United States
                     Environmental Protection
                     Agency
 Environmental Monitoring
 Systems Laboratory
 Research Triangle Park NC 27711
                     Research and Development
 EPA/600/S4-87/019Sept. 1987
x°/EPA         Project Summary
                    Quality Assurance  Audits  of  the
                    EPA State-Operated Precipitation
                    Collection  Network
                    W. Gary Eaton and Berne I. Bennett
                      Networks that collect and quantify
                    the constituents of precipitation in the
                    United States have increased in number
                    and size in recent years. Eleven states
                    presently participate in the EPA-spon-
                    sored State-Operated  Precipitation
                    Network that collects weekly samples
                    at 27 locations.  As networks have
                    grown, so  have the development and
                    application of quality assurance con-
                    siderations to  ensure  that accurate,
                    precise, complete,  and representative
                    data are obtained.
                      Quality assurance protocols for sys-
                    tem  and performance audits  of  the
                    State-Operated Network (SON) of wet
                    deposition collection sites are outlined.
                    The protocols address site characteris-
                    tics,  training, precipitation collection
                    and measurement equipment,  sample
                    retrieval and  handling, system audits,
                    and the use of simulated precipitation
                    test solutions in performance  audits.
                    Results from quality assurance studies
                    by Research Triangle Institute in 1985
                    and 1986 of the 27-site SON sites and
                    recommendations for corrective action
                    are given.
                      This Project Summary was developed
                    by EPA's  Environmental Monitoring
                    Systems Laboratory, Research Triangle
                    Park, NC, to announce key findings of
                    the research project that Is fully docu-
                    mented In a separate report of the same
                    title (see Project Report ordering In-
                    formation at back).

                    Introduction
                      In response  to the need for data to
                    determine the extent and nature of acidic
                    precipitation, wet deposition collection
                    networks in the United States have grown
in number and size in the last decade. As
the networks have grown, so has the
development of protocols and procedures
for external quality assurance. Benefits
of quality assurance studies of networks
include assuring that established proto-
cols for siting, sample collection,  and
analysis are being followed; identifing
non-complying equipment to be fixed and
operators who need further training; pro-
viding a means of documenting the data
base with respect to accuracy, precision,
completeness,  and representativeness;
and allowing the data quality of several
networks to be compared in a systematic
way.
  The 27-site SON has been in place
since  1982. The full report describes
quality assurance procedures established
for this network and gives  results of
1985 and 1986 site visits. Recommenda-
tions for improvement are also given. The
procedures are similar to those developed
and applied earlier by two other networks:
the Utility Acid Precipitation Study Pro-
gram,  (UAPSP), that collects on a daily
basis1  and the National Atmospheric
Deposition Program/National  Trends
Network, (NADP/NTN), that collects
weekly samples2.

Procedures
  Adherence to established siting guide-
lines is checked by comparing each site's
installation and nearby surroundings to
criteria given in  urban- or  regionally-
sited station checklists designed expressly
for the State-Operated Network. These
checklists are given in the full report.
Important criteria common to either type
station are: (a) type and height of nearby
groundcover; (b) distance of collector and

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rain gauge from obstructions; (c) distance
of the collector from sources of con-
tamination and pollution; (d) proximity of
human or animal activities to the collector;
and (e) nearby land and water features.
  During the visit the following system
audit topics are reviewed: (a) sample col-
lection equipment and  procedures (in-
cluding plastic bag bucket liners used in
the SON); (b) site laboratory facilities and
cleanliness; (c) analysis  procedures; (d)
communication  and  recordkeeping; and
(e) quality control tests  and  corrective
action procedures. Technical assistance
is provided whenever an operator is un-
certain of procedures or when equipment
needs maintenance or calibration.
  The accuracy of response of each site's
collection and measurement devices is
tested during the visit. The performance
audit techniques and designated  toler-
ances for the SON are described in Table
1.

Results and Discussion

Siting Criteria Checks
  At least one variation from the desig-
nated siting criteria  was found for most
of the SON sites. Many were minor and
should  have  negligible  effect  on the
physical  and  chemical  data base. The
most important  siting  exceptions are
noted below.
                               Collector/rain gauge obstructions
                                 Several collectors and  gauges were
                               near enough to trees, towers, or other
                               equipment such that the object projected
                               onto the collector at greater than a 45
                               degree angle. Since the  sample catch
                               and chemistry could be affected by this, it
                               was recommended that the samplers be
                               slightly repositioned or that the obstruc-
                               tions be removed.

                               Proximity to sources
                                 Several sites had sources nearby al-
                               though the criterion for collector/source
                               separation  was minimally satisfied.
                               Examples include asphalt plant, animal
                               stockade, and salt water.  It was recom-
                               mended that data users be made aware
                               of these facts and that the site be moved
                               or the source removed if possible.

                               Collector and rain gauge
                               positioning
                                 Ideally the collector and  rain gauge
                               orifices  should be  at  the same height
                               above ground (~1 m) and be separated by
                               at least 5 but no more than 30 m. Several
                               sites had the collector and  gauge posi-
                               tioned within 1 m of each other in the
                               horizontal;  others  were  separated by
                               several meters  in the vertical dimension.
                               It was recommended that the rain gauges
                               be  repositioned and inoperative gauges
                               be repaired or replaced.
  System Audits
    System  checks were made  of the
  precipitation collector, the rain  gauge,
  sample  collection  procedures, and the
  field laboratory. Results are noted below.

  Precipitation collector
    Eleven of 27  collectors  were higher
  above ground than the prescribed one
  meter. This exception was due to place-
  ment  on  platforms  or roofs to  avoid
  snowpack, for security, and to avoid ob-
  structions. The effect on the sample is
  thought to be  minimal. Ten collectors
  were installed with the wet bucket facing
  N or E rather than the prescribed W. If
  rainstorms approach predominantly from
  the S or  SW,  the collector itself may
  influence  the  collection process.  Eight
  collectors lacked the event marker cap-
  ability. Knowing when and for how long
  the collector is open is  an important
  quality control consideration. All  but two
  sites had properly seating bucket covers.
  A dry-site  bucket was missing at one site;
  another site had  a deteriorated  liner.
  Proper seating  is necessary to keep out
  dust.

  Rain gauge
    Variations from  the desired distance
  from the collector and height with respect
  to the collector were noted at about half
  of the sites. Six sites do not have record-
 Table 1.    Audit Techniques and Tolerance Limits For Collection and Measurement Methods


                                                   Audit Technique or Test
Measurement Device and
   Audit Observable
             Expected Results
 1. Recording Rain Gauge
   - Accuracy of precipitation depth on gauge
 2. Precipitation Collector
   - Lid liner-bucket-rim seal
   - Sensor activation and heating
                                 - Use calibration weights simulating
                                   precipitation.
                                 - Determine lid drop distance
                                   (Bucket in - bucket out).

                                 - Observe open/close cycle. Determine
                                 temperature with thermistor 5 min. after
                                   activation.
 Agreement within ±0.10 inch of audit weight.
- Distance >3 mm.
- Ambient temperature, prior to activation.
Temperature of50-70°C attained after
activation.
 3. Conductivity Meter
   - Accuracy of response to simulatd
  precipitation samples

   - Deionized water quality

 4. pH Meter
   - Accuracy of response to simulated
  precipitation samples

 5. Mass by Solution Balance
   - Accuracy of response to calibrated weights
                                 • Have operator determine conductivity of
                                 simulated sample.

                                 - Have operator determine.
                                   Have operator determine pH of
                                   simulated precipitation sample.
                                   Have operator determine mass of
                                   weights in the range 800 g to 330O g.
 Agreement within ± 4 nS/cm.
-  Conductivity <10 nS/cm.
- Agreement within ±0.1 pH unit of established
value.
- Agreement within ±5 g of stated mass.

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ing rain gauges; several sites had mal-
functioning tipping bucket gauges.

Same collection procedures
  Proper sample collection procedures
were followed in virtually all instances. It
was noted that not all operators visually
check  the sample  for  contamination
before returning it to the field laboratory.
It was recommended that this be done;
otherwise contaminants may dissolve and
be unnoticeable later.

Field laboratory
  The  field  laboratories had  adequate
space, were clean, and temperature-con-
trolled.  Operators  and  analysts were
trained  and familiar with  their duties.
Variations  in  measurement technique
were noted and discussed. It was recom-
mended that smaller sample aliquots be
used, that the network's central laboratory
have first priority for samples, and that
samples be shipped within three days of
collection.

Performance Audits
  Performance evaluations were made
of the rain gauge;  the precipitation  col-
lector;  and the pH meter, conductivity
cell, and solution  balance. Results are
given in Table 2 and discussed briefly
here.
    Rain gauge
      All 13  weighing-type recording rain
    gauges agreed  within  0.1  inch  of  the
    designated audit value over the range 0
    to 5 inches. Eight of the 13 gauges were
    out of tolerance above 5 inches. However,
    this is a seldom-used range as the guage
    bucket  is  usually  emptied  before this
    depth  is reached.  Most of  the gauges
    were recalibrated to meet specifications.

    Precipitation collector
      All collectors operated when the sensor
    was activated. The lid-liner/bucket  rim
    seal was adequate.  Several  problems
    were noted with  sensor  temperature
    range and control. If the sensor does not
    heat during and immediately following a
    rain, the collector's bucket cover will not
    close promptly and contamination  of the
    sample by dust or debris may occur.

    Conductivity meter
      Meter readings at 3 of 20  field labora-
    tories varied by more than 4 fiS/cm from
    the designated value of the audit solution.
    Results were quite acceptable otherwise.
    The quality of deionized water  in use at
    the sites also met specifications.

    pH meter
      Only 2 of 21 field laboratories had pH
    results that varied  by more  than 0.1 pH
                                            unit  from the  designated value. The
                                            average absolute variation was 0.054 pH
                                            unit.

                                            Mass
                                              Sixteen  of the  19 balances checked
                                            agreed within 1 g of the designated value
                                            at a loading of 1646 g. The worst case
                                            was a 10 g variation corresponding to 1.2
                                            percent at an 823 g loading or 0.3 percent
                                            at a 3292 g loading.

                                            Conclusions
                                              The EPA-sponsored SON is a weekly
                                            precipitation collection network of 27 sites
                                            located primarily  in the eastern and
                                            southeastern United  States. State
                                            agencies have provided personnel to ser-
                                            vice the sites and laboratories and to
                                            analyze and submit samples to a central
                                            laboratory  for analysis. The site super-
                                            visors,  operators,  and  analysts  were
                                            familiar with their duties,  handled the
                                            precipitation samples carefully, analyzed
                                            the samples accurately  in  most cases,
                                            and seemed genuinely interested in the
                                            network and the data.
                                              Several of the sites should be improved
                                            upon  in terms of siting and maintenance
                                            of sample collection and analysis equip-
                                            ment.  Emphasis should  be placed on
                                            proper placement and operation of pre-
                                            cipitation  collectors,  installation  and
TaWe 2.    Performance Audit Results: EPA State-Operated Network, 1985-1986
     Measurement Device Audited
Number
Audited
                flange of Response;
                 Average Response
                                                                                                Comments
 1. Rain Gauge
   - accuracy of precipitation depth
2. Precipitation Collector
   -lid liner/bucket rim seal

   - sensor activation and heating
3.  Conductivity Meter
   - accuracy of response
   - deionized water quality
4. pH Meter
   - accuracy of response
5. Solution Balance Mass
   - accuracy of response
   13      All within ±0.1 inch from OtoS
          inches.
  16      Range 7 to 33 mm; avg. 13.6 mm.

  27      All respond and open collector.
          Range 23 - 100°C; avg. 55°C.
20      0.3 to 5.80 nS/cm; " avg. 1.63
        ±7.3
   14      0.35 to 3.80 nS/cm; avg. 1.75
  21
   19
        0.01 to 0.18 pH unit;' avg. 0.054
        ± 0.04 pH unit.
                                         Out-of-tolerance readings occurred on 8 of 13
                                         but only at 6 inches or greater depth, a seldom-
                                         used range.
                                         All met 3 mm criterion of acceptability.

                                         Eight heated at all times. Six did not heat.
                                         Twenty-one heat; of these 10 attain temperature
                                         <50°C. three > 70°C.
                                           EPA performance audit sample; value is 20 or 24
EPA performance audit samples; designated
value is 4.28 or 4.39 pH units.
        16 of 19 agree within ±1 gat 1646    17 of 19 are accurate within ± 5g over 823 to
        g loading.                          3292 g range. All are within ±10 g agreement.
' Range of differences where difference = \ (site value) - (designated value) \.

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  proper operation  of  rain gauges,  and
  standardization  of  field  laboratory
  techniques.

  References
  1. W. C. Eaton, K. A.  Daum, E. D. Estes,
     and  F. Smith,  "Quality Assurance
     Results for the Utility Acid Precipitation
     Study Program (UAPSP),  1982 to
     1984," Transactions: Quality Assur-
     ance in Air Pollution Measurements,
     APCA Publication TR-3, Pittsburgh, PA
     (1985), pp. 488-499.
  2. D. S. Bigelow, "Quality Assurance
     Report; NADP/NTN Deposition Moni-
     toring.  Field Operations, July 1978
     through  December 1983." National
     Atmospheric Deposition Program,
     Coordinator's Office, NREL, Colorado
     State University,  Fort Collins,  CO,
     (August 1986).
         W. Gary Eaton is with Research Triangle Institute, Research Triangle Park. NC
           27709; and the EPA author, Berne I. Bennett (also the EPA Project Officer,
           see below), is with Environmental Monitoring Systems Laboratory, Research
           Triangle Park, NC 27711.
         The  complete report entitled "Quality Assurance Audits of the  EPA State-
           Operated Precipitation Collection Network," fOrder No. PB 87-208 740/AS;
           Cost: $13.95, 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:
                 Environmental Monitoring Systems Laboratory
                 U.S. Environmental Protection Agency
                 Research Triangle Park, NC 27711
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Official Business
Penalty for Private Use S300
EPA/600/S4-87/019
                   0000329   PS

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