent efficiency is met, a CE QCCS is
analyzed; the measured concentration must be within 10 percent of the actual
concentration.
9.4.9 Continuing Sample Analysis
The remaining samples are analyzed if the reagent blank, the analytical
laboratory duplicate, and the QCCS are within the control limits. After every
10 (or fewer) samples and after the last sample, a QCCS must be analyzed to
continually verify the calibration curve. If the measured value differs from
the theoretical value by more than the limits given in Table 9-2, the
instrument is recalibrated and the previous 10 samples are reanalyzed.
-------
Section 9.0
Revision 2
Date: 11/87
Page 10 of 16
9.5 OVERALL INTERNAL QUALITY CONTROL
Once the value of each sample is determined, several procedures are
followed to check the correctness of analyses:
9.5.1 Anion-Cation Balance
Theoretically, the ANC of a sample equals the alkalinity, or the difference,
(expressed as ueq/L), between the concentration of cations and the concentration
of anions in a sample (Kramer, 1982). In practice, this is rarely the case;
deviations are caused by analytical variability and the presence of ions
(protolytes) that are not measured (e.g., organic ions). The concentrations of
these unmeasured ions can be significant in natural lake water samples. The
percent ion balance difference (SIBD) calculation below utilizes the ANC value
to take these ions into account; as a result, the calculation is more accurate.
For each sample, the percent ion balance difference is calculated as follows:
ANC + I anions - I cations
%IBD = x 100
TI
where:
I anions = [CT] + [F~] + [N03~] + [S042"J
I cations = [Na+] + [K+] + [Ca2+] + [Mg2"*"] + [NH4+]
TI = total ionic strength = ANC + Z anions * £ cations + 2[H+]
ANC * Alkalinity
[H+] = (10-PH) x 106 ueq/L
All concentrations are expressed as microequivalents per liter. A list of
factors for converting the concentration of each analyte from mg/L to ueq/L
is given in Table 9-5.
If the ion balance for a sample does not meet the criteria given in
Table 9-6, the data should be examined for possible causes of an ion balance
that falls outside the criteria. This check may indicate which analytical
results give rise to the unusual ion balance and, hence, the parameters for
which the sample should be reanalyzed. Alternatively, it may be found that
reanalysis is unnecessary; for example, if the percent ion difference is nega-
tive and the DOC is greater than 3 mg/L, unmeasured organic anions are probably
responsible, not analytical error. The QA manager must be contacted when
questions arise regarding reanalysis.
-------
1
1
1
1
1
1
1
1
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1
1
TABLE 9-5. FACTORS
Ion Factor
Ca2+ 49.9
CT 28.2
Mg2+ 82.3
N03" 16.1
r 52.6
Section 9.0
Revision 2
Date: 11/87
Page 11 of 16
TO CONVERT mg/L TO ueq/L
~SSSSSSS«SSS«SSS SS£ZSSESSSSSSSSSwv««SvSZ«
Ion Factor
NH/1" 55.4
4
K+ 25.6
Na+ 43.5
S042' 20.8
TABLE 9-6. CHEMICAL REANALYSIS CRITERIA
A. Anion-Cation Balance
Total Ionic Strength (ueq/L)
<50
>50 <100
7100
B. Conductance
Measured Conductance (uS/cm)
<5
>5 <30
^30
alf the absolute value of the percent
Maximum % Ion Balance Difference3
60
30
15
Maximum % Conductance Differencea
50
30
20
difference exceeds these values, the
sample is reanalyzed. When reanalysis is indicated, the data for each
parameter is examined for possible analytical error. Suspect results are then
redetermined and the above percent di
fferences are recalculated (Peden, 1981).
If the percent differences for reanalyzed samples are still unacceptable, or
if no suspect data are identified, the QA manager must be contacted for
guidance.
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Section 9.0
Revision 2
Date: 11/87
Page 12 of 16
9.5.2 Conductance Balance
An approximation of the conductance of a sample can be calculated by
adding together the equivalent conductance for each measured ion at infinite
dilution. The calculated conductance is determined by multiplying the concen-
tration of each ion by the appropriate factor given in Table 9-7. The percent
conductance difference (%CD) is calculated as follows:
calculated cond. - measured cond.
% CD = x 100
measured conductance
Any sample which has a %CD that exceeds the limit listed in Table 9-5 -'s
reanalyzed. As with the calculation of percent ion balance difference, an
unacceptable value for ZCD indicates either the presence of unmeasured ions
in the sample or an analytical error in the measurement. For the surface
waters sampled during ELS-II, the ions included in the calculation of 2CD
are expected to account for 90 to 100 percent of the ions in a sample.
However, in contrast to the calculation of percent ion balance difference,
there is no term in the %CD calculation to account for protolytes that are
not specifically determined. The QA manager must be contacted when questions
arise regarding why a JCD is outside the criteria and whether reanalysis is
needed.
9.6 INSTRUMENTAL DETECTION LIMITS
Instrumental detection limits (IDLs) must be determined and ; eported
weekly for each parameter except chlorophyll £, pH, conductance, initial DIC,
ANC, and BNC. The IDL for chlorophyll a_ must be checked daily, ror this
study, the reported instrumental detection limit is defined as three times the
standard deviation of 10 nonconsecutive replicate reagent blank or calibration
blank analyses. Calibration blanks are analyzed when a method does not require
a reagent blank (see Hillman et al., 1986; Kerfoot et al., in final preparation]
In some determinations such as those using ion chromatography and automated
analysis, a signal may or may not be obtained for a blank analysis. If a
signal is not obtained for the analysis of a blank sample, the instrumental
detection limit is defined as three times the standard deviation of 10 noncon-
secutive replicate analyses of a standard whose concentration is two to three
times the required detection limit. Reported detection limits must not exceed
the required detection limits listed in Table 4-1.
9.7 DATA REPORTING
Results from each analysis are recorded on the appropriate data forms (listed
in Table 9-4 and shown in Appendix B). For each sample, the analytical
results for aliquots 1 through 7 are reported on Form 11, Summary of Sample
-------
Section 9.0
Revision 2
Date: 11/87
Page 13 of 16
TABLE 9-7. FACTORS FOR DETERMINING THE CONDUCTANCE OF IONS (uS/cm at 25 °C)a
Ion
Ca2+
cr
H+
OH"
HC03"
cos2-
Factor
per mg/L
2.60
2.14
3.5 x 105 (per mole/L)
1.92 x 105
(per mole/L)
0.715
2.82
Ion
Mg2+
Na+
NH4+
S042"
NOo"
K+
Factor
per mg/L
3.82
2.13
4.13
1.54
1.15
1.84
aTaken from American Public Health Association et al. (1985) and Weast (1972).
Ion concentration is multiplied by the listed factor to obtain the conductance
value. The concentrations of the ions that are not measured directly are
calculated by means of the following equations:
where:
pH = initial pH measured before BNC titration. (Brackets
represent molar concentrations,)
K
COH-]
w
where: KW = 1 x 10~13-8 moles/L
5.080 (mg DIC/L) [H+]
HCO," (mg/L) =
ru+~]<: + ["u"1""] |( +1/1
2-
(mg/L)
4.996 (mg DIC/L) KjK2
[H+]2 + [H+DK + KK
where: KX = 4.4463 x 10~7 moles/L K£ = 4.6881 x 10"11 moles/L
-------
Section 9.0
Revision 2
Date: 11/87
Page 14 of 16
Results, to the number of decimal places listed in Table 9-8. EMSL-LV
analytical results for iron and manganese in anoxics study samples and for
total N and total P are reported on Form lla. Results are annotated by the
data qualifiers (tags) listed in Table 9-9, where applicable. After a form is
completed, the analytical laboratory supervisor must sign it, indicating that
he or she has reviewed the data and that the samples were analyzed exactly as
described in the methods manual (Hillman et al., 1986; Kerfoot et al., in final
preparation). All deviations from the methods manual require the authorization
of the QA manager prior to sample analysis.
Copies of raw data must be submitted as requested by the QA manager. All
original raw data must be retained by the laboratory until notified otherwise
by the QA manager. Raw data include data system printouts, chromatograms,
notebooks, QC charts, standard preparation data, and all other information
pertinent to sample analysis.
9.8 DAILY EVALUATION OF QUALITY CONTROL DATA
During periods when survey samples are being analyzed, each laboratory
is required to make a verbal, written, or electronically transmitted status
report daily to the EMSL-LV QA staff. Usually a member of the QA staff
telephones the laboratories to obtain the status report. The objective of
these reports is to keep the QA staff informed of the status of the internal
and external QC checks in the laboratory in order to identify and solve any
problems that may arise. The reports also allow the QA staff to obtain
preliminary results for the blanks, duplicates, and laboratory and field
audit samples that are double-blind to the laboratories. (A discussion of
blind and double-blind samples is presented in Section 10.) Without this
sample status report, these data would not be available for evaluation until
the data packages were submitted by the laboratories, which may be as long
as 35 days after the samples are received. During the daily telephone
contact, the QA staff member records all communications in a bound notebook
in order to track and resolve all problems encountered during the analytical
laboratory operations.
Each week, the QC charts are updated and new control and warning limits
are determined. The QA chemist at the analytical laboratory then performs a
QC audit in which all the data are reviewed. Any values that lie outside the
control or warning limits are checked to verify that they are not the result of
a transcription error. If bias is indicated (seven successive points on one
side of the cumulative mean), analyses are stopped and an explanation is sought.
Copies of the plots are given to the analytical laboratory supervisor, the QA
chemist, and each analyst.
-------
Section 9.0
Revision 2
Date: 11/87
Page 15 of 16
TABLE 9-8. DECIMAL PLACE REPORTING REQUIREMENTS
Required Number of Decimal Places
in Reported Results
Spring Seasonal and Summer and Fall
Parameter Variability Surveys Seasonal Surveys3
Acid-neutralizing capacity 1 1
Aluminum, extractable 3 4
Aluminum, total 3 4
Ammoni urn 23
Base-neutralizing capacity 1 1
Calcium 2 3
Carbon, dissolved inorganic (DIC) 2 3
Carbon, dissolved organic (DOC) 1 2
Chloride 2 3
Chlorophyll £ --2
Conductance 1 1
Fluoride, total dissolved 3 4
Iron 2 3
Magnesium 2 3
Manganese 2 3
Nitrate 3 4
Nitrogen, total 3
pH 22
Phosphorus, total 3 4
Potassium 2 3
Silica 2 3
Sodi urn 23
Sulfate 2 3
aOn the data screens that are used to enter the summer and fall analytical
data, all results appear with four decimal places. However, results are
significant only to the number of decimal places given in this table.
-------
Section 9.0
Revision 2
Date: 11/87
Page 16 of 16
TABLE 9-9. NATIONAL SURFACE WATER SURVEY LABORATORY AND FIELD
DATA QUALIFIERS (TAGS)
Qualifier Indicates
A Instrument unstable
B Redone, first reading not acceptable
C Instruments, sampling gear not vertical in water column
D Slow stabilization
E Sample destroyed during shipment
F Result outside QA criteria (with consent of QA manager)
G Atypical result; already reanalyzed and confirmed by the
laboratory manager
H Holding time exceeded criteria (Form 19 only)
J Result not available; insufficient sample volume shipped
to laboratory from the field
K Result not available; entire aliquot not shipped
L Not analyzed as a result of interference
M Result not available; sample lost or destroyed by laboratory
N Not required
P Result outside QA criteria, but insufficient volume for
reanalysis
Q Result outside QA criteria
R Result from reanalysis
S Contamination suspected
T Leaking container
U Result not required by procedure; unnecessary
V Anion-cation balance (ilBD) outside criteria as a result of
high DOC
W Percent difference (%D) calculation (Form 14) outside criteria
as a result of high DOC
X Available for miscellaneous comments in the field only
Y Available for miscellaneous comments in the field only
Z Available for miscellaneous comments in the field only
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Section 10.0
Revision 2
Date: 11/87
Page 1 of 6
10.0 PERFORMANCE AND SYSTEM AUDITS
10.1 PERFORMANCE AUDIT SAMPLES
Audit samples are samples of known concentration that are incorporated
into the batches of routine samples. Analyzing audit samples and comparing
the results to the known values allows an assessment to be made of the quality
of the survey data. Both natural audit samples (quantities of lake water tnat
have been filtered, preserved, and extensively analyzed to determine the
chemical properties) and synthetic audit samples (laboratory preparations that
have predetermined compositions similar to lake water compositions) are used as
part of the QA activities of ELS-II. Chlorophyll a^ audit samples come from a
different source and are discussed in Section 10.1.2. The audit samples are
shipped to the analytical laboratories from the processing laboratory as though
they were routine lake samples. Every attempt is made to assure that the audit
samples are double-blind to the analytical laboratory; i.e., tnat the laboratory
neither recognizes them as audit samples nor knows their compositions.
10.1.1 Field Audit Samples
The purpose of including field audit samples is to identify sources of
error affecting data quality that may occur during sample processing, shipment,
or analysis. These problems could include sample contamination, sample degrada-
tion, solvent evaporation, and improper or inaccurate sample analysis. When
used in conjunction with the laboratory audit samples, the analysis of these
samples provides data that can be used to distinguish processing laboratory
problems from analytical laboratory problems. There are two types of field
audit samples: field synthetic audit samples and field natural audit
samples.
The field synthetic audit samples are prepared at a central facility
(a contract laboratory independent from those that analyze the ELS-II field
samples) and are sent in 2-L portions to the processing laboratory; there, they
are processed through all the filtration and preservation steps and are labeled
as though they were routine lake samples. Thus, the field synthetic audit
samples are single-blind to the processing laboratory (i.e., recognized as
audit samples but of unknown composition) and are double-olind to the analytical
laboratory.
During the spring and summer activities, the synthetic samples are used
to test the sampling and analysis systems at low concentrations of analytes;
no field synthetic audit samples are scheduled for the fall survey. The
theoretical compositions of the field (and laboratory) synthetic audit samples
are shown in Table 10-1. The compositions of the synthetic audit samples were
based on the expected compositions of lake-water samples.
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Section 10.0
Revision 2
Date: 11/B7
Page 2 of 6
TABLE 10-1. THEORETICAL COMPOSITION OF FIELD AND LABORATORY SYNTHETIC AUDIT
SAMPLES FOR THE EASTERN LAKE SURVEY - PHASE IIa
Field and
Laboratory
Synthetic
Audits:
Spring and
Parameter
Acid-neutralizing
capacity^
Aluminum,
extractable
Aluminum, total
Ammonium
Base-neutralizing
capacity6
Calcium
Carbon, dissolved
Inorganic (DIG)
Carbon, dissolved
organic (DOC)
Chloride
Conductance
Fluoride, total
dissolved
Iron
Magnesium
Manganese
Nitrate
pHb
Phosphorus, total
Potassium
Silica
Sodium
Sulfate
Summer
Surveys
0.020
...
0.19
0.96
1.0
0.34
...
0.042
0.06
0.45
0.10
0.467
, __
0.203
1.07
2.75
2.28
LSI
-39.0
0.0100
0.0200
0.04
49.9
0.030
0.120
0.40
25.000
17.0
0.0300
0.090
0.500
0.300
0.6000
4.40
0.0100
0.250
1.500
0.800
0.100
Laboratory Synthetic Audits
LS2
400.0
0.0150
0.0300
0.07
7.70
4.500
4.920
2.50
1.500
96.4
0.3000
0.040
0.020
0.060
0.1500
7.94
0.0200
1.500
0.100
10.000
6.000
LS3
140.0
0.0250
0.0500
0.10
10.00
9.000
1.800
3.50
0.800
45.5
0.0500
0.600
2.500
0.040
1.0000
7.49
0.0450
0.350
3.000
0.030
4.000
LS4
70.0
0.0080
0.1200
0.15
10.0
2.500
0.960
5.00
5.000
32.4
0.0050
0.060
0.800
0.020
0.3000
7.19
0.0900
0.020
0.700
3.500
15.000
: Fall Survey
LS5
15.0
0.0400
0.7500
0.50
10.4
7.000
0.310
10.00
0.400
1.4
0.0600
0.020
0.010
0.010
0.0200
6.53
0.2000
0.600
7.000
1.500
5.000
RWL RWM
... ...
50 248
0.014 0.049
... ...
...
26 130
0.054 0.098
0.024 0.051
.. *
0.501 7.06
4.30 3.59
0.052 0.106
0.205 0.419
2.69 10.8
Units
ueq/L
ng/L
ng/L
ng/L
ueq/L
mg/L
mg/L
ng/L
mg/L
uS/cm
mg/L
ng/L
ng/L
ng/L
ng/L
pH
mg/L
mg/L
ng/L
ng/L
mg/L
Values are reported to the number of decimal places specified in Table 9-8, except for the
NBS simulated rainwater audits (RWL and RWH) for which the certified values are given.
°These parameters are related and affect the analytical results of one another.
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The field natural audit samples are prepared from water collected from
Big Moose Lake and Seventh Lake in the Adirondack Mountains of New York. Big
Moose Lake is acidic and is susceptible to decreases in pH due to acidic
deposition; Seventh Lake has ANC values in the moderate range. These lake
waters are passed through a 0.45-um filter at the audit sample preparation
laboratory and are stored there at 4 °C to minimize changes in their chemical
compositions. The natural audit samples are 2-L portions of these waters.
For field natural audit samples, the 2-L portions are sent to the processing
laboratory, where they are incorporated into the sample batches and are
processed in the same manner as routine samples.
The numbers of field synthetic and natural audit samples used for the
ELS-II surveys are given in Table 10-2.
10.1.2 Laboratory Audit Samples
The purpose of using laboratory audit samples is to help verify the
accuracy of analytical procedures and to assure that the laboratory is main-
taining the capability to properly analyze the samples.
The laboratory natural audit samples (obtained from the same filtered
and preserved bulk lake water supply as the field natural audit samples)
are split into aliquots at the audit sample preparation laboratory and the
sets of aliquots are sent to the processing laboratory; at the processing
laboratory, the aliquots are relabeled and are incorporated into the sample
batches.
The laboratory synthetic audit samples are usually sent to the process-
ing laboratory from the audit sample preparation laboratory, already split
into aliquots. An exception to this practice is the handling of NBS
simulated rainwater audit samples (see Section 6.2.2); these samples are not
apportioned into aliquots. Because only small volumes of sample are available
and only some analytes of interest are present, many of the standard analyses
are not required on the simulated rainwater audit samples. The NBS samples
are only single-blind to the analytical laboratory, because they are readily
distinguishable from the other samples. All the audit samples are labeled by
the processing laboratory personnel, are included in a batch with routine lake
samples processed on the same day, and are shipped to the analytical laboratory
for analysis. The theoretical compositions of the laboratory synthetic audit
samples are given in Table 10-1.
The laboratory chlorophyll ji audit samples are filters through which
aliquots of an algae culture have been passed. They are not treated in any way
by the processing laboratory. The audit samples are analyzed by the contractor
laboratory that analyzes the routine samples and by a referee laboratory as a
check on the stability of the audit samples. These are the only audit samples
used in conjunction with the chlorophyll £ samples.
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TABLE 10-2. AUDIT SAMPLE SCHEDULE FOR THE EASTERN LAKE SURVEY - PHASE II*
Audit
Sample Type
Field Natural
Field Synthetic
Lab Natural
Lab Synthetic
Total
Spring
Variability
13
5
5
3
26
Survey
Spring
Seasonal
21
8
11
3
43
Summer
Seasonal
19
7
34
4
64
Fall
Seasonal
34
0
12
45b
91
Total
87
20
62
55
224
aNumbers given are the numbers of samples of each audit type analyzed during
the course of the survey.
bSix or seven of each of the five formulations prepared by the audit sample
preparation laboratory and six of each of the two simulated rainwater formula-
tions obtained from NBS.
The numbers of laboratory synthetic and natural audit samples used for
the ELS-II surveys are given in Table 10-2.
10.1.3 Applications of Audit Sample Data
Data are obtained from the analyses of the audit samples for the following
purposes:
To judge the performance of the processing laboratory in the processing
and shipment of samples.
To judge the ongoing capability of the analytical laboratories to
properly analyze the samples.
To establish a statistically valid estimate of the overall bias and
precision of the chemical analyses.
Acceptance windows are established for the measurement of each analyte
in the audit samples. The size of the windows is based upon the information
available for each analytical method at the time the study is initiated. If
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the analytical results for a measurement fall outside the acceptance window,
the EMSL-LV QA staff reviews the data to determine the cause of the problem
and immediately contacts the processing laboratory or the analytical labora-
tory, whichever is appropriate, to seek corrective action. Data for the
routine samples in the affected batch are checked to determine if they were
also affected by the problem. If the routine samples were affected, re-
analysis of the samples in question is requested. The establishment of the
acceptance windows for audit samples is described in Section 11.0.
A statistical evaluation of the audit sample data will provide an
estimate of the accuracy (bias) and precision of the analytical methods for
each of the required measurements; the laboratory bias study conducted during
the summer survey will provide supplemental information. Any changes over time
in the analytical results for the natural field and laboratory audit samples
without corresponding changes in the data for the synthetic audit samples may
be attributed to analyte instability.
10.2 QUALITY ASSURANCE SYSTEM AUDITS (ON-SITE EVALUATIONS)
The system audit is a qualitative evaluation of tne field, processing
laboratory, and analytical laboratory facilities, equipment, and operations
such as record keeping, data reporting, and QC procedures.
10.2.1 Field Operations and Processing Laboratory On-Site Evaluation
The EPA project officer and auditors from the EMSL-LV QA staff conduct
at least one on-site evaluation of the field and processing laboratory
operations during the course of the ELS-II sampling effort. The on-site
evaluation is conducted as soon as possible after the start of survey
operations. The questionnaire given in Appendix C is used to assist in the
evaluation.
The in-depth review of field operations includes interviews with the
field base coordinator and the members of each sampling crew. The QA auditor
accompanies one or more of the sampling crews on a sampling excursion. If any
problems are observed, the auditor brings them to the attention of the field
base coordinator. At the conclusion of the audit visit, a meeting is held with
the field personnel to discuss the findings of the audit.
At the processing laboratory, the QA auditor interviews the analysts
and evaluates the equipment, cleanliness, record-keeping, analytical and
sample-handling procedures, and implementation of QC protocols. Any problems
that are identified are brought to the attention of the laboratory supervisor
and the laboratory coordinator at the meeting following the audit.
10.2.2 Analytical Laboratory On-Site Evaluation
Each analytical laboratory participating in ELS-II can expect a minimum
of two in-depth, on-site evaluations conducted by the EPA QA manager or an
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authorized representative. The questionnaire in Appendix D is used to assist
in the on-site analytical laboratory evaluation.
The first on-site laboratory evaluation is performed after the laboratory
has successfully analyzed a set of preaward performance evaluation (PE) samples
for the contract-required parameters and before the actual survey analytical
work begins. The PE samples contain some or all of the analytes for which
determination is required, in the expected concentration ranges. The PE
sample results are scored in accordance with the ELS-II preaward audit sample
scoring sheet given in Appendix E. Grading emphasizes analytical accuracy, but
a substantial portion of the grade depends on meeting the requirements for
internal QC, data reporting, and delivery deadlines. The QA auditor summarizes
all observations from the on-site evaluation in a summary report and brings all
problems that are observed to the attention of the laboratory manager for
corrective action.
The second on-site laboratory evaluation is conducted after approximately
one-third of the ELS-II analyses have been completed. During the second on-
site evaluation, outstanding issues pertaining to the QA sample (audit, field
duplicate, and field blank) data and the QC sample (QCCS, laboratory duplicate,
and calibration blank) data received to date are discussed. The laboratory
questionnaire is updated, if necessary, noting all changes since the first
on-site evaluation. A summary report is written for this and for each additional
on-site laboratory evaluation.
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11.0 ACCEPTANCE CRITERIA
11.1 ACCEPTANCE CRITERIA FOR AUDIT SAMPLES
Acceptance windows for single values from audit samples are based on the
audit data from the NSWS stream survey, the ELS-II spring variability study,
and the ELS-II spring seasonal survey. The data for the synthetic audit samples,
which (except for the fall audit samples) all have the same theoretical concen-
tration, are checked for variability and then are pocled to provide the largest
possible number of observations. Data for each type of natural audit are
evaluated independently. The objective of creating windows is to predict
intervals for acceptable single future values based on <=. :ample mean ("X) and
sample standard deviation (s) computed from n previously observed values. The
limits of each window are determined by using a t-statistic (t).
is a Student's t
where:
Z is the standard normal variate, having a normal distribution with a mean
of 0 and a variance of 1
U is a variable with a chi-square distribution with r degrees of freedom,
and Z and U are independent
The observed values Xj, X£, X3 Xn are independent and have a normal
distribution (~N) with a population mean (u) and variance( 2). A prediction
interval of (1 - a) or a single future value, y, is needed. Let 7 = sample
mean and s = sample standard deviation. It is known that
y - N(u, o2) and I ~ N u
.(4)
Therefore,
y - T~ N
0,
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X2
(n-l)
r = n-1.
Substituting,
t =
(n-l)S2
(n-l)o2
The upper and lower limits of each window can be formalized as follows:
1
IT + (t) (s) >Ji + - = upper limit of the window
n
X - (t)(s)
+ - = lower limit of the window
n
The Student's t-value (t) has n-1 degrees of freedom. The t-value is for
a 2-tailed test with a cumulative probability of 0.95 (i.e., 2.5 percent
probability on either side).
Grubbs1 test (Grubbs, 1969) is applied to the data before interval estima-
tion to detect outliers. The outliers are excluded from the computation of the
windows.
11.2 ACCEPTANCE CRITERIA FOR DUPLICATE MEASUREMENTS
The same assumption of a normal data distribution made when audit windows
are set also is made when the acceptance criteria are determined for the
precision of routine/duplicate measurements. In addition, it is assumed
that o is proportional to the theoretical concentration (u) of the analyte.
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Therefore, the routine value minus the duplicate value (R-D) is a normal
distribution with a mean of 0 and a variance of
To identify a value difference in the routine/duplicate pair beyond
which analytical results may be questionable, the following equation
is applied.
Ic (R+D)
|R-D| > 1.96
where
k is an estimate of -
M
If the statement is true for a given routine/duplicate pair, the results for that
pair exceed the crieria and may be questionable.
11.3 ACCEPTANCE CRITERIA FOR BLANK SAMPLES
The acceptance criteria for blank samples are based on data from ELS-I
and WLS-I. The 95th percentile (p95) of the blank data is set as the upper
limit of acceptable blank values, and the lower acceptable limit is the
negative of the contract-required detection limit (CRDL). When the p95 is less
than the CRDL, the upper limit is the CRDL. For BNC, the criterion for the
upper limit is based on the p95 of data from WLS-I only.
11.4 CORRECTIVE ACTION
Laboratories which fail to meet the acceptance criteria for analysis of
audit samples or duplicates are required to repeat the analysis that produced
the erroneous results. If results from the second analysis are still unaccept-
able, further investigation is initiated and the data are qualified.
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12.0 DATA MANAGEMENT SYSTEM
The purpose of the data base management system (DBMS) is to assemble,
store, and edit data generated during ELS-II and other NSWS surveys. The DBMS
is also used to provide basic reports of the survey results, to perform certain
statistical analyses, and to provide data security. The relationship of data
base management to the overall ELS-II is shown in Figure 12-1.
The data are stored in four major data sets: Data Set 1 - the raw data
set, Data Set 2 - the verified data set, Data Set 3 - the validated data set,
and Data Set 4 - the enhanced data set. These four data sets make up the data
base and are discussed below. All data sets are protected from unauthorized or
accidental access by individual, system, and file passwords.
12.1 DATA SET 1 - THE RAW DATA SET
The raw data consist of the field data, which are reported on the lake
data and batch forms, and the data from the analytical laboratories, which are
reported on data forms 11, 11A, 13, 18, 18A, 19, 19A, 20, 20A, 21, 22, 22A,
and 23 (see Appendix B). (Analytical data from Form 26, Data Confirmation/
Reanalysis Request, are used only by the QA staff and are not entered in the
raw data set.) The data include all analytical results and data qualifiers
(given in Tables 9-9 and 12-1). For the spring variability and spring seasonal
surveys, operators at Systems Applications Inc. (SAI), the data base manager,
enter these data into the raw data set using the Statistical Analysis System
(SAS). For the summer and fall surveys, data are provided by the analytical
laboratories on floppy disks, and only the field data must be entered manually.
The SAS full-screen editor procedure is used to provide gross error check-
ing as data are entered. All data that must be entered manually are entered
into two separate data sets by two different operators. For the NSWS data
base, a custom program (COMPARE) has been developed in SAS to compare the two
data sets and identify any inconsistencies in numeric and alphabetic variables.
The advantages of this double entry and comparison process is that entry errors
are identified and are removed from the system.
The field personnel and the analytical laboratories also send copies of,
respectively, the field forms and data packages to the EMSL-LV QA staff for
concurrent data analysis. Thus, receipt of the field and analytical data forms
(and floppy disks, when applicable) by the QA staff verifies that all forms and
disks have been received by the data base management personnel.
Changes must be made in the field data if errors are identified through
the daily QA contact with the field personnel. If the data in question have
not been entered yet by SAI, the changes are included in the raw data set. If
the data have been entered already, the changes are included in subsequent data
sets.
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TABLE 14-1. PHYSICAL VARIABLES SUBJECT TO VALIDATION
:=============================================================;
Variable
General Description of Validation Checks
1. Latitude
2. Longitude
3. Lake Elevation
4. Lake Area
5. Watershed Area
6. Site Depth
7. Stream Inlets and Outlets
8. Lake Hydro!ogic Type
9. Shoreline Land Use
10. Water Temperature
11. Secchi Disk Transparency
12. True Color
13. Turbidity
Lake location, as measured by LORAN, is
compared to location measured on USGS maps.
Lake characteristics are checked against
state records, where available, to confirm
lake identification.
Data are compared to aerial photographs.
Recorded temperature is checked to see if it
falls in appropriate range.
Data are checked for internal consistency.
14.2.1 Univariate Analyses
An initial approach to outlier detection is to consider each variable
individually and to search for values that are extreme with respect to the
sample. The method used here is the box plot (Tukey, 1977) as implemented in
SAS (SAS Institute, 1982). The box plot summarizes the data for one variable
based on the median and upper (Fu) and lower (Fl) fourths or quartiles. The
difference between the upper and lower quartiles is known as the interquartile
range (Fu - Fl = dF); any value greater than the absolute value of 3 dF is
identified as an outlier.
14.2.2 Bivariate Analyses
Although values of two variables may not be outliers within their respec-
tive univariate distributions, that pair may be considered extreme relative to
some expected or typical relationship. Scatter plots are useful for examining
expected theoretical or empirical relationships between variables. The bivari-
ate relationships examined in this process are shown in Table 14-2. Outliers
are identified by visual inspection of the plots and by listing of residuals
(distances between the observed values and the fit line) based on a least-
squares regression analysis where a linear relationship exists. An observation
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TABLE 12-1. DATA QUALIFIERS (FLAGS) FOR THE RAW DATA SET
FLAGS USED WITH ANION/CATION BALANCE CHECK PROGRAM:
AO Anion/cation percent ion balance difference UIBD) is outside
criteria because of unknown cause.
Al Anion/cation percent ion balance difference UIBD) is outside criteria
because of nitrate contamination.
A2 Anion/cation percent ion balance difference UIBD) is outside criteria
because of anion (other than nitrate) contamination.
A3 Anion/cation percent ion balance difference UIBD} is outside criteria
because of cation contamination.
A4 Anion/cation percent ion balance difference UIBD) is outside criteria
because of unmeasured organic protolytes (fits Oliver Model).
A5 Anion/cation percent ion balance difference UIBD) is outside criteria
because of possible analytical error - anion concentration too high
(flag suspect anion).
A6 Anion/cation percent ion balance difference UIBD) is outside criteria
because of possible analytical error - cation concentration too low
(flag suspect cation).
A7 Anion/cation percent ion balance difference UIBD) is outside criteria
because of possible analytical error - anion concentration too low
(flag suspect anion).
A8 Anion/cation percent ion balance difference UIBD) is outside criteria
because of possible analytical error - cation concentration too high
(flag suspect cation).
FLAGS GENERATED BY APPROPRIATE BLANK EXCEPTION PROGRAM:
BO External (field) blank is above expected criteria for pH, DIC, DOC,
conductance, ANC, or BNC determination.
Bl Internal (lab) blank is >2 x CRDL for pH, DIC, DOC, conductance,
ANC, or BNC determination.
(continued)
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TABLE 12-1. (Continued)
B2 External (field) blank is above expected criteria and contributed
>20 percent to sample values. (This flag is not used for pH, DIG, DOC,
ANC, or BNC determinations.)
B3 Internal (lab) blank is >2 x CRDL and contributes >10 percent to the
sample concentrations. (THIS flag is not used for pH, DIC, DOC, ANC,
or BNC determinations.)
B4 Potential negative sample bias based on internal (lab) blank data.
B5 Potential negative sample bias based on external (field) blank data.
FLAGS USED WITH CONDUCTANCE BALANCE CHECK PROGRAM:
CO Percent conductance difference (ZCD) is outside criteria for unknown
cause (possible analytical error - ion concentration too highT
Cl Percent conductance difference (%CD) is outside criteria because of
possible analytical error - anion concentration too high (flag suspect
anion).
C2 Percent conductance difference (JCD) is outside criteria because of
anion contamination.
C3 Percent conductance difference (iCD) is outside criteria because of
cation contamination.
C4 Percent conductance difference (ZCD) is outside criteria because of
unmeasured organic ions (fits Oliver Model).
C5 Percent conductance difference (JCD) is outside criteria because of
possible analytical error in conductance measurement.
C6 Percent conductance difference UCD) is outside criteria because of
possible analytical error - anion concentration too low (flag suspect
anion).
C7 Percent conductance difference (JCD) is outside criteria because of
unmeasured protolyte ions (does not fit Oliver Model).
C8 Percent conductance difference (JCD) is outside criteria because of
possible analytical error - cation concentration too low (flag suspect
cation).
(continued)
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13.2.6 Preparation and Delivery of Verification Tapes
The steps identified in sections 13.2.1 through 13.2.5 are followed to
identify suspect data and to correct erroneous data. The information
obtained by this process is accumulated by the EMSL-LV QA staff and is
placed on magnetic tapes, which are sent to SAI. There, the new data are
entered into the raw data set to correct and flag the original data. The
identification and transfer of corrected data for entry into the verified
data set are described more fully in Section 12.0.
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14.0 DATA VALIDATION
14.1 OVERVIEW
Validation is the process by which the quality of data is evaluated in
terms of the intended use of the information. Validation is linked to the
goals and methods of a project and must be defined in terms of that project;
no single set of criteria can be applied to all situations. Each step of the
validation process further defines the quality of the data and the degree of
confidence the user can have in the data.
In the verification step, which precedes validation, the quality of the
analytical chemical data is determined through a rigorous protocol based on
known principles of chemistry. However, not all potential sources of error
in the data are evaluated in the verification process. Therefore, the purpose
of the validation process for ELS-11 is to identify errors in the chemical
analyses not detected in verification, and to provide a review of the quality
of the nonchemical variables. The physical variables subject to validation are
shown in Table 14-1. As in verification, data found to be erroneous are
identified so that correct data can be substituted, and data that are possibly
erroneous are flagged so that the user is alerted to their questionable status.
Two components of data validation are the identification of outliers and
the evaluation of possible systematic error in the measurements. The methods
used to accomplish these ends stress visual presentations and subjective, thougn
conservative, selection procedures. The objective is to attract attention to
certain data values or sets of values so that special thought and consideration
will be given to them when the user is analyzing the data or building models.
Ease of automation, including the ability to use available software, was also a
consideration in selecting the methods for detection of outliers and systematic
errors. The techniques to be used in validating ELS-II data are essentially
the same as those used for earlier surveys conducted as part of the NSWS. The
process of validation is summarized in Figure 14-1.
14.2 DETECTION OF OUTLIERS
Outliers are identified using univariate, bivariate, and multi-variate
analyses. These procedures assist in identifying outliers that require further
scrutiny. However, observations that are atypical with respect to the popula-
tion may result from either analytical error or heterogeneity in chemistry
among lakes. It is essential to separate analytical errors from abnormal lake
chemistry to avoid the undesirable effect of purging analytically correct
values from the data set (see Section 14.4).
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(SITE
SELECTION
^ ^
1
(i DATA SET 1 ^"^
RAW
DATA
SET
V x
DATA SET 2^
^^^11 ^^
VERIFIED
DATA
SET
l^__^J
DATA SCT 3
S^-
VALIDATED
DATA
SET
(^ J
(foATA SET 4J
^^^ B--*X
ENHANCED
DATA
SET
Y
ACCESS
DISTRIBUTION
ANALYSES
) /FIELD BASE SITES/\ f ANALYTICAL ^
\SSSS^J ^ORATORIESJ
1
/DATA ENTRY BY /
* I SAI /
VERIFICATION BY
BATCH RE'OKTS. ~^ ="««<>*
RAnr.r rurrK? _-,_,_
PRELIMINARY
ERL-C
/ /
SITE REPORTS. _ VALIDATION BY
..,*, -. . .* tRL-t
MAPS AND BY EMSL-LV QA.
f DATA EDITING, /
/ FLAGGING OF /
# ' / QUESTIONABLE / ~*
/ DATA /
FINAL
OF DATA
* *
REPORTS,
..... ... .^. MAf>s
STATISTICS
* DATA TRACKING SYSTEM
Figure 12-1. Data management for the Eastern Lake Survey - Phase II.
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UNIVARIATE
* BOX PLOTS
* PROBABILITY PLOTS
C)ATA SET 2
VERIFIED
MULTIVARIATE
ANALYSIS
CLUSTER ANALYSIS
TRILINEAR PLOTS
MULTIPLE LINEAR
REGRESSION
BIVARIATE
* SCATTER PLOTS
* REGRESSION
SYSTEMATIC
DIFFERENCES
FLAG OR
MODIFY
VALUES
MODIFY OR
DELETE VALUE
YES^SYSTEMATIC
ERROR?
/DATA SET 3
\ VALIDATED
* DATA TRACKING SYSTEM
Figure 14-1. Flowchart of the data validation process, Eastern Lake
Survey, Phase II.
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TABLE 14-2. PAIRS
==================
ANC
OF VARIABLES USED TO CHECK FOR RANDOM AND SYSTEMATIC ERRORS
=============================================================
Aluminum (total)
Calcium
Chloride
Conductance
Potassium
Ammonium
Silica
Turbidity
pH (processing
laboratory)
DIC (processing
laboratory)
vs.
vs.
vs.
vs.
vs.
vs.
vs.
vs.
vs.
vs.
vs.
Calcium
Conductance
Magnesium
Silica
pH (processing laboratory)
Ammoni urn
Turbidity
True color
Conductance
Fluoride (total dissolved)
Sulfate
Silica
Conductance
Sodium
Fluoride (total dissolved)
Potassium
Magnesium
Sodi urn
Silica
Sulfate
Magnesium
Turbidity
True color
BNC
pH (processing laboratory)
Magnesium
True color
Secchi disk transparancy
pH (initial and air-equilibrated)
DIC (initial and air-equilibrated)
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is identified as an outlier if the absolute value of its standardized residual
[(actual-predicted)/residual standard deviation] is generally greater than 3.
The standardized residual is defined as
actual value minus predicted value
standard deviation of the rediduals
Because the least-squares analysis can be strongly biased by certain
types of outliers, the residuals from resistant line fits, lines fit through
the medians of partitions of the data (Velleman and Hoaglin, 1981), are
examined for DOC, true color, turbidity, and Secchi disk transparency. Other
variables are treated by use of an iterative process of linear regression,
identification and removal of outliers, and repeated linear regression to
identify additional outliers that would not have necessarily been identified
had major outliers not been removed first.
14.2.3 Multivariate Analyses
Although examination of scatter plots is an important and necessary step
for evaluating possible errors in the data, bivariate analyses must be limited
to those variables that have obvious associations. The magnitude of the data
set precludes examination of all possible distributions and bivariate plots.
For example, the number of bivariate plots required for all combinations of the
analytical variables exceeds 4,600. Although many of these combinations of
variables are of no interest, many meaningful combinations remain. Clearly,
this is not a practical or efficient method for examining all the data.
An alternative method of examining data for systematic and random errors
is through multivariate analysis in which several variables are examined simul-
taneously. Because theoretical relationships are expected to exist among
certain chemical variables, it is useful to examine these sets of variables as
groups.
Two primary multivariate techniques are used to identify outliers: cluster
analysis and principal component analysis (PCA). Cluster analysis is a clas-
sification technique for identifying similarities (or, conversely, dissimilar-
ities) among observations. Each observation is compared to other observations
in the set and is assigned to a group or cluster using a measure of similarity.
The primary clustering technique used in the validation process is the
FASTCLUS procedure in SAS (SAS Institute, 1982). This method is a nonhierarchi-
cal divisive method that is sensitive to outliers. A less formal clustering
technique also used for selected samples is the Trilinear Diagram (Hem, 1970).
The Trilinear Diagram is useful for examination of possible errors associated
with the major cations and anions. The clustering techniques are used for the
related sets of variables shown in Table 14-3.
-------
Section 14.0
Revision 2
Date: 11/87
Page 6 of 8
TABLE 14-3. RELATED GROUPS OF VARIABLES USED IN MULTIVARIATE ANALYSES
Group Variables
1. Major anions and cations
2. pH, ANC, DOC, true color
3. Turbidity, Secchi disk transparency, true color
4. Nitrate, phosphorus, ammonium, turbidity, Secchi disk
transparency
5. An ion deficit, DOC, true color
6. pH, extractable aluminum, fluoride, DOC
7. Silica, major cations
8. Iron, manganese, extractable aluminum, DOC
9. ANC, DIC, pH
10. pH, sulfate, DOC
PCA is a technique that also is commonly used to reduce large data
matrices into manageable dimensions. New variables called principal components
are formed from linear combinations of the original variables so that the first
principal component reflects most of the variance or dispersion in the data.
Each successive principal component explains less variance, and examination of
the first several components is generally sufficient to describe the data. If
the original data are approximately normally distributed, the resulting
principal components are also approximately normal. Thus, a plot of any two
components typically results in an elliptical cluster with outliers displaced
from the ellipse.
Where appropriate, least-squares multiple linear regression techniques
also are used to identify observations with high absolute values of the
standardized residual.
14.3 DETECTION OF SYSTEMATIC ERROR
Methods for evaluating systematic error are less subjective because they
require a source of external comparison. Here the tests are similar to compar-
ison with standards with one major difference. The external references, con-
sisting of data sets obtained from other investigators, cannot be viewed as
"standards". Hence, a difference between data from ELS-II and another data
-------
Section 14.0
Revision 2
Date: 11/87
Page 7 of 8
source does not necessarily imply that the ELS-II data are in error. However,
comparisons with external data sources serve as aids for evaluating the quality
of the data by bringing attention to data that may require additional scrutiny.
Clearly, existence of systematic differences between the ELS-II data and several
external data sources would be cause for careful revaluation of the data in
question.
Two types of systematic errors are investigated in the ELS-II data base:
a constant additive effect (resulting in a nonzero intercept), or an effect
that is dependent on the magnitude of the variable being measured (causing a
slope ^ 1 or nonlinearity in the relationship).
14.4 TREATMENT OF OUTLIERS AND SYSTEMATIC DIFFERENCES
Data identified as outliers through the above procedures may be acceptable
when evaluated in the context of other variables or when considering limitations
of the methods used in the ELS-II. Therefore, before the original data sources
are rechecked, the outliers and systematic differences identified in the vali-
dating process are reviewed for plausibility by the staff at ERL-C. Data that
remain suspect following screening by staff scientists are sent to the appro-
priate organization for reexamination.
Outliers and systematic differences for all chemical variables are checked
against reported values by the QA staff at EMSL-LV; site location and watershed-
related variables are reviewed by the Geographic Research Team at ERL-C; and
remaining variables are checked by staff at SAI. When the data are rechecked
for suspect values that were identified during validation of the chemical
variables, the following possible conditions may be revealed. These conditions
may require the associated response listed:
Condition Response
(1) Suspect value in data set number Correct value is placed in data
2 (verified data set) is found set number 3 (validated data set).
to be a transcription or trans-
position error.
(2) Suspect value in data set number Value is flagged in data set
2 agrees with reported value, and number 3.
value was flagged in verification.
(3) Suspect value in data set number Value may be flagged in data set
2 agrees with reported value, number 3 depending on evidence
but value was not flagged in for possible error.
verification.
Values flagged in data set number 2, but not identified as aberrant in
data validation, remain unchanged and flagged except in cases where the flag
-------
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Section 14.0
Revision 2
Date: 11/87
Page 8 of 8
is not required for interpretation of the data; in these cases, the flag is
removed. The protocol for resolution of outliers for the nonchemical variables
is similar, with the exception that response (2) is omitted.
Resolution of systematic differences between the ELS-II and external
reference data involves reexamination of the methods used to collect the ELS-II
data. The effort involved in evaluating systematic differences depends on the
evidence available to suggest that a bias may exist in the ELS-II data
and the variable under consideration.
In most cases, sufficient information to perform an appropriate correction
for bias in the ELS-II data is not likely to be available. However, the identi-
fication of a possible bias is provided to assist the user in interpreting such
data.
-------
Section 15.0
Revision 2
Date: 11/87
Page 1 of 3
15.0 PREPARATION OF AN ENHANCED DATA SET
The enhanced data set (Data Set 4) is prepared from the validated data set
by replacing missing values, averaging field duplicate values, correcting
errors, and adjusting to zero any values that are reported as negative. The
process of preparing the enhanced data set is shown in Figure 15-1.
15.1 SUBSTITUTION OF VALUES
In those cases where a value is missing or incorrect (i.e., the value is
identified as an outlier during validation and the aberration is not a result
of an episode or some site condition) and a new value must be incorporated, the
new value is obtained from one of the following sources, listed in order from
most to least desirable:
1. Value from the duplicate of a routine/duplicate pair for the routine
value.
2. Value from an alternate sample. For example, both contract analytical
laboratories analyze comparable samples during the summer survey as part of the
laboratory bias study.
3. Value of a redundant measurement on the same sample. Redundant analyses
are performed for pH, DIG, and conductance.
4. Value predicted from the best regression of related variables (e.g.,
Ca vs. ANC, pH vs. ANC) or from the best regression of the same variables; these
regressions include all comparisons and combinations.
5. Value of the stratum mean within the subregion.
All substitute values are reexamined for acceptability before they are
included in the final data set.
15.2 AVERAGING OF FIELD DUPLICATE PAIRS
If field duplicate pairs have no validation flags present, the average of
the duplicate pair values is used in the final data set.
15.3 TREATMENT OF NEGATIVE VALUES
Negative values (for parameters other than ANC and BNC) that result from
analytical calibration bias (i.e., instrumental drift) are set to zero. The
bias in the estimate of variance due to this adjustment is not likely to affect
data analysi s.
-------
Section 15.0
Revision 2
Date: il/87
Page 2 ot 3
YES
SUBSTITUTE
WITH
DUPLICATE
CALIBRATION YES^XEVIDENCE^X.
FOR BIAS * ^\ OF BIAS ^
E
E
\
1
1
NO
SUBSTITUTION
WITH REDUNDANT
VARIABLE
i
\
FLAG
SUBSTITUTION
i
COMPUTE
SUBSTITUTION
1
MULTIPLE
REGRESSION
SUBSTITUTION
1
US
1
NO
/DATA SET /
USE STRATUM
AVERAGE
Figure 15-1. Flowchart of the development of the enhanced data set,
Eastern Lake Survey - Phase II.
-------
Section 15.0
Revision 2
Date: 11/87
Page 3 of 3
15.4 THE ENHANCED DATA SET
Data qualifiers (flags) are used to indicate all values that have been
modified for the enhanced data set. These flags are listed in Table 15-1. If
the values for four or more variables in the same sample are identified as
extreme, the site is considered unusual.
After the final data set is completed, all of the data sets will be
released by EPA and will be made available to data users.
TABLE 15-1. DATA QUALIFIERS (FLAGS) FOR VALIDATED DATA SET
UO Known error based on relationships with other variables and/or
impossible values; substitutions were made in data set 4.
Ul Value is a substitution; original value was missing.
U2 Value is a substitution; original value was considered to be in error.
VO Data value represents the average from a duplicate split and measure-
ment of the lake sample.
VI Data value is from the duplicate sample and is not averaged because
the regular sample had "WO" flag limitations.
WO Data value has possible measurement error based on relationships
with other variables, has QA violations, or is outside QA windows
for acceptable data.
ZO Original value was less than zero and has been replaced with zero.
-------
Section 16.0
Revision 2
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Page 1 of 4
16.0 REFERENCES
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Costle, D. M., June 14, 1979b. Administrator's Policy Statement, Quality
I Assurance Requirements for All EPA Extramural Projects Involving Environ-
" mental Measurements. U.S. Environmental Protection Agency, Washington,
D.C.
I DeWalle, D. R., 1986. Quality Control/Quality Assurance Plan - Pilot Snowpack
Chemistry Survey. Internal Report. U.S. Environmental Protection Agency,
Corvallis, Oregon.
I
I
American Public Health Association, American Water Works Association, and Water
Pollution Control Federation, 1985. Standard Methods for the Examination
of Water and Wastewater, 16th Ed. APHA, Washington, D.C.
American Society for Testing and Materials, 1984. Annual Book of ASTM Standards,
Vol. 11.01, Standard Specification for Reagent Water, D1193-77 (reapproved
1983). ASTM, Philadelphia, Pennsylvania.
Arent, L. J., M. n. Morison, and C. S. Soong, in preparation. National Surface
Water Survey, Eastern Lake Survey - Phase II, National Stream Survey -
Phase I Laboratory Operations Report. U.S. Environmental Protection
Agency, Las Vegas, Nevada.
Best, M. D., S. K. Drouse', L. W. Creelman, and D. J. Chaloud, 1987. National
Surface Water Survey, Eastern Lake Survey (Phase I -- Synoptic Chemistry)
Quality Assurance Report. EPA 600/4-86-011. U.S. Environmental
Protection Agency, Las Vegas, Nevada.
Bonoff, M. B., K. J. Cabbie, D. J. Chaloud, and L. A. Drewes, 1985. Phase II -
Eastern Lake Survey, Spring Variability - Pilot, Field Training and Opera-
tions Manual. Internal Report. U.S. Environmental Protection Agency,
Las Vegas, Nevada.
Chaloud, D. J., L. J. Arent, B. B. Dickes, J. D. Nitterauer, M. 0. Morison, and
D. V. Peck, 1986. National Surface Water Survey, Eastern Lake Survey -
Phase II, National Stream Survey - Phase I Processing Laboratory Training
and Operations Manual. Internal Report, U.S. Environmental Protection
Agency, Las Vegas, Nevada.
Costle, D. M., May 30, 1979a. Administrator's Memorandum, EPA Quality Assurance
Policy Statement. U.S. Environmental Protection Agency, Washington, D.C.
-------
Section 16.0
Revision 2
Date: 11/87
Page 2 of 4
Drewes, L. A., K. J. Cabbie, D. J. Chaloud, A. W. Groeger, and M. B. Bonoff,
1986. National Surface Water Survey, Eastern Lake Survey - Phase II
(Temporal Variability and Biological Resources) Field Operations Manual
for Summer Sampling. Internal Report. U.S. Environmental Protection
Agency, Las Vegas, Nevada.
Groeger, A. W., D. J. Chaloud, and M. B. Bonoff, 1985. National Surface Water
Survey, Eastern Lake Survey - Phase II (Temporal Variability and Biological
Resources) Field Operations Manual for Spring, Summer, and Fall Sampling.
Internal Report. U.S. Environmental Protection Agency, Las Vegas, Nevada.
Grubbs, F. E., 1969. Procedures for Detecting Outlying Observations in Samples.
Technometrics, TCMTA, v. 11, n. 4, pp. 1-21.
Hem, J. D., 1970. Study and Interpretation of the Chemical Characteristics of
Natural Water, 2nd Ed. U.S. Geological Survey Water Supply Paper 1473.
U.S.G.S., Washington, D.C.
Hillman, D. C., J. F. Potter, and S. J. Simon, 1986. National Surface Water
Survey, Eastern Lake Survey (Phase I Synoptic Chemistry) Analytical
Methods Manual. EPA 600/4-86-009. U.S. Environmental Protection Agency,
Las Vegas, Nevada.
Kerfoot, H. B., T. E. Lewis, D. C. Hillman, and M. L. Faber, in final
preparation. National Surface Water Survey, Eastern Lake Survey (Phase II
- Temporal Variability) Analytical Methods Manual. U.S. Environmental
Protection Agency, Las Vegas, Nevada.
Kramer, J. R., 1982. Alkalinity and Acidity. In: R. A. Minear and L. H.
Keith (eds.), Water Analysis, Vol. 1. Inorganic Species, Part 1. Academic
Press, Orlando, Florida.
Linthurst, R. A., D. H. Landers, J. M. Eilers, D. F. Brakke, W. S. Overton,
E. P. Meier, and R. E. Crowe, 1986. Characterstics of Lakes in the
Eastern United States. Volume I. Population Descriptions and Physico-
Chemical Relationships. EPA 600/4-86-007a. U.S. Environmental Protection
Agency, Washington, D.C.
McQuaker, N. R., P. D. Kluckner, and D. K. Sandberg, 1983.
of Acid Precipitation: pH and Acidity Determinations.
Technol., v. 17, n. 7, pp. 431-435.
Chemical Analysis
Environ. Sci.
Merritt, G. D., and V. A. Sheppe, in preparation. National Surface Water
Survey Eastern Lake Survey (Phase II Chemical Variability) Field
Operations Report. U.S. Environmental Protection Agency, Las Vegas,
Nevada.
-------
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Section 16.0
Revision 2
Date: 11/87
Page 3 of 4
Oliver, B. G., E. M. Thurman, and R. K. Malcolm, 1983. The Contribution of
Humic Substances to the Acidity of Colored Natural Waters. Geochim.
Cosmochim. Acta, v. 47, pp. 2031-2035.
Omernik, J. M., and C. F. Powers, 1983. Total Alkalinity of Surface Waters --
a National Map. Ann. Assoc. of Amer. Geographers, v. 73, pp. 133-136.
Omernik, J. M., and A. J. Kinney, 1985. Total Alkalinity of Surface Waters: a
Map of the New England and New York Region. EPA 600/D-84-216, U.S.
Environmental Protection Agency, Corvallis, Oregon.
Peden, M. E., 1981. Sampling Analytical and Quality Assurance Protocols for
the National Atmospheric Deposition Program. ASTM D-22 Symposium and
Survey, Eastern Lake Survey - Phase II (Temporal Variability and
Biological Workshop on Sampling and Analysis of Rain). American Society
for Testing and Materials, Philadelphia, Pennsylvania.
SAS Institute, Inc., 1982. SAS User's Guide: Statistics. SAS Institute,
Cary, North Carolina.
Todechiney, L. R., K. J. Cabbie, and J. R. Wilson, 1986. National Surface
Water Survey, Eastern Lake Survey - Phase II (Temporal Variability and
Biological Resources) Field Operations Manual for Fall Sampling. Internal
Report. U.S. Environmental Protection Agency, Las Vegas, Nevada.
Tukey, J. W., 1977. Exploratory Data Analysis. Addison-Wesley Publishing,
Reading, Massachusetts.
U.S. Environmental Protection Agency, 1980. Interim Guidelines and Specifica-
tions for Preparing Quality Assurance Project Plans. QAMS-005/80. U.S.
EPA, Washington, D.C.
U.S. Environmental Protection Agency, 1983 (revised). Methods for Chemical
Analysis of Water and Wastes. EPA-600/4-79-020. U.S. EPA, Cincinnati,
Ohio.
U.S. Environmental Protection Agency, 1984a. National Surface Water Survey,
Phase I. U.S. EPA, Office of Research and Development, Washington, D.C.
U.S. Environmental Protection Agency, 1984b. National Surface Water Survey,
Phase I. Research Plan, A Summary of Contents. U.S. EPA, Corvallis,
Oregon.
U.S. Environmental Protection Agency, 1986. Characteristics of Lakes in the
Eastern United States. EPA 600/4-86-007. U.S. EPA, Washington, D.C.
-------
Section 16.0
Revision 2
Date: 11/87
Page 4 of 4
Velleman, P. F., and D. C. Hoaglin, 1981. Applications, Basics, and Computing
of Exploratory Data Analysis. Duxbury Press, Boston, Massachusetts.
Weast, R. C. (ed.), 1972. CRC Handbook of Chemistry and Physics, 53rd
Ed., CRC Press, Cleveland, Ohio.
-------
Appendix A
Revision 2
Date: 11/87
Page 1 of 13
APPENDIX A
FIELD AND PROCESSING LABORATORY DATA FORMS AND LABELS
Page
Spring Variability Study Meteorological Form 1A 2 of 13
Spring Variability Study Sample Collection Form IB 3 of 13
Spring Variability Study Profile Data Form 1C 4 of 13
Phase II Spring Lake Data Form ID 5 of 13
Phase II Summer Lake Data Form ID 6 of 13
Phase II Fall Lake Data Form ID 7 of 13
Batch/QC Field Data Form 2 8 of 13
Shipping Form 3 9 of 13
Hydrolab Calibration Form 10 of 13
Aliquot Labels 11 of 13
Labels for Special Study Samples 12 of 13
Audit Sample Labels 13 of 13
-------
Appendix A
Revision 2
Date: 11/87
Page 2 of 13
NATIONAL SURFACE WATER SURVEY
Spring Variability Study
Meteorological Form 1A
Page.
. of-
DATE
D D M M M V
_ _ / _ _ _ / _
METEORUOGICAL DATA
Air Temp +/- ___ *C
EST WIND SPEED
Light Moderate Strong
EST WIND DIRECTION
LAKE NAME
CLOUD COVER
Clear 25% 50%
STATE
LAKE I D
LAKE VISIT
DATE
D D M M M Y <
METEORLOGICAL DATA
Air Temp */- *C
Strong
EST WIND SPEED
Light Moderate
EST WIND DIRECTION
100%
PRECIPITATION
None Rain
Snow
Sleet
RATE OF PRECIPITATION
Light
Moderate
Heavy
CLOUD COVER
Clear 25% 50% 75% 100%
PRECIPITATION
None
Rain
Snow
Sleet
RATE OF PRECIPITATION
Light
Moderate
Heavy
COMMENTS
COMMENTS
White - ORNL Pink EMSL-LV Yellow - FwlO
GUI'S ITOl X2-910C
-------
Appendix A
Revision 2
Date: 11/87
Page 3 of 13
NATIONAL SURFACE WATER SURVEY
DATE
DOM
LAKE 1 D
Site ID
Time
Total Depth
Sample Deptn
HjO Temp
PH
Cond
Sample Type
Team
Site 10
Time
Toui Depth
Sample Depth
HjO Temp
PH
Cond
Sample Type
Team
Site 1 D
Time
Toui Deptn
Simple Depth
H?O Temp
PH
Cond
Semple Type
Team
SPRING VARIABILITY STUDY
Sample Collection Form 1B
M M Y Y
LAKE NAME
o
. m
. m
-cO
Cooler Temp
Al EMSL-LV
-C
O
, m
m
cO
pnO
usO
Cooler Temp
Ai EMSL-LV
. -c
O
. m
_t__ . m
cO
pnO
usO
I Cooler Temp
At EMSL-LV
I 'C
Sue l 0
Time
Total Depth
Sample Depth
HjO Temp
PH
ConO
Sample Type
Team
Site ID
Time
Tola! Deol^1
Sample Depth
HJO Temp
pH
Cone
Sample Type
Team
Stte ID
Time
Total Deptn
Sample Deptn
H?O Temp
PH
Cond
Sample Type
Team
COMMENTS
HydfOi*b C***f»l»on Dai*
Meier
Initial . pM U
F.nai pH W
initial uS U
F.nai uS O
FieioOCCnecfc pM
Field OCCnech uS
o
m
-cO
pnO
usO
Cooler Temp
Al EMSL-LV
-C
o
__ . m
m
.c O
PsHO
Cooler Temp
Al EMSL-LV
"C
o
. m
m
'C vj
es8
Cooler Temp
Al EMSL-LV
'C
DATA Ou»hi»n
A instrument unstable
$) Slow Stabilization
0 Din Not Meet OCC
FtoMLa* UM Only
WHI
Field Lab UM Only
Tr»,l»i 1 n I
PUIrh 1 n
ReW Crew Del.
Quality Oeck Signature
M OMML MM* IMS* iv HUO*r fiUD
» o( «Mt*& S*mpi*>fl m $*'pn,a»m .
O 0 M M M Y Y
ft |n
'**
-------
Appendix A
Revision 2
Date: 11/87
Page 4 of 13
NATIONAL SURFACE WATER SURVEY
Spring Variability Study
Prolil* Oft* Form 1C
Page-
HrHroUb Calibration Data
DATE D D MM
Lake I D
Data Oualltiert
A Instrument unstable
D Slow Stabilization
O Die NOI Meet OCC
X » Z Other leiplam in
Meter
Initial
Final
Initial
PH O
PH O
O
Comment teciioni Frnai
llo
Lake Name
S-ie i D
Sie Dec
Team i
Field OC Check . pM
Freld OC Check us
tti . m tee Depifi . __^ m Site Depth . m Ice Depth . . . m
D Team iD
DepthfmlQ
T-C(
D
USO
PHO
OeplhtmlQ
T'CQ
usQ
PHQ
Comment!
Site I D Tima Site 1 D Time
Site Depth . m Ice Depth . m Site Depth . . m lea Depth m
Team I D Team 1 D .
OeptnlmiQ
T-CQ "SO
PHQ
CammwiU
ReM C
C/enf l
Quality
.nwDela
p
Check Signature
DepthimjQ
T-CQ
usQ
f»O
Commvnti
*,
-------
Appendix A
Revision 2
Date: li/87
Page 5 of 13
NATIONAL SURFACE WATER SURVEY
PHASE II SPRING/FALL
LAKE DATA FORM 1D
P«B«.
Lake ID
lake Name
SITE DEPTH (it)
SECCHI DEPTH
State
« 0 3048m 'It;
DISAPPEAR
REAPPEAR
O
o
Time
~
.-
T
Oata OueUilera
Instrument Unstable
Slow Stabilization
DID Not Meet OCC
in Comment section)
_rr,O SW.IMO VISIT D
Of ALL VISIT 1 O
F»LL VISIT? D
_ m O F"-L "SIT 3 D
Meier
Initial
Initial
Final
FwW OC Check -
Field OC Cried -
ZZ-TLpnO
onO
usO
LlS O
IN SITU LAKE OATA
DEPTH T'C DO
1 Sm O ^_ O O
BOTTOM - 1 5m _ O »_ O O
;(15-B-15m) . O
pH
O _.
o _.
._ o
._ o
06 SITE DEPTH j»C
_o _o o
&T-C O 5-06 DEPTH) __»_ O
IFAX- C PROCEED
IF NOT STOP HEBE
,S PH
____ O __ .
O
LAKE DIAGRAM (from topographic map)
lfiX'CFILLIN
FOLLOWING DATA BLOCK
SITt MUM
CHC«CWE
JW"
10 O
15 , O
20 ^O
1-1 30 _
16 as
18 40 _
» 4S
^
__O
^O
__O
__0
O
o
o
o
o
o
o
o
__0
METEOROLOGICAL DATA
Air Temp ;- 'C
EST WIND SPEED D No Wind
O Lighi O Moderate O Strong
EST WIND DIRECTION
CLOUD COVER
O Clear O ?5S O SO* D 7SS O 100*
PRECIPITATION
O None D Rain D Snow O Sleet
RATE OF PRECIPITATION
O Light O Moderate O Heavy
-------
Appendix A
Revision 2
Date: 11/87
Page 6 of 1J
NATIONAL SURFACE WATER SURVEY
PHASE II SUMMER
LAKE DATA FORM 1D
Page-
(Total shipment)
METEOROLOGICAL DATA
Air Temp . f~l -C
O LigM Q Moderate D Strong
EST WIND DIRECTION (lrom|
DM DNC Dl Ost D& O$w Dw OMW
§LOUD COVER
Cleat O25S OSO*D75»D100*
PRECIPITATION DPREV DCurrent
O None D Rain O Snow O Sleet
RATE
D Liflm O Macerate O Heavy
SAMPLES COLLECTED BLANK D
1 5m DO 1 .8 O
UKt Hyp n fj ._ O
Blm - 1 5m D D n
Lake I D
^ ~ ~~~~ ' ~*~~ ^~~ ~~' ' U»t
Lake Name *"'
Init
S DD MMM YY fcnl
° "Teem ~Siate~ f""
fD HELICOPTER
D DIRECT VEHICLE
*" D WILDERNESS
*ITE DEPTH. 6"
(III X 0 3048m/l! = __ - m O
MCCHI DEPTH:
-OR- nc»
DISAPPEAR . m \J
Ou.
_
IN (ITU LAKE DATA ""
DEPTH T.c cone oo pH r>p
:rsi oo oo
000 0
O O O O
.... 0 0 0 0
05 - O O O O
,5.O 0 0 O
25 O O
35 O O
45 O 0
55 _Q Of
65 O O '
75 O OS
5 O O|
" 0 Oi
105 O O
^ O Ol
14.. , O O '
'" 0 0 1
U.S O O
* . O O
22.S 0 0
24.S . Q O '
*» O O
2».5 . O O
Mi __O O
M-5 Q O
m _O O
».« O O
tU . 0 0
riELO CHEW DATA
MIT
Hydrotab Calibration Dau
" 'D ^.c. ^-- ^,f
I Th»n, , p 0 O
I Tneor D O O
Hrdrolat Quality Control Data
Initial PH O
Initial uS \J
Final uS \J
m
(blm-1 5)
hauls
FIELD NOTES: (NOT FOB KEYPUNCH)
TC «at»-i
H2S04 --
'C pn
KCL _ _
Prets firmly wtrh black ballpoint
-------
Appendix A
Revision 2
Date: 11/87
Page 7 of 13
NATIONAL SURFACE WATER SURVEY
PHASE II FALL
LAKE DATA FORM 10
Paoe_
(Total
METEOROLOGICAL DATA
A.r Temp 4- / *C
EST WIND SPEED oNowmo
D Ligni D Moderate O Strong
EST WIND DIRECTION (Iromi
Ox Oil Oi Dsi Ds Qs» O» O
CLOUD COVER
PRECIPITATION CPREV OCurrenl
O None D Ram D Snow O Sieet
RATE
O Lignt O Mooirate O Heavy
SAMPLES COLLECTED
ism O o BLANK o
NON-VARIABILITY LAKE ~
MU vtilT I ; KltiT | - M$IT 1 -
DEPTH
I.Sm O
BOTTOM - 1 Sm _ O
AT 'C (1 5-B-1 Sm
06 SITE DEPTH
Lake i D
Lane Name
^ DD MMM YY
" ACCIti state
t D HELICOPTER
E o DIRECT VEHICLE
~ O OTHER
SITE DEPTH.
it , X 0 X«»m/ll = m C
SECCHI DEPTH
VmDie To Bottom O
-OR-
DISAPPEAR - m V_/
REAPPEAR m C
IN SITU LAKE DATA
FIELD CREW DATA l.o I
^MOvS/cm
C (iS/em pH DO
o o o ,
_ O
Ift
C DO If
«!>* C PROCEED
NOT STO" «E = E
O _ __ O _ _ iiS/cm pw
WC HS-Ot DEPTH) O O _ O
LAKE DIAGRAM (from lopojr.ph.c map)
40 O O
0 « 0 0
so ~O O
Data OiulllMra
& Instrument unstable
O Slow staBHitation
O Die Not Mtet OCC
X 4 4 Omar (e«piam
in Comment lection)
FIELD NOTES. (NOT PQK KEYPUNCH)
X Jlftran
M.SO.
c a»
KCl _ .,_ . .. .
F«LD LA* UM
TRAILERS . ,
ATCH ID ,
aamut
DUPLICATE
LANK
COOLER TEMP ..
~'yt» ^» e«eSrV '"" P"M *""** <""h B"cl1 ""P0""
-------
Appendix A
Revision 2
Date: 11/87
Page 8 of 13
NATIONAL SURFACE WATER SURVEY
BATCH/QC FIELD DATA FORM
DATE RECEIVED
BVDATAUGT
RE INURED ________
D FORM 2 LAKES
OR
D FORM 5 STREAMS
-------
Appendix A
Revision 2
Date: 11/87
Page 9 of 13
NATIONAL SURFACE WATER SURVEY
SAMPLE MANAGEMENT OFFICE
P.O »OX 111
ALEXANDRIA. VA 22314
NSWS
FORM 3
SHIPPING
RECEIVED iY
IF INCOMPLETE IMMEDIATELY NOTIFY:
SAMPLE MANAGEMENT OFFICE
(7M) U7-MM
PAGE .
.Of.
FROM
(STATION ID)
S»MPL£
10
01
02
03
04
OS
06
07
06
09
10
11
12
13
14
15
16
17
It
19
20
21
22
23
24
25
76
27
21
2*
30
1
TO
(LAB)
BATCH
10
DATE PROCESSED
ALIOUOTS SHIPPED
(FOR STATION USE ONLY!
2
3
4
S
6
7
1
SPU
DATE SHIPPED DATE RECEIVED
AIR-BILL NO
TS
SAMPLE CONDITION UPON LAB RECEIPT
(FOR LAB USE ONLY!
_
QUALIFIERS
V
M
ALIQUOT SHIPPED
ALIQUOT MISSING DUE TO DESTROYED SAMPLE
OOIO - LA> COTr FO« IKTUKN TO MK>
-------
METER ID:
Appendix A
Revision 2
Date: il/87
Page 10 of 13
NATIONAL SURFACE WATER SURVEY
HYOROLAB SURVEYOR II CALIBRATION FORM
CREW 10:
NAME.
CALIBRATION INFORMATION
PRE-CAL
POST-CAL
DATE
TIME
BAROMETRIC
PRESSURE (nun Hq)
VOLTAGE
pH CALIBRATION
7.00 BUFFC'
4.00 BUFr-9
TEMP(OC)
7.00 aiJFrc* !
THEOR.
VALUE
INITIAL
ADJUSTED
Y/N
IF Y CO
rro RECAL
FINAL
RECAL
CONDUCTIVITY CALIBRATION CHECK
0. 1*7 mS/cm
TEMP(OC)
THEOR.
VALUE
INITIAL
ADJUSTED
Y/N -
FINAL
DO CALISRATION CHECK (IF APPLICABLE)
PRE-CAL
POST-CAL
TEMPC°C)
PRESSURE
THEOR.
VALUE"
INITIAL
ADJUSTED
Y/N
FINAL
CAL SAVED?
"CO2 QUALITY CONTROL CHECK SOLUTION
TE*P
PH
CONO.
fmScm -1)
NBS
TRUE*
TRUE-
PRE-OEPL
METER
FOUND
FOUND
OYMENT
DIFF (+1°C)
OIFF (*0.1i)
OIFF (»0.20)
P(
NBS
TRUE»
TRUE-
:ST-DEP
METER
FOUND
FOUND
.OYMENT
OIFF (»1°C)
DIFF (»O.IS)
DIFF (»0.20)
COMMENTS:
Table 2, surveyor II procedures
Table 1. surveyor II procedures
OOlSy
-------
Appendix A
Revision 2
Date: 11/87
Page 11 of 13
ALIQUOT 1
Filtered - 250 mL
Batch ID
Sample ID
Date
Sampled
Preservative:
HN03, 4 °C
Amount: mL
Parameters:
Ca.Mg.K.Na.Mn.Fe
ALIQUOT 2
Filtered - 10 mL
Batch ID
Sample ID
Date
Sampled
Preservative:
MIBK - HQ, 4 °C
Amount: mL
Parameters:
Extractable Al
ALIQUOT 3
Filtered - 250 mL
Batch ID
Sample ID
Date
Sampled
Preservative:
4 °C
Parameters:
Cl.F-.SOj-.NO,-.S10,
ALIQUOT 4
Filtered - 125 mL
Batch ID
Sample ID"
Date
Sampled
Preservative:
H2S04,4 8C
Amount:
Parameters:
DOC, NHA+
mL
ALIQUOT 5
Unfiltered - 500 mL
Batch ID _
Sample ID"
Date
Sampled
Preservative:
4 °C
Parameters: pH, Acidity,
Alkalinity, DIC,
Conductivity
ALIQUOT 6
Unfiltered - 125 mL
Batch ID _
Sample ID"
Date
Sampled
Preservative:
H2S04,4 °C
Amount:
Parameter:
Total P
mL
ALIQUOT 6
Filtered - 125 mL
Batch ID
Sample ID
Date
Sampled
Preservative:
H2S04,4 °C
Amount: mL
Parameters:
Total Soluble P
ALIQUOT 7
Unfiltered - 125 mL
Batch ID
Sample ID
Date
Sampled
Preservative:
HN03, 4 °C
Amount:
Parameters:
Total Al
Sample aliquot labels
-------
Appendix A
Revision 2
Date: 11/87
Page 12 of 13
INDIANA UNIVERSITY
LAKE SPLIT
Batch ID
Sample ID
Date
Sampled
Preservative:
HN03, 4 °C
Amount: ml
Parameter:
Metals
Lake ID
Crew
Date Sampled
Time Sampled
Depth
Tow A
meters
of
Batch ID
Sample ID
Preservative: Formalin
Parameter: Zooplankton
Label for trace metals
sample.
Label for zooplankton
tow.
Lake ID
Crew
Sample Type
Date Sampled
Volume Filtered
Time
mL
Batch ID
Sample ID
Preservative: -20 °C
Parameter: Chlorophyll
Chlorophyll label.
Lake ID
Crew
EMSL
Aliquot 1A
Date Sampled
Time Samp.
Batch ID
Sample ID
Preservative:
Amount:
Parameters: Fe
Sample Type
ANOXIC SPLIT
- Filtered - 125 mL
Time
Filtered
HN03, 4 "C
mL
, Mn
EMSL SPLIT
Unfiltered - 125 mL
Batch ID
Sample ID"
Date
Processed
Preservative: H2$U4, 4 C
Amount: mL
Parameter:
Total N and P
EMSL split label (total N
and P).
Label for anoxics study sample.
Labels for special study samples
-------
FIELD AUDIT SAMPLE
Radian ID No.
Date
Shipped
Code
Batch
Date
Received
ID
Field audit sample label.
LABORATORY AUDIT SAMPLE
Aliquot No.
Date Shipped
Code
Date Received
Preservative Amount
Laboratory audit sample label.
Appendix A
Revision 2
Date: 11/87
Page 13 of 13
Audit Sample Labels
-------
Appendix B
Revision 2
Date: 11/87
Page 1 of 28
APPENDIX B
ANALYTICAL LABORATORY AND QUALITY ASSURANCE DATA FORMS
Page
Form 11 - Summary of Sample Results 2 of 28
Form 11A - Summary of Sample Results 4 of 28
Form 13 - ANC and BNC Results 6 of 28
Form 14 - QC Data for ANC and BNC Analyses 7 of 28
Form 15 - Conductance 8 of 28
Form 16 - Anion-Cation Balance Calculation 9 of 28
Form 17 - 1C Resolution Test 10 of 28
Form 18 - Detection Limits 11 of 28
Form 18A - Detection Limits 12 of 28
Form 19 - Sample Holding Time Summary 14 of 23
Form 19A - Sample Holding Time Summary 16 of 23
Form 20 - Bl anks and QCCS 18 of 28
Form 20A - Blanks and QCCS 20 of 23
Form 21 - Dilution Factors 22 of 23
Form 22 - Duplicates 24 of 28
Form 22A - Duplicates 26 of 28
Form 26 - Data Confirmation/Reanalysis Requests 28 of 28
-------
1
1
Appendix B
(Revision 2
Date: 11/87
Page 2 of 28
1
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-------
Appendix B
Revision 2
Date: 11/87
Page 3 of 28
CM
t«-
o
CM
0>
o.
>
UJ
QC H-
^ 1? *
ce uj ^
1. 1 oc rf
a: -* -j
«* Q_ 4/1
£* 5 ^
« oc «/i
ac u_ u. uj
=> O o
>- Z
_J QC <
< < C
1 1 9
5
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-------
LAB NAME
NATIONAL SURFACE HATER SURVEY
FORM 11A
SUMMARY OF SAMPLE RESULTS
BATCH ID
LAB MANAGER'S SIGNATURE
Appendix B
Revision 2
Date: 11/87
Page 4 of 2d
Page 1 of 2
Sample ID
01
02
03
04
05
06
C7
08
09
10
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
Aliquot la
Anoxic Fe
KJ/L
Anoxic Mn
mg/L
Comments
Note: Approved Data Qualifiers and instructions for their use are listed in
Exhibit B. Table 4.
-------
Appendix B
Revision 2
Date: 11/87
Page 5 of 28
LAB NAME
NATIONAL SURFACE WATER SURVEY
FORM 11A
SUMMARY OF SAMPLE RESULTS
BATCH ID
Page 2 of 2
LAB MANAGER'S SIGNATURE
Sample ID
01
02
03
04
05
06
07
08
0?
10
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
Aliquot 6a
Total N
mg/L
Total ₯
mg/L
Comments
Note: Approved Data Qualifiers and instructions for their use are listed in
Exhibit B. Table 4.
-------
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
Lab Name
NATIONAL SURFACE HATER SURVEY
Form 13
ALKALINITY AND ACIDITY RESULTS
Batch ID
Appendix B
Revision 2
Date: 11/87
Page 6 of 23
Page 1 of 1
Sample ID
.ab Manager's Signature Analyst
EE SUITS
[Alk] - ueq/L
DATA
:A - eq/L
:B eq/L
ACID TITRATION
VOLUME HC1
(ml)
0.00
0.00 (with KC1)
MEASURED
PH1
CALCULATED
pH
INH
BLAK
DATE
DATE
IAL SAMPLE VOLUME
K ALKALINITY
ml
ueq/L
STANDARDIZED
STANDARDIZED
BASE TITRATION
VOLUME NaOH
(mL)
0.00
0.00 (with KC1)
MEASURED
PH1
CALCULATED
pH
-------
Appendix B
Revision 2
Date: 11/87
Page 7 of 23
NATIONAL SURFACE WATER SURVEY
Form 14*
QC DATA FOR ALKALINITY
AND ACIDITY ANALYSES
Page 1 of 1
LAB NAME
BATCH ID
LAB MANAGER'S SIGNATURE
SAMPLE
ID
o:
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Alk
ueq/L
C02-Acy
ueq/L
CALCULATED AH
RESULT
DIFFERENCE3
JDb
Form not required in data package but recommended for internal QC requirements.
* Difference - Calculated AH-Measured AH
DIC (in umoles/L)-([AH] + [C02-Acy])
x 100
DIC
-------
Appendi x B
Revision 2
Date: 11/87
Page 8 of 23
.^
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< L. l_)
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of u. u.
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«
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Measured
Calculated
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0
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-------
Appendix B
Revision 2
Date: 11/87
Page 9 of 2a
LAB NAME
NATIONAL SURFACE WATER SURVEY
Form 16*
ANION-CATION BALANCE CALCULATION
BATCH ID LAB MANAGER'S SIGNATURE
Page 1 of 1
'Sample
ID
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
16
19
20
21
22
23
24
25
ie
27
28
29
30
Z Ion
Difference **
Factors to Convert
mg/L to ueq/L
Ions - 1 ueq/L)
Ca+2
49.9
ci-
28.2
Mg+2
82.3
N03~
16.1
K*
25.6
Na+
43.5
S04-2
20. e
F-
52.6
NH4*
55.4
ALK
H^MK
H+***
^^v
*Form not required in data package but recommended for internal QC requirements.
ANC + r Anions - I Cations (except H+)
**l Ion Difference (JID)
(Alk ANC)
***[H+] - (10'PH) x 106
I Anions + I Cation + ANC + 2[H+]
x 100
-------
I
I
I
I
I
I
I
I
I
I
I
NATIONAL SURFACE WATER SURVEY
Form 17
1C RESOLUTION TEST
Appendix B
Revision 2
Date: 11/87
Page 10 of 28
Page 1 of 1
LAB NAME
BATCH ID
LAB MANAGER'S SIGNATURE
1C Resolution Test
1C Make and Model:_
Date:
Concentration: SO^
ug/mL,
ug/mL
Column Back Pressure (at max. of stroke):
Flow Rate: mL/min
Column Model:
psi
Date of Purchase:
Column Manufacturer:
Column Serial No:
Is precolumn in system _
(a) cm (b)
Yes
No
cm
Percentage Resolution: 100 x (1-a/b)
The resolution must be greater than 60%
Test Chromatogram:
-------
Appendix B
Revision 2
Date: 11/87
Page 11 of Z
LAB NAME
NATIONAL SURFACE WATER SURVEY
Form 18
DETECTION LIMITS
BATCH ID
Page 1 of 1
LAB MANAGER'S SIGNATURE
Required
Detection
Parameter Units Limit
Ca mg/L 0.01
Mg mg/L 0.01
K mg/L 0.01
Na mg/L 0.01
Mn mg/L 0.01
Fe mg/L 0.01
AT.
Extractable mg/L 0.005
CT mg/L 0.01
S042" mg/L 0.05
N03" mg/L 0.005
Si02 mg/L 0.05
F-. Total mg/L 0.005
NH4* mg/L 0.01
DOC mg/L 0.1
Conductance uS/cm **
DIC mg/L 0.05
P, Total mg/L 0.002
Al, Total mg/L 0.005
Instrumental
Detection
Limit*
Type
Flag
Date Determined
(DD MMM YY)
*To be calculated as requirea in Section 9.6 of the QA plan and filled
out by the analytical lab
"Report the Y, which must not exceed 0.9 uS/cm, of six (6) nonconsecutive
blanks
Note 1: Report with four significant figures or down to IDL
Note 2: Indicate the instrument for which the IDL applies with an "F" (for
furnace AA), a "P" (for ICP), or an "L" (for flame AA) after the IDL
value.
-------
LAB NAME
NATIONAL SURFACE WATER SURVEY
Form ISA
DETECTION LIMITS
BATCH ID
LAB MANAGER'S SIGNATURE
Appendix B
Revision 2
Date: 11/87
Page 12 of 28
Page 1 of 2
Aliquot 1A
==============================================================================
Parameter
Anoxic Fe
Anoxic Mn
Units
mg/L
mg/L
Instrumental
Detection
Li mi t*
0.01
0.01
Date Determined
(DD MMM YY)
Comments
*To be calculated as required in Exhibit E and filled out by the Contractor
Laboratory.
Note: Report with four significant figures or down to IDL.
-------
Appendix B
Revision 2
Date: 11/87
Page 13 of 28
LAB NAME
NATIONAL SURFACE WATER SURVEY
Form ISA
DETECTION LIMITS
BATCH ID
LAB MANAGER'S SIGNATURE
Aliquot 6A
Page 2 of 2
Parameter
Total N
Total P
Units
mg/L
mg/L
Instrumental
Detection
Limit*
Date Determined
(DD MMM YY)
Comments
*To be calculated as required in Exhibit E and filled out by the Contractor
Laboratory.
-------
Appendix B
Revision 2
Date: li/87
Page 14 of 28
LAB NAME
BATCH ID
NATIONAL SURFACE WATER SURVEY
FORM 19
SAMPLE HOLDING TIME SUMMARY
LAB MANAGER'S SIGNATURE
Page 1 of 2
DATE SAMPLED
DATE RECEIVED
Parameter
Holding
Time
Holding Tine
Plus
Date Sampled
Sample ID:
01
OZ
03
04
05
06
07
08
09
10
11
1Z
13
14
15
16
17
18
19
20
21
ZZ
23
24
25
26
Z7
28
29
30
31
32
33
34
35
36
37
38
39
40
Ca
28
Mg
28
K
28
Na
28
Mn
28
Fe
28
Extr. Al
7
CT
28
S042'
28
NO^
7
S102
28
ISE
Total F-
28
Date Analyzed
-------
Appendix B
Revision 2
Date: 11/87
Page 15 of 28
LAB NAME
BATCH 10
NATIONAL SURFACE WATER SURVEY
FORM 19
SAMPLE HOLDING TIME SUMMARY
LAB MANAGER'S SIGNATURE
Page 2 of 2
DATE SAMPLED
DATE RECEIVED
Parameter
Holding
Time
Holding Time
Plus
Date Sampled
Sample ID:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
Z7
28
29
30
31
32
33
34
35
36
37
38
39
40
DOC
14
NHa*
28
Eq. pH
7
Date
Acidity
(BNC)
14
Alkalinity
(ANC)
14
t
Conductance
14
analyzed
Eq. DIC
14
Init. DIC
14
Total P
28
Total Al
28
-------
Appendix B
Revision 2
Date: 11/87
Page 16 of 28
Aliquot 1A
LAB NAME
LAB MANAGER'S SIGNATURE
DATE SAMPLED
NATIONAL SURFACE HATER SURVEY
FORM 19A
SAMPLE HOLDING TIME SUMMARY
BATCH ID
DATE RECEIVED
Parameter
Holding Time (Days)
Holding Time Plus
Cj .- ._rpled (Days)
Sample ID:
01
02
03
04
05
06
07
OB
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
Anoxic Fe
28
DATE ANALYZED*
Anoxic Mn
28
DATE ANALYZED*
COMMENTS
*If parameter was reanalyzed due to QA problems, report the last date andlyzed.
-------
Appendix B
Revision 2
Date: 11/87
Page 17 of 28
Aliquot 6A
LAB NAME
LAB MANAGER'S SIGNATURE
DATE SAMPLED*
NATIONAL SURFACE HATER SURVEY
FORM 19A
SAMPLE HOLDING TIME SUMMARY
Page 2 of 2
BATCH ID
DATE RECEIVED*
Parameter
Holding Time (Days)
Holding Time Plus
Date Sampled (Days)
Sample ID:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
Total N
28
DATE ANALYZED*
Total P
28
DATE ANALYZED*
COMMENTS
Report these dates as Julian dates (i.e.. March 26, 1984 « 4086).
**If parameter was reanalyzed due to QA problems, report the last date analyzed.
(as Julian date).
-------
1
1
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Appendix B
Revision 2
Date: 11/87
Page 18 of 28
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-------
Appendix B
Revision 2
Date: 11/87
Page 19 of 28
NATIONAL SURFACE HATER SURVEY
FORM 20
LAB NAME
BATCH ID
BLANKS AND QCCS
LAB MANAGER'S SIGNATURE
2 of 2
Parameter
Cal i £>i :'.icn
Blank
Reagent Blank
DL theoretical
QCCS measured
High QCCS
True Value
Low QCCS Upper
Control Limit
Low QCCS Lower
Control Limit
Initial
Continuing I
Continuing 2
Continuing 3
Continuing 4
Continuing 5
Final
High QCCS
True Value
High QCCS Upper
Control Limit
High QCCS Lower
Control Limit
Initial
Continuing 1
Continuing 2
Continuing 3
Continuing 4
Continuing 5
Final
<
DOC
»g/L
N
N
N
NH4+
mg/L
N
N
N
Eq
pH
N
»
N
N
Measured
Alk
(ANC)
PH
N
N
N
N
ALIQUOT
Acy
(BNC)
pH
N
N
N
N
ID
5
Cond.
uS/cm
N
N
tf
Eq.
DIC
mg/L
N
N
N
Init.
DIC
mg/L
N
N
N
-
6
Total
P
mg/L
N
7
Total
Al
mg/ L
Note: Approved data qualifiers and instruction for their use are listed in Table 9-8
of the QA plan.
-------
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
LAB NAME
LAB MANAGER'S SIGNATURE
DATE SAMPLED*
NATIONAL SURFACE WATER SURVEY
FORM 20A
BLANKS AND QCCS
BATCH ID
Appendix B
Revision 2
Date: 11/87
Page 20 of 28
Page 1 of 2
DATE RECEIVED*
Parameter
Calibration Blank
DL Theoretical
QCCS Measured
Low QCCS True Value
Low QCCS Upper Control
Limit
Low QCCS Lower Control
Limit
Initial
Continuing 1
Continuing 2
Continuing 3
Continuing 4
Continuing 5
Final
High QCCS True Value
High QCCS Upper Control
Unit
High QCCS Lower Control
Limit
Initial
Continuing 1
Continuing 2
Continuing 3
Continuing 4
Continuing 5
Final
ALIQUOT 1A
Anoxic Fe
mg/L
Anoxic Mn
mg/L
Comments
Note: Approved data qualifiers and instruction for their use are listed in
Exhibit B, Table 4.
-------
Appendix B
Revision 2
Date: 11/87
Page 21 of 28
LAB NAME
LAB MANAGER'S SIGNATURE
DATE SAMPLED*
NATIONAL SURFACE WATER SURVEY
FORM 20A
BLANKS AND QCCS
BATCH ID
Page 2 of 2
DATt RECEIVED*
Parameter
Calibration Blank
DL Theoretical
QCCS Measured
Low QCCS True Value
Low QCCS Upper Control
Limit
Low QCCS Lower Control
Limit
Initial
Continuing 1
Continuing 2
Continuing 3
Continuing 4
Continuing 5
Final
High QCCS True Value
High QCCS Upper Control
Unit
High QCCS Lower Control
Limit
Initial
Continuing 1
Continuing 2
Continuing 3
Continuing 4
Continuing 5
Final
ALIQUOT 6A
Total N
mg/L
Total P
mg/L
Comments
Note: Approved data qualifiers
Exhibit B, Table 4.
and instruction for their use are listed in
-------
I
I
I
Appendix B
Revision 2
Date: 11/87
Page 22 of 28.
1
1
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-------
Appendix 3
Revision 2
Date: 11/87
Page 23 of 28
LAB NAME
NATIONAL SURFACE HATER SURVEY Page 2 of 2
FORM 21*
DILUTION FACTORS
BATCH ID LAB MANAGER'S SIGNATURE
SAM-
PLE
ID:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
IS
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
ALIQUOT ID
4~
DOC
mg/L
NH/
mg/L
5
Measured
Eq.
pH
Alk
Init. pH
Form not required in the data pac
Acy
Init. pH
C0?
Acy
ueq/L
AH
ueq/L
Cond.
uS/cm
Eq.
DIC
mg/L
Init.
DIC
mg/L
6
Total
P
mg/L
7
Total
Al
mg/L
Icage but recommended for QA purposes.
Note: Indicate samples run on higher concentration range by using a check nark for each
parameter.
-------
Appendix B
Revision 2
Date: 11/87
Page i>4 of 2
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-------
Appendix B
Revision 2
Date: 11/87
Page 25 of Z
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-------
Appendix B
Revision 2
Date: 11/87
Page 26 of 28
LAB NAME
NATIONAL SURFACE WATER SURVEY
FORM 22A
DUPLICATES
BATCH ID
Page 1 of 2
LAB MANAGER'S SIGNATURE
Parameter
Duplicate Sample ID
Sample Result
Duplicate Result
ZRSD
Second Duplicate
Sample ID
Sample Result
Duplicate Result
ZRSD
Third Duplicate
Sample ID
Sample Result
Duplicate Result
ZRSD
Al i quc
Anoxic Fe
mg/L
it la
Anoxic Mn
mg/L
Comments
Note: Approved data qualifiers and instructions for their use are listed in
Exhibit E, Table 4.
-------
Appendix B
Revision 2
Date: 11/87
Page 27 of 28
LAB NAME
NATIONAL SURFACE WATER SURVEY
FORM 22A
DUPLICATES
BATCH ID
Page 2 of 2
LAB MANAGER'S SIGNATURE
Parameter
Duplicate Sample ID
Sample Result
Duplicate Result
ZRSD
Second Duplicate
Sample ID
Sample Result
Duplicate Result
ZRSD
Third Duplicate
Sample ID
Sample Result
Duplicate Result
JRSD
Aliquc
Total N
mg/L
)t 6a
Total N
mg/L
Comments
Note: Approved data qualifiers and instructions for their use are listed in
Exhibit E, Table 4.
-------
Appendix B
Revision 2
Date: 11/87
Page 28 of 28
UAU itNl
OAll RtUIVlU
latch <
The following values
NSUS
N
Data Co
Contract Analytics
requ i re : (
Samplr I.D
ATIONAl SURI-ACL MAUK SURVIT
FORK 2k
nl irmation/keanalysis Request Forei
) Laboratory Laboratory Suoervisor
.onftmation (See
Suspect
Original
!
1
1 ) Reana 1 y
Reconfirm!/
New
Valur
is (See 11)
Uolanatton
Contract
Analytic*)
Laboratory
Ltnicq
I. Conf i nut ion Request: Did JKT Mines clunoe: Tes _ No
If yes, rtcsoft (note abort in cxp)«njtion coluwi):
(A) Reporting Irror (C) Orioiiul reported ollut did not clunge
(II Calculation Error (0) 04 La Pre>lous)y Omit Ire
(E) Other . EipUin
If values cMnoeC, submit supporting r*u data AS REQUIREO.
Additional COMwflU R«9ardin9 ConfinMtlon: ^
II. RMiulysi! Rrouested Pur to:*
External OA Pata
Internal DC Data Indicated Belon:
1C Resolution
IOL > CROl
Blank > 2 i CRDl (Reagent; Calibration)
OCCS Outside Criteria (DL: Low; High)
Sample Concent rat. i or* Outside Calibration Range
PCCS Mot in Hid-Rangc of Calibration Range
Duplicate Precision (* RSO) Outside Criteria; Insufficient Nuntier of Duplicates
Analytcd
Additional Caiments Regarding Reanalysis:
An abbreviated version or NSWS foms II, Id. IS, and 20 MSI be submitted for all reanalyzed dala.
KSWS Forms 13, 17, and 22 nsl be submitted unen applicable.
FOR UI6CO USE ONLT: INITIAL REVIEW .
VERIFICATION
. KMBEII OF VALUES SUBMITTED .
MBEB OF VALUES CHANCED
-------
Appendix C
Revision 2
Date: 11/87
Page 1 of 18
APPENDIX C
FIELD OPERATIONS AND PROCESSING LABORATORY
ON-SITE EVALUATION QUESTIONNAIRE
GENERAL (Page 1 of 1)
Questionnaire Completion Date
Field Base
Location
Processing Laboratory Supervisor
Questionnaire completed by (If more than one, indicate sections completed
by each auditor.)
-------
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Appendix C
Revision 2
Date: 11/87
Page 2 of 18
O)
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-------
Appendix C
Revision 2
Date: 11/87
Page 3 of 18
PROCESSING LABORATORY - STANDARD OPERATING PROCEDURES (Page 1 of 1)
Item
Is the training manual followed in detail?
Are copies available in the processing laboratory?
Are analysis logbooks kept up to date?
Are all on-site changes in procedures clearly documented and
justified in processing laboratory supervisor's logbook and
approved by appropriate personnel?
Yes
No
Comments:
-------
Appendix C
Revision 2
Date: 11/87
Page 4 of 18
PROCESSING LABORATORY FACILITIES (Page 1 of 1)
Item
Is the labortory kept clean and organized?
Are the refrigerator and freezer temperatures
monitored on a daily basis and recorded in a
logbook?
Are waste disposal containers available and
clearly labeled, and is waste disposed of
properly?
Are chemicals stored properly?
Is balance calibration checked daily and
recorded in a logbook?
Is water supply purity monitored daily and
recorded in a logbook?
Yes
No
Comment
General Comments:
-------
Appendix C
Revision 2
Date: 11/87
Page 5 of 18
PROCESSING LABORATORY EQUIPMENT (Page 1 of 7)
Color Test Kits
Item
Is manufacturer's operating manual readily
available?
Is kit cleaned and stored properly?
Are viewing tubes kept clean?
Is logbook kept up to date and signed daily?
Is centrifuge maintained and kept clean?
Yes
No
Comment
Comments:
-------
Appendix C
Revision 2
Date: 11/87
Page 6 of 18
PROCESSING LABORATORY EQUIPMENT (Page 2 of 7)
Nephelometer
Item
Is manufacturer's operating manual available?
Is instrument kept clean?
Are cuvettes kept clean and scratch-free?
Is logbook kept up to date and signed daily?
Is calibration checked before and after every
8 samples?
Are standards kept refrigerated when not in use?
Yes
No
Comment
Comments:
-------
Appendix C
Revision 2
Date: 11/87
Page 7 of 18
PROCESSING LABORATORY EQUIPMENT (Page 3 of 7)
Carbon Analyzer
Item
Is manufacturer's operating manual available?
Is instrument kept clean?
Is the injection valve flushed daily after use
with deionized water?
Is logbook kept up to date and signed daily?
Is IR analyzer power left on at all times?
Is standard stock solution prepared biweekly,
and is QC stock solution prepared weekly;
are they stored at 4°C?
Are working standards prepared daily?
Is exposure of samples and standards to the
atmosphere minimized?
Is required QC followed?
Are pump tubes checked for wear and
replaced on a regular basis (about every 2 weeks)?
Are syringes and glassware cleaned
properly after use?
Are C02 and moisture scrubbers on
standard bottles replaced when exhausted?
Is tin scrubber in IR analyzer checked
daily and refilled when necessary?
Yes
No
Comment
Comments:
-------
Appendix C
Revision 2
Date: 11/87
Page 8 of 18
PROCESSING LABORATORY EQUIPMENT (Page 4 of 7)
pH Apparatus
Item
Are meter and electrode operating manuals
available?
Is logbook kept up to date and signed daily?
Is j)H QC sample prepared daily?
Is electrode stored in 3M KC1?
Is required QC followed?
Are electrodes checked and filled (if
necessary) prior to use?
Are sample chambers cleaned after use?
Are buffers capped tightly after use?
Yes
No
Comment
Comments:
-------
Appendix C
Revision 2
Date: 11/87
Page 9 of 18
PROCESSING LABORATORY EQUIPMENT (Page 5 of 7)
Filtration and Preservation Apparatus
Item
Is hood kept neat and clean?
Is contamination evident?
Is hood sealed when not in use?
Is filtration apparatus kept ultraclean as
specified?
Are precautions taken to prevent contamination
of filtrators, filter funnels, filters, sample
bottles, and reagents?
Is a water trap used with the vacuum pump?
Are micropipets kept in an upright position
at all times?
Is the calibration of micropipets checked
weekly?
Are sample aliquots properly labeled?
Is vacuum maintained at 10 to 12 inches Hg while
f i Itering?
Yes
No
Comment
Comments:
-------
Appendix C
Revision 2
Date: 11/87
Page 10 of 18
PROCESSING LABORATORY EQUIPMENT (Page 6 of 7)
Flow-Injection Analyzer
Item
Is the FIA operating manual available?
Is the FIA logbook kept up to date and signed
daily?
Is the PCV reagent prepared fresh daily?
Is glassware labeled and each piece dedicated to a
particular reagent?
Are changes in the baseline recorded on a tally
sheet?
Are weekly and daily maintenance procedures
followed?
Is the flow cell regularly inspected for dirt
and scratches?
Yes
No
Comment
Comments:
-------
Appendix C
Revision 2
Date: 11/87
Page 11 of 18
PROCESSING LABORATORY EQUIPMENT (Page 7 of 7)
MIBK Extraction
Item
Is the centrifuge operating manual available?
Is the extraction logbook kept up to date and
signed daily?
Is leakage of sample volume (_> 8.5 ml) noted in
the logbook?
Are reagents (NaOAc and hydroxyqu incline) made
fresh daily?
Is NH40H made fresh weekly and the preparation
recorded in the logbook?
Are pipets calibrated weekly?
Is the 25 ml of standard measured accurately?
Is the sample buffered to pH 8?
Is the buffer/MlBK solution shaken vigorously
for 10 seconds?
Is disposal of solid and liquid wastes conducted
properly?
Yes
No
Comment
Comments:
-------
Appendix C
Revision 2
Date: 11/87
Page 12 of 18
SAMPLE PROCESSING (Page 1 of 1)
Item
Are all station documents kept in an orderly
fashion?
Are all forms completed as required and signed
by supervisor?
Is laboratory audit notebook kept up to date
(labels inserted, etc.)?
Are audit samples assigned different ID numbers
from day to day?
Are samples kept at 4°C when not being used?
Are coolers containing sample kept in the
shade and shut?
Are freeze-jjel j)acks kept frozen?
Are samples properly packed for shipping
(sealed, cooled to 4 °C, individually
wrapped, etc.)?
Are two copies of the completed shipping form
included with batch of samples?
Yes
No
Comment
Comments:
-------
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Appendix C
Revision 2
Date: 11/87
Page 13 of 18
-------
Appendix C
Revision 2
Date: 11/87
Page 14 of 18
FIELD SAMPLING (Page 1 of 1)
Item
Has adequate space been provided for
predeparture activities?
Are facilities clean and organized?
Is equipment clean and organized?
Yes
No
Comment
-------
Appendix C
Revision 2
Date: 11/87
Page 15 of 18
HYDROLAB CALIBRATION (Page 1 of 1)
Item
Are copies of the Hydrolab manual available?
Is the logbook kept up to date and signed daily?
Is the instrument cleaned and stored properly?
Is someone at the field base capable of performing
the maintenance procedures described in the
manual?
Has any other maintenance been necessary?
Are adequate spare parts (batteries, etc.)
available?
Are backup units available?
Is the instrument performing well in the field?
Are there any problems with the instrument?
Is the person performing the calibration
familiar with the procedures and control limits?
Have there been any deviations from the standard
procedures?
Are the QC samples prepared each day?
Is the instrument calibrated before and rechecked
after each excursion?
Yes
No
Comment
-------
Appendix C
Revision 2
Date: 11/87
Page 16 of 18
FIELD SAMPLING - PREPARATION (Page 1 of 1)
Item
Are checklists followed for loading equipment?
Was sampling ever aborted due to forgotten items?
Is equipment organized and easily accessible on
sampling craft or vehicle?
Is equipment stored properly to prevent injury
or damage during transport?
Are adequate plans for the excursion made and
understood by personnel?
Does the field base coordinator know where all
teams are at any given time?
Yes
No
Comment
-------
Appendix C
Revision 2
Date: 11/87
Page 17 of 18
FIELD SAMPLING - EN ROUTE (Page 1 of 1)
Item
Are the maps adequate?
Are there problems locating lakes?
Is camera operation understood?
Are lap cards photographed at each lake?
Are the lake data forms understood and
correctly filled out?
Yes
No
Comment
-------
Appendix C
Revision 2
Date: 11/87
Page 18 of 18
FIELD SAMPLING - ON SITE (Page 1 of 1)
Item
Are there problems finding the deepest part of
the lake?
Is the depth recorder performing well?
Are procedures clear and easily followed?
Is required QC followed?
Are required safety procedures followed?
Are there any problems in determining
stratification?
Are Secchi disk guidelines being followed?
Are adequate volumes of sample being taken?
Are rinse procedures followed carefully?
Are samples stored correctly?
Are all forms filled out correctly?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 1 of 53
APPENDIX D
ANALYTICAL LABORATORY ON-SITE EVALUATION QUESTIONNAIRE
GENERAL (Page 1 of 2J
Questionnaire Completion Date
Laboratory:
Street Address:
Mailing Address (if different from above):
City:
State: Zip:
Laboratory Telephone Number: Area Code: No.:
Laboratory Director:
Quality Assurance Officer:
(Quality Control Chemist)"
Type of Evaluation:
Contract Number:
Contract Title:
-------
I
I Appendix D
Revision 2
_ Date: 11/87
Page 2 of 53
I GENERAL (Page 2 of 2)
I
I
Personnel Contacted:
Name Title
I
I
I Laboratory Evaluation Team
Name Title
-------
Appendix D
Revision 2
Date: 11/87
Page 3 of 53
-------
Appendix D
Revision 2
Date: 11/87
Page 4 of 53
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-------
Appendix D
Revision 2
Date: 11/87
Page 5 of 53
ORGANIZATION AND PERSONNEL (Page 3 of 3)
Item
Do personnel assigned to this project have the
appropriate educational background to success-
fully accomplish the objectives of the program?
Do personnel assigned to this project have the
appropriate level and type of experience to
successfully accomplish the objectives of this
program?
Is the organization adequately staffed to meet
project commitments in a timely manner?
Does the QA officer report to senior
management levels?
Was the QA officer available during the
evaluation?
Yes
No
Comment
-------
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Appendix D
Revision 2
Date: 11/87
Page 6 of 53
LABORATORY MANAGER (Page 1 of 1)
Item
Does the laboratory manager have a copy of
the standard operating procedures?
Does the laboratory manager have a copy of
the instrument performance data?
Does the laboratory manager have a copy of
the latest monthly QC plots?
Is the laboratory manager aware of the most
recent control limits?
Does the laboratory manager review the
following before reporting data:
a. The data?
b. The QC data sheet with analyst's
notes?
c. The anion/cation balance check?
d. The calculated vs. measured
sample conductance?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 7 of 53
STANDARD OPERATING PROCEDURES (SOP) (Page 1 of 1)
Item
Has an SOP manual been written?
Is the SOP manual followed in detail?
Does it contain all QC steps practiced?
Is a copy of the SOP manual available to
each analyst?
Are plots of instrumental accuracy and
precision available for every analysis?
Are detection limit data tabulated for
each analysis?
Yes
No
Comment
-------
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Appendix D
Revision 2
Date: 11/87
Page 8 of 53
LABORATORY FACILITIES (Page 1 of 4)
When touring the facilities, special attention should be given to: (a; the
overall appearance of organization and neatness, (b) the proper maintenance of
facilities and instrumentation, (c) the general adequacy of the facilites to
accomplish the required work.
Item
Does the laboratory appear to have adequate
workspace (12 sq. feet, 6 linear feet of
unencumbered bench space per analyst)?
Does the laboratory have a source of
distilled or demineralized water?
Is the conductance of distilled or deminer-
alized water routinely checked and recorded?
Is the analytical balance located away from
draft and areas subject to rapid temperature
changes?
Has the balance been calibrated in the past
year by a certified technician?
Is the balance checked with a class S
standard before each use and is the check
recorded in a logbook?
Are exhaust hoods provided to allow effi-
cient work with volatile materials?
Is the laboratory clean and organized?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 9 of 53
LABORATORY FACILITIES (Page 2 of 4)
Item
Are contamination-free work areas provided
for the handling of toxic materials?
Are adequate facilities provided for
separate storage of samples, extracts, and
standards, including cold storage?
Is the temperature of the cold storage units
recorded daily in logbooks?
Are chemical waste disposal policies and
procedures adequate?
Are contamination-free areas provided for
trace-level analytical work?
Can the laboratory supervisor document that
water free of trace contaminants is avail-
able for preparing standards and blanks?
Do adequate procedures exist for disposal
of waste liquids from the ICP and AA
spectrometers?
Is the laboratory secure?
Are all chemicals dated on receipt and
thrown away when shelf life is exceeded?
Are all samples stored in the refrigerator
between analyses?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 10 of 53
LABORATORY FACILITIES (Page 3 of 4)
Item
Filter room or desiccator
(either is acceptable)
maintained at 15° to 35 °C and
50% relative humidity
Gas
Lighting
Compressed air
Vacuum system
Electrical services
Hot and cold water
Laboratory sink
Ventilation system
Hood space
Cabinet space
Storage space
(cite sq. ft. )
Shared space
Available
Yes
No
Comments
(where applicable, cite system,
QC check, adequacy of space)
-------
Appendix D
Revision 2
Date: 11/87
Page 11 of 53
LABORATORY FACILITIES (page 4 of 4)
COMMENTS ON LABORATORY FACILITIES
-------
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Appendix D
Revision 2
Date: 11/87
Page 12 of 53
EQUIPMENT - GENERAL (Page 1 of 1)
Item
Balance, analytical
NBS-calibrated
thermometer
Desiccator
Balance, top
loader
Class "S"
weights
Balance table
Distilled water or
deionized water -
to meet Type I
Reagent Grade
specifications
Glassware
Drying oven
Hot plates
Equipment
# of
Units
Make
Model
Condition/age
Good
Fair
Poor
% of Time
Used in
Survey
-------
Appendix D
Revision 2
Date: 11/87
Page 13 of 53
ICPES/AAS (Page 1 of 4)
Item
ICP
Flame AAS
Flame AAS
Graphite Furnace AAS
Data System
Data System
Manufacturer
Model
Installation
Date
Comments on ICP/AAS Instrumentation:
-------
Appendix D
Revision 2
Date: 11/87
Page 14 of 53
ICPES/AAS (Page 2 of 4)
Item
Has the instrument been modified in any way?
Is a permanent service record maintained in
a logbook?
Is service maintenance by contract?
Is preventive maintenance applied?
Does each analyst have a copy of the
standard operating procedures?
Are manufacturer's operating manuals readily
available to the analyst?
Is there a calibration protocol
available to analyst?
Are calibration results kept in a permanent
record?
Does each analyst have a copy of the
instrument performance data?
Does each analyst have a copy of
the latest weekly QC plots?
Is the analyst aware of the most recent
control limits?
Is a permanently bound notebook with
preprinted, consecutively numbered pages
being used?
Is the type of work clearly displayed on
the notebook?
Are the entries in the notebook legible?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 15 of 53
ICPES/AAS (Page 3 of 4)
Item
Are anomalies routinely recorded?
Has the analyst avoided obliterating
entries?
Are inserts (e.g., chromatograms, computer
printouts) permanently affixed in notebook
and signed across insert edge and page?
Has the supervisor of the individual main-
taining the notebook personally examined,
reviewed, and signed the notebook period-
ically, dating it and recording whether
the notebook is being maintained in an
appropriate manner?
Does the analyst have a copy of the most
recent list of in-house samples to be
analyzed?
Date of list
Are all solutions properly labeled?
Is the instrument properly vented?
Is the interference correction automatically
performed?
Are dilute calibration standards
prepared fresh weekly?
Source
Yes
No
Comment
-------
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Appendix D
Revision 2
Date: 11/87
Page 16 of 53
ICPES/AAS (Page 4 of 4)
Item
Is the QC check sample prepared from an
independent stock?
Source
Is the instrument allowed to warm up at
least 15 minutes with the flame on before
the final wavelength adjustment is made?
Is the calibration curve at least a five-
point curve?
Is the first calibration curve of the day
checked for detection limit and linearity?
Is each new calibration curve checked to see
that the change in instrumental response is
less than 5%?
Are the following control samples analyzed
with each run?
Blanks
QC Sample
Duplicates
Does the analyst review the QC data sheet
output by the data clerk, and then decide
whether or not to release the data for
reporting?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 17 of 53
ION CHROMATOGRAPH (Page 1 of 5;
Item
1C
1C
1C
Autosampler
Data System
Precolumn
Separator Column
Supressor Column
Manufacturer
Model
Installation
Date
Comments:
-------
Appendix D
Revision 2
Date: 11/87
Page 18 of 53
ION CHROMATOGRAPH (Page 2 of 5)
Item
Has the instrument been modified in any way?
Is a permanent service record maintained in
a logbook?
Is service maintenance by contract?
Is preventive maintenance applied?
Does each analyst have a copy of the
standard operating procedures?
Are manufacturer's operating manuals readily
available to the analyst?
Is there a calibration protocol available
to the analyst?
Are calibration results kept in a permanent
record?
Does each analyst have a copy of the
instrument performance data?
Does each analyst have a copy of the
latest weekly QC plots?
Is the analyst aware of the most recent
control limits?
Is a permanently bound notebook with
preprinted, consecutively numbered pages
being used?
Is the type of work clearly displayed on
the notebook?
Are the entries in the notebook legible?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 19 of 53
ION CHROMATOGRAPH (Page 3 of 5)
Item
Are anomalies routinely recorded?
Has the analyst avoided obliterating
entries?
Are inserts (e.g., chromatograms, computer
printouts) permanently affixed in notebook
and signed across insert edge and page?
Has the supervisor of the individual
maintaining the notebook personally
examined, reviewed, and signed the note-
book periodically, dating it and recording
whether the notebook is being maintained
in an appropriate manner?
Does the analyst have a copy of the most
recent list of in-house samples to be
analyzed?
Date of list
Are all solutions properly labeled?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 20 of 53
ION CHROMATOGRAPH (Page 4 of 5)
Item
Are dilute calibration standards
prepared fresh weekly?
Source
If manual techniques are used, is eluant
prepared fresh daily from the same
concentrated stock buffer?
Is the QC check sample prepared from an
independent stock?
Source
Is the calibration curve at least a four-
point curve for each analytical range?
Is the first calibration curve of the day
checked for detection limit and recovery?
Are the following control samples analyzed
with each run?
Blanks
QC Sample
Duplicates
Does the analyst review the QC data sheet
output by the data clerk, and then decide
whether or not to release the data for
reporting?
Is the drip tray examined daily for
reagent spills, and are spills cleaned up
daily?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 21 of 53
ION CHROMATOGRAPH (Page 5 of 5)
Item
Are pumps oiled once per week?
Is the anion precolumn cleaned as necessary?
Is the SO^'/NO-j" resolution checked once
per batch and documented?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 22 of 53
BNC AND ANC (Page 1 of 4;
A. Manual System
Item
pH Meter
Electrodes
Data System
Manufacturer
Model
Installation
Date
Titration Apparatus (burets, etc.):
B. Automated System
Item
System
Meter
Electrodes
Manufacturer
Model
Installation
Date
Autotitration Specifications:
Comments:
-------
Appendix D
Revision 2
Date: 11/87
Page 23 of 53
BNC AND ANC (Page 2 of 4)
Item
Has the instrument been modified in any way?
Is a permanent service record maintained in
a logbook?
Is service maintenance by contract?
Is preventive maintenance applied?
Does each analyst have a copy of the
standard operating procedures?
Are manufacturer's operating manuals readily
available to the analyst?
Is there a calibration protocol available
to the analyst?
Are calibration results kept in a permanent
record?
Does each analyst have a copy of the
instrument performance data?
Does each analyst have a copy of the
latest weekly QC plots?
Is the analyst aware of the most recent
control limits?
Is a permanently bound notebook with
preprinted, consecutively numbered pages
being used?
Is the type of work clearly displayed on
the notebook?
Are entries in the notebook legible?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 24 of 53
BNC AND ANC (Page 3 of 4)
Item
Are anomalies routinely recorded?
Has the analyst avoided obliterating
entries?
Are inserts (e.g., chromatograms, computer
printout permanently affixed in notebook
and signed across insert edge and page?
Has the supervisor of the individual
maintaining the notebook personally
examined, reviewed, and signed the note-
book periodically, dating it and recording
whether the notebook is being maintained
in an appropriate manner?
Does the analyst have a copy of the most
recent list of in-house samples to be
analyzed?
Date of list
Are all solutions properly labeled?
Are burets and micropipets calibrated
weekly or more often?
Is the stock 1.0 and 0.01 N NaOH standard-
ized as required in the methods manual?
Are the correlation coefficients of the
data examined to ensure that they are
greater than 0.9990?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 25 of 53
BNC AND ANC (Page 4 of 4)
Item
Does the analyst review the QC data sheet
output by the data clerk, and then decide
whether or not to release data for
reporting?
Are electrodes stored as recommended
by the manufacturer?
Are electrodes checked and filled, if
necessary, before each analysis?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 26 of 53
pH (Page 1 of 4)
Item
Meter
Electrodes
Manufacturer
Model
Installation
Date
Type of Temperature Compensation
Standard Gas Supplier
Standard Gas Specifications
Comments:
-------
Appendix D
Revision 2
Date: 11/87
Page 27 of 53
pH (Page 2 of 4)
Item
Has the instrument been modified in any way?
Is a permanent service record maintained in
a logbook?
Is service maintenance by contract?
Is preventive maintenance applied?
Does each analyst have a copy of the
standard operating procedures?
Are manufacturer's operating manuals readily
available to the analyst?
Is there a calibration protocol available
to the analyst?
Are calibration results kept in a permanent
record?
Does each analyst have a copy of the
instrument performance data?
Does each analyst have a copy of the
latest weekly QC plots?
Is the analyst aware of the most recent
control limits?
Is a permanently bound notebook with
preprinted, consecutively numbered pages
being used?
Is the type of work clearly displayed on
the notebook?
Are the entries in the notebook legible?
Yes
No
Comment
-
-------
Appendix D
Revision 2
Date: 11/87
Page 28 of 53
pH (Page 3 of 4)
Item
Are anomalies routinely recorded?
Has the analyst avoided obliterating
entries?
Are inserts (e.g., chromatograms, computer
printouts) permanently affixed in notebook
and signed across insert edge and page?
Has the supervisor of the individual
maintaining the notebook personally
examined, reviewed, and signed the notebook
periodically, dating it, and recording
wheter the notebook is being maintained in
an appropriate manner?
Does the analyst have a copy of the most
recent list of in-house samples to be
analyzed?
Date of list
Are all solutions properly labeled?
Is the pH meter calibrated before samples
are analyzed?
Is the pH meter calibration checked every
batch as required in the methods manual?
Is the pH electrode QC solution analyzed
first and as specified, and are the results
plotted immediately after determination?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 29 of 53
pH (Page 4 of 4)
Item
Does the material used as a QC sample meet
specifications?
Source of QCCS:
Are the following control samples analyzed
with each run:
QCCS
Duplicate
Does the analyst review the QC data sheet
output by the data clerk, and then decide
whether or not to release data for
reporting?
Are electrodes stored as recommended by
the manufacturer?
Are electrodes checked and filled, if
necessary, before each analysis?
Yes
No
Comment
-------
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Appendix D
Revision 2
Date: 11/87
Page 30 of 53
FLUORIDE ION SELECTIVE ELECTRODE (Page 1 of 3)
Item
Meter
Electrodes
Manufacturer
Model
Installation
Date
Comments:
-------
Appendix D
Revision 2
Date: 11/87
Page 31 of 53
FLUORIDE ION-SELECTIVE ELECTRODE (Page 2 of 3)
Item
Has the instrument been modified in any way?
Is a permanent service record maintained in
a logbook?
Is service maintenance by contract?
Is preventive maintenance applied?
Does each analyst have a copy of the
standard operating procedures?
Are manufacturer's operating manuals readily
available to the analyst?
Is there a calibration protocol available
to the analyst?
Are calibration results kept in a permanent
record?
Does each analyst have a copy of the
instrument performance data?
Does each analyst have a copy of the
latest weekly QC plots?
Is the analyst aware of the most recent
control limits?
Is a permanently bound notebook with
preprinted, consecutively numbered pages
being used?
Is the type of work clearly displayed on
the notebook?
Are the entries in the notebook legible?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 32 of 53
FLUORIDE ION SELECTIVE ELECTRODE (Page 3 of 3)
Item
Are entries noting anomalies routinely
recorded?
Has the analyst avoided obliterating
entries?
Are inserts (e.g., chromatograms, computer
printouts) permanently affixed in notebook
and signed across insert edge and page?
Has the supervisor of the individual
maintaining the notebook personally
examined, reviewed, and signed the note-
book periodically, dating it, and recording
whether the notebook is being maintained
in an appropriate manner?
Does the analyst have a copy of the most
recent list of in-house samples to be
analyzed?
Date of list
Are all solutions properly labeled?
Is there an electrode dedicated to low-
level F~ analysis?
Is all labware that comes in contact with
standards and samples made of plastic?
Is the temperature regulated?
Is a multipoint calibration used?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 33 of b3
CARBON ANALYZER (Page 1 of 3)
Make and Model:
Specifications:
Comments:
-------
Appendix D
Revision 2
Date: 11/87
Page 34 of 53
CARBON ANALYZER (Page 2 of 3)
Item
Has the instrument been modified in any way?
Is a permanent service record maintained in
a logbook?
Is service maintenance by contract?
Is preventive maintenance applied?
Does each analyst have a copy of the
standard operating procedures?
Are manufacturer's operating manuals readily
available to the analyst?
Is there a calibration protocol available
to the analyst?
Are calibration results kept in a permanent
record?
Does each analyst have a copy of the
instrument performance data?
Does each analyst have a copy of the
latest weekly QC plots?
Is the analyst aware of the most recent
control limits?
Is a permanently bound notebook with
preprinted, consecutively numbered pages
being used?
Is the type of work clearly displayed on
the notebook?
Are the entries in the notebook legible?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 35 of 53
CARBON ANALYZER (Page 3 of 3)
Item
Are anomalies routinely recorded?
Has the analyst avoided obliterating
entries?
Are inserts (e.g., chromatograms, computer
printouts) permanently affixed in notebook
and signed across insert edge and page?
Has the supervisor of the individual
maintaining the notebook personally
examined, reviewed, and signed the note-
book periodically, dating it, and recording
whether the notebook is being maintained
in an appropriate manner?
Does the analyst have a copy of the most
recent list of in-house samples to be
analyzed?
Date of list
Are all solutions properly labeled?
Is C02-free water used to prepare
standards?
Are precautions taken to prevent C02
contamination of samples and standards?
Is instrument designed to determine
both DOC and DIC? If not, what
modifications are necessary?
Yes
No
Comment
-------
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Appendix D
Revision 2
Date: 11/87
Page 36 of 53
AUTOMATED ANALYZER (Page 1 of 5j
Item
Automated Analyzer
Electrodes
Data System
Manufacturer
Model
Installation
Date
Comments:
-------
Appendix D
Revision 2
Date: 11/87
Page 37 of 53
AUTOMATED ANALYZER (Page 2 of 5)
Item
Has the instrument been modified in any way?
Is a permanent service record maintained in
a logbook?
Is service maintenance by contract?
Is preventive maintenance applied?
Does each analyst have a copy of the
standard operating procedures?
Are manufacturer's operating manuals readily
available to the analyst?
Is there a calibration protocol available
to the analyst?
Are calibration results kept in a permanent
record?
Does each analyst have a copy of the
instrument performance data?
Does each analyst have a copy of the
latest weekly QC plots?
Is the analyst aware of the most recent
control limits?
Is a permanently bound notebook with
preprinted, consecutively numbered pages
being used?
Is the type of work clearly displayed on
the notebook?
Are the entries in the notebook legible?
Yes
No
Comment
-------
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Appendix D
Revision 2
Date: 11/87
Page 38 of b3
AUTOMATED ANALYZER (Page 3 of 5]
Item
Are anomalies routinely recorded?
Has the analyst avoided obliterating
entries?
Are inserts (e.g., chromatograms, computer
printouts) permanently affixed in notebook
and signed across insert edge and page?
Has the supervisor of the individual
maintaining the notebook personally
examined, reviewed, and signed the note-
book periodically, dating it, and recording
whether the notebook is being maintained
in an appropriate manner?
Does the analyst have a copy of the most
recent list of in-house samples to be
analyzed?
Date of list
Are all solutions properly labeled?
Are dilute calibration standards
prepared fresh daily?
Source
Is the QC check sample prepared fresh
daily from an independent stock?
Source
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 39 of 53
AUTOMATED ANALYZER (Page 4 of 5)
Item
Is the calibration curve at least a five-
point curve?
Is the first calibration curve of the day
checked for detection limit(s) and
linearity?
Are the analyst QC sample data calculated
and plotted real time?
Is there an automated analyzer dedicated to
each analysis (Total P, NH4+, Si02)?
Is each new calibration curve checked to
see that the change in instrumental response
is less than 5 percent?
Are the following control samples analyzed
with each run?
Reacjent Blanks
QCCS
Duplicates
Does the analyst review the QC data sheet
output by the data clerk, and then decide
whether or not to release the data for
reporting?
Is water pumped through all lines daily,
before and after analysis?
Are pump tubes changed at least once every
three days?
Is the pump cleaned when the pump tubes
are changed?
Yes
_j
No
Comment
-------
1
1
1
Appendix D
Revision 2
Date: 11/87
Page 40 of 53
AUTOMATED ANALYZER (Page 5 of 5)
Item
Is soap solution that does not contain
1 phosphorus pumped through all lines once
a week?
Is the flowcell
1 acid-potassium
once a month?
Is the pump oil
Date of
cleaned with a sulfuric
dichromate solution
ed once every three months?
last service
* Is the colorimeter mirror assembly and
color filter cl
optimized once
Date of
1
1
1
1
1
1
1
1
eaned and the alignment
every three months?
last service
Yes
No Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 41 of b3
CONDUCTANCE (Page 1 of 3)
Item
Meter
Conductivity Cell
Manufacturer
Model
Installation
Date
Is temperature compensated to 25 °C?
What is the cell constant?
Comments:
-------
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Appendix D
Revision 2
Date: 11/87
Page 42 of 53
CONDUCTANCE (Page 2 of 3)
Item
Has the instrument been modified in any way?
Is a permanent service record maintained in
a logbook?
Is service maintenance by contract?
Is preventive maintenance applied?
Does each analyst have a copy of the
standard operating procedures?
Are manufacturer's operating manuals readily
available to the analyst?
Is there a calibration protocol available to
the analyst?
Are calibration results kept in a
permanent record?
Does each analyst have a copy of the
instrument performance data?
Does each analyst have a copy of the
latest weekly QC plots?
Is the analyst aware of the most recent
control limits?
Is a permanently bound notebook with
preprinted, consecutively numbered pages
being used?
Is the type of work clearly displayed on
the notebook?
Are the entries in the notebook legible?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 43 of 53
CONDUCTANCE (Page 3 of 3)
Item
Are anomalies routinely recorded?
Has the analyst avoided obliterating
entries?
Are inserts (e.g., chromatograms, computer
printouts) permanently affixed in notebook
and signed across insert edge and page?
Has the supervisor of the individual
maintaining the notebook personally
examined, reviewed, and signed the note-
book periodically, dating it and recording
whether the notebook is being maintained
in an appropriate manner?
Does the analyst have a copy of the most
recent list of in-house samples to be
analyzed?
Date of list
Are all solutions properly labeled?
Yes
No
Comment
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Appendix D
Revision Z
Date: 11/87
Page 44 of 53
DOCUMENTATION AND TRACKING (Page 1 of 1)
Item
Is a sample custodian designated? If yes, what
is the name of the sample custodian?
Name
Are the sample custodian's procedures and
responsibilities documented? If yes, where
are they documented?
Are written standard operating procedures (SOPs)
developed for receipt of samples? If yes,
where are the SOPs documented (laboratory
manual, written instructions, etc.)?
Are written standard operating procedures (SOPs)
developed for compiling and maintaining sample
document files? If yes, where are the SOPs
documented (laboratory manual, written
instructions, etc.)?
Are samples that require preservation stored in
such a way as to maintain their integrity? If
yes, how are the samples stored?
After completion of the analysis, are the
samples properly stored for 6 months or
until laboratory personnel are told otherwise?
Are the magnetic tapes stored in a secure area?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 45 of 53
ANALYTICAL METHODOLOGY (Page 1 of 2)
Item
Are the required methods used?
Is there any unauthorized deviation from contract
methodology?
Are written analytical procedures provided to
the analyst?
Are reagent-grade or higher purity chemicals
used to prepare standards?
Are fresh working standards prepared daily?
Are reference materials properly labeled with
concentrations, date of preparations, and the
identity of the person preparing the sample?
Is a standard preparation and tracking logbook
maintained?
Do the analysts record bench data in a neat and
accurate manner?
Is the appropriate instrumentation used in
accordance with the required protocol (s)?
Yes
No
Comment
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Appendix D
Revision 2
Date: 11/87
Page 46 of 53
I
COMMENTS ON ANALYTICAL METHODS AND PRACTICES
ANALYTICAL METHODOLOGY (Page 2 of 2)
/»nut!r~ HT f* r\M fitiAi VT T /* A i
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Appendix D
Revision 2
Date: 11/87
Page 47 of 53
QUALITY CONTROL (Page 1 of 3)
Item
Does
Does
of a
the
the
QC
a.
b.
c.
d.
e.
f.
9'
h.
laboratory maintain a QC manual?
manual address the important elements
program, including the following:
Personnel?
Facilities and equipment?
Operation of instruments?
Documentation of procedures?
Procurement and inventory practices?
Preventive maintenance?
Reliability of data?
Data validation?
1 ; Feedback and corrective action?
o. Instrument calibration?
k.
1.
Recordkeejnng?
Internal audits?
Yes
No
Comment
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Appendix D
Revision 2
Date: 11/87
Page 48 of 53
QUALITY CONTROL (Page 2 of 3)
Item
Are QC responsibilities and reporting
relationships clearly defined?
Have standard curves been adequately
documented?
Are laboratory standards traceable?
Are QC charts maintained for each routine
analysis?
Do QC records show corrective action
when analytical results fail to meet
QC criteria?
Do supervisory personnel review the data and
QC results?
Does each analyst have a copy of the
standard operating procedures?
Does each analyst have a copy of the
instrument performance data?
Does each analyst have a copy of the
latest QC plots?
Is the analyst aware of the most recent
control limits?
Does the analyst routinely review and
report blank audit data to the laboratory
manager?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 49 of 53
QUALITY CONTROL (Page 3 of 3)
Item
Does the analyst update control limits
and obtain new control chart plots once
each week of analysis?
Are all QC data (control charts,
regression charts, QC data bases, etc.)
up to date and accessible?
Are minimum detection limits calculated
as specified?
Is QC data sheet information reported to
the analyst?
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 50 of 53
DATA HANDLING (Page 1 of 2)
Item
Does data clerk do a 100 percent check for
accuracy of data input to the computer?
Are data calculations checked by another
person?
Are data calculations documented?
Does strip chart reduction by on-line
electronic digitizing receive at least
5 percent manual spot checking?
Are manually interpreted strip chart
data spot-checked after initial entry?
Do laboratory records include the following
information?
Sample identification number
Station identification
Sample type
Date sample received in laboratory
Time, date, and volume of collection
Date of analysis
Analyst
Result of analysis (including raw
analytical data)
Receiver of the analytical data
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 51 of 53
DATA HANDLING (Page 2 of 2)
Item
Does laboratory follow required sample
tracking procedures from sample receipt
until discard?
Does the data clerk routinely report
QC data sheet information to the analyst?
Does the data clerk submit QC data sheet
information to the lab manager along with
the analytical data to be reported?
Do records indicate corrective action
taken?
Are provisions made for data storage for
all raw data, calculations, QC data, and
reports?
Are all data and records retained the
required amount of time?
Are computer printouts and reports
routinely spot-checked against laboratory
records before data are released?
Yes
No
Comment
-
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Appendix D
Revision 2
Date: 11/87
Page 52 of 53
SUMMARY (Page 1 of 2)
Item
Do responses to the evaluation indicate that
project and supervisory personnel are aware of
QA and its application to the project?
Do project and supervisory personnel place
positive emphasis on QA/QC?
Have responses with respect to QA/QC aspects of
the project been open and direct?
Has a cooperative attitude been displayed by all
project and supervisory personnel?
Does the organization place the proper emphasis
on QA?
Have any QA/QC deficiencies been discussed before
leaving?
Is the overall QA adequate to accomplish the
objectives of the project?
Have corrective actions recommended during
previous evaluations been implemented?
Are any corrective actions required? If so,
list the necessary actions below.
Yes
No
Comment
-------
Appendix D
Revision 2
Date: 11/87
Page 53 of 53
SUMMARY (Page 2 of 2)
Summary Comments and Corrective Actions
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Appendix E
Revision 2
Date: 11/87
Page 1 of 3
Laboratory:
Quantitation:
Sample Set
PART I
APPENDIX E
EASTERN LAKE SURVEY - PHASE II
PREAWARD AUDIT SAMPLE SCORING SHEET
Date:
jn:
>t 1
>t 2
Total Score
(Maximum = 200 f
QUANTITATION
Aliquot 1
(Number of parameters within
acceptance criteria x 12/6*)
Aliquot 2
(Number of parameters within
acceptance criteria x 8/1*)
Aliquot 3
(Number of parameters within
acceptance criteria x 14/5*)
Aliquot 4
(Number of parameters within
acceptance criteria x 8/2*)
Aliquot 5
(Number of parameters within
acceptance criteria x 30/5*)
Aliquot 6
(Number of parameters within
acceptance criteria x 4/1*)
Aliquot 7
(Number of parameters within
acceptance criteria x 4/1*)
QA/QC
Deliverables
>oints)
Points Awarded
Sample Set 1
(Low Cone.)
Points Awarded
Sample Set 2
(High Cone.)
Total
Score
D.
E.
F.
G.
*Denominator is number of parameters measured.
based on the air-equilibrated values.
The scoring for pH and DIC is
-------
Appendix E
Revision 2
Date: 11/87
Page 2 of 3
Laboratory:
Date :
PART II. QUALITY ASSURANCE
A. Calibration/Reagent
Blank Analyses:
1. All results less than
2 x CRDL.
2. One result greater than
2 x CRDL.
3. Two results greater than
2 x CRDL.
4. Three or more results
greater than CRDL.
B. Quality Control Check Sample:
1. All verifications within
acceptance criteria.
2. One or more verifications
outside acceptance criteria.
C. Duplicate Sample Analyses:
1. All XRSD within acceptance
criteria.
2. 1-2 outside acceptance
criteria.
3. 3-4 outside acceptance
criteria.
4. 5 or more outside
acceptance criteria.
D. An ion-Cation Balance
Calculation:
1. Within acceptance criteria.
2. Outside acceptance
criteria.
Possible
Points
6
4
2
0
10
0
6
4
2
0
4
0
Points
Awarded
Sample Set 1
Points
Awarded
Sample Set 2
Total
Score
-------
1
1
^m
1
1
1-
1
1
1
Laboratory:
Appendix E
Revision 2
Date: 11/87
Page 3 of 3
Date:
PART II. QUALITY ASSURANCE (Continued)
E. Detection Limi
Point
Possible Award
Points Sample
ts:
1. All instrumental detection
limits within acceptance
criteria.
2. One or more
acceptance
PART III. REPORTING
4
outside
criteria. 0
AND DELIYERABLES
s Points
ed Awarded Total
Set 1 Sample Set 2 Score
Possible Points
A. Data results submitted in acceptable format
on standard forms.
1
1
1
2
B. Quality assurance/quality control data
supplied
C. Raw data
D. Tabulated
in acceptable format.
supplied.
1
5
instrument detection limits and associated
blank data supplied.
1
E. Validation of results with signature
1
1
1
1
1
1
of laboratory manager supplied.
1
-------
APPENDIX F
EASTERN LAKE SURVEY - PHASE II
VERIFICATION REPORT
SURVEY:
BATCH ID:
CONTRACT LABORATORY:
SAMPLING SITES:
TOTAL NO. OF SAMPLES:
NO. OF AUDIT SAMPLES: TYPE:
NO. OF FIELD DUPLICATE SAMPLES:
NO. OF FIELD BLANK SAMPLES:
DATE CONFIRMATION REQUESTS RECEIVED:
DATE REANALYSIS REQUESTS SENT:
DATE REANALYSIS REQUESTS RECEIVED:
DATE AUDITED: BY:
DATE REVIEWED: BY:
DATE MAGNETIC TAPE SENT TO SAI:
DATE CONFIRMATION REQUESTS SENT:
I. OUTSTANDING ISSUES - CONTRACT LABORATORY
A. The Sample Data Package (was, was not) complete as submitted. TTI<
items that are identified as missing should be resubmitted befor^
process can begin:
1. a. Required forms (11, 13, I/, 18, 19, 20,
and 22) submitted.
Yes
Par-
tial
No
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Appendix F
Revision 2
Date: 11/87
Page 2 of 34
b. Lab name, batch ID, and lab manager's
signature submitted on all forms.
c. Sample ID reported on Forms 13 and 22.
d. Correct units indicated on all forms.
Form 11:
a. Correct number of samples analyzed and the
results for each parameter tabulated.
b. Correct data qualifiers reported as needed.
c. Initial alkalinity pH and Initial acidity
pH are within +0.1 pH units.
d. For all sample data, pH (Initial/Equilibrated)
increases as DIC (Initial/Equilibrated)
decreases and vice versa.
e. Extractable Al < Total Al for all samples.
f. The field routine/duplicate pairs meet
the %RSD requirements.
g. The field blank concentrations are less than
or equal to criteria ^95)
established for each parameter.
h. The audit sample data meet the criteria
established for each parameter.
Form 13:
a. The results on Form 13 (ANC, BNC, PHAC, and
PHAL values) match those on Form 11 an Form 22.
b. Correct increments of acid and base titrants
used during ANC and BNC titrations.
c. Analyst's name recorded on Form 13.
Form 17:
a. 1C Resolution data reported for each batch of
analyses. Resolution must be greater than 60%.
Form 18:
a. Instrumental detection limits and associated
dates of determination tabulated.
b. The IDL is less than or equal to the contract
required detection limit (CRDL).
Form 19:
a. Date processed, date received, holding time
plus date processed and dates of analyses for
the correct number of samples are tabulated.
b. Date analyzed is less than or equal to the
reported holding time plus date processed.
c. pH measurements are performed on the same
day as the DIC analysis for each sample.
Yes
Par-
tial
No
Comments
-------
Appendix F
Revision 2
Date: 11/87
Page 3 of 34
7. Form 20:
a. Calibration blanks, reagent blanks, correct
number of QCCS runs, and DL QCCS reported
where required.
b. If high QCCS true values are reported, the
samples analyzed on high range are discussed
in the cov°r letter or any dilutions are
indicated on Form 21 (Dilution Factors).
c. QCCS true values are approximately in the mid-
range of the sample concentrations for each
parameter.
d. Calibration blank data are indicative of
instrument drift (greater than 2*CRDL for
positive values or less than -CRDL for
negative values).
e. Calibration blank data indicate trends
throughout all batches for each analytical
laboratory.
8. Form 22:
a. Duplicate precision results are reported for
each parameter.
b. Correct standard deviation formula (using
n-1) is used to calculate %RSD.
c. Samples selected for duplicate analysis
contained sufficient amounts of analytes
(10*CRDL if possible) to yield reliable
precision.
d. If %RSD criterion is not met, another sample
is selected to be analyzed in duplicate.
e. Sample results on Form 22 match sample
results on Form 11.
9. Any information pertinent to sample analyses
is noted on the cover letter.
Yes
Par-
tial
No
Comments
-------
I
Appendix F
Revision 2
Date: 11/87
Page 4 of 34
IB. The Sample Data Package (was, was not) complete as submitted, but the
following sample results should be confirmed by the contract laboratory
(Reference Form 26):
I Sample Form Date Date
ID Number Parameter Requested Confirmed Reason for Confirmation
I
I
I
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I
C. Sample analysis (was, was not) complete based on data submitted. Reanalysis
is recommended for the following samples (Reference Form 26):
Sample Reported Date Date
ID Parameter Value Requested Submitted Reason for Reanalysis
I
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-------
Appendix F
Revision 2
Date: 11/87
Page 5 of 34
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-------
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Appendix F
Revision 2
Date: 11/87
Page 6 of 34
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-------
Appendix F
Revision 2
Date: 11/87
Page 7 of 34
IV. ANION/CATION BALANCE CHECK
Note: The flagged samples and parameters listed in the following
sections must be consistent with the most current computer-
generated exceptions.
A. Based on Anion/Cation balance check program, all samples submitted for this
batch (were, were not) within criteria. Using the anion/cation balance
check flowchart, the following conclusions were made for the samples that
did not meet criteria:
Total
Sample Ion
ID Strength
Reported %
Ion Bal.
Diff. (IBD)
Required %
Ion Bal.
Diff. (IBD)
Parameter
in
Question
Explanation
1. Contamination (was, was not) indicated in the field and/or laboratory
blank data for the above exceptions. Contamination was apparent in
the following parameters and samples:
Sample
ID
Contaminated
Parameter
Recalculated ZIBD
Field/Lab (Contaminated Blank Cone.
Blank Cone. Excluded)
Explanation
-------
Appendix F
Revision 2
Date: 11/87
Page 8 of 34
The sample(s) listed above should be flagged using the appropriate
sample flags "Al. A2, or A3".
2. Unmeasured organic protolytes (were, were not) indicated by the Protolyte
Analysis Program for the exceptions listed in Section IV-A. The
following samples appear to have %IBD outside criteria due to un-
measured organic protolytes:
Non-titrated
Sample Reported DOC (unmeasured) Recalculated JIBD
ID (mg/L) Organic Ions (Organic Ions Included) Explanation
The sample(s) listed above should be flagged using the sample flag "A4".
3. Analytical error (was, was not) indicated in measurement of one or more
of the anions or cations (including ANC measurement) contributing to
the Anion/Cation balance check calculation. Analytical error was
apparent in the following parameters and samples.
Sample ID Parameter In Question Explanation
-------
Appendix F
Revision 2
Date: 11/87
Page 9 of 34
The sample(s) listed above should be flagged using the appropriate sample
flags "A5, A6, A7, A8, or A9."
V. CONDUCTANCE BALANCE CHECK
A. Based on conductance balance check program, all samples submitted for this
batch (were, were not) within criteria. Using the conductance balance
check flowchart, the following conclusions were made:
-. The % conductance difference (SCO) between the Form 11 measured
conductance* and the calculated conductance (did, did not) meet criteria.
The following samples were listed as exceptions:
Sample ID Form 11 Conductance Calculated Conductance ZCD Explanation
2. The % conductance difference between the field conductance and the
Form 11 measured conductance (did, did not) meet criteria. The following
samples did not meet criteria:
Sample ID Form 11 Conductance Field Conductance tCD Explanation
*The Form 11 measured conductance value is considered to represent the "TRUE"
conductance measurement. Therefore, all other conductance measurements are
compared to Form 11 conductance values.
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3.
4.
5.
Appendix F
Revision 2
Date: 11/87
Page 10 of 34
Contamination (was, was not) indicated by the field and/or laboratory
blanks for the above exceptions. Contamination was apparent in the
following samples:
Sample
ID
Contaminated
Parameters
Field/Lab
Blank Cone.
Recalculated
%CD
(contaminated
blank cone, excluded)
Explanation
The sample(s) listed above should be flagged using the appropriate
sample flag "C2 or C3".
The % Conductance Difference (%CD) indicates possible analytical error
in the contract analytical laboratory conductance measurement for the
following parameters and samples:
Sample
ID
Parameter
Laboratory
Contract Required
Max %CD
Explanation
The above sample(s) should be flagged using the sample flag "C5".
The % Conductance Difference (ZCD) indicates analytical error in the
field conductance measurements for the following samples:
Sample
ID
Field
%CD
Contract Required
Max ZCD Field
Explanation
-------
Appendix F
Revision 2
Date: 11/87
Page 11 of 34
The above sample(s) should be flagged using the sample flag "FO" (field)
6. Based on review of the data, unmeasured protolyte (were, were not)
suspected in the samples. The followiig samples are suspected to
contain unmeasured protolyte ions:
Sample ID Reported DOC Uig/L) Explanation
All samples listed above should be flagged unmeasured organic ions
using the sample flags "C4" and "C7".
7. Analytical error (was, was not) indicated in the calculated value for
conductance. Analytical error was apparent in the following parameters
and samples.
Sample Contract Required
ID Parameter ZCD Max %CD Explanation
The sample(s) listed above should be flagged using the appropriate
sample flags "Cl, C6, C8, or C9."
-------
1
1
1
1
1
1
1
1
1
1
1
1
1
1
VI. INTERNAL AND EXTERNAL QA/QC DATA REVIEW
A. All data for the following parameters and samples were
on the following:
1. The field blank (did, did not) exceed expected val
contribute greater than 20% to the other samples i
(except for other blanks). The contaminated sampl
Sample Contaminated
ID Parameter % Contribution
All samples for the parameters listed above should
the flags "B0", "B2". or "B5".
2. The ZRSD for a routine-duplicate sample (was, was
Appendix F
Revision 2
Date: 11/87
Page 12 of 34
not acceptable based
ues and (did, did not
n the batch
es follow:
Explanation
be flagged using
not) greater than
1.96K.* The expected XRSD exceeded the criteria for the following
parameters:
Contract
laboratory Calculated
Parameter Reported ZRSD ZRSD
Explanation
The parameters listed above should be flagged using the parameter flag
"D2".
*1.96 is the Pgs of a standard normal distribution and k is
a constant
representing the variance divided by the mean for the natural audit samples.
-------
Appendix F
Revision 2
Date: 11/87
Page 13 of 34
3. Audit sample data (were, were not) within the expected performance
range. The following audit samples were outside of the expected
ranges:
Audit Reported Expected
Parameter Sample Type Value Range Explanation
All samples in the batch for the parameters listed above should be
flagged using the appropriate parameter flag "N0 or Ml".
4. The calibration and/or reagent blank data (did, did not) meet criteria.
a. The calibration and/or reagent blank values (were, were not) greater
than 2 X CRDL and (did, did not) contribute greater than 10% to the
other samples in the batch. The affected samples are as follows:
Sample ID Parameter Duplicate % Contribution Explanation
All samples listed above should be flagged using the parameter flag
"Bl" or sample flag "B3."
b. The calibration and/or reagent blank values (were, were not) less
than [-CRDL]. If they are, this could be an indication of negative
bias for the following parameters.
-------
1
1
1
1
1
1
1
1
1
1
1
^B
1
1
1
Sample ID Parameter
All samples listed above
"B4".
5. Detection Limit Quality
were not) within 20% of
cal concentration of the
Appendix F
Revision 2
Date: 11/87
Page 14 of 34
Duplicate % Contribution Explanation
should be flagged using the parameter flag
Control Check Sample (DL QCCS) analyses (were,
the theoretical concentration and the theoreti-
QCCS (was, was not) 2 to 3 times the CRDL.
The following DL QCCSs did not meet contractual criteria:
Parameter Reported
All samples listed above
6. Internal Quality Control
within contractual requi
complete. The following
Required
Value Range Explanation
should be flagged using the sample flag "Q5".
Check Sample (QCCS) analyses (were, were not)
rements and the number of runs (were, were not)
QCCSs did not meet contractual requirements:
Reported Required No. of No. of QCCS
Parameter Value Range
All samples in the batch
QCCS Runs Runs Required Explanation
for the parameters listed above should
be flagged using the appropriate parameter flags "Ql or Q2" or if
appropriate Q3 or Q4.
Issues concerning 15% QC
withholding should be noted on page 4.
-------
Appendix F
Revision 2
Date: 11/87
Page 15 of 34
7. The contract laboratory duplicate precision (was, was not) met. If
initial precision was outside criteria, up to two additional duplicates
(were, were not) analyzed as required by the contract.
Program
Calculated Contract
Parameter Reported %RSD -ERSD Required SRSD Explanation
All samples in the batch for the parameters listed above should be
flagged using the parameter flag "D3".
Instrumental detection limits (did, did not) exceed the CRDL. The
following sample values reported at less than 10 times the IDL could
be in question:
Sample Reported Reported
ID Parameter Cone. IDL CRDL Explanation
All samples having concentrations <10 x IDL for the parameters listed
above are in question and should be flagged using the sample flag
"LI".
-------
I
I
I
I
I
I
I
I
I
I
Appendix F
Revision 2
Date: 11/87
Page 16 of 34
VII. SUMMARY OF FLAGGED DATA
All internal QC data (calibration blanks, reagent blanks, DL QCCS and
QCCS, and duplicate precision) and external QA data (audits, field blanks,
and field duplicates) were not within contractural and/or expected criteria
for all the samples and the associated parameters listed below:
(Parameter Flags: B0, Bl, B4-B5, D2, D3, N0-N2, Q1-Q5)
(Sample Flags: A0-A9, B2-B3, C0-C9, F0-F5, H0, LI, P0-P7, X0-X4)
PARAMETER FLAG LISTING:
Sample ID Parameter Flag
SAMPLE FLAG LISTING:
Sample ID Parameter Flat
-------
Appendix F
Revision 2
Date: 11/87
Page 17 of 34
NATIONAL SURFACE WATER SURVEY
EASTERN LAKE SURVEY - PHASE II
FINAL PASS VERIFICATION REPORT
SURVEY:
DATE CONFIRMATION REQUEST SENT:
DATE CONFIRMATION REQUESTS RECEIVED:
DATE REANALYSIS REQUESTS SENT:
DATE REANALYSIS REQUESTS RECEIVED:
DATE AUDITED: BY:
DATE REVIEWED: BY:
DATE MAGNETIC TAPE SENT TO SAI:
-------
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Appendix F
Revision 2
Date: 11/87
Page 18 of 34
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Appendix F
Revision 2
Date: 11/87
Page 18 of 34
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Appendix F
Revision 2
Date: 11/87
Page 19 of 34
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-------
Appendix F
Revision 2
Date: 11/87
Page 20 of 34
IV. ANION/CATION BALANCE CHECK
Note: The flagged samples and parameters listed in the following
sections must be consistent with the most current computer-
generated exceptions,
A. Based on Anion/Cation balance check program, all samples submitted for this
batch (were, were not) within criteria. Using the anion/cation balance
check flowchart, the following conclusions were made for the samples that
did not meet criteria:
Sample
ID
Total
Ion
Strength
Reported %
Ion Bal.
Diff. (IBD)
Required %
Ion Bal.
Diff. (IBD)
Parameter
in
Question
Explanation
1. Contamination (was, was not) indicated in the field and/or laboratory
blank data for the above exceptions. Contamination was apparent in
the following parameters and samples:
Sample
ID
Contaminated
Parameter
Recalculated ZIBD
Field/Lab (Contaminated Blank Cone.
Blank Cone. Excluded)
Explanation
-------
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
Appendix F
Revision 2
Date: 11/87
Page 21 of 34
The sample(s) listed above should be flagged using the appropriate
sample flags "Al, A2, or A3".
2. Unmeasured organic protolytes (were, were not) indicated by the Protolyte
Analysis Program for the exceptions listed in Section IV-A. The
following samples appear to have 2IBD outside criteria due to un-
measured organic protolytes:
Non-titrated
Sample Reported DOC (unmeasured) Recalculated %IBD
ID (mg/L) Organic 'Ions (Organic Ions Included) Explanation
The sample(s) listed above should be flagged using the sample flag "A4".
3, Analytical error (was, was not) indicated in measurement of one or more
of the anions or cations (including ANC measurement) contributing to
the Anion/Cation balance check calculation. Analytical error was
apparent in the following parameters and samples.
Sample ID Parameter In Question Explanation
-------
I
Appendl
Re v i s i o
Date:j
Page 2|
The sample(s) listed above should be flagged using the appropl
flaas "A5. A6. A7. A8. or A9."
A. Based on conductance balance check program, all samples submitted fi
batch (were, were not) within criteria. Using the conductance bali
check flowchart, the following conclusions were made: I
1. The % conductance difference (%CD) between the Form 11 measured
conductance* and the calculated conductance (did, did not) meeB
The following samples were listed as exceptions:
Sample ID Form 11 Conductance Calculated Conductance %CD Lm
flags "A5, A6, A7, A8, or A9.
V. CONDUCTANCE BALANCE CHECK
I
I
I
Sample ID Form 11 Conductance Field Conductance %CD
2. The % conductance difference between the field conductance and
11 measured conductance (did, did not) meet criteria. The fol
samples did not meet criteria:
I
I
I
I
*The Form 11 measured conductance value is considered to represent, the
conductance measurement. Therefore, all other conductance measurements
compared to Form 11 conductance values.
I
I
-------
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
Appendix F
Revision 2
Date: 11/87
Page 23 of 34
3. Contamination (was, was not) indicated by the field and/or laboratory
blanks for the above exceptions. Contamination was apparent in the
following samples:
Recalculated
SCO
Sample Contaminated Field/Lab (Contaminated
ID Parameters Blank Cone. Blank Cone. Excluded) Explanation
The sample(s) listed above should be flagged using the appropriate
sample flag "C2 or C3".
The % Conductance Difference UCD) indicates possible analytical error
in the contract analytical laboratory conductance measurement for the
following parameters and samples:
Sample Laboratory Contract Required
ID Parameter %CD Max %CD Explanation
The above sample(s) should be flagged using the sample flag "C5".
5. The % Conductance Difference (%CD) indicates analytical error in the
field conductance measurements for the following samples:
Sample Field Contract Required
ID %CD Max %CD Field Explanation
-------
Appendix F
Revision 2
Date: 11/87
Page 24 of 34
The above sample(s) should be flagged using the sample flag "FO" (field)
6. Based on review of the data, unmeasured protolyte ions (were, were not)
suspected in the samples. The following samples are suspected to
contain unmeasured protolyte ions:
Sample ID Reported DOC (mg/L) Explanation
All samples listed above should be flagged unmeasured organic ions
using the sample flags "C4" and "C7".
7. Analytical error (was, was not) indicated in the calculated value for
conductance. Analytical error was apparent in the following parameters
and samples.
Sample Contract Required
ID Parameter %CD Max %CD Explanation
The sample(s) listed above should be flagged using the appropriate
sample flags "Cl, C6, C8, or C9."
-------
I
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I
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I
I
I
I
I
I
I
Appendix F
Revision 2
Date: 11/87
Page 25 of 34
VI. INTERNAL AND EXTERNAL QA/QC DATA REVIEW
A. All data for the following parameters and samples were not acceptable based
on the following:
1. The field blank (did, did not) exceed expected values and (did, did not)
contribute greater than 20% to the other samples in the batch
(except for other blanks). The contaminated samples follow:
Sample Contaminated
ID Parameter % Contribution Explanation
All samples for the parameters listed above should be flagged using
the flags "B0", "B2", or "B5".
2. The ZRSD for a routine-duplicate sample (was, was not) greater than
1.96K.* The expected ZRSD exceeded the criteria for the following
parameters:
Contract
Laboratory Calculated
Parameter Reported JRSD 2RSD Explanation
| The parameters listed above should be flagged using the parameter flag
11 n?"
*1.96 is the Pg5 of a standard normal distribution and k is a constant
representing the variance divided by the mean for the natural audit samples.
-------
Appendix F
Revision 2
Date: 11/87
Page 26 of 34
3. Audit sample data (were, were not) within the expected performance
range. The following audit samples were outside of the expected
ranges:
Audit Reported Expected
Parameter Sample Type Value Range Explanation
All samples in the batch for the parameters listed above should
be flagged using the appropriate parameter flags "N0 or Ml".
4. The calibration and/or reagent blank data (did, did not) meet criteria.
a. The calibration and/or reagent blank values (were, were not) greater
than 2 X CRDL and (did, did not) contribute greater than 10Z to the
other samples in the batch. The affected samples are as follows:
Sample ID Parameter Duplicate % Contribution Explanation
All samples listed above should be flagged using the parameter flag
"81" or sample flags "B3."
b. The calibration and/or reagent blank values (were, were not) less
than [-CRDL]. If they are this could be an indication of negative
bias for the following parameters.
Sample ID Parameter Duplicate % Contribution Explanation
-------
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Appendix F
Revision 2
Date: 11/87
Page 27 of 34
All samples listed above should be flagged using the parameter flag "B4"
5. Detection Limit Quality Control Check Sample (DL QCCS) analyses (were,
were not) within 20% of the theoretical concentration and the theoreti-
cal concentration of the QCCS (was, was not) 2 to 3 times the CRDL.
The following DL QCCSs did not me*et contractual criteria:
Parameter Reported
All samples listed above
6. Internal Quality Control
not) within contractual
were not) complete. The
requirements :
Reported Required
Parameter Value Range
Required
Value Range Explanation
should be flagged using the sample flag "Q5".
Check Sample (QCCS) analyses (were, were
requirements and the number of runs (were,
following QCCSs did not meet contractual
No. of No. of QCCS
QCCS Runs Runs Required Explanation
All samples in the batch for the parameters listed above should
be flagged using the appropriate parameter flags "Ql or Q2" or if
appropriate Q3 or Q4.
Issues concerning 15% QC withholding should be noted on page 4.
7. The contract laboratory duplicate precision (was, was not) met. If
initial precision was outside criteria, up to two additional duplicates
(were, were not) analyzed as required by the contract.
Parameter Reported XRSD
Program
Calculated Contract
iRSD Required ZRSD Explanation
-------
Appendix F
Revision 2
Date: 11/87
Page 28 of 34
All samples in the batch for the parameters listed above should be
flagged using the parameter flag "D3".
8. Instrumental detection limits (did, did not) exceed the CRDL. The
following sample values reported at less than 10 times the I PL could
be in question:
Sample Reported Reported
ID Parameter Cone. IDL CRDL Explanation
All samples having concentrations <10 x IDL for the parameters listed
above are in question and should be flagged using the sample flag
"LI".
-------
Appendix F
Revision 2
Date: 11/87
Page 29 of 34
VII. SUMMARY OF FLAGGED DATA
All internal QC data (calibration blanks, reagent blanks, DL QCCS and
QCCS, and duplicate precision) and external QA data (audits, field blanks
and field duplicates) were not within contractural and/or expected criteria
for all the samples and the associated parameters listed below:
(Parameter Flags: B0, Bl, B4-B5, D2, D3, N0-N2, Q1-Q5)
(Sample Flags: A0-A9, B2-B3, C0-C3, F0-F5, H0, LI, P0-P7, X0-X4)
PARAMETER FLAG LISTING:
Sample ID Parameter Flag
SAMPLE FLAG LISTING:
Sample ID Parameter Flag
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Appendix F
Revision 2
Date: 11/87
Page 30 of 34
TABLE 1. FLAGS FOR RAW DATA BASE
FLAGS TO USE WITH ANION/CATION PROGRAM:
A0 Anion/Cation % Ion Balance Difference UIBD) is outside of criteria due
to unknown cause.
Al Anion/Cation % Ion Balance Difference UIBD) is outside of criteria due
to other anion/cation not considered in %IBD calculation.
A2 Anion/Cation % Ion Balance Difference UIBD) is outside of criteria due
to anion contamination.
A3 Anion/Cation % Ion Balance Difference UIBD) is outside of criteria due
to cation contamination.
A4 Anion/Cation % Ion Balance Difference UIBD) is outside of criteria due
to unmeasured organic protolytes (fits Oliver Model).
A5 Anion/Cation % Ion Balance Difference UIBD) is outside of criteria due
to possible analytical error - anion concentration too high (flag suspect
anion).
A6 Anion/Cation % Ion Balance Difference UIBD) is outside of criteria due
to possible analytical error - cation concentration too low (flag suspect
cation).
A7 Anion/Cation % Ion Balance Difference UIBD) is outside of criteria due
to possible analytical error - anion concentration too low (flag suspect
anion).
A8 Anion/Cation % Ion Balance Difference UIBD) is outside of criteria due
to possible analytical error - cation concentration too high (flag
suspect cation).
A9 Anion/Cation %Ion Balance Difference UIBD) is outside of criteria due to
possible analytical error - alkalinity measurement.
FLAGS TO USE WITH APPROPRIATE BLANK PROGRAM (MORE THAN 1 PROGRAM):
B0 External (field) blank is above expected criteria for pH, DIC, DOC, (field)
specific conductance, ANC and BNC determinations (flag all samples except
the suspect blank).
Bl Internal (lab) blank is above criteria for DIC, DOC, specific conductance.
(Flag all samples.)
(continued)
-------
Appendix F
Revision 2
Date: 11/87
Page 31 of 34
TABLE 1. (Continued)
FLAGS TO USE WITH APPROPRIATE BLANK PROGRAM (MORE THAN 1 PROGRAM) (continued):
B2 External (field) blank is above expected criteria and contributed >20% to
sample concentrations. (This flag is not used for pH, DIG, DOC, specific
conductance, alkalinity, and acidity determinations. Flag all samples
affected by the >202 contribution except the suspect blank).
B3 Internal (lab) blank is >2 x CRDL and contributes >10% to the sample
concentrations. (This flag is not used for pH, DIC, DOC, specific conduc-
tance, acidity, and alkalinity determinations. Flag all samples affected
by the >10% contribution except the suspect lab blank.)
B4 Potential negative sample bias based on internal (lab) blank data. (Flag
all samples.)
B5 Potential negative sample bias based on external (field) blank data. (Flag
all samples except the suspect blank.)
FLAGS USED WITH CONDUCTIVITY CHECK PROGRAM:
C0 % Conductivity Difference UCD) is outside of criteria due to unknown
cause.
Cl % Conductivity Difference (ZCD) is outside of criteria due to possible
analytical error - anion concentration too high (flag suspect anion).
C2 % Conductivity Difference (ZCD) is outside of criteria due to anion
contamination.
C3 % Conductivity Difference (2CD) is outside of criteria due to cation
contamination.
C4 % Conductivity Difference (ZCD) is outside of criteria due to unmeasured
organic anions (fits Oliver Model).
C5 % Conductivity Difference (JCD) is outside of criteria due to possible
analytical error in conductivity measurement.
C6 % Conductivity Difference (ZCD) is outside of criteria due to possible
analytical error - anion concentration too low (flag suspect anion).
(continued)
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Appendix F
Revision 2
Date: 11/87
Page 32 of 34
TABLE 1. (Continued)
FLAGS USED WITH CONDUCTIVITY CHECK PROGRAM: (Continued)
C7 % Conductivity Difference UCD) is outside of criteria due to unmeasured
anions/cations - anions/cations not considered in %CD calculation.
C8 % Conductivity Difference (ZCD) is outside of criteria due to possible
analytical error - cation concentration too low (flag suspect cation).
* V
C9 % Conductivity Difference (%CD) is outside of criteria due to possible
analytical error - cation concentration too high (flag suspect cation).
FLAGS USED WITH DUPLICATE PRECISION PROGRAM:
Dl External (field) duplicate precision exceeded the maximum expected %
Relative Standard Deviation URSD) and either the routine or duplicate
sample concentrations were >_10 x CRDL. (Flag all samples in the batch
including the suspect R/D pair.)
D2 The external field duplicate precision URSD) exceeded the system precision
(the Pgs of a standard normal distribution based on known audit concentra-
tions.) (Flag all samples in the batch including the suspect R/D pair.)
D3 Internal (lab) duplicate precision exceeded the maximum contract required
% Relative Standard Deviation (XRSD) and both the routine and duplicate
sample concentrations were >1Q x CRDL. (Flag all samples in the batch
including the suspect R/D pair.)
FLAGS USED WHEN FIELD DATA OUT OF CRITERIA (MORE THAN 1 PROGRAM):
F0 % Conductivity difference UCD) exceeded criteria when in-situ field
conductivity value was substituted.
Fl Hi 11 man/Kramer protolyte analysis program indicated field pH problem when
streamside pH value was substituted.
F2 Hillman/Kramer protolyte analysis program indicated unexplained field pH/
PIC problem when streamside pH value was substituted.
F3 Hi 11 man/Kramer protolyte analysis program indicated field problem -
mobile processing laboratory pH.
F4 Hillman/Kramer protolyte analysis program indicated field problem -
mobile processing laboratory PIC.
(continued)
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Appendix F
Revision 2
Date: 11/87
Page 33 of 34
TABLE 1. (Continued)
FLAGS USED WHEN FIELD DATA OUT OF CRITERIA (MORE THAN 1 PROGRAM): (Continued)
F5 Hill man/Kramer protolyte analysis program indicated field problem -
unexplained (pH/DIC).
F6 % Conductivity Difference (%CD) exceeded criteria when mobile processing
laboratory conductivity value was substituted.
FLAGS GENERATED BY HOLDING TIME PROGRAM:
H0 The maximum holding time criteria were not met. (Flag the sample
identification and parameter which exceeded the holding time).
FLAG GENERATED BY IDL PROGRAM:
LI Instrumental Detection Limit (IDL) exceeded Contract Required Detection
Limit (CRDL) and Form 11 sample concentrations was <10 x IDL. (Flag the
sample and parameter which is out of criteria.)
FLAGS GENERATED BY AUDIT CHECK PROGRAM:
N0 Audit sample value exceeded upper control limit. (For the suspect
parameter, all samples in the batch, excluding the audit that is out of
criteria, should be flagged.)
Nl Audit sample value below control limit. (For the suspect parameter, all
samples in the batch, excluding the audit that is out of criteria, should
be flagged.)
N2 Audit sample exceeded control limits due to suspect audit sample preparation
(for the suspect parameter(s) for the audit sample only) should be flagged.
HILLMAN/KRAMER PROTOLYTE ANALYSIS PROGRAM INDICATED THE FOLLOWING FLAGS:
P0 Lab problem - initial alkalinity pH.
PI Lab problem - initial acidity pH.
P2 Lab problem - unexplained - initial pH (alkalinity/acidity).
P3 Lab problem - initial DIC.
P4 Lab problem - air equilibrated pH/DIC.
(continued)
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Appendix F
Revision 2
Date: 11/87
Page 34 of 34
TABLE 1. (Continued)
HILLMAN/KRAMER PROTOLYTE ANALYSIS PROGRAM INDICATED THE FOLLOWING FLAGS:
(Continued)
P5 Lab problem - unexplained - initial pH/DIC.
P6 Lab problem - alkalinity (ANC) determination.
P7 Lab problem - acidity (BNC) determination.
FLAGS USED WITH QCCS PROGRAM(S):
Ql Quality Control Check Sample (QCCS) was above contractual criteria. (For
the suspect parameter, all the samples in the batch should be flagged.)
Q2 Quality Control Check Sample (QCCS) was below contractual criteria. (For
the suspect parameter, all the samples in the batch should be flagged.)
Q3 Insufficient number of QCCS were measured. (For the suspect parameter,
all the samples in the batch should be flagged.)
Q4 No Quality Control Check Sample (QCCS) was performed. (For the suspect
parameter, all the samples in the batch should be flagged.)
Q5 Detection Limit QCCS was not 2 to 3 X CRDL and measured value was outside
of 20% of the theoretical concentration. (For the suspect parameter, all
the samples in the batch should be flagged.)
MISCELLANEOUS FLAGS:
X0 Invalid but confirmed data based on QA review. These data should not
be included in any statistical analysis.
XI Alex >A1 Tl where Alex >_0.015 mg/L and Alex >A1 Tl by 0.010 mg/L.
X2 Invalid but confirmed data - potential aliquot switch.
X3 Invalid but confirmed data - potential gross aliquot or parameter
contamination.
X4 Invalid but confirmed data - potential sample (all aliquots) switch.
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