AIL
United States
Environmental Protection
Agency
Environmental Monitoring
Systems Laboratory
Las Vegas NV 89193-3478
                                 Research and Development
                                EPA/600/S4-86/011  Jan. 1988
              SEPA         Project Summary
                                 National  Surface Water Survey
                                 Eastern Lake Survey
                                 (Phase  I - Synoptic Chemistry)
                                 Quality Assurance   Report

                                 M.D. Best, S.K.Drouse, LW. Creelman, DJ. Chaloud, and D.W. Sutton
                                   The quality assurance program for
                                the Eastern Lake Survey - Phase I
                                included quality assurance and
                                quality control activities for field and
                                laboratory operations  and for
                                verification and validation of the data.
                                A combination of blank, duplicate,
                                and audit samples were analyzed  to
                                provide  an  external check on the
                                quality of 32 physical and chemical
                                parameters and to  allow  early
                                detection of problems in sample
                                collection, processing, and analysis.
                                   The statistical analysis of the
                                verified data set included  estimates
                                of instrumental and system detection
                                limits, system decision limits, overall
                                and analytical within-batch
                                precision, and overall and  analytical
                                among-batch  precision.  Quantita-
                                tion limits also were calculated for
                                use in evaluating the precision of the
                                survey data. The results  of  these
                                statistical analyses were compared
                                to the data quality objectives for
                                detectability and precision.
                                   This report was submitted  in
                                partial  fulfillment  of Contract
                                Numbers  68-03-3050 and  68-03-
                                3249. This report covers a planning,
                                implementation,  and  data review
                                period from March 1983 to January
                                1986, and work was completed as  of
                                December 1986.
                                   This  Project Summary was
                                developed by  EPA's Environmental
                                Monitoring Systems Laboratory, Las
                                Vegas, NV, to announce key findings
                                of the research project that is fully
                                 documented in a separate  report of
                                 the same  title (see Project Report
                                 ordering information at back).

                                 Introduction
                                    The National Surface  Water Survey
                                 (NSWS) is  a three-phase  project within
                                 the  National  Acid  Precipitation
                                 Assessment Program (NAPAP). The U S.
                                 Environmental Protection Agency  (EPA)
                                 initiated the NSWS in 1983. The purpose
                                 of Phase I of the NSWS was to document
                                 the present chemical status of lakes and
                                 streams in areas of the United States that
                                 are potentially susceptible  to the effects
                                 of acidic deposition. This report provides
                                 an overview of the quality assurance (QA)
                                 activities and results for one component
                                 of the NSWS, the Eastern  Lake Survey -
                                 Phase I (ELS-I),  which evaluated the
                                 chemical status of 1,798  lakes in the
                                 eastern United  States. The lakes were
                                 selected from three regions east of the
                                 Mississippi River that are  potentially
                                 susceptible to  acidification.  The  EPA
                                 Environmental  Monitoring  Systems
                                 Laboratory  in Las  Vegas, (EMSL-LV),
                                 Nevada, had primary responsibility for
                                 the ELS-I QA  program and sampling
                                 operations.
                                    Thirty-two  chemical  and physical
                                 parameters  were selected  for in situ or
                                 laboratory measurement. Data from these
                                 measurements  of single  lake samples
                                 provided information to  evaluate the
                                 present status  of lakes on  a regional
                                 basis. Data quality objectives (DQOs)
                                 were defined in terms of  the precision
                                 and accuracy of measured  values for

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each  parameter   and   of   the
representativeness,  comparability,  and
completeness of the resulting data base.
The anticipated range of values and the
required  detection  limits were  also
specified for  each  measurement.
Equipment and  protocols for  sampling,
chemical analysis, and  data processing
were  based  on the  best  available
methods and were standardized in order
to achieve the DQOs.
    A draft QA plan and a draft analytical
methods manual were used during  pilot
studies which were conducted to test all
aspects of the ELS-I research plan.
Activities tested  include  the  lake
selection process,  the  proposed
sampling  and analytical  protocols, the
DQOs, the QA  program, and the  data
management system. The final QA  plan
and  the final  methods   manual
incorporated  revisions based  on  results
obtained from the pilot studies  and on
changes implemented during the ELS-I.

Sampling   and  Analytical
Methodologies
    The  primary QA  goals  of ELS-I
base  site operations  were  to  obtain
accurate  physicochemical   and
geographical data at each lake site,  to
collect  representative  lake samples
without  introducing  contamination,  to
preserve  the integrity of samples  until
their analysis at contract laboratories,
and to perform selected analyses at field
laboratories. Field  personnel used
helicopters equipped with fixed floats to
collect samples.
    Activities  of  field  laboratory
personnel included:
     1.  Receiving lake and QA samples
        and  field  data from each
        sampling team  and  assessing
        sample condition upon receipt.
     2.  Reviewing field data  forms and
        field  laboratory  forms  for
        accuracy and completeness.
     3. Incorporating audit samples with
        lake samples to form  a batch of
        samples for analysis.
     4. Analyzing the batch of samples
        for  pH, dissolved  inorganic
        carbon (DIG), true  color,  and
        turbidity.
      5. Performing  aluminum  extrac-
        tions.
      6. Filtering,   preserving,  and
        shipping samples to contract
        analytical  laboratories for
        additional analyses.
      7. Coordinating  sample shipment
        information  with  the  EPA
        Sample  Management Office in
       Alexandria, Virginia, and with the
       EMSL-LV  in Las Vegas.
     8. Distributing copies of  data and
       data forms to the appropriate
       offices.
    Standardized forms  were developed
to record measurements made at each
lake and  at the field and  contract
analytical laboratories. One copy of each
form was sent to Oak  Ridge National
Laboratory for entry into the NSWS data
base, and a second copy was sent to QA
personnel in Las Vegas. Figure 1 shows
the flow of  samples and data from  the
field to the field laboratory and to  the
analytical laboratory.

Data Comparability Studies
    Standardized  techniques  for
sampling and chemical analyses of water
samples from the ELS-I  ensured that
the  effect  (if any)  of  variance from
sampling and analysis procedures on the
differences  between lakes  could  be
identified.
    Studies were also undertaken  to
determine whether ELS-I data could be
compared to survey data from other
countries and to data obtained by using
different analytical methods. Subsamples
from 215 ELS-I  samples  collected in
the southern Blue  Ridge Mountains were
shipped  via commercial courier  to
Norway for chemical  analysis of 14
parameters.  Similarly,  105 subsamples
from the Adirondack  Mountains were
analyzed in Canada for 18  chemical
parameters.
    A second  study used 2,047  split
samples  from the  ELS-I  to  compare
data from chemical  analyses  by flame
atomic absorption spectroscopy (AAS)
and inductively coupled  plasma emission
spectroscopy (ICPES).  The  ICPES
analyses  were performed at  the  EPA
Environmental Research Laboratory in
Corvallis,  Oregon, and by  ELS-1
contract  laboratories.  The flame  AAS
analyses  were  performed  by  ELS-I
laboratories only.
Procedures

Operational  Quality  Assurance
and Quality Control Program
     The QA program used a combination
of blank,  duplicate, and  audit samples to
provide an  external check on  the quality
of the data obtained from measurements
of  the 32  physicochemical parameters
and to allow early detection of problems
in  sample  collection, processing,  and
analysis.  Quality control (QC) protocols
for field  sampling, field and  analytical
laboratory  activities,  and data base
management  were  implemented
ensure reliability of the data.
    The estimated number of samples
be analyzed and the estimated rate
sample  collection  required  contract!
with more than one analytical laborati
to meet the QA and QC requiremer
Laboratories that submitted  low bids
response to the formal  bidding proce
were evaluated on  the basis  of th
analytical laboratory performance. The
that passed were  visited to  verify th
qualifications and capabilities.
    Data quality also depended on i
ability  of  the  field  and  laboratc
personnel to  properly collect,  proce
and analyze the samples. Training v\
essential to ensure consistent applicati
of  all   operational   and  QA-C
procedures.
    Coordination  of  the   ELS
operations required close communicat
among all participants to ensure that 1
program objectives  were  met. Da
monitoring  of  field sampling,  fie
laboratory, and  analytical   laboratc
activities facilitated safety and  logisti
coordination. During the actual  sampli
phase,  the  most  critical  lines
communication  were  between  t
logistics personnel in  Las Vegas and I
field  stations and  between  the  <
personnel in Las Vegas  and  the contr
analytical  laboratories.   Logisti
personnel also coordinated  and track
the shipment of samples to the analyti
laboratories  and  coordinated  t
shipment of supplies to field stations. 1
QA staff made daily calls to the analyti
laboratories  to  ensure  that  the <
procedures  were being  implement
according to  survey  requirements  a
that the samples were being  handled z
analyzed properly.

Sampling  and Field Laboratc
Quality Control
    Field sampling QC  procedur
included daily calibration of the  Hydro
units,  measurements  of  QC  che
samples for pH  and conductance,  a
sampling  site verification. The <
procedures for field laboratory operatic
included  daily instrument  calibrate
measurements of QC check samples <
laboratory duplicates, and preservation
sample  aliquots  for  additior
measurements  by  the   analytii
laboratories.
    The   objectives  of   samp
preservation at the field  laboratories w
to (1) inhibit chemical and biologi
activity, (2)  prevent changes due
volatilization,  and (3)  prevent effects c

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Routine
Lake
Samples
Field Blank
Samples
1
1


— — — - 11
Daily S<
of Sam
Field Duplicate
Sample
\
Field Laboml

itch
pies __
Field/Laboratory
Audit Sample(s)
ory
\

r
Relabeling




                                 Analysis

                       (DIC. pH, Turbidity, True Color)
               OC Check       Batch       Trailer Duplicate
               Samples      Samples          Sample
                              -*• Data  "•*-
Aliquot Preparation
Aluminum Extraction

   Preservation
                                                                                         Shipment to
                                                                                     Analytical Laboratory
                                                                                                Analytical Laboratory
                                                                                            Analysis
                                                                                r
                                                                              Internal
                                                                            OC Samples

                                                                          Laboratory Blank,
                                                                            Matrix Spike,
                                                                         OC Sample Check
    t
 Batch
Samples
                 Laboratory
                  Duplicate
                                                                                          -»-  Data -*-
Figure 1.   Flow of samples and data through field and analytical laboratories, Eastern Lake Survey - Phase I.

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to precipitation or  adsorption. Seven
preserved  aliquots were prepared from
each  bulk  sample  (routine,  field
duplicate, field blank, or field audit). Four
parameters (pH, DIG,  true color,  and
turbidity) required immediate  analysis.
Use of a mobile  field laboratory for these
analyses  permitted  these   four
measurements to be  completed within 16
hours of sample  collection.

Analytical  Laboratory  Quality
Control Protocols
    Analytical laboratory QC included
the use of  QC charts,  calibration of
instruments and analysis of  QC  check
samples (QCCS), detection limit QCCS,
and  duplicate  samples. A  maximum
sample  holding  time, from the time of
sample  collection  to sample  analysis,
was  established for each parameter
measured  in the analytical laboratories.
These holding  times were based upon
information from the literature,  the  best
scientific judgment related to the defined
needs, and the logistical demands and
limitations of the ELS-I.

Data Base Quality  Assurance
    Oak Ridge National Laboratory
(ORNL)  personnel  managed  the  data
base  for the ELS-I.  The data are  stored
in four major data sets: (1) a raw data set
of field and analytical laboratory data, (2)
a verified  data  set,  (3)  a validated  data
set, and (4) a final data set. Oak Ridge
personnel  entered  the  field  and
laboratory data  into the data  base and
used  a  double  entry and comparison
process to minimize data entry  errors.
The  verified data set  provides a  data
base  in which any  values  that are
questionable on the basis  of  known
physicochemical   relationships  are
qualified with a flag. The validated  data
set  provides   data that have   been
evaluated, using all available information,
for internal and regional consistency. The
final data  set provides a representative
summary  of sample values for  use  in
generating population estimates.

Data Verification
    The raw data were verified  by: (1)
communicating  daily with the field and
analytical  laboratories; (2) assessing the
completeness and  consistency of  each
data package (one per  sample batch) on
receipt,  and reviewing any comments or
questions associated with the  batch  or
sample  under evaluation; (3)  evaluating
the preliminary routine and QA  sample
data;  (4) obtaining  confirmation,
correction, or  reanalysis data  from the
laboratories  as needed  to address
atypical  values; and  (5)  providing
correcting  entries  to  ORNL  for
establishing  the verified  data  set.
EMSL-LV  QA personnel developed a
computer software package (AQUARIUS)
to automate this procedure as much as
possible.
    These five steps produced a verified
data set in which all values that did not
meet a number of criteria based on
physicochemical relationships were
flagged, replaced with either corrected or
reanalyzed data, or replaced  with codes
indicating a missing value.

Data Validation
    The data  validation  process
identified potential errors in chemical
analyses that could  not  be revealed by
the  verification  procedures.  The
validation  process also evaluated  the
quality of nonchemical  variables.  Data
validation  employed  pre-existing
software to identify possible outliers and
to evaluate possible systematic  error in
the measurement process.  Both of these
aspects were  exploratory (as  opposed to
test-oriented).  The  objective  of  data
validation was  to  identify  individual
values or sets of  values  that  warrant
special  attention or  caution  when  used
for analysis  of survey results  or when
used for building models based upon
survey data.  Final decisions regarding
data quality were based on all available
information.

Data Base Review
    An  independent  data  audit team
inspected routine and  duplicate  data
from  each  of the four  data sets  (raw,
verified,  validated,  and   final)  that
constitute the ELS-I  data  base.  The
data base review included an evaluation
of the adequacy of  documentation for
value changes made  between the  raw
and the final  data sets.  For some of the
parameters, the audit team evaluated the
documentation by a search and review of
all of the data. For other  parameters,
they  selected a random subsample of
the  changed  values  for  review.  The
review consisted of a  comparison of the
old and new values against the field and
laboratory records and  the  verification
reports.
     The  review  also  included  a
determination  of the correctness  of data
entry. The completeness of  the  data
base was estimated for each  of the
parameters   by   examining   the
justifications  for missing  value  codes.
The correctness of the calculations of
population  estimates was verified  I
implementing the estimation algorithr
on a test data set which was a  subset
the final ELS-I data set.

Results

Operations Evaluation
    The  ELS-I was  completed with
the time  required by the research  plj
and  the statistical  requirements f
adequate sample  size were achieved
all field stations.  There  were  no maj
interruptions in field  operations  due
accidents, weather, or equipment failui
The  sampling  and laboratory  protocc
were  successful for  most procedure
This survey design should serve  as
model for future field  studies of a simi
nature.

Lake and Sample Information
    Approximately 90 percent  of tl
lakes initially selected for sampling  we
visited by sampling crews. Of those  lak
visited, 96 percent (1,612) were actua
sampled. In  addition to those lakes, 1
special-interest  lakes  were sampled  1
a total sample of 1,798 lakes.
    Less than 20  percent  of  the  lak
visited were sampled at a depth  otr
than the one originally specified. Only
percent  of  the lakes  sampled  we
thermally stratified; thus,  95 percent of
samples were acceptable in terms of t
research plan  requirement  that a sin(
water sample  was to be collected frc
each lake during a period when the  lak
were isothermal.
    In total, 2,389 routine, field  duplica
and  field blank samples  were  deliver
from the field laboratories to the contr<
analytical laboratories. One matrix  spi
and  one laboratory duplicate  we
analyzed  for  each  batch of  sampl
making a total of 2,639 sets of analyses

Field Problems and  Resolution;
    The field crews collected samples
planned during the ELS-I  with
average yield  of 20  processed sampl
per  operating  day  from  each  fie
laboratory.  Problems  which  we
identified and corrected prior to or duri
field  operations  included  an  inaccur.
pH meter,  use of contaminated  bla
sample water at one field laboratory, a
destruction of one set of split samples
the commercial courier.
    At the conclusion of  the  survey,
number of  recommendations were  ma
for improving field operations.  A syst<
for efficient and complete informati
transfer  should  be  used  between  t
management team and field personnel

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ensure that  all  new  developments  or
modifications in operational protocols are
consistently  disseminated  and
understood. Field  personnel should  be
prepared to make special arrangements
for shipment of samples to the analytical
laboratories  on weekends.  All  field
samplers should receive comprehensive
instruction  to ensure consistency  of
sample collection  and  processing
activities. Rotation or replacement of field
personnel should be minimized because
it may lead to  inconsistencies in  data
reporting and it  requires additional time
and effort for training.

Analytical  Laboratory  Problems
and Resolutions

    Several  problems  were identified
and  corrected  during  the  analytical
laboratory  operations.  Two significant
difficulties  centered on the inaccurate
calibration  method  used  with  silica
measurement at one  laboratory and  on
aluminum  contamination problems  at
three laboratories.

Methods Evaluation
    Methods studies  addressed  a
number of  analytical  questions  before
and during  the  survey operations. The
measurement of free  dissolved fluoride
was found  to be  impractical,  and ion-
selective electrodes (ISE) were favored
over  ion  chromatography  (1C) for
measurement of total  dissolved fluoride.
The Gran analysis method was found to
be useful  for determinations of  acid-
neutralizing capacity   (ANC);  however,
problems  were encountered  with the
calculations for  base-neutralizing
capacity  (BNC).  The procedure for
measuring  total extractable aluminum
and  the  design  of  the pH sample
chamber were modified during the pilot
study.  Effects of filtration on  dissolved
iron and aluminum concentrations in the
audit samples were detected during the
survey operations and were attributed to
sample instability.
    A nitrate  contamination  problem in
blank samples was also encountered.  To
meet analytical laboratory quality  control
specifications, nitrate  concentrations in
field blank samples were required to  be
less than  0.01 mg I/1. During the pilot
study,  up  to  18 mg   L'1 nitrate  were
detected in field blanks, suggesting  a
serious contamination problem.  This
contamination was  not present  in the
analytical  laboratory  blank samples.
During the  pilot study, two sources of
contamination  were found  to be the
deionized  water  and  the  sample
containers.   Contamination from the
filtration apparatus was a  third  source.
The  ELS-I  was  about half  completed
before  nitrate  contamination from the
filtration  apparatus was  isolated  and
eliminated.  Nitrate data from samples
that  were processed on or  before the
change  in  the filtration protocol  were
replaced with data from  reanalyzed
samples.

Evaluation  of Split  Sample
Analyses  from  Norway  and
Canada
    In a  study undertaken  to determine
whether data obtained using analytical
methods used   in this  survey  are
comparable to the data  obtained  by
methods  used in other regions where
surface  water  surveys  take  place,  110
pairs of aliquots (split  samples) from 97
lakes  in  the southern   Blue   Ridge
Mountains were  sent to the Norwegian
Institute for Water Research in Oslo and
to an ELS-I analytical  laboratory. Each
laboratory analyzed the split samples for
11 chemical parameters.
    This study  also   used 105 split
samples from 92 lakes in the Adirondack
Mountains.  Some  of these  split samples
were shipped  to the Water  Quality
National Laboratory  of  the  Canada
Centre for  Inland Waters in Burlington,
Ontario,  and  to  an  ELS-I analytical
laboratory. Other split samples were sent
to the Water Quality Section  of the
Ontario  Ministry  of  the Environment  in
Rexdale  and  to  an  ELS-I analytical
laboratory. Analytical data from the three
laboratories  were  compared  for  17
parameters by using linear regressions
and sign tests.
    The  data  from  the  pairs   of
laboratories that  analyzed  the samples
for the same parameters are comparable
for most  of the parameters  as indicated
by the high  values of the  regression
coefficients (r2  >  0.95 for 38 of 56
comparisons and r2 > 0.90 for 48 of 56
comparisons). The linear  regression
analysis  also indicated that there are
significant differences  (uniform  bias  or
concentration-dependent bias) between
the    ELS-I    and   Norwegian
measurements and  between the ELS-I
and  Canadian  measurements for nearly
all of the parameters.
    The sign  test results show that as a
set,  the  ELS-I values are  greater  in
magnitude than the Norwegian values for
5 of the 11  parameters and less than the
Norwegian  values   for  3  of  the
parameters;  there is no significant
difference  between  the  ELS-I  and
Norwegian values for  the  remaining 3
parameters. The magnitude of the set of
ELS-I  values  is greater  than  the
magnitude of the Canadian values for 11
of the 17 parameters and it is less  than
the magnitude of the Canadian values for
4 of  the parameters;  there  is  no
significant difference between the ELS-I
and Canadian values for the remaining 2
parameters.
    The components of overall variability
in these split sample data include random
error  (measurement imprecision)  and
systematic error (accuracy and specificity
of the method). Measurement imprecision
and   differences  in  the  sample
composition  over time  may have
contributed to the overall variability for all
of the  parameters  measured  by  the
ELS-I  laboratories and by  the
Norwegian and Canadian  laboratories.
Differences in analytical methodology
contributed  to  the overall variability for
some parameters.

Evaluation of Data Base Quality
    A review  of the data base  showed
that less than 3 percent of the raw  data
was classified as reporting errors. These
errors were corrected in the verified  data
set. Sample reanalysis was requested for
less  than 4  percent  of  the originally
reported raw  data values. Less than 1
percent  of the  reported data  required
correction because  of transcription or
data entry errors.
    An  independent review of the  data
base indicated that nearly all of the value
changes had  been documented;  that
there were few if  any  data entry errors;
that  the data  base  was  essentially
complete; and that  the calculations  of
population estimates were correct.

Evaluation of Quality  Assurance
Data

Blank Sample Data
    Field blanks and analytical laboratory
blanks were  analyzed  during the ELS-I.
The 245 field blanks were analyzed for
turbidity at the field laboratory and for 21
physicochemical parameters  at  the
analytical laboratory. The analytical
laboratories used  calibration blanks or
reagent  blanks to  determine background
levels and to calculate instrumental
detection limits.
    Evaluation  of the blank sample  data
demonstrated  that  the   goals   for
instrumental  detection  limits were
generally achieved. However, to interpret
the  data, results  from the field blanks

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must also be taken into  consideration.
Extremely low detection limits achieved
in the laboratory are of limited  value in
defining usable data when they are lower
than the system  detection  limit  (the
background from  sample collection and
handling). The  system  decision  limit
should  be  considered  during  data
interpretation when comparing population
estimates.

Duplicate Sample Data

    Analysis of field duplicate  samples
provided  data for estimating  the overall
within-batch precision. The 125  field
duplicate samples that were processed
by the field laboratories  were analyzed
with the routine samples and field blanks
at  the  analytical  laboratories. The field
and  analytical  laboratories   also
performed duplicate chemical analyses
on one sample per batch  as a QC check
on analytical within-batch  precision.
    Overall within-batch  precision
estimates  were  numerically  larger,  as
was  expected,  than the  analytical
within-batch  precision  estimates for  all
but five  parameters. The  estimated
overall  and  analytical  within-batch
precision was considered to be adequate
to meet the DQOs.

Audit Sample Data

    Six types of audit samples (2 field
naturals,  2 field  synthetics,  and  2
laboratory synthetics) were analyzed  for
23  parameters during  the ELS-I.  Field
naturals  and  field synthetics  were
handled  in the same  manner  as  were
routine,  field blank, and field duplicate
samples  to estimate the  overall among-
batch precision (including the effects of
sample  processing, but  not of sample
collection).  Laboratory  synthetics  were
prepared as processed  aliquots by  a
support laboratory;  these were relabeled
at  the  field  laboratory  and  were
incorporated with  the  sample batch to
estimate the analytical  among-batch
precision.
    The  among-batch  precision
estimates from field natural audit sample
measurements were within the DQOs for
all  of the  parameters  except  total
extractable Al, total Al,  and Cl-  in the
FN2 (low ANC) samples, and they were
within the DQOs for all of the parameters
in  the FN3 (high  ANC)  samples.  The
among-batch precision estimates from
field  and  laboratory synthetic  audit
sample measurements were generally
within  the  DQOs  for  parameters  with
sample values  above the quantitation
limit, and they were generally not within
the DQOs for  parameters with values
below the quantitation limit.
    The natural  audit samples were also
used to estimate the amount of relative
interlaboratory  bias  by comparing
measured values from  the  contract
laboratories with each other and with the
referee  laboratory  measurements.  The
synthetic audit  samples were  used to
provide  information  on  absolute
interlaboratory bias, and thus had to be
prepared  from  solutions of  known
composition.  Examination  of  the
theoretical values and the  measured
values for the synthetic audit  samples
indicated that  the  actual  sample
composition  may  have  differed  on
different days;  the  amounts  of
measurement   imprecision   and
interlaboratory bias were  thought to be
small by comparison to the differences in
sample composition.
    Quantitation limits were a useful
means of classifying the data in order to
objectively evaluate the  among-batch
precision estimates  for  the  23
parameters.  High  relative  precision
(percent relative standard  deviation) was
not expected for measurements close to
the  detection  limits,  and it  was not
achieved for any parameters with means
less than quantitation  limits  except
dissolved organic carbon  (DOC).
Conversely, high  relative  precision was
expected and was generally achieved for
measurements with higher mean values.
The overall and analytical within-batch
precision   estimates  for   DOC
measurements showed patterns which
were opposite to the patterns shown by
all other parameters; i.e.,  measurements
at higher concentrations exhibited greater
variability  than  measurements  at  lower
concentrations.
    An  independent  statistical  analysis
concluded that, overall, the imprecision
of a perfectly calibrated instrument  under
constant  conditions  is  small in
comparison  to the  bias and  trend
introduced by  procedural variations and
by changes in  the sample composition
over time, that  precision estimates from
field natural  audit  samples are the best
indicators of measurement uncertainty in
the routine samples; that  measurements
of  laboratory synthetic audit  samples
provide estimates  of accuracy and
relative interlaboratory  bias; that  daily
lots of audit samples should be prepared
and divided into aliquots and  the aliquots
should be assigned to different  analytical
laboratories   at   random;   that
interlaboratory comparisons  should be
made using data from the same audi
sample lot; that audit sample compositioi
should be varied among the lots in orde
to estimate the precision and accuracy 2
various  concentrations and to  prever
recognition  of the audit samples by th<
analytical  laboratories;  and  that a
empirical approach  should  be used  t
calculate detection limits.  An  EMSL-L1
review  of this  independent  analysi
questioned  two  of the statistic*
assumptions:  a zero   median  wa
assumed    for   blank   sampl
measurements,  and  the  measuremer
error variance  was  assumed  to b
independent of the analyte concentratio
for some purposes but to be proportion;
to concentration for  other purpose;
Other issues raised by  the  EMSL-L
reviewers concern the evidence used t
support  the  statement  describing  th
blank sample  data  as non-normal; us
of the root mean square for  estimatin
the mean of the percent relative standar
deviation;  use  of  a single  slope  i
correcting the bias  and  trend in aud
sample  data; use of standard  deviatic
instead  of  standard error  to  estimal
precision in  the corrected data; an
omission of the DQOs as a basis for ft
data quality evaluations.
Variability
    Four types  of precision  estimate
(overall  within-batch, overall  amont
batch,  analytical  within-batch,  an
analytical among-batch) identify  th
amounts of  data variability that can t
attributed  to  sample   collectioi
processing,  storage,  and analysis.  Fi
the  ELS-I,  each  type  of  precisic
estimate was used to estimate a differe
aspect of data variability.
    Overall  within-batch  precisic
estimates  were  expected  to  t
numerically larger than analytical withi
batch precision estimates by an amou
equal  to the variability  from  samp
collection,  processing,  and  storag
Similarly, overall among-batch precisii
estimates  were  expected   to  t
numerically  larger  than  analytic
among-batch   precision  estimate
Analytical  and overall  among-bat<
precision estimates were expected to I
numerically larger than the correspond'!!
analytical  and overall  within-bati
precision estimates by amounts that we
equal to the temporal variability.
     Exceptions  to  the  expect!
relationships  were generally associat
with  the presence  of  one  or me
extreme outliers in the verified data s
with values close to  the detection limit,
with  a  methodological  problem. Ma

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exceptions involved small differences  in
the estimated precision. In several cases
it was necessary to retain confirmed but
questionable  values  in the verified data
set; these values  were  later  deleted
during data validation.  The  confirmed
questionable values  influenced the
statistical  evaluation  of the  ELS-I  data.
For subsequent surveys,  a data qualifier
was added to ensure that such values
are retained in the verified data set but
are not included in statistical calculations.

Summary
    Data   quality   objectives   were
established  for precision,  accuracy,
representativeness,  comparability, and
completeness.  Pilot  studies   were
conducted prior to the ELS-I to identify
and correct problem areas in field and
laboratory  operations. Field  and
laboratory QA and  QC  protocols  were
implemented  during the survey to detect
and eliminate equipment  and procedure
problems.  QA and QC procedures in the
data entry and verification  provided  a
means  for detecting  and  correcting
transcription,     transposition,      and
typographical errors as well as analytical
errors in  the data base.  The raw data
were  verified using  physicochemical
relationships.  Values that did  not  meet
criteria  were flagged,  corrected,   or
replaced with codes for missing values.
    The data quality objectives that were
specified  for  detectability and precision
were generally achievable. On the  basis
of a limited  amount of  information the
amount  of bias in the data appeared  to
be  small  in relation  to the imprecision.
Field operations  were  a  successful
means for obtaining samples  and field
data consistent with  the  ELS-I  research
plan.  The statistical requirments for
adequate  sample size were achieved  at
all  field stations. Comparability of data
obtained by different analytical  methods
and different laboratories  was addressed
by  independent studies.  Less  than  3
percent of the raw data was classified as
reporting  errors,  and  these   were
corrected in the verified data set.

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  M.D. Best, S.K. Drowse', LW. Creelman, D.J. Chaloud, and D. W. Sutton are
   with Lockheed Engineering and Management Services Co. ,lnc..
   Las Vegas. NV 89119.
  Eugene P. Meier is the EPA Project Officer (see below).
  The complete report, entitled "National Surface Water Survey, Eastern Lake
   Survey (Phase I - Synoptic Chemistry) Quality Assurance  Report," (Order No.
   PB 88-1337491 AS;  Cost:  $19.95, subject to change)  will be available only
   from:
       National Technical Information Service
       5285 Port Royal Road
       Springfield, VA22161
       Telephone:  703-487-4650
  The EPA Project Officer can be contacted at:
       Exposure Assessment Research Division
       Environmental Monitoring Systems Laboratory
       Las Vegas, Nevada 89193-3478
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
     BULK RATE
POSTAGE & FEES PAID
         EPA
  PERMIT No. G-35
Official Business
Penalty for Private Use $300

EPA/600/S4-86/011
               0000329   PS

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