v>EPA
United States      Office of Acid Deposition, Environmental  EPA/600/8-87/026
Environmental Protection Monitoring and Quality Assurance     June 1987
Agency         Washington DC 20460
Research and Development
Western Lake  Survey
Phase I

Quality Assurance
Plan

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Pacific
Northwest (4B)
  California (4A
                                                   Northern
                                                   Rockies (4C)
Central
Rockies  (4D:
  	J
                                                                                         Southern
                                                                                         Rockies (4E)
                                                                                           J
                            Subregions of the Western  Lake Survey - Phase  I

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                                            EPA 600/8-87/026
                                            June 1987
Western  Lake Survey
            Phase  I
    Quality  Assurance Plan
           A Contribution to the
 National Acid Precipitation Assessment Program
                  U.S. Environmental Protection Agency
                  Office of Research and Development
                      Washington, DC 20460
       Environmental Monitoring Systems Laboratory - Las Vegas. NV 89119
           Environmental Research Laboratory - Corvallls, OR 97333

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                               Notice
The information in this document has been funded wholly or in part by the U.S.
Environmental  Protection  Agency  under contract numbers 68-03-3249  and
68-03-3050 to Lockheed  Engineering and  Management Services Company,
Inc.,  No.  68-03-3246 to Northrop Services, Inc., and Interagency Agreement
Number 40-1441-84 with the  U.S.  Department of  Energy.   It  has been
subject to the Agency's  peer and administrative  review, and  it has been
approved for publication as an Agency document.

Mention  of  trade  names or  commercial  products does  not constitute
endorsement or recommendation for use

This  document is one volume of a set which fully describes the Western Lake
Survey-Phase I. The complete document set includes the major data  report  (2
volumes),  quality assurance plan, analytical methods  manual, field operations
report,  and quality assurance report. Similar sets are being produced for each
Aquatic Effects  Research  Program  component project.  Colored covers,
artwork, and use of the project name in the  document title serve to identify
each companion document set.

Proper citation of this document is:

Silverstein, M.E., S.K. Drouse, J.L. Engels,  M.L. Faber, and T.E.  Mitchell-Hall.
National  Surface Water Survey,  Western  Lake Survey  (Phase l-Synoptic
Chemistry) Quality Assurance Plan. EPA-600/8-87/C26.  U.S. Environmental
Protection Agency, Las Vegas, Nevada.

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                               Abstract
The  purpose of the  National Surface  Water Survey  of  the National  Acid
Precipitation Assessment Program is to evaluate the present water chemistry of
lakes and streams, to determine  the status of certain biotic  resources, and to
select  regionally representative  surface  waters  for  a  long-term monitoring
program to study changes in  aquatic resources. The Western Lake Survey is
part of the National Surface Water Survey.

The  U.S. Environmental  Protection  Agency requires that  data  collection
activities  be based on a program  which  ensures that the resulting data are of
known quality and are  suitable for their intended  purpose.  In addition, it is
necessary that  the  data obtained be consistent and comparable.  For  these
reasons,  all analysts  participating  in the study  must use  the same  reliable,
detailed analytical methodology.

The quality assurance plan and the analytical methods used during Phase I of
the Western  Lake  Survey are based on those  used during Phase  I of the
Eastern Lake Survey; analytical  laboratory methods  are identical for  the two
surveys,  but some of  the field  laboratory  methods were  modified  for the
Western  Lake Survey.  Sampling protocols are  significantly different in  that
ground access as well as helicopter  access was used  to collect samples for
the Western Lake Survey.

This  quality  assurance plan describes in  detail  the  quality  assurance
requirements and  procedures that are unique to the Western  Lake  Survey -
Phase I.  Quality assurance requirements and procedures  that were  adopted
verbatim from the  Eastern  Lake Survey -  Phase  I are referenced here and are
discussed in detail in the quality assurance plan prepared for that survey.

This report was submitted in  partial fulfillment of Contract No.  68-03-3249 by
Lockheed Engineering and Management Services  Company, Inc.,  under the
sponsorship of the U.S.  Environmental Protection Agency. This report covers a
period from September 10, 1985,  to November 4, 1985. Work was completed
as of May 14, 1986.

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                          Table of Contents
                                                                    Page
Abstract  	   iii
List of Figures  	   vii
List of Tables  	   viii
Abbreviations  	    ix
Acknowledgments  	    xi

1.0 Introduction  	   1

2.0 Project Description   	   5

3.0 Project Organization  	   7

4.0 Quality Assurance Objectives  	   9
    4.1  Precision, Accuracy, and Detectability  	   9
    4.2  Completeness  and  Comparability  	   9
    4.3  Representativeness  	   9
    4.4  Samples Used  to Monitor Data Quality  	   9

5.0 Sampling Strategy  	   15
    5.1  Overall Sampling Strategy  	   15
    5.2  Sampling Strategy for the Calibration Study   	   15

6.0 Field Operations 	   27
    6.1  Activities of the Helicopter Sampling Crews   	   27
    6.2  Activities of the Ground Sampling Crews  	   33
    6.3  Field Base Operations  	   38
    6.4  Training 	   42

7.0 Field Measurement  Quality Control Checks  	   45
    7.1  Quality Control Checks for Measurements Taken   	   45
          by Helicopter Crews
    7.2  Quality Control Checks for Measurements Taken   	   46
          by Ground Crews
    7.3  Field Laboratory Measurements  	   46

8.0 Analytical Procedures   	   47

9.0 Analytical Internal Quality Control 	   49

10.0 Performance and  System Audits  	   51
    10.1  Performance Audit Samples	   51
    10.2  Quality Assurance System Audits (On-Site  Evaluations)    	   52

11.0 Acceptance Criteria   	   55

12.0 Data Management System   	   57
    12.1 Data Set 1  - The Raw Data Set   	   57
    12.2 Data Set 2 - The Verified Data Set      	   57

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                       Contents (continued)

                                                                   Page
    12.3 Data Set 3 - The Validated Data Set    	  58
    12.4 Data Set 4 - The Final Data Set    	  59

13.0 Data Evaluation and Verification 	  63
    13.1 Field Data Review  	  63
    13.2 Analytical Data Review  	  64

14.0 Data Validation  	  69

15.0 Development of a Final Data Set  	  71
    15.1 Missing Data Substitution   	  71
    15.2 Averaging of Field Duplicate Pairs  	  71
    15.3 Treatment of Negative Values 	  72

16.0 References 	  73

Appendix  	  75
                                   VI

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                            List of Figures

Number                                                            Page

    1-1    Timetable for field activities of the National Surface
            Water Survey  	   2
    3-1    National Surface Water Survey internal management
            structure 	   7
    4-1    Flow of quality assurance and quality control samples,
            Western Lake Survey - Phase I   	   12
    5-1    Subregions of the Western  United States that are potentially
            susceptible to acidic deposition. Western Lake
            Survey - Phase I   	   16
    5-2    Alkalinity map of the California subregion,Western Lake
            Survey - Phase I   	   17
    5-3    Alkalinity map of the Pacific Northwest subregion,
            Western Lake Survey - Phase I   	   18
    5-4    Alkalinity map of the Northern Rocky Mountain  subregion,
            Western Lake Survey - Phase I   	   19
    5-5    Alkalinity map of the Central Rocky Mountain subregion,
            Western Lake Survey - Phase I   	   20
    5-6    Alkalinity map of the Southern Rocky Mountain  subregion,
            Western Lake Survey - Phase I   	   21
    5-7    Sample flow for the calibration study, Western Lake
            Survey - Phase I   	   23
    5-8    National Surface Water Survey Form 2 - Batch QC Field Data     24
    5-9    Preparation, identification, and shipment of sample batches
            for the calibration study, Western  Lake  Survey - Phase I    . .   25
    6-1    Flowchart of sampling activities, Western Lake Survey -
            Phase I  	   28
    6-2    Flowchart of helicopter crew activities, Western Lake Survey -
            Phase I  	   29
    6-3    National Surface Water Survey Form 1 - Lake Data    	   30
    6-4    Determination of temperature stratification class and lake
            temperature profile, Western  Lake Survey - Phase I    	   32
    6-5    Field sample label, Western Lake Survey - Phase I     	   33
    6-6    Aliquot label, Western Lake Survey - Phase I   	   34
    6-7    Flowchart of ground crew activities, Western Lake Survey -
            Phase I  	   35
    6-8    National Surface Water Survey Sample Tracking and
            Custody Form  	   37
    6-9    Flowchart of daily field base activities, Western Lake Survey -
            Phase I  	   39
    6-10  Field audit sample label, Western Lake Survey -  Phase I   ....   39
    6-11   National Surface Water Survey Form 3 - Shipping    	   43
   12-1    Data management,  Western Lake Survey  - Phase I     	   58
   14-1    Flowchart of the data validation  process, Western Lake Survey -
            Phase 1  	   69
   15-1    Development of Data Set 4, Western Lake Survey - Phase I      72

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                            List of Tables

Number                                                            Page

    1-1    Cross-References to Quality Assurance Subjects, Western
             Lake Survey- Phase I    	  3
    4-1    Data Quafity Objectives for Precision, Accuracy, and
            Detectability, Western Lake Survey - Phase I   	  10
    5-1    Variables Selected for Lake Classification, Western Lake
            Survey - Phase I    	  15
    6-1    Data Forms and Labels Used in the Field, Western Lake
            Survey - Phase I    	  31
    6-2    Sample Codes Used to Complete Lake Data Forms,
            Western Lake Survey-  Phase I    	  40
    6-3    Aliquots, Containers, Preservatives, and Corresponding
            Analyses, Western Lake Survey - Phase I    	  41
    6-4    Split Sample Descriptions, Western Lake Survey - Phase I    .  .  41
    9-1    Summary of Internal Quality Control Checks for Analytical
            Methods, Western Lake Survey - Phase I    	  49
   10-1    Desired Composition of Field Synthetic Audit Samples,
            Western Lake Survey - Phase I   	  52
   12-1    National Surface Water Survey Laboratory Field Data
            Qualifiers (Tags)   	  59
   12-2    Data Qualifiers (Flags) for the Verified Data Set, Western
            Lake Survey - Phase I    	  60
   13-1    Exception-Generating and Data Review Programs, Western
            Lake Survey- Phase I   	  65
   15-1    Validation Data Qualifiers (Flags) for the Final Data Set,
            Western Lake Survey - Phase I   	  71
                                   VIII

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                           Abbreviations^
AA
ANC
APHA
ASA
ASTM
BNC
CD
Cl
CRDL
DIG
DL QCCS
DOC
DQO
ELS-I
EMSL-LV

EPA
ERL-C
IBD
ICP

ID
IDL
IFB
IR
Lockheed-EMSCO

MIBK
NAPAP
NBS
NCC
NILS
NSWS
NTU
ORNL
PE
QA
QC
QCCS
RSD
RTP
SAS
atomic absorption spectroscopy
acid-neutralizing capacity
American Public Health Association
American Statistical Association
American Society for Testing and Materials
base-neutralizing capacity
conductance difference
confidence interval
contract-required detection limit
dissolved inorganic carbon
detection limit quality control check sample
dissolved organic carbon
data quality objective
Eastern Lake Survey - Phase I
Environmental Monitoring Systems Laboratory -
        Las Vegas
Environmental Protection Agency
Environmental Research Laboratory  - Corvallis
ion  balance difference
inductively coupled plasma atomic emission
        spectroscopy
identification
instrument detection limit
Invitation for Bid
infrared
 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
National Surface Water Survey
nephelometric turbidity unit
Oak Ridge National Laboratory
performance evaluation
quality assurance
quality control
quality control check sample
relative standard deviation
Research Triangle Park
Statistical Analysis System
  aThis list does not include units of measurement or chemical symbols.
                                   IX

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                   Abbreviations (continued)

SMO            -    Sample Management Office
SOW            --    Statement of Work
USGS           --    United States Geological Survey
UV              --    ultraviolet
WLS-I           --    Western Lake Survey - Phase I

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                        Acknowledgments

The authors express their sincere appreciation for the valuable suggestions
provided by the following  reviewers:  David Peck (Lockheed  Engineering and
Management  Services  Company,  Inc.), Joseph Eilers and  Susan  Christie
(Northrop  Services, Inc.), Lynn  Creelman (Radian  Corporation),  Gordon
Bradford  and  Mohammed EI-Amamy (University of  California,  Riverside),
Michael Goggin and Richard  Krebill (U.S.  Department of Agriculture  - Forest
Service), Wesley Kinney  (U.S.  Environmental Protection Agency),  and Frank
Sanders (University of Wyoming).  The assistance provided by the Lockheed
graphics  department  and the word  processing staff at Computer  Sciences
Corporation was essential  to  the completion  of  this document.  Finally,
recognition belongs to Robert Schonbrod who has served as technical  monitor
of this project.
                                   XI

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                                          1.0 Introduction
 The National Acid Precipitation Assessment  Program
 (NAPAP)  was  initiated  at  the  request  of  the
 Administrator  of  the  U.S.  Environmental  Protection
 Agency (EPA) to  evaluate the extent  of the effects of
 acidic  deposition on  aquatic  resources  within  the
 United States. When it became apparent that existing
 data could not be used to assess quantitatively the
 present  chemical  and biological  status  of  surface
 waters  in  the  United  States, the National  Surface
 Water  Survey (NSWS) program was incorporated as
 part of NAPAP to obtain that information. The National
 Lake Survey (NLS) component of  NSWS  comprises
 Phase   I - Eastern Lake  Survey (ELS--I),  Phase  I
 -  Western Lake  Survey (WLS-I),  and Phase  II   -
 Temporal Variability (see Figure 1-1).

 Data published in earlier studies are consistent with
 the hypothesis  that certain  surface waters within the
 United  States have decreased in pH or alkalinity over
 time.  Acidic  deposition has  been suggested  as  a
 contributor  to  such  decreases.  Also,   numerous
 studies have led to the conclusion that the effects of
 acidic  deposition on  surface-water chemistry  are
 influenced  by variations  among lake,  stream, and
 associated watershed  characteristics.  Existing  data
 were  compiled  largely from  numerous  individual
 studies.  Extrapolating  these data to  the regional  or
 national scale was difficult because the studies often
 were biased in terms of site  selection. Additionally,
 many previous  studies were incomplete with respect
 to  the  chemical  variables  of  interest,  were
 inconsistent  relative  to  sampling  and  analytical
 methodologies,  or were highly  variable in terms  of
 data quality.

 ELS-I,  a synoptic survey of the chemistry of  1,612
 lakes in the Eastern United  States, was conducted to
 obtain  a regional and national data base of  water
 quality  parameters that are pertinent to evaluating the
 effects   of acidic  deposition. To provide a  base  of
 information that is complete and consistent in  terms
 of the  variables  measured and the  sampling and
analytical  procedures  used, ELS-I was carried out
on  representative lakes  in  the   Southeastern,
 Northeastern, and  Upper Midwestern regions of  the
 United  States. Detailed sampling procedures (Morris
et al.,   1986),  standardized  analytical  protocols
 (Hillman et  al.,  1986),  and  a  rigorous  quality
 assurance (QA) program (Drouse et al., 1986) were
 implemented,  the  purposes of WLS-I, a  synoptic
 survey of the  chemistry of 757 lakes in the Western
 United States, are parallel to those of ELS-I.


 WLS-I was designed  to  minimize uncertainty  in
 making regional assessments based on  existing data.
 The five major design elements were as follows:

   • Provide data from a  subset  of  lakes  that are
     characteristic of the  overall population of lakes
     within a region.

   • Use  standardized  methods to collect chemical
     data.

   • Measure  a complete  set of variables thought  to
     influence or to be influenced by  surface-water
     acidification.

   • Provide data that  can be  used to  investigate
     statistical  relationships  among  chemical
     variables  on a regional basis.

   • Provide reliable estimates of the chemical status
     of lakes within a region of interest.


 The goals  in  designing  WLS-I were  to  identify
 objectives,  develop an  overall  conceptual and
 practical approach to meeting the objectives,  identify
 intended  uses  and   users of the data,  identify the
 quality of data  needed, develop an appropriate survey
 design,  develop analytical  protocols   and  quality
 assurance/ quality control  (QA'QC) procedures, and
 revise and  modify  approaches  and  methods as
 needed.  Thus,  WLS-I  was  designed   to  provide
 statistically  comparable  data  that  could  be
 extrapolated, with a known  degree of confidence, to  a
 regional or national  scale.  The  conceptual approach
 emphasized  that the data would  not   be used  to
 ascribe observed   effects  to  acidic   deposition
 phenomena;  rather,  through comprehensive
 monitoring activities,  WLS-I  would  provide
 information that could be used to develop correlative,
 not cause-and-effect, relationships.


The conceptual  approach  to  the  program  was
developed by  EPA personnel  and   cooperating

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                   Figure 1-1 Timetable for field activities of the National Surface Water Survey.
                                  National Surface Water Survey (NSWS)

                                 	I	
                       National Lake Survey (NLS)
National Stream Survey (NSS)
                      Phase I - Synoptic Chemistry

                          Eastern Lakes (1984)

                          Western Lakes (1985)
 Phase I - Synoptic Survey

    Pilot Survey (1985)
   Synoptic Survey (1986)
 Southeast Screening (1986)
    Episodes Pilot (1986)
                      Temporal Variability (1986-87)  |       j Episodic Effects (1988) [
scientists.  Planning  for  WLS-I began in October
1983. The research plan for Phase I of the NLS was
initially reviewed late in 1983  by  a large  number of
scientists who have expertise  in the areas of  study.
Fifty scientists discussed the plan during a workshop
held in December; suggested modifications were
incorporated by March  1984. The research plan was
submitted to members of the American  Statistical
Association  (ASA) for  review  in June 1984;  a final
ASA review was conducted in October 1984.

The QA  plan and the  analytical methods for  WLS-I
are  based  on those used   during ELS-I. The
analytical laboratory methods are identical for the two
surveys,  but some field  laboratory  methods were
modified  for  WLS-I  on  the   basis   of   ELS-I
experience  and on  the  basis of constraints that
resulted  from  the special geographic   limitations
associated  with the high-altitude  lakes in  the West.
New field laboratory protocols also  were  added to
accommodate changes between   ELS-I and  WLS-I
field  sampling methods.  Sampling  protocols  are
significantly  different in that ground access as well as
helicopter access is  used  to collect samples  for
WLS-I (Bonoff  and Groeger,  1987).  The sampling
protocols differ  from those used  during  ELS-I
because  400  of  the  WLS-I  lakes are   within
designated  wilderness areas that  are  closed  to
helicopter access.  The  ground  sampling  protocol
developed  for use in sampling the restricted-access
lakes  was  first  evaluated in a  WLS  pilot study
conducted by EPA Region VIII  office in the autumn of
1984.

A specialized  calibration study is  included in  WLS-I
to compare the effects of the two different sampling
  methods  on analytical  results.  The  purpose  of  the
  comparison  is  to derive  calibration  factors, if
  necessary,  that can be applied to data for samples
  collected by ground crews so that these data  will be
  equivalent to data for samples collected by helicopter
  crews.


  EPA requires that data collection  activities be based
  on a program that ensures that  the resulting data are
  of  known quality and  are suitable for  their intended
  purpose.  The purpose of a QA plan is to provide that
  assurance.  Therefore,  EPA policy requires that every
  monitoring  and measurement project 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  project
  plan should  specify  the  policies,  organization,
  objectives,  functional activities,  and QA/QC activities
  designed to achieve  the data  quality goals  of  the
  project.  All project personnel should be familiar with
  the policies and objectives outlined in the  QA  project
  plan to  ensure proper  interactions among the  field
  operations,  laboratory operations,   and  data
  management.

  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
  addressed  extensively  in other manuals  (Hillman et
  al.,  1986;  Kerfoot and Faber,  1987;  Morris  et
  al.,1985);  therefore,  as  allowed  by the  guidelines,
  these specific  discussions are not  repeated  in  this
  document.

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               Table 1-1.
Cross-References to Quality Assurance Subjects, Western Lake Survey -
Phase >a
Subject
Title Page
Table of Contents
Project Description
Project Organization and Responsibility
QA Objectives
Sampling Procedures
Sample Custody
Calibration Procedures
Analytical Procedures
Data Analysis, Validation, and Reporting
Internal QC Checks
Performance and System Audits
Preventive Maintenance
Assessment of Precision, Accuracy, and
Completeness
Corrective Actions
QA Reports to Management
Quality
Assurance
Plan

Contents
2
3
4
6
6
6
8
6, 9, 12, 13, 14
7,9
10
6
4,11
9,11
9,10
Field Operations
Report6





Field Sampling
Operations
Field Sampling
Operations
Field Sampling
Operations
Field Laboratory
Operations







Methods
Manualc




1
2
2, 3
2
4 to 13
3
3

2, 3

3

              a The requirement to address these 16 QA subjects is stated in U S EPA (1980).
              t> Bonoff and Groeger (1987).
              c Hillman et al. (1986).  Summary in Kerfoot and Faber (1987)
Quality  assurance requirements  and procedures that
were adopted  verbatim from  ELS-I  are  referenced
here  and are  described in detail  in the  ELS-I QA
plan (Drouse  et  al.,  1986). ELS-I  recommendations
that led to WLS-I protocol changes are discussed  in
the  ELS-I  QA  report  (Best  et  al.,  1987).   The
sections that follow describe in detail only those QA
requirements  and procedures that  are specific to
WLS-I.

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                                     2.0  Project Description
The WLS-I portion of NSWS is a synoptic survey of
757 lakes in the Western United  States that  will be
conducted  during fall  overturn. During this overturn
period, chemical variability within a lake is expected to
be minimal as a  result  of circulation within the water
column. WLS-I is designed to  meet the following
objectives  for  designated regions of the  Western
United States:

  •  Determine the percentage (by number and area)
     and  location  of  lakes  that  are  potentially
     susceptible  to change as  a result  of  acidic
     deposition and that have low  acid-neutralizing
     capacity (ANC).

  •  Investigate  the   relationships  among  water
     chemistry, regional  acidic deposition patterns,
     land  use,   physiographic  features,  lake
     morphology,  and  basin   geometry within  and
     among regions.

  •  Identify smaller subsets of representative lakes
     for more intensive sampling in future surveys.

Of the lakes  to  be sampled  during  WLS-I,  455 lie
within  designated wilderness  areas.  In  order to
observe the guidelines and regulations set forth in the
Wilderness Act,  almost all  lakes   located  within
wilderness areas that  have  been selected  for
sampling must be sampled by ground crews  of  the
U.S.  Department  of Agriculture  - Forest  Service.
The  ground crews  travel to   lakes  by  foot  or on
horseback. The lakes that are not in wilderness areas
are  sampled by helicopter crews under the direction
of EPA.


Selected  wilderness-area  lakes that  have  been
determined to  be inaccessible  by ground crews  are
sampled  by helicopter crews  during  periods when
disturbance to wildlife or hikers  is minimal. In addition,
45 wilderness-area  lakes are  sampled by  ground
crews  and by helicopter  crews. The results  for
samples collected from these 45 calibration lakes will
be used to evaluate the comparability  of ground crew
and helicopter crew sampling protocols for collecting
and handling water samples.
This calibration study is designed to meet three goals:

   • Quantify the  differences  between  the  two
     sampling methods  (helicopter  and  ground
     access).

   • Quantify  the effects  of  holding   samples for
     different  lengths of time prior to processing,
     preservation, and analysis.

   • Quantify any  significant  mterlaboratory bias
     between  the two  analytical  laboratories  that
     analyze WLS-I samples.

Data derived from the  chemical  analyses conducted
during  the study  will be used to establish  calibration
factors  that  can  be applied to  analytical  values
reported for  all  WLS-I  samples.  The calibration
factors  are  intended to  eliminate  value differences
that result  from variations  in  sampling protocol,
sample holding time, or laboratory bias.


Two other  studies  are being conducted as  part of
WLS-I. The  purpose of one study, the  nitrate/sulfate
stability study, is to compare  sample  preservation
methods and to study the effects of holding samples
for different  lengths of time before  preserving them.
The nitrate/sulfate sample  is an extra  aliquot taken
from the Van Dorn sampling unit,  preserved with
HgCl2, and analyzed at the  U.S. EPA Environmental
Monitoring  Systems  Laboratory  -   Las   Vegas
(EMSL-LV).  The  purpose of the second study, the
Corvallis study, is to compare results for splits of the
same sample when the splits have  been analyzed by
different  methods.  The analytical  laboratories  use
NSWS protocols  for atomic absorption  spectroscopy
(AA),  inductively  coupled   plasma emission
spectroscopy  (ICP), automated  colorimetry, and ion
chromatography,  according to the  analyte;  the
Environmental Research  Laboratory  at  Corvallis,
Oregon (ERL-C),  used ICP  only  and  is  not restricted
to the NSWS protocols and detection limits. A further
purpose of the Corvallis study is to determine if the
ICP  data  can be substituted  in the  data  base  if
problems  arise  with  the  standard  analysis.  Both
studies can  provide checks on sampling, processing,
and analytical performance.

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-r          «u » IA/I £> r       _i             ^     ^    tne survey and the effectiveness of this QA plan will
To  ensure that WLS-f procedures  are  performed    be tssuedyafter these factors have been evaluaPted.
consistently and that the quality of the data generated
can be determined, the  QA project  plan  for WLS-I
specifies the following measures:


  • Provide  detailed, written sampling methodology
     (Morris  et  al.,  1985, and Peck et al.,  1985;
     summarized in Bonoff and Groeger,  1987).

  • Simultaneously  train and  test  all  personnel
     participating in field activities.

  • Conduct on-site  visits to  each  field operations
     base  and  remote  site  soon  after  sampling
     begins,  and  maintain  daily telephone  contact
     throughout the sampling period to ensure that all
     methods are being performed properly.

  • Perform extensive   evaluation  of  analytical
     laboratories throughout their participation.

  • Assess  variability introduced  at  each  level of
     activity  in  field  and  analytical laboratories  by
     processing audit samples  (synthetic and natural
     lake samples),  duplicate  samples,  and  blank
     samples along  with routine samples.  (Field
     laboratory  refers  to  the  on-site  mobile
     laboratory  that performs  preliminary  analyses
     and  aliquot preparation;  analytical laboratory
     refers to  the off-site  contract  laboratory  that
     performs the more sophisticated analyses.)

  • Provide  detailed, written analytical methodology
     (Hillman et al., 1986; summarized in Kerfoot and
     Faber, 1987).

  • Use internal QC procedures at the  analytical
     laboratory to detect  potential contamination and
     to verify established detection limits.
  • Enforce holding-time  requirements.

  • Use protocols in the field and in the  analytical
     laboratory  to  confirm that reported  data are
     correct.
  • Enter data  from standardized  data  reporting
     forms into the data  base twice, and scan for
     outlying  values  to eliminate  effects of
     transcription errors.

  • Verify data by means of  range  checks,  internal
     consistency checks,  and QA evaluations.

  • Validate  verified data by  identifying  values that
     are not  typical of values observed for the group
     of lakes (e.g., stratum) from which the sample or
     samples were drawn.


This QA plan is the final version of the draft plans that
were  written  before and  were  modified during WLS-I
activities. A QA report that describes the findings  of

-------
                                    3.0  Project Organization
Figure  3-1   illustrates the  NSWS  management
structure.  The  program director is  the  EPA official
who has overall responsibility  for the program. The
responsibilities  of  the  program  manager, technical
director, and  administrative coordinator are discussed
in detail in Drouse et al. (1986)  as are the roles of the
Environmental  Research  Laboratory  at  Corvallis,
Oregon  (ERL-C), the  Environmental  Monitoring
Systems Laboratory  at Las  Vegas, Nevada (EMSL-
LV),  and the  Oak Ridge National  Laboratory (ORNL)
at Oak Ridge, Tennessee.
                    Figure 3-1. National Surface Water Survey internal management structure.
                                          I Program Director
NAPAP Acid Deposition


I Program


Manager I


NAPAP Task


Technical
Director



Administrative
Coordinator
                                Peer Review
I
ERL-C

Sampling Design
Site Selection
Site Description
Data Validation
Data Interpretation
Reporting



I
EMSL-LV

Field Ope
and Loc
Analytics
QA/QC (
data ver

rations
sties
Methods
ncluding
ification)



ERL-C
and
ORNL
Data Management

-------

-------
                               4.0  Quality Assurance Objectives
The statistical  design,  sampling  and  analytical
methods, and  QA activities for WLS-I are structured
to meet specific data quality objectives (DQOs)  for
the measurement of sampling,  field laboratory,  and
analytical laboratory performance.  These  DQOs are
designed to facilitate checking for chemical variability
and to provide confidence levels for reporting
population estimates.

4.1  Precision, Accuracy, and Detectability

The primary  DQOs  are  measures  of precision
(expressed as relative standard deviation), accuracy
(expressed  as  maximum  absolute  bias),  and
detectabihty  (expressed as an expected value range
and a required  detection  limit). These DQOs  are
applied  to each parameter  measured  at the  lake
sampling site, in the field laboratory, and in  the
analytical laboratory. Appropriate values and ranges
were established for each  DQO (for each parameter
and measurement site) during  ELS-I (Drouse et al.,
1986).  The values and ranges  used for  WLS-I are
based  on experience gained during ELS-I  and  on
standard laboratory QA/QC requirements.  Table 4-1
summarizes the  primary  DQOs  used for  WLS-I;
further discussion can be  found  in  Drouse et  al.
(1986).

4.2 Completeness and Comparability
Certain other DQOs  also have been considered in the
survey  design. Completeness  (the  quantity  of
acceptable data  actually collected in relation to the
total quantity that is expected to be  collected) is set
at 90 percent or better for  all variables,  on the basis
of experience  gained during  ELS-I. Comparability (a
measure of the confidence  with which one  data set
can be compared to another) is  ensured by requiring
that  standard  procedures  be  used  for  laboratory
analyses and that a  uniform set of units be  used  for
reporting data.  The calibration study was performed to
ensure that differences in  the  sampling and on-site
analytical procedures used by  helicopter crews and
ground crews did not reduce data comparability.

4.3  Representativeness

Representativeness (the  degree to  which  data
accurately and precisely represent a characteristic of
a population) is an important concern of IMSWS. The
sampling  scheme for WLS-I  was  designed  to
maximize  representativeness. A  systematic random
sample  drawn  within  strata  ensured  good
geographical coverage  without bias  (Landers  et al.,
1987).

WLS-I  is not intended to characterize the chemistry
of any given lake spatially or temporally.  Therefore,
achieving WLS-I objectives does not require that the
only sample  taken  from  a lake  be completely
representative of the  lake.  In most cases (except for
the lakes to be sampled during the calibration  study)
only one sample  per lake  is taken during WLS-I. A
determination  of  whether  one sample per lake  is
sufficient to achieve the general objectives of NSWS
Phase  I,  however, can  be  made  from estimates  of
" withm-lake"   and  "among-lakes"  variances.
Although  some  estimates of these  variances will be
made  for WLS-I  lakes  in  accordance with the
statistical  sampling design,  future,  more  intensive
studies of individual lakes will provide more complete
data on representativeness.

Although  the  individual  sample is  not necessarily
representative  of  the  lake,  the  subset of  lakes
sampled  should  be representative  of  the  sub-
regional  or regional  population   of  lakes.  The
systematic sampling design that was adopted for this
survey is  intended to ensure representativeness  at
this level.


4.4 Samples Used to Monitor Data Quality
Several types of  QA and QC samples are  used  to
ensure that  sampling and  analytical  methods are
performed according to the  NSWS Statement of Work
(SOW) and this QA  plan (Figure 4-1).  QA  samples
are used by the QA staff to  evaluate overall method
performance  for  field   sampling,  field laboratory
procedures, and analytical laboratory procedures and
to evaluate overall data quality  for  the survey. QC
samples allow  field samplers and personnel at the
field  and analytical laboratories to identify and correct
local  problems  (e.g.,  providing the  analyst with
immediate feedback  on reagent  contamination  or
questionable instrument  performance). The  use  of QC
samples in the field is discussed in Section 7 of this
document;  QC  samples and procedures  for the

-------
     Table 4-1.    Data Quality Objectives for Precision, Accuracy, and Detectability, Western Lake Survey - Phase I
Site3
2, 3



2, 3



3

3

3

3
1, 3

2, 3



3



3

3

3
3

3

3
3


3

Parameter6
Al,
Extractable


Al, Total



ANC

BNC

Ca

Cl"
Conductance

DIC



DOC



F", Total
dissolved
Fe

K
Mg

Mn

Na
NH4 +


N03

Method
Extraction with 8-
hydroxyquinoline
into MIBK followed
by AAe (furnace)
AAe (furnace)



Titration and Gran
analysis
Titration and Gran
analysis
AAe (flame) or
ICP9
Ion chromatography
Conductivity cell
and meter
Instrumental
(acidification, CC>2
generation, IR
detection)
Instrumental (UV-
promoted oxidation,
CC>2 generation, IR
detection)
Ion-selective
electrode and meter
AAe (flame) or
ICP9
AAe (flame)
AAe (flame) or
ICP9
AAe (flame) or
ICP9
AAe (flame)
Automated
colonmetry
(phenate)
Ion chromatography

Units
mg/L



mg/L



ueq/L

(jeq/L

mg/L

mg/L
US/cm

mg/L



mg/L



mg/L

mg/L

mg/L
mg/L

mg/L

mg/L
mg/L


mg/L

Expected
Range0
0.005 - 1.0



0.005 - 1.0



-100 -
1,000
-10 - 150

05-20

02-10
5 - 1,000

0.05 - 15



0.1 - 50



0.01 - 02

0.01 - 5

01-1
01-7

0.01 - 5

0.5 - 7
001-2


001-5

Required
Detection
Limits
0.005



0.005



f

f

0.01

0.01
h

005



0.1



0.005

0.01

001
0.01

0.01

0.01
0.01


0.005

Precision
Relative Standard
Deviation (RSD)
Upper Limit (%) <*
10 (Al cone.
>0.01)
20 (Al cone
<001)
10 (Al cone
>001)
20 (Al cone
<001)
10

10

5

5
2

10



5 (DOC cone
>5)
10 (DOC cone
<5)
5

10

5
5

10

5
5


10

Accuracy
Max. Absolute
Bias (%)
10

20

10

20

10

10

10

10
5

10



10



10

10

10
10

10

10
10


10
(continued)
analytical laboratories are discussed  in Section 9 of
Drouse  et  al.  (1986).  The  types of  QA  and  QC
samples  to  be used  during  WLS-I are described in
subsections 4.4.1 and 4.4.2.

4.4.1  Quality Assurance Samples
QA samples that are  introduced in the field or at the
field laboratory are analyzed at  the field laboratory
and at the analytical  laboratory.  These samples are
used  to  judge  the  overall  performance of WLS-I
sampling and analytical activities and to establish data
quality.  The  QA  samples are  "double blind" to the
analytical  laboratories  (i.e., the  laboratories  do  not
know the  origin, identity, or  composition  of  the
samples). Consequently,  the  analytical laboratories
process  QA  samples  as  they  would  any other
routinely  analyzed sample. The QA samples used are
(1) field blanks,  (2) trailer blanks,  (3) field duplicates,
and (4) field audits.

  •  Field  Blank -

     A field  blank,  which  is prepared at  the  field
     laboratory,  is  a deionized  water sample  that
                                                   10

-------
 Table 4-1    (Continued)
   Sitea    Parameter*3
    Method
                                         Units
                                  Precision
                     Required    Relative Standard     Accuracy
         Expected     Detection    Deviation (RSD)   Max. Absolute
         Range0       Limits     Upper Limit (%)d     Bias (%)
    1,2     pH, Field     pH electrode and
                            meter
                  PH
                 units
     3    pH, Analytical   pH electrode and     pH
            laboratory         meter         units
             P, Total




              SiO2



             SO42"


            True color



            Turbidity
  Automated
  colorimetry
  (phospho-
  molybdate)

  Automated
  colorimetry
(molybdate blue)
     Ion          mg/L
chromatography
  Instrument       MTU*
 (nephelometer)
                           3-8
                           3 - 8
mg/L   0 005 - 0.07
mg/L    0 1  - 25
         1 - 20
                      0002
0.05
                      005
   ±0.1'


  ±0.05'


10 (P cone.

20 (P cone.
 Comparison to     PCU/     0 - 200
platinum-cobalt
 color standards
         2 - 15
                                    ±5'
                                     10
                                                  ±0.1'
                                                                   ±005'
                             10
                             20
                             10
                                                   10
                                                   10
 a 1  = lake site, 2 = field laboratory, 3 = analytical laboratory
 b Dissolved ions and metals are being determined, except where noted
 c Ranges are for lake waters.
 d Unless otherwise noted, this is the %RSD at concentrations greater than 10 times required detection limits
 6 AA = atomic absorption spectroscopy
 f Absolute blank value must be < 10.
 9 ICP = inductively coupled plasma atomic emission spectroscopy
 h Blank must be < 0 9 tiS/cm
 ' Absolute precision goal in terms of applicable units.
  American Public Health Association platinum-cobalt units.
 * Nephelometnc turbidity units
meets specifications of the American Society for
Testing  and  Materials  (ASTM)  for  Type  1
reagent-grade  water  (ASTM,   1984).  The
sampling crew transports the blank water to the
lake  in  Cubitainers  and  processes the  blank
through  the Van Dorn sampler as  if the  blank
were a  lake  sample.  Because  the  action of
pouring  the blank water  through the  Van Dorn
sampler  creates the  possibility of changing  the
C02  concentration  in  the sample,  which would
affect the  pH  and DIG field measurements,  pH
and  DIG syringe  samples are  not taken for  the
field  blanks. True color and turbidity, however,
are determined for  each  field  blank at the field
laboratory.  Each helicopter crew  collects   one
field blank on  each operating day;  each ground
crew collects two field  blanks during the course
of the survey.

Field  blanks are  inserted  in the sample batches
that  are  sent to the analytical laboratories. They
are used to identify contamination problems  that
                                  may  occur  during the  sampling  and  analytical
                                  processes and to provide data that are used to
                                  establish the  estimated  system  decision  limit,
                                  quantitation  limit, and background levels  that
                                  could be expected  for  each  variable.  For data
                                  interpretation,  any data point above the  expected
                                  value for the blank is considered to be a positive
                                  response for a given analyte.

                                  • Trailer Blank  -

                                  The trailer blank  is used instead of a field blank
                                  when a field  blank  is not collected  for a
                                  particular sample batch. The sampling design of
                                  WLS-I   occasionally  results  in  situations  in
                                  which a field blank  is  not  scheduled to  be
                                  processed   at any  lake site  for a  particular
                                  sampling day.  When this  situation  occurs, a
                                  deionized water  sample  is processed in  the field
                                  laboratory as  if  it were  a  field blank  that  has
                                  been delivered  to the  field laboratory by   the
                                  sampling crew. The chief difference between  the
                                                 11

-------
Figure 4-1. Flow of quality assurance and quality control samples, Western Lake Survey - Phase I.
Field
Samplers
X
I Field Blank I k






Field
Laboratory
1




Trailer Blank
(in Lieu of
Field Blank)
Contract
Laboratorry

ki Fieln1 Blink 1






                Field Duplicate
                         Field Duplicate
                                             Trailer Duplicate
                                            (Split of a randomly
                                             selected routine
                                              lake sample)
                  QCCS
             Hydrolab pH, Cond
    Natural
    Audits
  Lake Superior
     (FN3)
 Big Moose Lake
     (FN4)
  Bagley Lake
  (FN5, FN6)
                                               Field Audits
                            QCCS
                        pH, DIC, Turbidity
    Audit Sample
Preparation Laboratory
Prepared Natural Audits
(FN3, FN4, FN5, FN6)
 and Synthetic Audits
    (FL 11, FL 12)
                        Calibration Blank
                             DIC
                                                                           Field Duplicate   I
                                                                            Field Audits
                                                                              QCCS
                                                                             (Form 20)
   Calibration/
  Reagent Blank
   (Form 20)
  Matrix Spike
(on Field Sample)
   (Form 21)
   Laboratory
    Duplicate
  (Split of Field
Sample) (Form 22)
two types  of  blanks is  that the trailer  blank  is
never processed through the Van Dorn sampler.
The trailer blank is  then inserted (in  place of a
field  blank) in the sample batch that is  sent  to
the analytical laboratory.

•  Field Duplicate -

A field duplicate is a second sample collected  at
the lake   site immediately after  the   routine
sample is  collected.  The  field  duplicate  is
collected   by  the  same  sampling crew that
collects the routine sample; the same procedure
is  used to collect both  samples.  For each field
base,  one helicopter  crew  collects   a  field
duplicate  on each  sampling day.  Each  ground
crew  collects two   field  duplicates  during the
course of  the   survey. Field duplicates  are
processed  by  the  field laboratory  and  are
inserted as double-blind  samples in the  sample
                                   batches  that  are  sent  to  the  analytical
                                   laboratories.

                                   Field  routine/duplicate  pairs  are  used  to
                                   determine the precision of the  field  samplers'
                                   technique in sampling,  the precision of the field
                                   laboratory in analyzing  and processing samples,
                                   and the precision of the analytical laboratory in
                                   analyzing samples.  The routine/duplicate pair is
                                   also used to  determine the homogeneity of the
                                   lake sample.

                                   NOTE: Duplicate  samples  that are collected for
                                           the  calibration  lake study are not used
                                           as  QA  samples  because  sampling
                                           methods,  holding  times, and  batches
                                           differ  for  the five  comparable  samples
                                           collected  from  one  lake (routine and
                                           duplicate  collected by  the ground crew
                                           and routine,  duplicate,  and triplicate
                                               12

-------
            collected  by the helicopter crew).  See
            Section 6 for a discussion of calibration
            study procedures.
   • Field  Audits -

     Two types of  audit samples  (field natural audit
     samples  and field synthetic audit samples)  are
     used  to  establish overall  field  and  analytical
     laboratory performance.  A third  type  of  audit
     sample, a laboratory audit, which was used for
     ELS-I, is not  being used  for  WLS-I.  ELS-I
     results showed that the  practical  significance of
     the difference in precision between  laboratory
     audits and field audits was negligible; therefore,
     the use of laboratory audits was determined  not
     to be  cost effective.

     Field  natural audit  samples  are  composed  of
     natural lake  water; field synthetic audit  samples,
     which  are prepared to   simulate  natural lake
     water, are reagent-grade water  that  contains
     the analytes of interest  at specified theoretical
     concentrations.

     Field  audit samples  are  used (1) to determine
     the relative bias  between analytical  laboratories,
     so  that  measurements made  by  the  two
     laboratories can be compared and (2) to indicate
     precision of  those  measurements  through
     repeated analysis of the same sample type.

     Both types of field audit samples are received in
     2-L portions from a central source; at the field
     laboratory,  the  samples  are  filtered and
     preserved.   Aliquots  are  taken from the filtered
     audit samples as from routine lake samples, and
     these aliquots are  shipped  to the  analytical
     laboratory as double-blind samples.

     Only low-concentration synthetic  audit samples
     are used for  this survey. High-concentration
     synthetic  samples  are   not  utilized  because
     concentrations of analytes in WLS-I lakes  are
     anticipated to be  low.
4.4.2 Quality Control Samples

4.4.2.1  Hydrolab Quality Control Samples-
Quality control check  samples (QCCSs) are used by
the  helicopter crews to  check  Hydrolab  pH  and
conductance  measurements in the morning (prior to
sampling activity) and in  the  evening  (after sampling
activity  is completed  for  the day).    The  morning
QCCSs are  used  to  check  the calibration  of the
Hydrolab;  the evening QCCSs  indicate instrument
drift over time.
4.4.2.2  Field Laboratory Quality Control
        Samples--
Three  types  of  QC samples  are used by  the  field
laboratory staff to ensure that instruments and  data
collection are within specified  control limits. The QC
samples are  (1) calibration  blanks, (2)  QCCSs, and
(3) trailer duplicates.
   •  Calibration  Blank  - A  calibration  blank
     (deionized water drawn directly from the water
     purification  unit located in the field  laboratory) is
     used to check for baseline drift of the carbon
     analyzer and  to check for  contamination.  The
     calibration blank is  analyzed  prior to  sample
     analysis for dissolved inorganic carbon (DIG).

   •  Quality Control Check Sample  -  QCCSs are
     prepared   in  the  field laboratory  or  are
     purchased.  They  are used  to  check  initial
     instrument  calibration  and,  during  sample
     analysis, to  check  at specified  regular intervals
     for  instrumental drift. QCCSs  are  analyzed for
     pH, DIG, and  turbidity. The QCCS for pH  is a
     0.0001  N H2SO4 solution with a pH  of 4.0; for
     DIG, QCCSs of 2  mg  L  and 20 mg L  NapCOa
     are prepared;  for  turbidity, the  QCCSs are
     turbidity standards  of 10.00, 20.00, 100.00, and
     200.00 nephelometric turbidity units (NTU).

   •  Trailer  Duplicate  -  The trailer  duplicate,  a
     second  measurement  of   a  routine sample,  is
     used to check the  precision of measurements
     made in the field laboratory. The field laboratory
     supervisor  randomly selects one  lake  sample
     per trailer operating day; this sample is analyzed
     in duplicate for pH,  DIG, true color, and turbidity.
4.4.2.3  Analytical Laboratory Quality Control
        Samples--
Six types  of QC samples are used by the analytical
laboratories  to  ensure  that  instruments and data
collection  are within control limits.  These six sample
types are   (1) calibration  blanks, (2) reagent blanks,
(3) detection limit QCCSs, (4) low-concentration  and
high-concentration  QCCSs, (5)  matrix  spikes,  and
(6) laboratory duplicates.  The sources, compositions,
and  concentration ranges of these  QC  samples are
described  in Hillman et al.  (1986).

  •  Calibration Blank -  For  each sample batch, the
     analytical  laboratory must analyze one calibration
     blank for  each  required  analyte.  For each
     analytical  procedure,  the calibration blank, which
     is  a  0-mg L  standard,  is  analyzed after  the
     initial instrument  calibration  to  check for drift in
     the measured signal and to check for  potential
     contamination during  the analytical process.  The
     observed  analyte  concentration  for  the
     calibration  blank must  not exceed  twice  the
                                                  13

-------
  contract-required  detection  limit  (CRDL)  for         intralaboratory  precision limits  established  for
  that analyte.                                          these variables  (see Table 4-1).

• Reagent Blank  - A reagent blank is required for
  dissolved SiC>2  and total  aluminum  analyses
  because additional reagents are added during a
  digestion  step  prior to analysis.  The reagent
  blank comprises all the reagents (in  the same
  volumes)  used  in  preparing a lake sample for
  analysis. The reagent  blank  and  lake samples
  are carried through the same preparation steps
  (e.g.,  digestions)  prior to  analysis.  Values
  obtained for the reagent blank must not exceed
  twice the CRDL for the analyte.

• Detection Limit  Quality Control Check Sample -
  A detection  limit  QCCS  (DL QCCS)  is  also
  analyzed for  required variables. The DL QCCS
  is used to determine and verify the low end of
  the  calibration  curve  and  the  values  for  the
  low-level samples that are near  the detection
  limits. The  DL  QCCS concentration must be
  between 2  and 3  times the CRDL.  The  DL
  QCCS is analyzed once, prior to regular sample
  analysis.

• Low-Concentration and  High-Concentration
  Quality Control  Check  Samples -  The analytical
  laboratory   QCCS is  a  commercially  or
  laboratory-prepared sample that  is prepared
  from a stock solution different from the one that
  is used to prepare the  calibration standards. The
  QCCS  is analyzed to verify calibration at  the
  beginning of  sample  analysis,  after  each
  specified number of sample analyses, and  after
  the  final sample  in the batch is analyzed. The
  observed concentrations must  be  within  the
  specified control limits.

• Matrix Spike  - A matrix  spike,  which  is
  analyzed for specified  analytes in  each sample
  batch,  is a  check to  determine  the level of
  analytical interference  that is  caused by  the
  matrix  of  the  water  sample on  a particular
  analyte. The analyst "spikes" (i.e., enriches) an
  aliquot of sample with a known quantity  of an
  analyte  and then analyzes  the  spiked   and
  unspiked samples. The percentage  of spiked
  analyte  recovered  (percent  recovery)  is  then
  calculated to determine whether or not there is a
  matrix  effect on  the  analytical  value of  the
  original sample.

•  Laboratory Duplicate  - An  analytical laboratory
  duplicate is required for each batch of samples.
  A duplicate analysis is  performed on one sample
  for  each required  variable  in each  batch to
  establish  within-laboratory precision.   The
   observed  precision must  meet  the required
                                                14

-------
                                       5.0  Sampling Strategy
5.1  Overall Sampling Strategy

The sampling strategy  for selecting NSWS  lakes  is
discussed  in detail in Landers  et al.  (1987) and  is
summarized in Drouse et al. (1986).

The lakes  are  selected by means of a  systematic,
stratified design. There are three stratification factors:
regions, subregions, and alkalinity classes (see Table
5-1).  Each  stratum is  an  alkalinity class  within  a
sub- region within  a  region. In the Western United
States (defined as  NLS Region 4) all  three alkalinity
classes are found within each of the five subregions
designated 4A  through  4E, so  the  total  number  of
strata  in WLS-I is  fifteen.  Figures 5-1 through 5-6
depict  the  region, subregions,  and alkalinity classes
the strata comprise.

Table 5-1. Variables Selected for Lake Classification,
         Western  Lake Survey - Phase I
       Level
       Divisions within Levels
 Region

 Subregion
 Alkalinity Class
Western United States

4A, California
4B, Pacific Northwest
4C, Northern Rocky Mountains
4D, Central Rocky Mountains
4E, Southern Rocky Mountains
1. Alkalinity < 100neq/L
2 Alkalinity 100 to 200
3. Alkalinity >200 neq/L
5.2  Sampling Strategy for the Calibration
      Study

As  a  part  of  the  overall  WLS-I  sampling  and
analytical  strategy,  45  of the  455 wilderness-area
lakes being studied are included in a calibration study.

Legislation restricts  activities  that  jeopardize  the
pristine   character  of  wilderness  areas,  and
considerable precedent  has  been established to limit
helicopter and other motorized access to such areas.
However,  because  information  obtained from WLS-I
might be  of great help  in long-term  maintenance of
wilderness  characteristics,  the  Forest  Service
approved  helicopter access to  the 45  lakes so that
the established sampling method (by helicopter) could
be  compared to the new method (ground  access).
Each calibration  lake  is  sampled by  one helicopter
crew and by one ground crew. The two crews collect
samples from approximately the same location (the
deepest spot) on the lake. The ground crew samples
the  lake  from  a boat,  then the  helicopter  crew
samples the  lake  as soon  as  possible thereafter
(optimally, within  1 hour). The ground  crew collects a
routine  sample and a duplicate sample; the helicopter
crew collects a  routine  sample,  a  duplicate sample,
and  a triplicate sample. Both  types of sampling crews
use  standard WLS-I sample  collection techniques.

Because collecting samples  by  ground  access is a
new protocol, it  is important to  be certain  that this
protocol is applied uniformly  to  all WLS-I lakes. To
ensure  that each ground crew's sampling procedure
is  representative  of  the  sampling done at all  WLS-I
lakes, the  ground crews are not told (i.e.,  they  are
"blind"  to)  which lakes  are calibration  lakes.  The
helicopter sample collection  procedure  is a proven
protocol that was tested during  ELS-I; therefore, it is
not necessary for the WLS-I helicopter crews  to be
blind to  the identity of calibration lakes.

The  logistics of  the  sampling  design  raised the
possibility that the ground samples might arrive at the
field laboratory 1  to 5 days after  they were collected.
Therefore,  the possible  effects  of  delayed  sample
preservation (or "holding time") are of interest. Three
processing procedures have  been developed to allow
for  possible  delays  in  delivering samples from  the
lake site to the field laboratory and to allow the effects
of  different holding  times  to  be observed.  Each
procedure  assumes  a different  relationship  between
the sampling and  arrival times of the helicopter crew's
samples and the ground crew's samples.

For each of the three processing procedures, the field
laboratory preserves the  ground crew's  samples on
the collection date (or on the date the samples  arrive
at  the   field  laboratory)  and   preserves  two of the
helicopter crew's  samples on the collection date. The
third sample collected by the helicopter crew is not
preserved on the  collection date  Instead, this sample,
which is randomly selected  from among the  three
samples collected by the helicopter crew, is held at
the  field laboratory  for  a specified  length  of time
                                                   15

-------
Figure  5-1.    Subregions of  the Western United States that are potentially susceptible to acidic deposition.  Western Lake
              Survey - Phase I.

                                                              Northern Rocky
                                                              Mountains (4C)
                               Pacific
                               Northwest (4B)
                                 California (4A)
Central
Rocky      j
Mountains (40)
                                                                                       Southern Rocky
                                                                                       Mountains (4E)
                                             Subregion Boundary
                                                           16

-------
Figure 5-2.    Alkalinity map of the California subregion. Western Lake Survey - Phase I.
                                                       OR
                                                                         CD  < 100
                                                                         t3  100 to 200
                                                                             >200
                                                                               Alkalinity Classes
                                                                                    (/ueq/L)
                                                                                 Subregion Boundary
                                                          17

-------
Figure  5-3.    Alkalinity map of the Pacific Northwest subregion. Western Lake Survey - Phase I.
                                                                                Alkalinity Classes
                                                                                     (Aieq/L)

                                                                                  CD <100
                                                                                  [3 100 to 200
                                                                                  [3] >200
                                                                                      Subregion Boundary
                                                           18

-------
Figure  5-4.    Alkalinity map of the Northern Rocky Mountain subregion. Western Lake Survey - Phase I.
                                                                                    Alkalinity Classes
                                                                                        (//eq/L)
                                                                                        <100
                                                                                        100 to 200
                                                                                        >200
                                                                                         Subregion Boundary
                                                         19

-------
Figure  5-5.    Alkalinity map of the Central Rocky Mountain subregion. Western Lake Survey - Phase I.
                                                                                  Alkalinity Classes
                                                                                       (Aieq/L)

                                                                            Q] <100
                                                                            [2] 100 to 200
                                                                            LI >200
                                                                                   Subregion Boundary
                            UT
                                                                   CO
                                                           20

-------
Figure 5-6.
Alkalinity map of the Southern Rocky Mountain subregion. Western Lake Survey - Phase I.



                                      X
                                   s                                Alkalinity Classes
                                 /                                     (yueq/L)

                                        /Pv^                   CO 200
                                                                                    i Subregion Boundary
                                                      21

-------
before it is preserved.  The holding  time imposed on
the withheld sample depends on  which of the  three
processing procedures  is applied.

The  calibration study  has also  been designed  to
provide data  that  can  be  used  to  evaluate
interlaboratory bias. To meet  this goal,  the field
laboratory  sends   one  sample  from  each
routine/duplicate pair collected by  a  ground crew and
one  sample from  each routine duplicate triplicate  set
collected by  a helicopter  crew  to  each  analytical
laboratory.

The  remaining  sample from  each  set  collected by
helicopter is  the  one  that is withheld at the field
laboratory for later processing  and preserving;  the
assignment of a  sample (routine, duplicate,   or
triplicate) to a particular analytical laboratory is made
randomly  and individually  for  every  pair or set  of
samples.  Figure  5-7 illustrates  the  sample
assignment procedure that is used.

Specific sample codes are  recorded on NSWS Form
2  -  Batch/QC   Field  Data,  Figure 5-8,  (1)   to
distinguish  the calibration  lake  samples  from  the
routine  lake  samples,  (2) to  distinguish  samples
collected  by the helicopter crews  from  samples
collected by the ground crews,  and (3) to distinguish
helicopter samples withheld for  later processing from
samples processed on  the day of sample collection.

Samples collected  by  the  ground crews  are  coded
RGC (routine ground calibration) and  DGC (duplicate
ground  calibration).  The samples  collected  by  the
helicopter crews  are coded RHC (routine  helicopter
calibration),  DHC (duplicate  helicopter calibration),
and  THC (triplicate helicopter  calibration)  on  the
batch/QC form. A "W"  is added after the last letter of
one  of  the helicopter  sample codes to indicate that
the sample is being withheld (e.g., if the RHC sample
is withheld, it is coded  RHCW on the batch form).

When  the calibration lake  samples collected by  the
helicopter crew arrive at the field  laboratory, they  are
separated into  batches, are  assigned  identification
(ID)  numbers, and  are shipped to the  analytical
laboratory. This process is shown in Figure 5-9. The
laboratory coordinator  uses  the random  selection
procedure mentioned above to determine  (1) which
sample to withhold at the field laboratory (at 4  °C in
the  dark),  (2) which  samples  to  process  with  the
corresponding samples collected by the ground crew,
and  (3) which analytical  laboratory  analyzes  each
sample.

Thus,  the five   samples  collected  from a  single
calibration lake  are  processed  in  three  different
batches: one sample collected by the helicopter crew
and  one sample  collected by  the  ground crew  are
incorporated in the  sample batch that is sent to the
"regular" analytical laboratory (the laboratory to which
the field  base  ships its  usual, daily  sample  batch).
One sample collected  by each crew  is incorporated
into the sample batch  that is  sent to the  "alternate"
analytical laboratory (the  laboratory used regularly by
another field base). The last sample  (the withheld
sample designated from among the samples collected
by the helicopter crew) is  kept at the field base  for
incorporation into a  sample  batch  shipped  on  a
different day.

Calibration lake samples  that are incorporated in the
daily  sample batch  to be  shipped  to the regular
analytical  laboratory receive  appropriate  batch  and
sample  ID  numbers.  A  complex batch and sample
numbering scheme  is necessary to enable calibration
samples  to  be  associated  with their  QA  samples in
the data verification  step. For  the  two  or  three
calibration lake samples  that constitute a  batch  that
will be sent  to the alternate laboratory, the laboratory
coordinator  obtains  batch  and sample ID numbers
from  the  laboratory coordinator  at  a  second  field
base; these  numbers correspond to the batch that the
second  field laboratory is  processing that day.  This
second field laboratory is called the "reference" field
laboratory, and  it, in turn,  uses the alternate analytical
laboratory of the first  field  laboratory as   its  regular
analytical laboratory.

This  cross-laboratory  procedure  allows the two  or
three samples  destined  for  the  alternate  analytical
laboratory to  be incorporated  into the larger  daily
sample batch from the  reference field laboratory when
the shipments  from the  two  field  laboratories  are
received. In  this way, the  two or three samples do not
constitute a  separate batch and,  thus, do not have to
be accompanied by a separate set of field blank and
audit  samples.

To  obtain the  batch and  sample  ID numbers  for the
calibration lake samples  that  are to  be sent to the
alternate analytical  laboratory, the  field   laboratory
coordinator  calls the  laboratory  coordinator  at the
appropriate  reference field laboratory. The  reference
laboratory coordinator assigns the sample ID numbers
in order,  according  to  the  order  of  phone  calls
received from the requesting field  laboratories.

The  laboratory  coordinator  who is preparing  the
samples  for shipment  fills out a separate  batch/QC
form for the  calibration samples that will  be shipped to
the alternate analytical laboratory. This form shows
the batch ID  assigned by the reference  laboratory.
Field  laboratory data for  each calibration  sample are
entered  on  the line  of  the  batch/QC   form  that
corresponds  to the  assigned sample  ID.  The
reference field laboratory coordinator should note  in
the comment section  on  the batch/QC form  which
                                                  22

-------
Figure 5-7.   Sample flow for the calibration study. Western Lake Survey - Phase I.
                       Ground Samples
                       (Forest Service)
    Helicopter Samples
  (Lockheed-EMSCO, EPA)
Routine
1st
Sample
Taken
I

RGC

{
Duplicate
2nd
Sample
Taken
DGC
1
Routine ^ Duplicate ^ Triplicate
1st 2nd 3rd
Sample Sample Sample
Taken Taken Taken
L RHC DHC THC
i '
Field Laboratory

\
WW
1 J , I
RGC
7
Aliquots

DGC
7
Aliquots
RHC DHC THC
777
Aliquots Aliquots Aliquots
' Randomly Selected T
L Sample Shipment 1
                               I    ."
                               I    I
                               I    I
                              t    t
                         Analytical
                         Laboratory
                                                 1      1
        ._J    I
               I    I
         __J    I
               I    I
               t    t
                Alternate
                Analytical
                Laboratory
                                                 Legend
                      RGC-Routme Ground Calibration
                      DGC-Duplicate Ground Calibration
RHC-Routine Helicopter Calibration
DHC-Duphcate Helicopter Calibration
THC-Triphcate Helicopter Calibration
                                                     23

-------
Figure  5-8.     National Surface Water Survey Form 2 - Batch/QC Field Data.
                National Surface Water Survey
                            Form 2
                     Batch/QC Field Data
                                               Date Received
                                               By Data Mgt	
                                               Entered	
                                               Re-Entered —
        Batch ID
                                           Lab to Which
                                           Batch Sent  _
        No Samples
        in Batch 	
        Base Site ID .
                          Date Shipped


                          Lab Crew ID _
                                                           Date Processed -


                                                           Air-Bill No 	
                                                                            Field Laboratory
                                                                            Supervisor  	
         Field
         Crew
          ID
  Lake
   ID
(XXX-XXX)
Sample
 Code
 OIC(mg/LI
QCCS Limits
 UCL—2 2
 LCL—1 8
                                    Value   QCCS
 Statoin pH
QCCS Limits
 UCL—4 1
 LCL—3 9
                                                  Value  QCCS
Turbidity (NTU)
 QCCS Limits
  UCL—5 5
  LCL—4 5
                                                                Value
                                                                         QCCS
Color
(APHA
Units)
                                                                                Value
Split
Codes
(EU
      Comments
                   White—ORNL Copy    Yellow—Field Copy     Pink—EMSL-LV Copy
                                                 24

-------
Figure 5-9.
Preparation, identification, and shipment of sample batches for the calibration study. Western Lake Survey
Phase).
                                                Regular
                                          Analytical Laboratory

                                            Samples Received
                                            i      and
                                            Analyzed Normally
                                                          Alternate
                                                     Analytical Laboratory

                                                        Shipment from
                                                        Both Field
                                                        Laboratories
                                                        Combined into
                                                        One Field Batch
                                                        and Analyzed
                                                        Normally
1 Normal Lake •
Samples • "
\- J

0<\ -^-$1.
tf^XN,^
G'^X>ielicoptervv%/s,
^^ Samples ^O
^X. 2 Ground y^
^s^amples^^

<
L »




c 'AT 7
o ^ w
Principal
Field Laboratory
• Calibration Lake
Samples (3 of 5)

from Normal Sample
Batch
• Reference Field (|
Laboratory
Coordinator Called
for "Borrowed" Batch
ID and Two Sample ID
Numbers
Sample from Each
Calibration Lake
Withheld for Future
Processing
c/»
f/S
/A?
J
*l
I



Reference
Field Laboratory

• Reference Field '
Laboratory in
Normal Sample
Processing Mode
IPR
• Two Sample IDs frorr
Day's Batch "Lent" t
Principal Field
Laboratory

"o



i
0

H                                                                                                        Normal Lake .
                                                                                                          Samples   '
                                                         25

-------
sample ID numbers were  assigned  to the other field
laboratories for calibration samples. Explanation of the
qualifier should be  in the comments section  of  the
batch/QC form.
                                                  26

-------
                                       6.0  Field Operations
Field operations are coordinated at field bases under
the supervision  of  an EPA  field  base coordinator.
Each field base contains a mobile field laboratory that
is  operated by  a  five-person  crew.  One  or  two
helicopter crews operate from each field base through
an EPA duty officer. Each helicopter crew makes one
or more excursions to lake sites each  day. Ten  to
fifteen  ground crews  operate from  each base  site
through  a Forest  Service  field manager. Each
helicopter crew samples as  many as  10 lakes per
day, and each ground crew samples  1 or 2 lakes per
day (or per excursion). The  field base coordinator and
the field manager coordinate lake sampling so that no
more than 30  field samples are processed at a field
base on any day to prevent an overload of  samples
arriving at the analytical laboratories.
Sections 6.1 through 6.3 describe the activities of the
helicopter crews, the ground crews, and field base
crews. Bonoff and Groeger  (1987)  provide a  further
description of field operations. Section 6.4 of this QA
project  plan  refers to the  field  personnel  training.
Quality  control  checks  for  field  measurements are
presented in  Section  7. Figure  6-1  depicts  the  flow
of samples and data forms for WLS-I.
6.1  Activities of the Helicopter Sampling
      Crews

Activities that are conducted by the helicopter crews
during  WLS-I are similar to those conducted  during
ELS-I.  Each helicopter crew  consists of a  pilot, an
observer,  a sampler, and a  support person  who
remains  at the  field   base.  The  observer's
responsibility is to ensure  that all  measurements and
sampling operations are performed correctly and that
data are recorded  accurately.  The sampler  must be
qualified  to  operate  all  equipment  and must follow
prescribed  procedures.  For  each  excursion,  the
activities of each  helicopter  crew  are  divided  into
three sections:  (1)  activities at the field base prior  to
sampling, (2) activities en route to or at the lake  site,
and  (3) activities at the field base after the sampling
day  is  completed.  These  activities  are described  in
the  following  three subsections.  A  flowchart  of
helicopter field  crew activities  is shown on  page 29
(Figure 6-2).
6.1.1  Field Base Activities Conducted Prior to
      Sampling

Before  leaving the field base,  the  helicopter crew
must perform the following tasks:

    •    Prepare a detailed navigation sheet that gives
        courses  and distances for the  excursion and
        the  navigational coordinates  of each lake  to
        be  sampled. Preliminary information about  a
        lake, such as latitude, longitude, and name, is
        supplied  by  ERL-C and  local  authorities.  If
        possible, the location of the  deepest part  of
        each lake is predetermined (i.e.,  interpolated
        from topographic maps) and is  indicated on  a
        map as the preferred sampling site.

    •    File a flight  plan  with the  field  base
        coordinator so that sample arrival  time can be
        predicted and so that safety requirements can
        be  met.  (Any deviations from  the  flight  plan
        that occur during an  excursion  are  relayed
        immediately to the field base coordinator.)

    •    Calibrate the Hydrolab unit, which is used  to
        obtain  pH,  conductance,  and temperature
        profiles of each lake. Hydrolab calibration data
        are recorded on the Hydrolab calibration form.

    •    Using  a checklist, ensure that all the required
        supplies  are on  hand.  The  crew packs the
        supplies and loads the helicopter.

While the helicopter crew performs these  operations,
the pilot must carry out the following activities:

    •    Calibrate and program the loran-C.

    •    Confer with  the  mechanic about maintenance
        checks and possible refueling stops.

Once  these steps are  performed, the helicopter
proceeds to the lake.
6.7.2  Lake Site Activities
As  the  helicopter  approaches a  lake,  one  crew
member  takes  photographs of the area. Preceding
each set of  lake photographs, a photograph is  taken
                                                  27

-------
         Figure 6-1. Flowchart of sampling activities, Western Lake Survey - Phase I.



                              Field Sampling Sites
                         Audit Sample
                          Preparation
                          Laboratory

Transf
toF
Labor
at 4
•>

)orted
eld
atory
°C
r
Field
Laboratory
^ Samples
	 7 Organized
into Batch
Shipped
to Field
Laboratory
at4°C
^


r


f



+
Closed-
System
PH



i
4r
Turbidity
Measured




^
r
r
True Color
Measured




^
Aliqi
Prep.
an
u^
                                                                                  at 400
                                                  Data
                                               Transcribed
                                               to Data Forms
                                                      Next Day
                                  Next Day
                                              Copies of Lake
                                              Data and Batch
                                              Forms Sent to
                                             Data Management
                                               Center and
                                             Qual ty Assurance
                                                Personnel
                        Al quots Shipped
                              to
                           Analytical
                          Laboratory
                       with Shipp ng Form
                                                                                 Copy of Sh pping
                                                                                   Form Sent to
                                                                                     Sample
                                                                                   Management
                                                                                    Office and
                                                                                 Quality Assurance
                                                                                    Personnel
of a card (lap card) that shows the date, the lake ID
number, the  lake name,  and  the crew ID.  These
photographs are  useful as  an  additional  check in
verifying that the correct lake was sampled.  After the
photographs  are  taken,  the  photograph  frame
numbers  are  written on Form 1  -  Lake Data,  which
                                                      28

-------
                  Figure 6-2.  Flowchart of helicopter crew activities, Western Lake Survey - Phase !
                          Activities Conducted
                             at Field Base
                           before Departure
                    1. Prepare Site Description.
                    2. Calibrate Hydrolab.
                    3. Check List of Supplies
                      for Day's Sampling.
                    4. Load Helicopter.
                    5. Check List of Lakes to be
                      Sampled, and File Flight Plan
                      with Field Base Coordinator
                                                       No
                         Activities Conducted
                            at Field Base
                               after
                         Sampling Excursion

                     1. Unload Samples.
                     2. File Lake Data Forms with
                       Field Base Coordinator.
                     3. Transfer Samples to
                       Laboratory Coordinator;
                       Jointly Check Lake ID and
                       Number of Cubitainers and
                       Syringes.
                     4 Check Hydrolab Calibration
                       and Perform Required
                       Equipment Maintenance.
       Activities Conducted
          at Lake Site

    1  Take Aerial Photographs
    2. Verify Lake Identity.
          Activities Conducted
               on Lake

   1.  Measure Site Depth.
   2.  Profile Conductance.pH, and
      Temperature. Determine
      Stratification Status
   3.  Determine Secchi Disk
      Transparency.
   4  Prepare Blank (at First Lake
      Only).
   5.  Collect Water Sample in
      Van Dorn Sampler
      -Withdraw DIG and pH Syringe
      Samples
      -Withdraw and Preserve
      Nitrate/Sulfate Aliquot.
      -Transfer Remaining Sample
      to a 4-L Cubitainer.
   6  If Necessary, Obtain a
      Duplicate Sample.
   7  If Necessary, Obtain a
      Triplicate Sample.
   8.  Verify that Form and Labels are
      Correctly Filled Out.
is  shown  in  Figure  6-3.  (Table  6-1  lists the  data
forms  and  labels used in  the field.) The  observer
notes  watershed characteristics (e.g., inlets, outlets,
dams, and local disturbances) that can be determined
from the air. The lake data form contains an outline of
the lake, sketched  previously from  U.S.  Geological
Survey (USGS) or equivalent topographic  maps.  The
sampling location is  marked  on the  sketch  with an
"X." The pilot then lands at or near the  deepest  part
of the lake.  This  point is  determined  by  using a
combination of visual observations  from  the air  and
the electronic depth recorder.
When  the  helicopter  crew  arrives  at  the  given
coordinates,  the members may  find  conditions that
require  special  procedures.  No  sample  is  taken  if
there is found to be:  (1) no lake, (2)  more than one
lake, (3) a stream  or other flowing water,  (4)  a lake
too  shallow (<0.75  m) to allow  a debris-free  water
sample to be obtained,  (5) an inaccessible  lake, (6) a
lake  with high  conductance  (>  1500 nScm),  (7)  a
frozen lake, (8)  an  urban or industrial site, (9) a stock
pond  (i.e.,  agricultural  watering  pond),  or  (10)  no
permission for  access.  For a multilobed or  dendritic
lake, the observer determines the location of the best
                                                       29

-------
Figure 6-3.     National Surface Water Survey Form 1 - Lake Data.

                        National Surface Water Survey
                              Form 1 Lake Data
                           Helicopter
        D Ground Team
                                                                   D  D M M M Y  Y
                                                             Date ,—._. — ^_»_-^._-
                                                    Sampling Time   .
                                                          Meter ID- l_l ,
             State
                            Lake ID
                                                Lake Name
                Map Coordinates
                  Photographs^ )
              Frame ID  Azimuth
               „.-     Lap Card
          Loran Readings ()
       Lat ^_ *_, ^'^ u_..^J .
      Long i__i i_i i_i*i__i •  f  • i
                                                                                       . —h
                                                             Initial  *—^-~.
                                                             Final  •  *.  -*
                                                             Initial  ^-•.^4
                                                             Final  _- —.
                                                                                       , i_, pH
                                                                      Altimeter .  ,,
                                                                                       i i—i i_i\_/
            Disturbances Within 100 Meters of Shore
 Q Roads      D Livestock   D Mines/Quarries  D Fire
D Dwellings   D Industry   D Logging   D Other
                                  Secchi Depth Disappear  , ..
                                       Reappear
            Site Depth  u_))_t_lft Q|Site Depth (ft)xQ 3048 m/ft =i—»t—i m Q[ Air Temp-—' ^^°
                                           Lake Stratification Data
                           Depth
                                             T°C
Bottom-1 5m  .  ..  v  . (""")

            AT°C(1 5, B-1  5m)  ^-
                                           .,.  v  .Q
                                           ~-~O
                                                      O
                                  US
     pH

-—Q
^"^ *     *	>^^
                               If A > 4°C Proceed
                                If Not, Stop Here
Site Depth T°C /jS
^,^^,0 - o _-~^_
AT°C(1 5, 06 Depth) _^^ Q I If AT >
Lake Diagram (from topographic map)


IN Inlets ( ) 	
Rpsprvoir







Verified by

1
Site Depth
Check One T°C
D<20m D>20m
fi in . . ,_ -p .
8 1 R t_^ • — .
m 9n v.^.rt, rf
•] 2 ^Pi , 	 	
14 30 ^. ^. .
16 1s -_ •-
18 1" ^.
20 45 • •• i- •
50 ~ 	 ,
pH
O - . -Q
4°CFillln '
Data Block j
1

O
o
0
0
o
0
o
o
o
o

„
_~-^o
^^^-^-O
«^--O
u-^^-^,O
^^_^ ^o
^^k—^-w^O
o
_, 	 o
^^--0
_, 	 o
             Comments  D Not Sampled, See Below
                                        Data Qualifiers
                                      (A) Instrument Unstable
                                      (n\ Redone, First Reading Not
                                      ^ Acceptable
                                      (c) Instruments, Sampling Gear
                                         Not Vertical in Water Column
                                      (D) Slow Stabilization
                                      ©Cable Too Short
                                       • Do Not Meet QCC
                                       < Sample Collected at 0 5m
                                   CYj(z)Other (explain m Comments section)
            Reason Lake n Flowing Water D Inaccessible G No Access Permit  D Urban/Industrial  O Frozen
Field Lab Use Only




Time Received 	
Field Crew Date
[ Helicopter ID 	 j Crew ID
Observer (Print) 	
Sampler (Print)
Obs Sign
Ground Crew Member

Form Distribution
White Copy — ORNL
Pink Copy— EMSL-LV
Yellow Copy— Field

                                                   Sign
                                                           30

-------
 Table 6-1.  Data Forms and Labels Used in the Field,
          Western Lake Survey - Phase I
Data Form
Number
1
2
3
Description
Lake Data Form
Batch QC/Field Data Form
Shipping Form
Hydrolab Calibration Form
Location of
Facsimile
Figure 6-3
Figure 5-8
Figure 6-1 1
            Sample Tracking and Custody    Figure 6-8
               Form

            Field Sample Label            Figure 6-5

            Field Audit Sample Label        Figure 6-10

            Aliquot Label                Figure 6-6
sampling site, following specific guidelines; for small
lakes, sampling procedures are modified.

The rotor wash of the helicopter can create a  surficial
disturbance. The disturbance is normally  away from
the sampling  point and  is minimized  by  the pilot's
positioning of the helicopter.

While the pilot maintains position by visual reference
to landmarks  or an  anchored  buoy,  as  conditions
dictate, the  sampler  must  perform  the following
operations in the order given:

  1. Measure the lake depth at the sampling site with
    a  calibrated  sounding line, then record the result
    on the lake data form.

  2. Use the Hydrolab to  profile  the pH, conductance,
    and temperature measured at 1.5 m  below  the
    surface and  at 1.5 m above the  lake  bottom. (In
    shallow lakes,  only one set of readings is taken,
    at 0.75 m.) If the temperature difference exceeds
    4°C,  the sampler  takes  a  third   set  of
    measurements at  60  percent of the lake depth. If
    the temperature difference  between the top and
    the  60  percent depth is   <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,
    the sampler  obtains  a   temperature  and
    conductance  profile  at 5-m  intervals  for lakes
    greater  than 20 m deep and  at 2-m intervals for
    lakes less than  20  m deep.  Figure  6-4  shows
    how the profile is  taken and how the stratification
    is determined. The sampler records the results on
    the lake data form.

 3. Measure  the  Secchi disk  transparency  by
    lowering a Secchi disk secured  on a calibrated
    line into  the water  on the shady  side  of the
   helicopter  until  the disk  disappears from  view,
   then  raising the  disk  until  it reappears.  The
   observer records both of these depths on the lake
   data  form.  Their average  is the  Secchi  disk
   transparency. If  the  Secchi  disk is still  visible
   when  it rests  on  the  bottom of the  lake, the
   observer does not enter a reappearance depth on
   the  lake  data  form but  makes  an explanatory
   notation in the comments section of the form. The
   observer  must not wear sunglasses unless  they
   have photogray  prescription lenses. If sunglasses
   are worn, the observer makes a notation of this in
   the comments section  of  the form.  In addition,
   any  conditions such as glare, choppy  water,  or
   other physical interferences that are hindrances to
   taking the reading are  documented on the  lake
   data form.

4.  Collect the sample from the  upwind side  of the
   helicopter, where  the potential for  contamination
   from  engine exhaust  is  minimal.  The  sampler
   rinses  the  6.2-L  Van  Dorn  sampling  unit  with
   surface water, lowers the unit to 1.5 m below the
   lake surface, triggers it to collect a sample, raises
   it  to  the  surface,  then sets  it on  the  pontoon
   platform  in  a vertical position.  This  position
   prevents  the  sample  from  leaking  out  and
   prevents air  from  leaking  in.  It is imperative that
   air is  not introduced before step 5 is performed.

5.  Take  DIG and  pH  syringe  samples from the
   Luer-Lok syringe port on the Van  Dorn sampling
   unit.   The  sampler  uses  a 60-mL  syringe
   equipped with  a valve to  withdraw  a  20-mL
   aliquot, rinses the syringe with this aliquot and
   discards  the rinse,  then withdraws a  60-mL
   aliquot  and  seals  the  syringe.  Repeating the
   procedure, the sampler obtains a second  syringe
   sample. The sampler fills  out field  sample labels
   (see  Figure 6-5), excluding  "Batch  ID"  and
   "Sample ID" which are assigned at the field base,
   and  attaches the labels  to  the  syringes.  After
   labeling the syringes, the sampler places them  in
   a  plastic  bag and stores them  in  the  cooler
   (maintained at 4°C).

6.  Prepare the Cubitainer sample.    The sampler
   rinses  a  clean  4-L Cubitainer with three  500-
   mL portions of  sample,  fills  it  with  as  much
   sample as possible, compresses it  to remove all
   headspace,  then caps  it securely.  The  field
   sample label is attached and completed. After it is
   labeled, the Cubitainer is stored with the syringes
   in  the cooler.

7.  Collect a  duplicate sample.  At  the  first lake
   sampled each day, one helicopter crew from each
   field  base  (as   assigned  by  the field   base
   coordinator) collects  a  duplicate  sample  by
                                                  31

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Figure 6-4.    Determination of temperature stratification class and lake temperature profile. Western Lake Survey - Phase I.

±                                                                                    Water Line
                                                     -^.~.-.-_-.-_-_-_-_-LJ-_-LJ-_- -_---_- .--..-_-_-_-_-_-_-.-,_n_r_j-	
                                                  1 5 m
         If A°T <4°C, lake is
           not stratified (no
             additional °T
          measurements are
              necessary)
                                          If A°T >4°C, then °T
                                            measured at 60%
                                              of lake depth

                                           If A°T <4°C, lake is
                                             weakly stratified
                                             (no additional °T
                                           measurements are
                                               necessary)
  If A°T >4°C, lake is
   strongly stratified
(additional incremental
 °T measurements are
      necessary)
                                                                           (60% depth)
                                                                                  •Depth at Which °T
                                                                                   Measurement Taken
                                                                                                              E  E
                                                                                                              & in
                                                                                                              >•  >-
                                                                                                              0)  0>
                                                                                                              >  >
                                                                                                              o>  o>
0) 03
E E
                                   d d.
                                   0) 01
                                   0) O
                                  T3 T3
                                   E E
                                  o o
                                  CM CM
                                  A V
                                   CD 0
                                   -^ J*
                                   CD CD
                                                        Deepest Spot
                                                              32

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   Figure 6-5.  Field sample label, Western Lake
             Survey - Phase I.
Lake ID

Date Sampled

Crew ID

Time Sampled

Sample Type
(Check One)
Routine
Duplicate
Blank
Batch ID




Sample ID

  repeating steps 4 through 6. On  the label, sample
  type "Duplicate" is checked.

8. Collect a field blank sample. Each helicopter crew
  prepares one  field blank at the first lake  sampled
  each day before collecting the routine sample.  In
  place of  step  4, the sampler rinses the Van Dorn
  sampling unit with  three 200-mL  portions  of
  deionized water, then fills it with deionized water.
  Step 5 is omitted, and step 6  is performed as for
  a  lake  sample.  The  sample type  "Blank"  is
  checked  on the label.

9. Collect  and  preserve  the nitrate-sulfate aliquot
  (the  EMSL-LV split  sample). Helicopter  crews
  collect nitrate/sulfate ahquots  at calibration  lakes
  only.

  The sampler  must prepare one 125-mL aliquot
  as follows:

  •   Complete and  affix  an   aliquot  label  (see
      Figure 6-6) to a 125-mL  Nalgene bottle. Fill
      the  bottle to  the  shoulder with sample from
      the Van Dorn.

  •   Using a dropper bottle, add 2 drops  (0.1  ml_)
      of a  5 percent  solution of  reagent-grade
      mercuric chloride (HgCl2) to the aliquot bottle,
      record the amount of preservative  used on
      the aliquot label,  cap the aliquot bottle tightly,
       and invert the bottle several times to mix the
       contents.

   • Tape  the cap  on with electrician's tape, and
     place  the bottle in a plastic bag in the cooler for
     transport.

10. Upon completion of steps 1 through  9, rinse the
    Hydrolab sonde and  the  Van Dorn sampler with
    deionized water, and store them securely in the
    helicopter. The observer  verifies that the  lake
    data  form is properly completed and  that all
    sample containers are correctly labeled.

11. The helicopter proceeds to the next  lake, where
    the same lake site activities are performed. When
    time  or  weather  conditions  necessitate, the
    helicopter returns to the field base. The helicopter
    is refueled, when necessary, at remote airports or
    by fuel  truck. In some cases, where sampling
    sites are more than 150 miles from the field base,
    remote bases are established. The helicopter and
    its crew remain  at the remote base overnight, but
    the samples  are flown to the field base by fixed-
    wing aircraft.

6.7.3 Field Base Activities  Conducted at the End
      of the Sampling Day
Upon the  return  of the helicopter crew  to  the field
base, the  field  samples  are  transferred  to the
laboratory coordinator. The Hydrolab  calibration  is
checked  at  the  end of each  day.  Any  instrumental
drift is noted on  the calibration form and  on the lake
data  form,  and  the  affected  data are  qualified
appropriately.  If  a drift problem is  significant and a
reliable Hydrolab is available,  the faulty  Hydrolab is
not  used  on   the   next  sampling  day.  The
manufacturer's instructions for care and maintenance
of  the pH  meter and electrode are followed.  The
rechargeable batteries are charged overnight,  and the
electrodes are stored in tap water or 3M KCI.

All lake data forms are  checked for consistency. After
supplies and equipment are checked and are stored
for the next sampling day, the helicopter crew,  duty
officer, and field base coordinator participate  in a
debriefing  to  discuss  the day's  activities  and to
prepare for the next day's sampling activities.

6.2 Activities of the Ground Sampling
     Crews
Each ground  sampling crew  is  composed  of two
samplers. Depending on the circumstances (i.e., lake
location and availability of  pack animals),  as many as
three logistics support  personnel may aid in carrying
equipment to the lake.  A local  Forest Service expert
travels with  the  samplers to  ensure that the  proper
lake is located.  Both samplers must be  qualified to
                                                 33

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                        Figure 6-6.  Aliquot label, Western Lake Survey - Phase I.
                            Aliquot
                            Batch ID


                            Sample ID


                            Date Sampled
                            Preservative


                            Amount


                            Parameters
          Note. The aliquot
          number, preservative,
          and parameters are
          preprinted on the
          aliquot labels
operate all  equipment and must follow  prescribed
procedures. For  each excursion, the activities  are
divided into those conducted (1) at the field base (or
remote base) prior to sampling,  (2) en route to or at
the lake site, and  (3) after  lake-site activities  are
completed  (see  Figure 6-7).

6.2.7  Field Base Activities
Before  leaving  the  field  base  (or  remote  base),
ground crews perform the following tasks:

    •   Check and  calibrate the temperature meter
       (see Section  7.2.1).

    •   Check and pack  the equipment and supplies
       necessary for the sampling excursion. Sample
       containers are  prepackaged into kits for each
       lake. Sampling crews should obtain additional
       kits as  reserves  and  in  case additional  QA
       samples  (including  field  blanks) are required
       for  a given excursion.

    •   Coordinate the sampling plan with  the  field
       manager, and  file  an  appropriate  sampling
       itinerary. The itinerary includes the estimated
       duration  of  the  excursion,  a  check-in
       schedule, and, when applicable,  the location
       of overnight stops and a time and location for
       samples  to be transferred for delivery to the
       field laboratory.

6.2.2  Lake Site Activities

6.2.2.1  Verification  of Lake Location-
The ground crew must verify the map coordinates of
the lake as follows:
  •  Compare the lake shape  to that shown on the
     map (USGS 7.5  minute  topographic  map or
     equivalent).

  •  Determine  the  position of the  lake  relative to
     identifiable  topographic features  shown  on the
     map.

  •  Determine the position of the lake  by compass
     triangulation on suitable landmarks.

  •  Use maps  other than  USGS topographic maps
     (e.g., Forest Service maps) to confirm  the  lake
     location.

  •  Obtain  assistance  from a local person (usually
     from the  Forest Service) who is familiar with the
     area.

If the lake in question is confirmed as the proper lake
to be sampled,  the ground  crew completes the site
description portion of the data  in the field logbook.
When exceptional conditions are found  at the given
coordinates,  the  ground  crew  follows the  same
procedures  as the  helicopter  crews  follow. These
procedures are listed in  Section 6.1.2.

6.2.2.2  On-Shore Activities-
The  ground crew must perform  the following on-
shore activities prior to sampling:

  •  Collect and clean rocks (if available)  for use as
     an anchor.

  •  Inflate  the  boat,  and  load the equipment and
     supplies.
                                                   34

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        Figure 6-7. Flowchart of ground crew activities, Western Lake Survey - Phase I.
                    Activities Conducted
                       at Field Base
                     before Departure

         1.  Check Instruments.
         2.  Pack Equipment and Supplies
           Activities Conducted
              at Lake Site
           before Boarding Boat

1.  Verify Lake Identity.
2.  Record Site Characteristics.
                                                                        Activities Conducted
                                                                           at Lake Site
                                                                             on Boat

                                                             1  Select Sampling Site on Lake.
                                                             2.  Determine Sampling Site Depth.
                                                             3.  Determine Secchi Disk Transparency
                                                             4.  Determine Stratification Status through
                                                                in situ Temperature Profile
                                                             5  Prepare Blank (at First Lake Only)
                                                             6.  Collect Water Sample in Van Dorn
                                                                 Sampler
                                                                -Withdraw DIG and pH Syringe Samples.
                                                                -Withdraw Nitrate/Sulfate Aliquot
                                                                -Transfer Remaining Sample to a
                                                                 4-L Cubitainer.
                                                             7  If Necessary, Obtain a Duplicate Sample
                                                       No
                   Activities Conducted
                           after
                    Sampling Excursion

          . Check Samples and Data Forms and
           TransferThem to Transfer Personnel or to
           Forest Service Field Manager at Field
           Base.
          . Discuss Day's Sampling Excursion Plan
           and Prepare for Next Day's Sampling.
           Activities Conducted
              at Lake Site
                on Shore

1. Transfer Data Entered in Logbook During
  Lake Site Activities to Lake Data Form
2. Determine pH (Use Indicator Strips)
3. Preserve Nitrate/Sulfate Aliquot
4. Pack Samples for Transport.
5. Verify that Form and Labels are  Correctly
  Filled Out.
Complete field sample and nitrate sulfate aliquot
labels (except for "Batch ID" and  "Sample  ID")
for all samples to be collected.

Record  site  description  information on the  lake
data form provided in the field logbook.
 Check the  operation of the temperature meter
 according  to  the  directions in  the  operations
 manual for the instrument.

 Check the  calibration  of  the temperature meter
 and thermistor as described in Section 7.2.1.
                                                     35

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6.2.2.3 On-Lake Activities--
On the lake, the ground crew locates the part of the
lake  that  is estimated to be  the deepest  and, if
weather conditions  require,  anchors the boat.  The
crew then  must perform the following operations:

 1. Measure the depth at the  sampling site.  Use a
   weighted calibrated sounding  line, and record the
   result on the lake data form in the field logbook.

 2. Profile the temperature at  1.5 m below the  lake
   surface and at  1.5  m  above  the  bottom by
   lowering the thermistor probe  to the proper depth,
   allowing the reading to  stabilize, and recording the
   temperature on the data form  in the field logbook.
   In  shallow  lakes (less  than 3 m deep),  the
   temperature is measured  at  0.75  m below  the
   surface.

   If the  temperature difference between the  two
   depths exceeds  4°C, the crew  takes  a  third
   measurement at  60 percent of the  lake depth If
   the temperature  difference between the top  and
   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 profile is obtained at
   5-m intervals  for lakes greater than 20 m deep
   and at 2-m intervals for lakes  less  than 20 m
   deep  (see Figure 6-3).

 3. Measure  the  Secchi  disk transparency  of  the
   water  on  the shady side  of  the  boat.  The
   samplers  in  boats use the same  procedure for
   this measurement as the samplers in helicopters
   do; the procedure is  described  in Section 6.1.2,
   step 3.

 4. Collect samples  of the same types as helicopter
   crews collect (see Section  6.1.2,  step 4).  The
   ground crews, however, collect a nitrate sulfate
   aliquot for  every routine,  duplicate, and  blank
   sample they collect. Also, a  crew member fills a
    10-mL vial with  lake  water  from  the Van  Dorn
   sampler for pH determination  on  shore.

6.2.2.4  On-Shore Activities After Sample
       Collection-
On   shore, following  sample collection,  the  ground
crew performs the following activities:

  1. Measure the pH of the samples. Because neither
    pH  meters nor  Hydrolabs are  available  to the
    ground crew, a crew member  makes on-site pH
    determinations with ColorpHast pH indicator strips
    that cover two pH ranges  (4.0 to  7.0 and 6.5 to
    10.0).  The crew member places  a pH indicator
    strip in the vial, allows the  color to develop for 10
   minutes, compares the color of the strip to the
   color chart, and records the pH value on the lake
   data form in the field logbook.

 2. Preserve the nitrate-sulfate  aliquot  (split) by
   adding two drops (0.1 ml) of a 5 percent solution
   of reagent-grade HgCl2; then  tape  the  cap on
   the aliquot bottle with electrician's tape.

 3. Pack the  Cubitainers, syringes,  and split samples
   in  coolers  with  frozen  gel   packs  and
   thermometers  for  transporting  to  the  field
   laboratory.

 4. Transcribe all field logbook data  onto the lake
   data form. The member of the crew who does not
   transcribe  the  data  checks  the  form  for
   transcription errors.

 5. Initiate a  sample  tracking and  custody form (see
   Figure  6-8).

6.2.3  Activities Following Completion of Lake
      Site Activities

6.2.3.1  Delivery of Samples and Data Forms to
       the  Field Laboratory--
If a ground crew returns to  the  field base  after  a
sampling excursion,  the crew members report to the
field manager upon arrival.

  •  The crew transfers custody of the samples and
     the data  forms  to  the  field manager,  who
     records the time of receipt and   signs  the
     custody form.

  •  The field  manager  conveys  custody of forms
     and samples to the laboratory coordinator, who
     measures  the  temperature of  each cooler and
     records the results on the custody form  and on
     the appropriate lake data form.  The laboratory
     coordinator also records  the  date  and  time of
     receipt  of each sample  on  the corresponding
     lake data form.

     NOTE:  The  custody form must be signed by the
             field  manager or the  field   manager's
             designee  before the  field  laboratory will
             accept  samples.  The  field  base
             coordinator  must also be  informed of
             sample  arrivals and of the total  number
             of samples received.

If the ground crews do not return to  the  field  base,
they are met at a pick-up point by  a transfer crew.

  •  A  member  of  the  ground  sampling  crew
     measures the  temperature of each 30-qt ice
     chest  (or  portable  cooler)  with  a  field
                                                  36

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       Figure 6-8. National Surface Water Survey Sample Tracking and Custody Form.
                           National Surface Water Survey
                                 Western Lake Survey

                          Sample Tracking And Custody Form
         Base Site: _


         Crew ID:
                           Date Out:  __


                           Date Returned:
                                  Number of Containers
           Lake ID
  4-L
Cubitainer
Syringes
Nitrate/Sulfate
  Aliquot
Conpleted
Lake Data
  Form
                                                                  Comments
1 Relinquished by
(Sampler)
3. Received by.
(Field Manager)
Date

Time

Temps

2. Received by:
(Pick-up Crew)
4 Received by
(Lab Coordinator)
Date

Time

Temps

       Comments.
       Copies: Base Coordinator, Field Manager, Field Lab, EMSL-LV (Comm. Ctr.)
thermometer  and records the temperature on
the custody  form.  The  field  thermometer is
placed in a corner of the cooler or is taped to an
inner wall so  that the temperature of the cooler,
not of a gel pack or sample, is measured.

The  Cubitamers,   syringes,  and  splits  are
transferred to ice chests or Styrofoam coolers
containing new frozen gel packs.
                                 The samplers  give  the  lake  data forms  and
                                 custody forms to the transfer crew.
                                The  transfer  crew  conveys any  necessary
                                supplies or  information to the ground sampling
                                crew  and  obtains  information and  supply
                                requests from the sampling  crew for the field
                                manager.
                                            37

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6.3  Field Base Operations

The  field  base includes a  fully  equipped  mobile
laboratory that is  staffed  by  a  field laboratory
coordinator, a  field  laboratory supervisor, and three
analysts.  The field  laboratory  coordinator  is
responsible for the overall operation of the laboratory
(sample tracking and logistics,  data, forms,  safety,
etc.)- The  field laboratory supervisor and the analysts
are responsible for  sample measurements made at
the  field  base  and for  sample  processing.  If
necessary, the field laboratory  coordinator  also
assists with   sample  processing.  This section
describes  the  field base activities that are outlined in
Figure  6-9.   Section  6.3.1   refers  to  reagent
preparation, and  Section  6.3.2 describes sample
processing.

6.3.1  Reagent Preparation
Reagents for aluminum extraction, DIG determination,
and  pH  determination  must be prepared  before
helicopter  crews return with samples.  Reagents used
for lake-site   measurements  must  be  made  as
required.  Detailed procedures  for  reagent
preparations are given in Morris et at. (1985).

6.3.2  Sample  Processing
The  following  steps  describe  sample  processing
operations. These operations fit  into the sample flow
as shown  in Figure 6-1. They are  performed in the
order given.

6.3.2.1 Sample Description and Identification-
Samples  are  organized  into  batches  that  are
processed together. A batch consists of all samples
(approximately  20  to 30, including routine,  duplicate,
blank, split, and audit samples) that are processed at
a field base on a given day. Each batch is assigned a
unique batch  ID  number, which is recorded  on the
labels of all samples and of corresponding aliquots.
Each sample is then randomly assigned a sample ID
number as follows:

   •  Routine  Samples  -  Three  sample containers
     are  filled at each  lake,  namely  two  60-mL
     syringes  (for  DIG and pH determinations) and a
     4-L   Cubitainer.  One  sample   ID  number is
     assigned  to all three containers and is recorded
     on each container label.

   •  Duplicate, Triplicate,  and  Blank  Samples  -
     Sample ID numbers are assigned in  the same
     manner as for the routine samples. There are no
     syringe samples for the blanks.

   •  Field Audit  Samples  -  One or two  2-L  field
     audit samples (received each day from a central
     source) are  included in each  day's  batch of
     samples.  The label for the field audit container is
     shown in  Figure  6-10.  Two syringes  are
     labeled, filled,  and sealed  for  pH  and  DIG
     determinations. The code (Table  6-2) indicates
     what kind of a sample  it is and the concentrate
     lot number. A  field audit sample  is assigned a
     sample ID number in  the  same  manner as a
     routine sample.  The  sample ID  number  is
     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/QC form. Also,
the lake ID and the appropriate code for each sample
(from Table 6-2) are entered on  the batch/QC  form.

The sample ID  numbers are  assigned at random to all
samples in a batch,  except for certain calibration lake
samples  (see Section 5.2).  Furthermore, sample ID
numbers run consecutively  from 1 to the number of
samples in the  batch. Audit  samples must not  always
be assigned the same sample ID number.

     NOTE 1:  Field  audit  samples are  processed
              exactly like routine lake  samples.

     NOTE 2:  Seven different aliquots (numbered as
              in  Table  6-3)  are  prepared  from
              each field sample (routine,  duplicate,
              audit,  and  blank   samples).  Each
              aliquot is assigned  the  same batch
              and  sample  ID numbers  as  the
              sample  from which  it  is prepared.
              (This is  not always the  case  for all
              calibration lake samples:  see Section
              5.2).  Additional aliquots are taken for
              split samples.

6.3.2.2  DIG Determination-
Immediately after assignment of  batch and sample ID
numbers,  the laboratory  supervisor begins  the  DIG
analyses. DIG is determined in routine, lake duplicate,
and  field audit  samples.  The routine and  lake
duplicate samples  are contained in sealed  syringes
(filled at the lake site) and are kept in refrigerators in
the field laboratory at  4°C  until analysis. For  field
audit samples, a  syringe sample is taken from  the
refrigerated 2-L sample prior to  analysis. The  results
are  recorded  on the  batch/QC  form.   The
measurement procedures are discussed in Section
7.2.1 of Drouse et al. (1986). Copies of all raw  data
are kept in a DIG logbook and must be sent to the QA
manager when  requested.

6.3.2.3  Sample Filtration, Preservation, and
        Aliquot Preparation-
The  aliquot bottles are  pre-labeled and  pre-
numbered  before filtration  and aliquot preparation
begin.  One analyst  filters the samples  in a laminar-
flow  hood  referred  to as the "clean air station"; a
                                                 38

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Figure 6-9. Flowchart of daily field base activities, Western Lake Survey - Phase I
    Before
 Sample Arrival
       1. Prepare reagents for analysis:
         a) Total extractable Al
         b)DIC
         c)pH

       2. Warm up and calibrate instruments.
         a) Turbidimeter
         b) Carbon analyzer
         c) pH meter
                                4 Sample Arrival
                                   1  Confirm with sampling crews delivery
                                     of samples and forms
                    1  Insert required audit samples, assign batch
                       and sample ID numbers, start batch form

                    2  Measure DIG

                    3. Mnasuro pH

                    4. Measure turbidity

                    5. Measure true color

                    6. Complete batch and shipping forms
               Shipment
              of Supplies
              and Forms
       Figure 6-10. Field audit sample label, Western Lake Survey - Phase I.
Field Audit Sample
Radian ID No
Date
Shipped
Code
Batch
Date
Received

ID
                                       39

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                Table 6-2. Sample Codes Used to Complete Lake Data Forms,
                         Western Lake Survey - Phase I
Sample Type
Normala
Code
RH
RG
OH
DG
BH
BG
TB
TD
Description
Routine lake sample - helicopter
Routine lake sample - ground
Duplicate lake sample - helicopter
Duplicate lake sample - ground
Field blank - helicopter
Field blank - ground
Field laboratory (trailer) blank
Field laboratory (trailer) duplicate
                 Calibration Study3    RHCt>
                 Audit
                                  THCb
                                  RGC
                                  DGC

                                  F  L
                 Split
 Routine calibration - helicopter
 Duplicate calibration - helicopter
 Triplicate calibration - helicopter
 Routine calibration - ground
 Duplicate calibration - ground
• Radian ID number
• Concentrate (or lake) lot number
• Natural or synthetic (concentration level)
   N = natural L = low synthetic
• Type of audit sample
    F = field (no other type used)

• Shipping destination of split sample
 E = ERL-C
 L = EMSL-LV
 A split sample is an additional aliquot from a routine,
 duplicate,  audit, or blank sample,  and  has the same ID
 number as the original sample.  However,  the aliquot has
 an additional sample code. For example, if the original
 sample is  assigned the ID number 4, the split sample also
 receives the ID number 4, with the  letter E (or L) recorded
 in the Split Code column on the batch/QC form.
                a Samples require a lake ID, except for TB
                b This sample can have a "W" as a fourth character, indicating that it was withheld as part of the
                 calibration study
second analyst  prepares aliquots  and  split  samples
and preserves them if necessary. Both  analysts wear
disposable gloves while performing these tasks.  The
seven aliquots   prepared  from  each  sample  are
specified  in Table  6-3.

There are two  types  of  split samples  for  WLS-I.
Descriptions  of both  are  given  below  and  are
summarized  in  Table 6-4.  When  a sample is split,
the  appropriate split  code  is  recorded  on  the
batch/QC form.
   • ERL-C  (Corvallis)  Split  -  An  ERL-C  split
     consists of one  aliquot that  is prepared  in the
     same way as aliquot 1  (Table 6-3),  except that
     the sample volume  is  125 mL and a 125-mL
     container is used.  If  the  volume  permits,  all
     samples  are  split for  shipment  to Corvallis.
     When  volume  limitations exist,  routine aliquots
     and  analyses take precedence. At  ERL-C, the
     samples  are  analyzed  by  inductively  coupled
               plasma atomic emission  spectroscopy  (ICP),
               which provides checks on the performance of
               the analytical  laboratories  as well  as additional
               data that  are potentially useful in  understanding
               lake chemistry. This split (annotated by an  "E"
               on the  batch/QC  form)  is  shipped  to  the
               Corvallis  laboratory  on a  multiple-batch  basis
               (e.g.,  weekly).  This split  sample  need not  be
               stored at 4°C.

               EMSL-LV  Split -  An  EMSL-LV split  consists
               of  one 125-mL aliquot  that is  collected  and
               preserved  as  described  in  Sections  6.1.2,
               6.2.2.3,  and  6.2.2.4.  At  Las  Vegas,  the split
               samples are analyzed by ion  chromatography for
               NOs"  and  SO42'.  The  purpose  of  analyzing
               this split  sample  is  to  compare  preservation
               methods, to  compare the effects of  different
               holding  times before  preservation,  and  to
               provide  an  additional  check  on  sampling,
               processing,  and  analytical performance.  Split
               samples (indicated  by an "L" on the batch/ QC
                                                    40

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                        Table 6-3. Aliquots, Containers, Preservatives, and Corresponding
                               Analyses, Western Lake Survey - Phase I
                               Aliquot
                          (Container Volume)
      Preservative and
        Description
     Analyses
                                 1
                              (250 mL)

                                 2
                               (10 mL)

                                 3
                              (250 mL)
                                 4
                              (125 mL)

                                 5^
                              (500 mL)

                                 6
                              (125 mL)

                                 7
                              (125 mL)
Filtered, preserved with
HNO3 to pH < 2

Filtered, preserved with
MIBK-HQ extract

Filtered, no  preservative
Filtered, preserved with
H2S04 to pH < 2

Unfiltered, no preservative
Unfiltered, preserved with
H2SO4 to pH < 2

Unfiltered, preserved with
HNO3 to pH <  2
Ca, Mg, K, Na,
Mn, Fe

Extractable Al
CI-, total dissolved
F-, S042-, N03-,
Si02

DOC, NH4*
pH, BNC, ANC,
conductance, DIC

Total  P
Total Al
                        a There must be no headspace in the Aliquot 5 bottle.
                        b Aliquots 2, 3, 4, 5, and 6 must be stored at 4°C in the dark
                    Table 6-4. Split Sample Descriptions, Western Lake Survey - Phase I

                     Split         Quantity      Number               Description
                     ERL-C
                                 125 mL
                     EMSL-LV     125 mL
                                              All samples3
                                              All samples collected
                                              by ground crews, all
                                              calibration lake samples
                                              collected by helicopter
                                              crews, and all natural
                                              audit samples.
                       Filtered sample acidified with
                       HNO3 to pH <2

                       Unfiltered sample preserved in
                       field with 0.1 mL 5% HgCI2
                   a Except when there is insufficient sample as a result of other splits
     form)  are stored  in  the dark  at 4°C and are
     shipped to Las Vegas on a daily basis.
6.3.2.4 Extractable Aluminum-
The WLS-I procedure for processing  the  sample for
extractable aluminum  is identical  to  the  procedure
used during  ELS-I. The  third  analyst begins  this
procedure when  the  DIC measurements  are  begun.
The aluminum in the sample is extracted  into  MIBK,
which  is transferred to a 10-mL  centrifuge tube  that
is  capped  tightly. An aliquot label is attached.  This is
aliquot  2  in Table 6-3. The aliquot  is stored at  4°C
in  the dark until shipment.
              6.3.2.5 pH (Field Laboratory)--
              The  WLS-I  procedure  for  field  laboratory  pH
              determination  is  identical to  the  procedure  used
              during ELS-I.  After  determining  DIC, the  laboratory
              supervisor determines the pH  of the sample  in  the
              second syringe,  which has been  allowed to come to
              room temperature. The QC procedures are  discussed
              in  the ELS-I  QA  plan (Drouse et  al., 1986, Section
              7.2.2).
              6.3.2.6 Turbidity--
              The  WLS-I  procedure  for  turbidity determination  is
              identical  to  the  procedure used  during ELS-I.  The
                                                      41

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analyst who prepares the aliquots also measures  the
turbidity of raw portions of the routine,  duplicate, and
blank samples. A  Monitek Model  21   laboratory
nephelometer  is  used  for this  procedure. The
nephelometer  is calibrated directly  in  nephelometnc
turbidity  units (NTUs).  The  QC  procedures are
discussed in the ELS-I QA plan (Drouse et al.,  1986,
Section 7.2.3).

6.3.2.7 True Color--
The  WLS-I procedure for  true color  determination is
identical  to  the procedure  used  during  ELS-I. The
same analyst  who performs the turbidity  analysis
centrifuges raw portions  of routine  and  duplicate
samples  (as well as audit and blank samples  when
sample volume permits) and measures the color of
the supernatants with  the  Hach  Model CO-1  Color
Test Kit,  following the manufacturer's instructions.
The  QC  procedures are described  in  the  ELS-I  QA
plan  (Drouse et al., 1986, Section 7.2.4).
6.4  Training

The  WLS-I  procedure for  training  helicopter
sampling and field laboratory personnel  is identical to
the procedure  used during  ELS-I.  Ground  sampling
creates new  safety and  technical  considerations,  so
additional  training is  provided  for  ground  sampling
participants. This training is carried out  at Las Vegas
and  at  the field bases  and  remote sites.  Further
discussion  of training activities can be found in Morris
et al. (1985).
6.3.2.8  Sample Shipment-
When a batch is completely processed  and is ready
for shipment, the samples are  assembled into groups
according to their shipping  destinations.  Except for
ERL-C  splits,  all samples are stored  at  4°C  until
they leave  the  field  laboratory.  Split samples are
shipped  to  ERL-C  and to  EMSL-LV.   All  other
samples are shipped to an analytical  laboratory  (see
variations in sample shipment  protocol for  calibration
lake samples in Section 5.2). Before shipping, the cap
of each aliquot bottle is  taped on,  and the bottle is
sealed in a plastic bag that is  placed in  a  Styrofoam-
Imed  shipping  carton, along  with  8 to  12 frozen
freeze-gel packs to  maintain  the  aliquots at  4°C.
(Approximately  eight  samples  will fit in  one shipping
carton.)  One multicopy  set of  Form  3 -  Shipping
(see Figure  6-11) is  completed for  each carton, and
two copies  (sealed in a plastic bag) are enclosed in
the carton. The  carton then  is sealed and is shipped
by overnight delivery to its destination.

Upon receiving  the shipment, the  analytical laboratory
checks  the  temperature inside  the shipping  carton
and checks  the condition of the shipping  carton and
the aliquot  bottles.  The  analytical laboratory  also
verifies  that all  the  aliquot  bottles listed  on the
shipping form are included in the shipment. If there is
any  discrepancy, the field  laboratory  coordinator
should  be notified  immediately,  and the  deviations
should be noted in a cover letter to the QA manager.

6.3.2.9  Data Distribution-
The WLS-I  procedure for distribution  of  field  data
forms is identical to the procedure  used during ELS-
I. A flowchart of the  process is included on page 28
(Figure  6-1).
                                                  42

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Figure 6-11  National Surface Water Survey Form 3 - Shipping.
National Surface Water Survey
Sample Management Office
P.O. Box 818
Alexandria, VA 22314
 NSWS
 Form 3
Shipping
Received by	
 If Incomplete Immediately Notify
   Sample  Management Office
        (703) 567-2490
                                                                Page
                                         of
From
(Station ID)
Sample
ID
01
02
03
04
05
06
07
08
09
10
1 1
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
To
(lab)
Batch
ID

Date Processed

Aliquots Shipped
(For Station Use Only)
1






























2






























3






























4






























5






























6






























7






























8






























Splits































Date Shipped Date Received
Air-Bill No.
Sample Condition Upon Lab Receipt
(For Lab Use Only)






























 Qualifiers
          X   Aliquot Shipped
          M   Aliquot Missing Due to Destroyed Sample

 While - Field Copy   Pink - Lob Copy  Yellow - SMO Copy  Gold - Lab Copy tor Return to SMO
                                       43

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                      7.0  Field Measurement Quality Control Checks
Field measurements are those made by the helicopter
sampling crews, the ground sampling crews, and the
field  laboratory  crews.  The QC checks  associated
with  these measurements are  described in Sections
7.1, 7.2, and 7.3, respectively.
7.1  Quality Control Checks for
     Measurements Taken by Helicopter
     Crews

The  lake  site  measurements taken  by helicopter
crews  consist  of  three  Hydrolab determinations
(lake-water  temperature,  pH,  and  conductance),
Secchi disk  transparency, air  temperature,  and site
depth.  All  measurements  are  recorded  on  the  lake
data form.

7.1.1  Hydrolab
The  Hydrolab instrument is used  to measure in situ
lake-water temperature, pH,  and conductance.

The  QC  procedures consist  of calibrating  the
instrument at a  designated clean  work station at the
base  (or remote) site before and  after each  daily
sampling excursion. Any  instrumental drift  between
calibrations  is  monitored.  These  procedures  are
adapted from Hydrolab (1985).  The following  is  a
summary of QC  procedures for the Hydrolab.

  •  Lake-water  temperature   -  There  is  no
     calibration control for  temperature.  The
     instrument  is calibrated at the factory and should
     be accurate to 0.2°C. The accuracy is checked
     each  day  against  a  National  Bureau of
     Standards  (NBS)-traceable  thermometer,  and,
     if an  error of  1°C or  more is  found,  the
     manufacturer  should be  consulted  and  the
     discrepancy should be recorded on the  lake  data
     form. An error of this  size  usually indicates a
     malfunction of  the  instrument. If a  reserve
     Hydrolab is available that meets specifications,
     the faulty Hydrolab is replaced.

  •  pH  - Following the  daily  calibration  with
     commercial standard buffer solutions,  a QC
     check  sample   (QCCS) of  CO2-saturated
     deionized water  is measured. The QCCS has a
    theoretical  pH  value  of  3.91 at  standard
    temperature and pressure. The  instrument drift
    is determined  by remeasunng the QCCS after
    completion of all  sample analyses. If  either
    QCCS reading deviates from the theoretical pH
    by  more  than  ±0.15  pH unit,  the data tag
    qualifier "Q"  (Table  12-1) is recorded  on the
    lake data form.

   •   Conductance  -  A  KCI  standard of  147
       uS/cm  is used to calibrate the conductance
       function. The same QCCS used to check the
       pH function of the Hydrolab is used to check
       the  conductance function.  The allowed error
       on the  QCCS, which has a standard specific
       conductance value of  50 pS/cm, is  ±20
       uS/cm. This error is 1  percent of the highest
       reading on the conductance meter scale used
       (2,000 uS/cm).

7.7.2  Secchi Disk Transparency
There  are  no applicable QC  checks for  this
measurement.

7.7.3  Air Temperature
Ambient air temperature is measured  by  an outdoor
thermometer affixed to the outside of the helicopter.
The temperature is recorded  on the  lake data form.
There  are  no applicable QC  checks for  this
measurement.

7.7.4  Srte Depth
Ideally, the  sampling site should be the deepest part
of the lake.  This point  is located  with an electronic
depth  recorder that is  mounted  to  the  helicopter.
Once  daily, at the first lake to be sampled, the depth
recorder  is checked  against a calibrated sounding
line.  The depth,  which  is  measured  in feet,  is
recorded on the lake data form, where it is converted
to meters by multiplying the measurement in feet by
0.3048.

7.7.5  Elevation
Site elevation  is taken  from  the  map reading. This
elevation is  confirmed  by  the helicopter  altimeter,
which is  periodically checked by the  pilot. The map
contour  reading  and  the  altimeter reading  are
recorded on the lake data form.
                                                45

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7.1.6  Lake Location
The lake location is determined from map coordinates
(i.e.,  latitude and longitude) and is confirmed by the
loran-C instrument  readout and by a comparison of
observed and  map topographic  features.  The map
coordinates and  loran-C readings are  recorded  on
the lake data form.

7.2  Quality  Control Checks for
      Measurements Taken by Ground
      Crews
Ground  crew samplers  measure   lake-water
temperature,  pH,  Secchi disk  transparency,  air
temperature, and site depth. The  ground crew does
not use a Hydrolab. All measurements  are  recorded
on the lake data form.

7.2.7  Lake-Water Temperature
A  temperature meter  is calibrated before  the  first
sampling  excursion of  the  day  by measuring the
temperature  of an ice  slurry  (4°C)  and  a water
sample (15 to  20°C) with the thermistor and with an
NBS-traceable thermometer.  If  the thermistor
readings  differ from the  thermometer  readings  by
0.5°C or more, the problem with  the meter must be
identified  and   resolved  by  following  the
manufacturer's instructions. A calibration check at the
lake  site  is done by comparing  the reading  of the
thermistor with that of  a field  thermometer in  a
sample of lake surface  water collected in  a  plastic
beaker. If the two readings differ by 2°C or more, the
in situ readings are qualified  on the lake data form.

7.2.2  pH
No QC  checks are available  for  pH determinations
that are made with pH indicator strips.

7.2.3  Secchi Disk Transparency
There are  no  applicable QC  checks  for  this
measurement.

7.2.4  Air Temperature
Ambient air temperature is measured by reading an
NBS-traceable  thermometer above the ground in the
shade. There  are no applicable  QC checks for this
measurement.

7.2.5  Site Depth
The samplers  locate the sampling site  by observing
shoreline  topography  and by  performing  a visual
inspection of  the  site  while they are  on  the  lake
surface. A calibrated, weighted sounding line is used
to determine  sampling  site  depth  in  feet.  The
measurement  is recorded on the  lake  data  form,
where it is converted  to meters by multiplying by a
conversion factor of 0.3048. Ideally, the sampling site
should be the deepest  part of the lake.
7.2.6  Elevation
Site elevation is taken from the map reading and is
recorded on the lake data  form.  There  are  no
applicable QC checks for this measurement.

7.2.7  Verification of Lake Location
The  map coordinates of  the lake are verified as
described in  Section  6.2.2.1.

7.3  Field  Laboratory Measurements
See the ELS-I QA plan (Drouse et al., 1986, Section
7.2) for QC  checks  for DIG, pH,  turbidity, and true
color determinations.
                                                46

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                                    8.0 Analytical Procedures
WLS-I  analytical procedures  are  identical  to  those     These procedures,  listed in  Table 4-1, are  described
used for ELS-I. The Las Vegas  laboratory  uses the     fully in the ELS-I  methods manual (Hillman  et  al.,
same procedures for  sulfate  and nitrate  analysis of     1986)  and  are  summarized  in  the  WLS-I  methods
the EMSL-LV splits as the analytical  laboratory  does     manual (Kerfoot and Faber, 1987).
for analysis of the conventional nitrate, sulfate aliquot.
                                                 47

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                                9.0  Analytical  Internal Quality Control
Analytical  internal  QC  provisions  for  WLS-I  are
identical to those  for ELS-I.  They  are discussed fully
                             in Section 9.0 of the  ELS-I QA  plan (Drouse et  al.
                             1986) and are summarized in Table 9-1.
   Table 9-1. Summary of Internal Quality Control Checks for Analytical Methods, Western Lake Survey -Phase I
            Parameter
        QC Check
        Control Limits
                                                                                           Corrective Action3
ANC, BNC, pH 1.

2


3.

4

5



6
Ions (CI", total dissolved F", la.
NH4f. NO3", SO42'

Titrant Standardization
cross-check
Electrode calibration
(Nernstian response
check)
pH QCCS (pH 4 and 10)
analysis
Blank analysis (salt spike)

Duplicate analysis



Protolyte comparison
Initial QCCS analysis
(calibration and
verification)
1.

2.


3.

4.

5



6
la,


Relative differences < 5%

Slope = 1.00 ±0.05


pH 4 = 4.00 ±005
pH 10 = 10 00 ± 0.05
[Blank] < 1 0 ueq/L (ANC
and BNC)
RSD <10% (ANC and
BNC) + 0 05 pH unit
(pH)

See Hillman et al (1986)
,b The lesser of the 99% CI
or value given in
Table 9-2 of Drouse et
1

2


3

4

5.



6
la.


Restandardized titrants.

Recalibrate or replace
electrode.

Recalibrate electrode.

Prepare fresh KCI spike
solution.
Refine analytical
technique,
analyze another
duplicate
See Hillman et al. (1986).
Prepare new standards
and
recalibrate
    Metals (total Al. extractable
        Al, Ca, Fe, K, Mg,  Mn,
        Na)
    SiO2, total P, DIG, DOC,
        Conductance
ib.  Continuing QCCS anal-
     ysis (every 10 samples)
2a  Detection limit determi-
     nation (weekly)

2b.  DL QCCS analysis (daily,
     metals and total P only)
                                                               al  (1986)
2a  Detection limits given in
     Table 4-1

2b  % Recovery  = 100 ±
     20%
!b  Recalibrate Reanalyze
     associated samples.
2a,b.Optimize instrumentation
     and technique.
3 Blank analysis






4 Duplicate analysis



Ions, (CI", total dissolved F", 5 Matrix spike (except ext.
NH/, NO3", SO42~) Al,
DIC, and conductance




Metals (total Al, extractable 6 Resolution test (CI",
Al, Ca, Fe, K, Mg, Mn, NO3 ,
Na) SO4 only)
SiO2, total P, DIC, DOC,
conductance
3a. Blank < 2 x DL (except 3a,b. Determine and eliminate
conductance)



3b. Blank < 0 9 nS/cm
(conductance only)
4. Duplicate precision 4.
(%RSD)
limits given in Table 4-1

5. % Recovery = 100 ± 5.
1 5%





6 Resolution >60% 6




contamination source
Prepare fresh blank
solution Reanalyze
associated samples


Investigate and eliminate
source of imprecision.
Analyze another
duplicate
Analyze 2 additional
spikes.
If one or both outside
control limits, analyze all
samples in that batch by
method of standard
additions.
clean or replace 1C
separator column.
Recalibrate.


   a To be followed when QC check is outside control limits.
                                                        49

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                             70.0 Performance and System Audits
10.1  Performance Audit Samples

Field  audit samples  are used  as part of the  QA
activities  of  WLS-I.  The  purpose  of field  audit
samples is to identify  problems  affecting data quality
that may occur during  sample processing, shipment,
or analysis. These  problems could  include sample
contamination,  sample  degradation,  solvent
evaporation,  and  improper or  inaccurate  sample
analysis.

The  audit  samples are  shipped to  the  analytical
laboratories from the field bases as though the audit
samples were ahquots of routine lake samples.  Every
attempt  is  made  to  ensure  that  the  analytical
laboratory does not recognize the audit samples as
different from the routine  lake  samples. As a result,
the audit  samples  are double blind  to the  analytical
laboratory.

There are two types  of  field  audit  samples:  field
synthetic  audit  samples and   field  natural  audit
samples.

70.7.7 Field Synthetic Audit Samples
The  field  synthetic audit samples are prepared at a
central laboratory and are sent to the field laboratory
to be processed through all  the  filtration  and
preservation steps and to be labeled as though they
were authentic lake samples. Thus,  they are single-
blind  samples  to   the  field  laboratory  and,
concurrently, double-blind samples to the  analytical
laboratory.

The  desired composition of the field synthetic audit
samples is shown in Table 10-1 and  reflects the low
concentrations of analytes expected  in actual WLS-I
lake samples.  Synthetic lots are prepared in bulk as
stock solutions.  The stock solution  is diluted to the
desired  concentration and the dilute  sample  is
shipped  to the  field   laboratories one day  before
aliquot processing is scheduled.

70.7.2 Field Natural Audit Samples
Waters  collected from Big Moose  Lake  in  the
Adirondack Mountains, from Lake Superior at Duluth,
Minnesota,  and  from  Bagley Lake   in the Cascade
Range of Washington State are used  as natural audit
samples for the  survey.  The  waters of Big Moose
Lake are acidic; the Lake Superior waters represent a
buffered  system;  and  Bagley Lake  represents a
partially buffered  system.  In  bulk, these  natural
samples are  passed  in  50- to  200-L increments
through a  0.45-u-m filter  into 2-L bottles  and  are
maintained  at  4°C  to   minimize  changes  in
composition. These 2-L quantities are the individual
natural audit samples that are included in the sample
batches.

70.7.3 Application of Field Audit Sample Data
Data are obtained from the analyses of the field audit
samples for the following purposes:

  •  to judge the  performance  of the field  bases in
     the processing and shipment of samples

  •  to judge the continued capability of the analytical
     laboratories to analyze the samples properly

  •  to establish a statistically  valid estimate of the
     overall bias and precision of the analyses

  •  to establish a statistically  valid estimate of the
     stability of a typical lake sample when  stored at
     4°C  by evaluating the natural lake sample over
     the period of the study.

Acceptance  windows  are  established  for  the
measurement of each parameter in the audit samples.
A preliminary determination of the size of the windows
is based  upon  the  information available for each
analytical method at the time the study is initiated; the
final  determination is  made after data  verification is
completed. If 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 calls  the  analytical
laboratory or field  base, whichever is  appropriate, to
seek corrective  action. Data  for routine  samples
analyzed with the  audit samples also are  checked to
determine  if they  were affected  by  the  problem.  If
they  were affected, reanalysis  of  the samples in
question may be requested. The establishment of the
acceptance windows is summarized in Section 11 of
this QA plan and is described in more detail in Drouse
et al. (1986, Section 11).

Approximately 75  synthetic audit samples  and  150
natural-water audit samples are  scheduled to  be
                                                  51

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                         Table 10. 1. Desired Composition of Field Synthetic Audit
                                  Samples, Western Lake Survey - Phase I
                                    Parameter
   Concentration
                                                                         Units
Acid-Neutralizing Capacity (AIMC)a
Al (total and extractable)
Base-Neutralizing Capacity (BNC)a
Ca
cr
Conductance^
DIC*
DOC
F", total dissolved
Fe
K
Mg
Mn
Na
NH/
NCV
P, total
pHa
Si02
S042-
10-50
001-0.10
10-50
0.1-1
0.1-1
1-50
0.1-1 0
0.1-1 0
0 01-0.05
0.02-1 0
0 1-1
0.1-1
002-1 0
0 5-3
001-0 50
001-050
0 005-0 03
4-5
1-5
1-5
lieq/L
mg/L
neq/L
mg/L
mg/L
uS/cm
rng/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
PH
mg/L
mg/L
                         a These parameters are related, and they affect the analytical results of
                           one another
                         b To be determined by concentration of other parameters.
                         Note Mass balance  (anions versus cations) in  the composition of field
                              synthetic audit  samples must be maintained  Nitrogen/phosphorus
                              ratio must be reasonable (10/20).
processed  during  WLS-I. A statistical  evaluation of
the audit data, including the setting of audit windows,
should provide  a  good  estimate  of  the bias  and
precision of the  analytical methods for each  required
measurement. Furthermore, any change over time in
analytical results for the  natural-water audit  samples
without  a corresponding  change  in  results  for the
other audit  samples  can  be attributed  to  lack of
analyte stability.  The findings of a comparative study
between  audit sample  types will provide an  estimate
of the true maximum holding times allowable  for each
type of analyte.
10.2 Quality Assurance System Audits
      (On-Site  Evaluations)
The system audits consist of qualitative evaluation of
field and  analytical  laboratory facilities,  equipment,
and  operations  such  as  record  keeping,  data
reporting, and QC  procedures.

70.2.7  Field Operations On-Site Evaluation
Each  field  base and helicopter  sampling crew can
expect  at  least one on-site  evaluation  during the
course  of  the  sampling effort.  The  purpose of the
on-site inspection  is  to  review  the  sampling
procedures, field base operations, and  QA efforts;  in
addition, as many of the 60 ground  sampling crews
as possible will  be evaluated in  the field.  The on-site
evaluation  for each  field base and its  corresponding
sampling crews should  be  conducted as soon  as
possible   after  the  start of  operations.  The
questionnaire in Appendix A of this document is used
to assist in the evaluation of ground sampling crews.
The questionnaire given in Appendix  C of Drouse  et
                                                   52

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al. (1986) is used for the evaluation of field base and
helicopter crews.

The  field auditor  conducts an in-depth  review of all
field  operations.  This  includes,  but is not limited to,
(1) interviewing the field base coordinator, the Forest
Service field  manager,  and the  field  laboratory
supervisor;  (2) observing the field base operations
(including field laboratory operations); (3) interviewing
sampling crews;  (4) accompanying one or more of
the sampling crews during a sampling excursion; and
(5) writing  a summary  report that includes  results.
observations, and recommendations. If there are any
problems,  the  evaluator must  either  have  the
individuals involved correct them or must bring  them
to the attention  of the  field  base  coordinator  for
resolution.

70.2.2 Analytical Laboratory  On-Site Evaluation
Each analytical laboratory participating in  WLS-I can
expect a  minimum  of  two  m-depth,  on-site
evaluations conducted by the EPA QA manager or his
authorized  representative.  The  questionnaire in
Appendix D of Drouse et al. (1986) is used to assist
in the on-site  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 analyses and  before the actual
survey  analytical work  begins.  The  PE  samples
contain up to the maximum  number of analytes for
which measurement  is  required,   in the  expected
concentration  ranges.  The PE  sample results are
scored using the ELS-I  Preaward Score Sheet given
in Appendix  E  of  Drouse et  al.  (1986).  Grading
emphasizes analytical accuracy,  but  a  substantial
portion of  the grade  depends  on  meeting the  QA,
internal QC, reporting, and deliverable requirements.

The  auditor summarizes  all  observations in an on-
site  laboratory  evaluation report  and  brings all
problems to the attention of  the laboratory  manager
for corrective action.

The  second  on-site   laboratory  evaluation is
conducted after  approximately  one-third  of  the
WLS-I analyses  have been  completed. During the
second  on-site  evaluation,  QA  sample  (audit,
duplicate,  and blank)  data and  QC data received to
date  are reviewed. The  laboratory  questionnaire  is
updated, if  necessary, and all changes since the first
on-site  evaluation are noted. An  on-site  laboratory
evaluation  report  is written  for this and for  each
additional  on-site laboratory evaluation.
                                                  53

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                                    1 1.0 Acceptance Criteria
Acceptance criteria for audit sample values are the       where:
same for WLS-I as for ELS-I. These criteria are               Z is the standard normal variate, having a normal
discussed fully in Section 1 1  of the ELS-I QA plan            distribution with a mean of 0 and a variance of 1 .
(Drouse et al., 1986). The limits of the windows are           ^ is a variable that has a chi-square distribution
determined by using a t-statistic (t).                         with r degrees of freedom, and Z and n are
                                                         independent.

                    Z
               t =  - is a Students t
                                                 55

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                                 12.0 Data Management System
The purpose of the data base management system is
to assemble, store, and edit data generated during
WLS-I  and during other NSWS  surveys. The  data
base management system  also  is  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 other survey
activities 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 final data set. These four data sets
make up the WLS-I data base and  are  discussed in
the following subsections. Individual, system, and file
passwords  protect all data sets from unauthorized or
accidental access.

12.1  Data Set 1  - The  Raw Data Set

At Oak  Ridge National  Laboratory (ORNL), the field
data,  which  are reported  on   the lake data and
batch/QC forms (forms 1 and 2, respectively), and the
analytical  laboratory  data,  which are   reported on
analytical data forms 11, 13, 18,  19, 20, 21, 22, and
23 (see Drouse et al., 1986, Appendix A), are entered
into the raw data base.  Data entry operators use the
Statistical Analysis System  (SAS) for  this purpose.
Analytical data from form 26, which is  used only by
the QA staff for confirmation/reanalysis procedures,
are not entered into the raw data set  (see Section
12.2). The  raw  data set includes all  analytical results
and data qualifiers (see Table 12-1).

The SAS  full-screen editor procedure  is used  to
provide  gross error checking as data are entered. All
data are entered  into two separate data sets by two
different operators.  For the NSWS  data base,  a
program (COMPARE) has been  developed in SAS to
compare the  two data sets and  to  identify any
inconsistencies.  The advantage  of this  double entry
and  comparison  process is  that entry errors  are
removed from the system. The  field personnel and
the analytical laboratories also send copies of the field
forms  and  data packages, respectively, to  the
EMSL-LV QA  staff  for concurrent data  analysis.
Thus, receipt of the field and analytical data forms by
the QA  staff verifies that all forms 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 communication with
the field personnel.  The checks for identifying  errors
are given in Sections 13.1.1 and 13.1.2. If the data in
question  have not been  entered  yet by  ORNL, the
changes are included in the raw data set.  If the data
have been entered already, the changes are included
in subsequent data sets.
12.2  Data Set 2 - Verified Data  Set

When  the field  and analytical  laboratory data are
transmitted through  magnetic tapes and the raw data
are made available to  the EMSL-LV  QA group,  all
data are evaluated  and  verified  as  described  in
Section 13.0. The data  are processed by "Automated
Quality Assurance Review, Interactive Users System"
(AQUARIUS), an on-line QA system  developed  by
the  EMSL-LV  QA staff.  Reports  generated  by
AQUARIUS range in subject from a complex protolyte
analysis to simple external/internal blank  checks for
QA purposes. AQUARIUS generates  "tuples" that
direct ORNL to mark problem data with flags (given in
Table  12-2),  as deemed  necessary  by  the EMSL-
LV  QA staff. Tuples are defined as SAS observations
generated by  an  exception  program  or manually
created by an auditor,  which are intended either to
change or to annotate a value in a copy of Data Set 1
(the raw data set).  Because the raw data set  is  never
changed, a revised  data'set  (the  verified data set) is
generated. Tuples have a fixed number of fields that
specify the batch, the sample, and the variable to  be
flagged, modified, or verified.  The tuples  are sent to
ORNL via magnetic tape and are entered  into the
verified data  set.  Tuples should only have  to  be
transferred twice, once  for initial verification and once
for  final  verification. The originally reported  data
values are maintained in Data Set 1 (the raw data set)
for  a historical record.
In  addition to the standard QA analyses,  AQUARIUS
is  used  to  generate  numerous  printouts that are
supplied to the QA  manager  to indicate  intra-
laboratory,  field  interlaboratory,  and  analytical
interlaboratory  bias, as  well as  discrepancies  in
blanks, duplicates,  audits, and other QA/QC samples.
The overall outcome is a verified data set in  which
any suspicious  values  or observations are  qualified
with a flag (listed  in Table 12-2). When  a datum is
not reported,  the missing value code "."  is assigned
                                                  57

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             Figure 12-1. Data management, Western Lake Survey - Phase I.
/F.eldB^eS.esA

\^ Laboratory J
                                                                    Laboratones
                                       / Data Entry by
                                     7    ORNL


                                       Batch Reports,
                                       Range Checks
/






4 	
^
W


^



Verification by
FM^I I \/ OA



Preliminary

ERL-C






^^^^•n





—^,




^



Validation by
ERL-C
and by EMSL-C


                                                 *  Data Tracing System
(in numeric fields only) with an  accompanying data
qualifier for explanation. The QA personnel coordinate
with  the  field   bases  and  with  the  analytical
laboratories 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 ORNL provides the ERL-
                 C staff with a computerized version of the verified
                 data  set through the computing facility at Research
                 Triangle Park  (RTF),  North Carolina,  the validation
                 process can  be completed. The  validation  process
                 increases  the  overall  integrity of  the  data  base  by
                 using all the QA/QC  information available  to evaluate
                 all data for internal and regional consistency.

                 In the  validation  process,  known  relationships  in
                 aquatic chemistry and limnology are used to identify
                 intrasite sample inconsistencies within  data  for a set
                                                   58

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                Table 12-1. National Surface Water Survey Laboratory/Field Data Qualifiers (TAGS),
                           Western Lake Survey - Phase I

                   Qualifier                                   Indicates

                      A       Instrument unstable
                      B       Redone, first reading not acceptable
                      C       Instruments, sampling gear not vertical in water column
                      D       Slow stabilization
                      E       Hydrolab cable too short
                      F       Result outside QA criteria  (with consent of QA manager)

                      G       Result obtained from method of standard additions
                      H       Holding time exceeded criteria
                      J       Result not available; insufficient sample volume shipped to laboratory from the field


                      K       Result not available; entire aliquot not shipped
                      L       Not analyzed because 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/QC criteria

                      R       Result from reanalysis
                      S       Contamination  suspected
                      T       Leaking container
                      U       Result not required by procedure; unnecessary

                      V       Anion/cation balance outside criteria because of high DOC
                      W       % Difference (%D) calculation (Form 14) outside criteria because 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
                      <       Measurements taken at < 1.5 m (in situ lake measurement only)
of variables.  Intersite validation consists  of comparing
single site values with values for adjacent sites within
a region. Data for groups of sites  are compared and
mapped  to   check  for consistency.  The  validation
process is summarized further in Section 14.0. After
undergoing this reviewing process, the  data, lake  by
lake, are transferred to the validated data base.


12.4 Data  Set 4  - The Final Data  Set
 The calculation of population  estimates is  difficult if
the data  set  contains missing values  (Linthurst et al.,
1986).  To resolve the problems  in the  validated  data
set that result from missing values,  a final data set
(Data Set 4)  is prepared. This data set  is modified  by
averaging the  field routine/duplicate  pair values that
are  within  desired  precision limits and  by  replacing
analytical  values  determined to  be  in  error  during
validation.  The  values  used  for substitution  are
determined in  one  of several ways,  as described in
Section 15.0.
                                                         59

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Table 12-2. Data Qualifiers (FLAGS) for the Verified Data Set, Western Lake Survey  - Phase I
   AO    Anion/cation percent ion balance difference (%IBD) is outside criteria for unknown cause.
   A1    Anion/cation percent ion balance difference (%IBD) is outside criteria because of nitrate contamination
   A2    Anion/cation percent ion balance difference (%IBD) is outside criteria because of anion (other than nitrate)
          contamination.
   A3    Anion/cation percent ion balance difference (%IBD) is outside criteria because of cation contamination.
   A4    Anion/cation percent ion balance difference (%IBD) is outside criteria because of unmeasured organic
          protolytes (fits Oliver Model).
   A5    Anion/cation percent ion balance difference (%IBD) is outside criteria because of possible analytical
          error - anion concentration too high (flag suspect anion)
   A6    Anion/cation percent ion balance difference (%IBD) is outside criteria because of possible analytical
           error - cation concentration too low (flag suspect cation)
   A7    Anion/cation percent ion balance difference (%IBD) is outside criteria because of possible analytical
           error - anion concentration too low (flag suspect anion).
   A8    Anion/cation percent ion balance difference (%IBD) is outside criteria because of possible analytical
          error - cation concentration too high (flag suspect cation)

   BO    External (field) blank is above expected criteria for pH, DIC, DOC, conductance, ANC, and BNC
          determinations
   B1    Internal  (laboratory) blank is  >2 x CRDL for pH, DIC, DOC, conductance  ANC, and BNC determinations.
   B2    External (field) blank is above expected criteria and contributed  >20% to sample values   (This flag is not
          used for pH, DIC, DOC, ANC,  or BNC determinations )
   83    Internal  (laboratory) blank is  >2 x CRDL and contributes > 10% ;o the sample concentrations  (This flag is
           not used for pH, DIC, DOC, ANC, or BNC determinations )
   B4    Potential negative sample bias  based on internal (laboratory) blank data
   B5    Potential negative sample bias  based on external (field) blank data.

   CO    Percent conductance difference (%CD) is outside criteria for unknown cause (possible analytical error - ion
           concentration too high)
   C1    Percent conductance difference (°oCD) is outside criteria because of possible analytical error - anion
          concentration too high (flag suspect anion)
   C2    Percent conductance difference (%CD) is outside criteria because of anion contamination
   C3    Percent conductance difference (%CD) is outside criteria because of cation contamination.
   C4    Percent conductance difference (%CD) is outside criteria because of unmeasured organic ions (fits Oliver
          Model).
   C5    Percent conductance difference (%CD) is outside criteria because of possible analytical error in
          conductance measurement.
   C6    Percent conductance difference (%CD) is outside criteria because of possible analytical error - anion
          concentration too low  (flag suspect anion)
   C7    Percent conductance difference (%CD) is outside criteria because of unmeasured protolyte  ions (does not
          fit Oliver Model)
   C8    Percent conductance difference (%CD) is outside criteria bacause of possible analytical error - cation
          concentration too low  (flag suspect cation)
   C9    Percent conductance difference (%CD) is outside criteria because of possible analytical error - cation
          concentration too high (flag suspect cation).

   D2    External (field) duplicate precision exceeded the maximum expected percent relative standard  deviation
          (%RSD), and the routine and duplicate sample concentrations both were > 10 x CRDL
   D3    Internal (laboratory) duplicate precision exceeded the maximum contract-required percent relative standard
          deviation (%RSD), and the routine and duplicate sample concentrations both were 2 10 x CRDL

   FO    Percent conductance difference (°'cCD) exceeded criteria when Hydrolab conductance value  was substituted.
   F1    Hillman/Kramer protolyte analysis program indicates field (Hydrolab) pH problem when  Hydrolab pH value
          is substituted for field laboratory pH
   F2    Hillman/Kramer protolyle analysis program indicates unexplained field pH or DIC problem when Hydrolab
          pH value is  substituted for field laboratory pH.
                                                                                               (continued)
                                                      60

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Table 12-2 (Continued)
   F3     Hillman/Kramer protolyte analysis program indicates field problem - field laboratory pH
   F4     Hillman/Kramer protolyte analysis program indicates field problem - field laboratory DIC
   F5     Hillman/Kramer protolyte analysis program indicates unexplained field problem - pH or DIC

   HO     The maximum holding time criteria were not met.

   L1     Instrumental detection limit (IDL) exceeded CRDL and sample concentration was < 10 x IDL.

   MO     The method used to obtain the value is not acceptable according to the IFB contract.

   NO     Audit sample value exceeded upper control limit.
   N1     Audit sample value was below lower control limit.

   PO     Hillman/Kramer protolyte analysis program indicates laboratory problem - initial pH (ANC)
   P1     Hillman/Kramer protolyte analysis program indicates laboratory problem - initial pH (BNC).
   P2     Hillman/Kramer protolyte analysis program indicates laboratory problem - unexplained - initial pH (ANC
          or BNC)
   P3     Hillman/Kramer protolyte analysis program indicates laboratory problem - initial DIC.
   P4     Hillman/Kramer protolyte analysis program indicates laboratory problem - air-equilibrated pH or DIC
   P5     Hillman/Kramer protolyte analysis program indicates laboratory problem - unexplained - initial pH or
          DIC
   P6     Hillman/Kramer protolyte analysis program indicates laboratory problem - ANC determination
   P7     Hillman/Kramer protolyte analysis program indicates laboratory problem - BNC determination

   Q1     QCCS value was above contractual criteria.
   O2     QCCS value was below contractual criteria
   03     Insufficient number of QCCSs were measured
   Q4     No QCCS analysis was performed
   Q5     Detection limit QCCS was not 2 to 3 times the CRDL, and measured value differed  more than 20 percent
          from theoretical concentration.

   SO     Matrix spike percent recovery (%REC) was above contractual criteria
   S1     Matrix spike percent recovery (%REC) was below contractual criteria.

   XO     Questionable data point.  Recommendation is to remove point from subsequent data sets and from any
          statistical analyses.
   X1     Extractable aluminum (ALEX)  > Total aluminum (ALTL) by 0 01 mg/L or more  (ALEX > 3 X CRDL and
  	ALEX >  ALTL by 0 01 mg/L or more)
                                                   61

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                             73.0  Data  Evaluation and Verification
Data  review  begins with the daily  telephone  calls
made to each field laboratory and analytical laboratory
(1) to  ensure that QA/QC guidelines are  being
followed,  (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  verbally,  by
computer, or  by  TELEFAX  from  the  different
laboratories. The  preliminary data  are evaluated  by
comparing the QA sample data to acceptance criteria.

Responsible parties are  notified of problems, and all
interactions  are recorded in  bound notebooks.  If
necessary, a letter of documentation is sent.

As the field  and  analytical  laboratory  data  are
received by the  EMSL-LV  QA staff, all  data  are
evaluated  on  the  basis of the  available QA/QC
information.  The established and  organized  review
process described here  is used  for this process. The
objective of the data verification process is to identify
data of unacceptable quality and to correct them, flag
them, or target them for  possible sample reanalysis or
for elimination  of the data  from future data sets.
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 subsections.

13.1  Field Data  Review

As a result of the complexities involved in this survey,
such as the calibration study, the WLS-I data require
more  extensive review than  did the ELS-I data. The
two data  forms filled out by  field personnel  are
reviewed individually for completeness of data, and
then the two forms are compared.

13.1.1  Lake Data Form
The following checks are required on data on the lake
data form:

   •  Hydrolab  Calibration Data  -  Compare  pH and
     conductance calibration  data  on the lake  data
     form to data on the Hydrolab calibration forms to
     ensure that  initial calibration, initial QCCS,  and
     final QCCS criteria are met; if the criteria are not
     met, insert appropriate data qualifiers.

   • Stratification  -  Check that stratification  data
     were collected if the  temperature at the surface
     of the lake minus the temperature at the bottom
     was greater than 4°C.

   • Map Coordinates -  Check  that  the loran-C
     readings match the map coordinates.

   • Site  Drawing - Check that  the  lake  outline is
     drawn,  that  the  sample site and any  inlets or
     outlets  are  marked, and that the map elevation
     and altimeter readings are noted.

   • Signatures - Check that all  required  signatures
     are present.

   • Secchi  Disk  Transparency  -  Check  that  the
     Secchi  disappearance depth is greater than or
     equal to the Secchi reappearance depth.

   • Conversion Factors - Check that the  site depth
     has  been  converted  correctly  from  feet  to
     meters.

   • Comments  - Check if any comments  noted  by
     the  sampling crew need additional explanations
     or if data  qualifiers  need  to be  applied to the
     data.

13.1.2 Batch/QC Form
The following  checks  must be completed on  the
batch/QC form:

   • Trailer  Duplicate  - Check that this sample is
     recorded  on the bottom of the batch/QC  form
     and  that  it  has  a sample code  of TD with a
     sample ID of Dup. This sample  should  have a
     lake  ID that  matches a routine lake sample  ID
     within that batch.

   • Field Laboratory QA Samples - Evaluate results
     of   DIG,   pH,   turbidity,  and  true  color
     measurements of field routine duplicate pairs in
     accordance with associated acceptance criteria
     for precision; evaluate field audit  samples  in
     accordance with  associated acceptance criteria;
     check  results  of turbidity  and  true  color
                                                 63

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    measurements  of  field  and trailer  blanks for
    indications of contamination.

  • Field  Laboratory QCCS  -  Evaluate results  of
    DIG, pH, turbidity, and true  color measurements
    of QCCSs in accordance with QCCS criteria.

  • Split Codes - Split samples go  to  ERL-C and
    to  EMSL-LV.  Check  that  split  codes are
    correct.

  • Dates  -  Check that date processed and date
    shipped  are correct. Date  shipped  is  one day
    after date processed, except on weekends.

  • Analytical  Laboratory  -  Check that the
    analytical laboratory  to which  the batch  is
    scheduled to be shipped is the correct one. This
    is especially important  for tracking calibration
    study samples.

  • Lake  ID and  Sample  Code  -  Check  for
    consistency (i.e., that a field duplicate has  a field
    routine with the same lake ID; that audit samples
    are coded properly).

  • Signature  of  Field  Laboratory Supervisor  -
    Check that the form is signed.

  • Comments - Check if any  comments noted  by
    the sampling crew need additional  explanations
    or if data qualifiers need to be applied  to the
    data.

13.1.3  Comparison of Lake Data  Form to
       Batch/QC Form
  • Identification  Numbers and  Codes - Check that
    the lake  IDs,  batch IDs, sample IDs,  and sample
    codes on both forms match.

  • Hydrolab pH -  Compare the  pH reading  taken
    at 1.5  m (recorded on the lake data form)  to the
    field laboratory pH reading on the batch form.

  • Calibration Study  Lakes - Check  batch IDs,
    sample  IDs,  lake  IDs,  and sample codes for
    calibration lake samples. Because samples with
    the same lake ID are included in more than one
    batch, sample codes must be  checked carefully;
    therefore,  an  extensive  tracking  system  is
    required. The calibration study  is discussed in
    Section 5.2.

  • Data  Qualifiers  and Comments -  Check that
    comments are reasonable  and  that they  are
    consistent between forms.

  • Crew  ID -  Check  for  correct  transcription  of
    crew ID  from the lake data form to the batch/QC
    form.

Data anomalies are reported to the  field laboratory
coordinator for review,  and data-reporting errors are
transmitted to ORNL  to be  corrected  before the
improper data are entered 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

73.2.7  Preliminary Review of Sample Data
       Package
The  sample data packages  are  reviewed for
completeness,  internal  QC  compliance,  and
appropriate use  of  data qualifiers. The Data Package
Completeness Checklist  (like that shown  in Appendix
F of  Drouse et al. (1986) but with an  appropriate title
change) is used to ensure 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 the
Sample Management  Office  (SMO) or  ORNL  is
notified. Comments provided in the cover  letter also
are reviewed to  determine their effect 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 have
been met for the purpose of  payment.

73.2.2 Review of QA/QC Data
The  analytical  data reported on  data  forms are
entered into the raw  data set by ORNL  as the data
packages  are received.  A magnetic  tape  containing
raw data is sent to the EPA for the IBM  3081 at the
National Computer Center (NCC) at RTP. 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 the
exception-generating  programs listed  in  Table  13-1
are run.

The  WLS-I  Verification  Report  (like  that  shown  in
Appendix  G of Drouse et  al.  (1986)  but with an
appropriate title  change) is  completed. Outputs from
exception  reports,  original data, and  field  notebooks
are used in  this process. The verification report is a
worksheet  designed  to  guide  the  auditor
systematically through  the  verification  process.  It
explains how to flag data, tracks data resubmissions
and  reanalysis  and confirmation requests, lists the
steps  used to  help  explain the  QA  exceptions,
summarizes all modifications (e.g., value  changes)  to
the raw data base,  and lists  all verified sample data.

One hundred  percent  of  the  analytical data are
verified, sample  by sample and  for  the batch as a
whole.  A  routine lake  sample has to  meet the
anion/cation  percent  ion balance difference  (%IBD)
and  the percent  conductance  difference  (%CD)
criteria in order to be verified, unless  the discrepancy
can be explained by the presence of  organic species
                                                 64

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               Table 13-1. Exception-Generating and Data Review Programs, Western Lake Survey -
                       Phase I
                                           Program
                            Type
                Exception-Generating Programs:

                      1  = Audit Sample Summary                                    (FL.FN)
                      2  = Laboratory/Field Blank Summary                             (BH.BG.TB)
                      3  = Field Duplicate Precision Summary                            (R/D Pairs)
                      4  = Instrumental Detection Limit Summary                          (All Species)
                      5  = Holding Time Summary                                    (All Species)
                      6  = Percent Conductance Difference Calculations                    (All Species)
                      7  = Anion/Cation Balance Calculations                            (All Species)
                      8  = Internal Laboratory Duplicates
                      9  = Matrix Spike Summary
                     10  = Protolyte Analysis (DIG, DOC, pH, ANC, and BNC Data Evaluation)
                     11  = Reagent/Calibration Blanks and QCCS
                     12  = Comparison of Total Aluminum to Extractable Aluminum
                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
                      4  = Comparison of Form 2 and Form 11
                      5  = QA/QC Flag Summary
                      6  = Modified Gran Analysis Program
                        (pH and DIC)
                        (pH and DIC)
(as indicated by the protolyte analysis program) or by
an obvious correctable reporting error.

Additional flags  are  applied to  a given parameter  for
all the samples  within the batch when the batch QA
sample data do not meet the acceptance criteria  for
QA samples such as field blanks, field duplicates, or
field audit samples.  Each sample in the batch is also
flagged by parameter if  internal QC  checks such  as
matrix spike recovery, calibration and reagent blank
analytical  results,  internal  (analytical  laboratory)
duplicate precision, instrumental  detection limits,
QCCS  analytical results,  and  holding times  do not
meet specifications. The final  source of flags is the
protolyte analysis  program. A  detailed description of
the evaluation of DIC, DOC, pH, ANC, and BNC data
by the protolyte analysis  program is  given in Section
13.2.4.  In all cases,  the  flags  that are generated  by
the computer programs  are  reviewed  by  the  auditor
for  reasonableness and  consistency  before  the  flags
are entered into the data base.

73.2.3  Computer Evaluation of DIC, 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 the sample. The DIC, 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
13.2.32)  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 CO2
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:

      C-|  = pH/DIC of "closed system" syringe
             samples (field laboratory)

      C2 = pH/DIC of "open system" samples
             (analytical laboratory)

      £3 =  pH/DIC of "air-equilibrated system"
             samples (analytical laboratory)
The third data pair (C$) is obtained on an aliquot that
has  been  equilibrated  with  standard air (300  ppm
CO2).  If  there  is  no  analytical  error,  the  three
calculated  alkalmities  should  agree  within
                                                    65

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experimental error.  The  precision  for  calculated
alkalinity  values of less than or  equal  to  100 peq/L
should be within ±10 ueq.L and within ±10 percent
for calculated alkalinity values greater than 100 ueq/L.
The  precision windows are  based on the estimated
precision of the pH and DIG measurements used in
the  calculations.   If  this  comparison indicates  a
potential  analytical error  (i.e., the precision  limit is
exceeded), the redundant  pH and DIG  values  are
compared to identify the  source  of  error. Further
evaluation of the QAQC information for the individual
data pairs  usually  identifies one  of  the  pH or  DIG
measurements within the outlier pair as the  source of
error. Because  of  the  redundancy in measurement,
for every sample that is analyzed,  an acceptable pH
or DIG value from one of the data pairs  should be
available to the data user.

13.2.3.2 Verification of Measured ANC --
The  measured ANC  is evaluated  by comparing it to
the average of  the acceptable calculated  values for
alkalinity  determined  during the evaluation  of pH  and
DIG.

Carbonate  Systems  - For a  true carbonate system,
the measured ANC should equal (within experimental
error)  the  calculated  alkalinity.  The  difference
between  measured ANC and the calculated alkalinity
should be within ±15 ueq L for calculated alkalmities
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  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 often  are present
and  can  make a significant  contribution to  the ANC.
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 to DOC,  and the 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,  if  it  is  assumed  that  significant
concentrations of  other (non-organic)  protolytes are
not  present and if there is no analytical  error.  The
precision  should be  within  ±15  peq/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
CO2  concentration. Therefore,  evaluation and
verification  of BNC  data  cannot  utilize  as  much
redundancy as that of ANC data. Only the initial  pH
and DIG values determined in the  analytical  laboratory
(data pair  C2, see Section 13.2.3.1) can be used to
calculate BNC  for  comparison with  the measured
value. As with ANC, other protolytes can contribute to
the measured BNC. An  estimate of CO2-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  peq/L should  be
within  ±10 peq  L and within ±10 percent for larger
values.  If  the calculated  acidity  is greater than the
measured BNC.  an analytical error in the pH, DIG, or
BNC determination is indicated.

The pH and  DIG 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.

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,
as  an additional  check  of the data, the  calculated
values of  alkalinity and acidity can be combined and
can  be compared to the sum of  the measured ANC
and  BNC.  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 nmole/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
12-2) on  the basis of  the  data checks  described
above to indicate the source of problems.
                                                  66

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13.2.4 Follow-up with Analytical Laboratories
After  all  data have  been  reviewed,  the analytical
laboratories  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.  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.

73.2.5 Preparation and Delivery of Verification
      Tapes
The steps identified  in sections 13.2.2 through 13.2.4
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 subsequently
are sent to ORNL. There, the new data are entered
into the raw data set to correct  and flag the  original
data. These steps may have  to  be repeated  several
times before all  the  data  are verified; however, the
aim is to have only two iterations.
                                                 67

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                                         74.0 Data Validation
The  system  of data validation  developed  for ELS-I     in  Section  14 of  the  ELS-I  QA  plan  (Drouse  et
also  is used  for WLS-I.   Data validation  is discussed     al.,1986).   A  flowchart  of  the  validation process  is
                                                        shown in  Figure  14-1.
            Figure 14-1. Flowchart of the data validation process, Western Lake Survey - Phase I.
                                              (Data Set 2  \
                                               Verified   J
\
1
r
Univanate
* Box Plots
* Probability Plots
1



1
r
4
Multivanate
* Principal Component
Analysis
* Cluster Analysis
* Tnlmear Plots
* Multiple Linear
Regression


Bivanate
* Scatter Plots
* Regression
Relational Comparative
Systema
Differenc
r Outliers T ^ r
*r 1 '
                   * Data Tracking System
                                                      c
    Flag or
    Modify
    Values
/  Data Set 3 \
\  Validated   I
                                                    69

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                              75.0  Development of a Final Data Set
The calculation of population  estimates is  difficult if
values are missing from the data set. A final data set
(Data Set  4) is prepared to resolve problems in  the
validated  data  set that result  from missing  values.
Data  Set  4 also is  modified  by averaging field
duplicate  values,  substituting  for  analytical  values
determined to  be  in  error  during  validation  (Figure
15-1),  and modifying  (i.e.,  adjusting to zero)  values
reported as negative  (except for ANC and BNC). The
values that have been modified for the final data set
are flagged with the appropriate data  qualifiers (see
Table  15-1).

15.1   Missing Data Substitution

Substitution  for missing values  is done in  one  of
several possible ways. Values from  duplicate samples
are used  when  available.  Redundant  analyses  are
performed  for pH,  DIG, and  conductance (see Section
13.2.4).  Redundant measurements on  split samples
(see Section 6.3.2.3.1) are  performed for metals and
other elements.  If a  duplicate  measurement is not
available, a comparable measurement is  chosen and
is substituted  for  the  missing  value.  A linear
regression  routine  is  used  for  this  purpose.  If
redundant measurements  are not available or are not
acceptable,  observed  relationships   with other
variables  (e.g.,  sodium and chloride)  are  used to
calculate a  substitution value from the available  data.
The  last option for identifying a substitution value is to
use  the stratum  mean  within  the subregion. All
substitution  values are  examined  a second time for
acceptability before they are included in the final data
set.  Substituted  values are flagged  as such 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. Averaged  values are flagged in the final
data set.
                         Table 15-1. Validation Data Qualifiers (Flags) for the Final Data
                                   Set, Western Lake Survey - Phase I
                           UO   Known error based on relationships with other variables or on
                                  impossible values; substitutions were made in Data Set 4.

                           U1   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
                                  measurement of the lake sample.

                           V1   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.
                                                    71

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     Figure 15-1. Development of Data Set 4, Western Lake Survey - Phase I.
                                  /Data Set  /
                                     3   /
                                                                                    No
                                 /Data Set  /

                                    4   /
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  likely
does  not affect data  analysis.  All negative values
modified in the final data set are flagged.
                                                  72

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                                        16.0  References
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.

Best, M. D., S. K.  Drouse, L. W. Creelman, and D. T.
  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., and A.  W.  Groeger. 1987. National
  Surface  Water  Survey,  Western  Lake  Survey
  (Phase  I --  Synoptic Chemistry)  Field Operations
  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.

Costle, D. M., June 14, 1979b. Administrator's Policy
  Statement, Quality Assurance Requirements for All
  EPA Extramural Projects Involving Environmental
  Measurements.  U.S.   Environmental  Protection
  Agency, Washington, D.C.

Drouse, S. K.,  D. C. Hillman, L. W. Creelman,  and S.
  J. Simon, 1986.  National Surface Water  Survey,
  Eastern  Lake  Survey  (Phase  I  --  Synoptic
  Chemistry)  Quality Assurance  Plan.  EPA  600 4-
  86-008. U.  S.  Environmental Protection Agency,
  Las Vegas, Nevada.

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.

Hydrolab  Corporation,  1985 (revised). Operation  and
  Maintenance Manual  for  Hydrolab  Surveyor II.
  Hydrolab Corporation, Austin, Texas.

Kerfoot, H. B., and M.  L. Faber,  1987.  National
  Surface  Water  Survey,  Western  Lake  Survey
  (Phase I --  Synoptic  Chemistry)  Analytical
  Methods Manual. U.S. Environmental Protection
  Agency, Las Vegas, Nevada.
Landers,  D.  H.,  J. M.  Eilers, D. F. Brakke,  W.  S.
  Overton, P. E.  Kellar, M. E.  Silverstem,  R.  D.
  Schonbrod,  R.  E. Crowe,  R.  A.  Linthurst, J. M.
  Omernik, S. A.  Teague, and  E.  P.  Meier, 1987.
  Characteristics  of Lakes  in the  Western  United
  States.  Volume I. Population Descriptions  and
  Physico-Chemical  Relationships.   EPA/600/3-
  86 054a. U.S.  Environmental  Protection  Agency,
  Washington, D.C.
Linthurst. R. A.,  D. H.  Landers, J.  M.  Eilers, D.  F.
  Brakke, W.  S.  Overton, E. P. Meier, and R.  E.
  Crowe,  1986.  Characteristics 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.
Morris, F.  A., D.  V. Peck, M. B. Bonoff, and K.  J.
  Cabbie, 1986   National Surface  Water  Survey,
  Eastern  Lake   Survey (Phase   I  -- Synoptic
  Chemistry) Field  Operations  Report.  EPA  600/4-
  86-010. U.S.  Environmental  Protection  Agency,
  Las Vegas, Nevada.
Morris, F. A., D. V. Peck, D. C. Hillman, K. J. Cabbie,
  S. L. Pierett,  and W.  L.  Kinney, 1985.  National
  Surface  Water  Survey,  Western  Lake  Survey
  (Phase  I)  Field  Training and  Operations Manual,
  Internal  Report. U.S.  Environmental Protection
  Agency, Las Vegas, Nevada.
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.
Peck, D. V., R. F.  Cusimano, and W. L. Kinney, 1985.
  National  Surface Water Survey,  Western  Lake
  Survey  (Phase I -  Synoptic  Chemistry)  Ground
  Sampling Training and Operations Manual, Internal
  Report.  U.S. Environmental Protection Agency, Las
  Vegas, Nevada.
U.S. Environmental Protection Agency,  1980. Interim
  Guidelines and  Specifications for Preparing Quality
  Assurance Project  Plans. QAMS-005/80.  U.S.
  Environmental  Protection  Agency,  Washington,
  D.C.
                                                73

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                                  Appendix

          Form Used in On-Site Evaluation of Ground Crews,
                      Western Lake Survey - Phase I
             Western Lake Survey Ground Crew Audit Questionnaire 1.2
Subregion
Field Base Location
Remote Site Location
EPA Base Coordinator

USFS Field Manager	

Dates
Auditors
Note 1. Circle one or more contact modes on page heading:

         R  = radio
         T = transfer point
         L = laboratory or base (sample inspection, no contact)
         P = personal contact (on site, transfer point, or laboratory)
Note 2. In left margin indicates questions to be asked during radio contact time.
                                     75

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                   GROUND CREW STATISTICS - P
Crew ID
Samplers' Names
Agency
Academic Training
Experience Type
   and Years
                                76

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SAMPLERS' NAMES.






CREW ID
DATE
                            STAGING AREA - P
Item
Has adequate space been provided for predeparture
activities?
Are facilities clean and organized?
Is equipment clean and organized?
Is all equipment operational?
Has the thermistor been through a two-point calibration
check? Results?



Yes








No








Comments








Notes:
                                  77

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SAMPLERS' NAMES.






CREW ID
DATE
                      EN ROUTE ACTIVITIES - P - R - T
Item
* Are the maps adequate?
* Are there any problems in locating lakes?
Are the field data forms and notebooks understood?
Correctly filled out? Transcriptions verified?
Are identifications of target lakes verified? How?
Are pack and riding animals adequate for safe
transportation of personnel and gear?




Yes









No









Comments









Notes:
                                    78

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SAMPLERS' NAMES
DATE
CREW ID
                            PREPARATION - P
Item
Are checklists followed for loading equipment?
Is equipment organized and easily accessible on pack
animals.
Is equipment stored properly to prevent injury or damage
during transport?
Are excursion plans made? Adequate? Understood by all
personnel?
Do the field manager and base coordinator know where crew
is at any given time?
Is communication between field base and field crew
adequate?
Are check-in times prearranged? Are there deviations from
the times? If so, explain.
Has trip departure been delayed significantly for any reason?
Reasons?



Yes











No











Comments











Notes:
                                  79

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SAMPLERS' NAMES.






CREW ID
DATE
                       ON-SITE SAMPLING - P- R - T
Item
* Are there problems finding the deepest sampling site while
on lake?
Are the sounding, Secchi, and thermistor lines adequate?
* Are the procedures clear and easily followed?
Are required procedures for blanks and duplicates
followed?
Are required safety procedures followed?
'Are there any problems in obtaining samples?
Are adequate volumes of sample being taken?
Are procedures being followed that avoid contamination?
Are rinse procedures followed correctly?
Are samples stored correctly?
Are appropriate comments being recorded in logbook?
Form 1?


Yes













No













Comments











(continued)

                                   80

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SAMPLERS' NAMES
DATE
CREW ID
                   ON-SITE SAMPLING - P - R - T (Continued)
Item
Are all labels filled our correctly?
* Is there effective coordination between the sampling crew
and the field laboratory?
Are samples arriving at the field laboratory within required
time?
Are there any problems loading equipment on horses or
llamas? On rafts?
How long did finding the deep site take?
Was 10 minutes allowed for pH strip development?
Were there any problems with air bubbles?
Were there any problems with cables?



Yes











No











Comments











                                     81

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SAMPLERS' NAMES.






CREW ID
DATE
                      THERMISTOR GENERAL - P - R
Item
Are copies of the operations manual available?
Is the instrument cleaned and packed properly?
Are all personnel capable of routine maintenance?
Troubleshooting meter problems?
Have any maintenance problems occurred?
Are adequate spare parts available?
Is meter performing well?
Are there any continuous problems with the meter?
Have there been any deviations from standard procedures?
Describe.
Were there any problems in determining stratification?
What were the meter deviations from field thermometer?
Were temperature QC checks performed at each lake?

Yes












No












Comments












Notes:
                                  82

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SAMPLERS' NAMES
DATE
CREW ID
                   ACTIVITIES FOLLOWING SAMPLING - L - P
Item
Are samples packed properly at lake site?
Is equipment packed properly after sampling?
Are samples transferred properly at transfer point?
Are sufficient supplies provided at transfer point?
Are supplies being requested in sufficient time to avoid
delays.
Is sample tracking and custody form properly completed?
Are cooler temperatures being recorded?
Are gel packs arriving from field still frozen?
Were cooler temperatures spot-checked when coolers
arrived at field base? What were the temperatures? Are
they recorded properly?
Were data forms checked for problems? Were they signed
by field manager?

Yes











No











Comments











                                   83

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SAMPLERS' NAMES
DATE
CREW ID
                     POST SAMPLING ACTIVITIES - L - P
Item
What was the elapsed time between sample collection and
laboratory receipt?
Were phone check-ins received at field base?
Were any calibration lakes sampled? Which?
How were they identified as calibration lakes?
Were the samplers aware that the lake was a calibration
lake?



Yes








No








Comments








Notes:
                                    84

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