xvEPA
United States Atmospheric Research and Exposure
Environmental Protection Assessment Laboratory
Agency Research Triangle Park NC 27711
EPA/600/3-89/006
January 1989
Research and Development
National Performance
Audit Program
Ambient Air Audits of
Analytical Proficiency
1987
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EPA/600/3-89/006
January 1989
NATIONAL PERFORMANCE AUDIT PROGRAM
AMBIENT AIR AUDITS OF ANALYTICAL PROFICIENCY
-1987-
Elaine F. Parr, Robert L. Lampe,
Elizabeth T. Hunike and William J. Mitchell
Quality Assurance Division
Atmospheric Research and Exposure Assessment Laboratory
Research Triangle Park, North Carolina 27711
ATMOSPHERIC RESEARCH AND EXPOSURE ASSESSMENT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
U.S. Environmental Protection Agency
]>-;:! on 5, Library (5PL-16)
r. ,'C ,0. Bsarborn Street, Room 1670
Chicago, IL 60604
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NOTICE
This document has been reviewed in accordance with U.S. Environmental
Protection Agency policy and approved for publication. Mention of trade
names or commercial products does not constitute endorsement or recommenda-
tion for use.
11
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ABSTRACT
This report presents the results of the U.S. Environmental Protection
Agency's 1987 National Ambient Air Performance Audit Program by pollutant and
by analytical method. Semiannual audits were conducted for Pb, No3 and SO4~
on filter strips and for acid rain and CO. One audit was conducted for high-
volume sampler flow rate. Continuous SO2 monitors were audited throughout
the year, with no monitor being audited more than once. The results for each
1987 audit are presented in tabular form for each concentration level. The
overall performance for all participants for each audit conducted since the
beginning of the program is also shown graphically. The results of the 1987
audits are essentially the same as those from the audits conducted from 1983
to 1986.
111
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CONTENTS
Abstract . . t ill
Tables v
Figures . vi
Acknowledgments vii
1. Introduction .... ....... 1
2. Results and Discussion U
References 8
Tables 9
Figures ...... 30
iv
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TABLES
Number Page
1 Agency Participation 9
2 Audit Results for Carbon Monoxide 10
3 Audit Results for Carbon Monoxide by the NDIR
and GFC Methods 11
U Percent of Carbon Monoxide Measurements Within
Indicated Percentage of Assigned Value 12
5 Audit Results for Sulfate on Filter Strips 13
6 Audit Results for Sulfate by the Automated Methods .... lU
7 Percent of Sulfate Measurements Within Indicated
Percentage of Assigned Value 15
8 Audit Results for Nitrate on Filter Strips 16
9 Audit Results for Nitrate by the Automated Methods .... IT
10 Percent of Nitrate Measurements Within Indicated
Percentage of Assigned Value 18
11 Audit Results for Lead on Filter Strips 19
12 Percent of Lead Measurements Within Indicated
Percentage of Assigned Value 20
13 Audit Results for Sulfur Dioxide Continuous Monitors ... 21
Ik Percent of High Volume Flow Measurements Within
Indicated Percentage of Assigned Value (All Data) .... 21
15 Acid Rain Results for pH, Conductivity and Acidity
(All Data) 22
16 Acid Rain Audit Results for pH, Conductivity and
Acidity (Outliers Removed) 23
IT Acid Rain Audit Results for Anions (All Data) 2U
18 Acid Rain Audit Results for Anions (Outliers Removed). . . 25
19 Acid Rain Audit Results for Cations (All Data) 26
20 Acid Rain Audit Results for Cations (Outliers Removed) . . 2T
21 Acid Rain Audit Results for Trace Metals (All Data). ... 28
22 Acid Rain Audit Results for Trace Metals
(Outliers Removed) 29
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Number
1 Carbon Monoxide Audits .
2 Sulfate Audits
3 Nitrate Audits
h Lead Audits
5 Acid Rain Audit Results
6 Acid Rain Audit Results
7 Acid Rain Audit Results
8 Acid Rain Audit Results
9 Acid Rain Audit Results
10 Acid Rain Audit Results
11 Acid Rain Audit Results
12 Acid Rain Audit Results
13 Acid Rain Audit Results
Ik Acid Rain Audit Results
15 Acid Rain Audit Results
16 Acid Rain Audit Results
17 Acid Rain Audit Results
18 Acid Rain Audit Results
19 Acid Rain Audit Results
20 Acid Rain Audit Results
21 Acid Rain Audit Results
22 Acid Rain Audit Results
23 Acid Rain Audit Results
for pH ,
for Conductivity ...
for Acidity ,
for SO^ (Reported as S)
for NOj (Reported as N)
for Cl
for F ,
for NHj^ (Reported as N)
for Ca
for K ,
for Mg ........
for Na
for Mn
for Fe
for Cd
for Cu
for Ni
for Pb
for Zn
30
31
32
33
35
35
36
36
37
37
38
38
39
39
1*0
Uo
41
Ul
42
42
43
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ACKNOWLEDGMENTS
Recognition is due to the technical staff of NSI Technology Services,
Inc., Research Triangle Park, North Carolina, who produced and analyzed all
of the high quality chemical samples utilized in the audits. Also, ve
thank the staff of Global Geochemistry, Inc. for their responsive analytical
services as the referee laboratory.
vii
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SECTION 1
INTRODUCTION
The National Performance Audit Program (NPAP) for ambient air is con-
ducted by the Atmospheric Research and Exposure Assessment Laboratory (AREAL)
of EPA at Research Triangle Park, NC. NPAP provides EPA management a means
to assess the compliance of agencies operating monitors in the SLAMS (State
and Local Air Monitoring System) network to one aspect of the minimum QC
program required under Section 2.0 of kO CFR Part 58, Appendix A. The NPAP
complements the biannual systems audits conducted on the SLAMS network by the
EPA regional offices. Organizations operating SLAMS samplers and PSD samplers
are required by HO CFR 58 to participate in the appropriate NPAP audits.
Although participation is mandatory, organizations operating SLAMS and
PSD samplers can benefit from participation in NPAP because it provides them
a means to compare their performance on the audit to that obtained by all
organizations who participated in that audit. Participation in the NPAP can
also identify out-of-control situations in the participant's QC program.
However, an organization cannot validly use NPAP data to adjust or invalidate
monitoring data unless there is a basis for doing so from its internal QC
program.
Until the 1987 audits, potential NPAP participants were primarily iden-
tified using input from the EPA regional offices and the previous year's
mailing lists. This system was only moderately effective in assuring that
organizations operating SLAMS and PSD sites participated in the NPAP as re-
quired under kO CFR Part 58. Significant improvements were made in this area
in 1987 due to changes in the SLAMS regulations that required each agency to
report their precision and accuracy data from each monitor. Additional
improvements were made in the 1988 audits and by 1989 we expect to be able to
identify all organizations that must participate in the NPAP.
In 1987, audits were done on the following criteria air pollutants: SC>2,
CO, high volume/PM-10 size selective inlet sampler (flow only), and lead
(analysis only). In 1989, audits will be initiated for dichot sampler (flow
only), N02 and 0^. The addition of these audits will permit EPA to audit all
the criteria air pollutant measurements under NPAP. Audits for sulfate and
nitrate on filter strips and for acid rain are also done under the NPAP
program for reasons of cost. These latter non-criteria pollutant audits,
which check only the analytical portion of the method, are optional and are
open to governmental, academic and commercial organizations. (Most of the
criteria pollutant audits are restricted to SLAMS and PSD site operators.)
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Approximately U50 organizations participated in NPAP in 1987. The
total number of participants has remained essentially unchanged since I98k
for all the audits concerned with criteria pollutants and for the sulfate
and nitrate audits. There was a 7 percent increase in the acid rain audit
from 1985 to 1986 and this increase remained in the 1987 audits. The num-
ber of participating organizations and/or samplers audited are summarized
in Table 1 for the 1987 audits. The percentage of the participants by
organization type is also presented in this table. Both the percentage of
participation by organization type and the number of participants/samplers
audited has remained quite constant since 198*+ for all audits.
All participants receive an evaluation of their performance shortly
after the audit is completed. When practical, those submitting abnormally
high or low results are offered an opportunity to analyze another set of
samples. However, the retest results are not included in this summary
report. In any case, participants with excessively deviant values can
investigate their operations to identify and correct the cause of the large
errors.
Throughout this report, reference is made to "assigned values." These
values are the standards against which reported results are evaluated and
have been so designated after consideration of the analytical results of
the referee laboratory, the QAD/AREAL Standards Laboratory, and the manu-
facturer of the audit material.
The audit materials used in the NPAP in 1987 are described below.
CARBON MONOXIDE AUDIT
These audit materials consist of a mixture of CO, C02 and CHlj. and zero
air in a disposable pressurized gas cylinder that simulates an ambient air
sample. Directions specify that the gas sample be introduced into a con-
tinuous analyzer in the "sample" mode to permit the analyzer to draw the
sample in the same fashion and at the same flow rate ao during ambient air
monitoring.
SULFATE, NITRATE, AND LEAD ON FILTER STRIPS
The filter strip samples used are 1.9 cm wide by 20 cm long. They are
cut from 20- by 2U-centimeter glass fiber filters, spiked with an aqueous
solution of the appropriate solution and oven dried. After analysis, pol-
lution concentrations are computed by assuming that the samples were col-
lected on the prescribed high volume filter with a sample air volume of
2000 m3. Six sample strips comprise a set. The sulfate, nitrate, and lead
samples were prepared from a^ieous solutions of sodium sulfate, potassium
nitrate, and lead nitrate, respectively.
PM-10(SSI)/HIGH VOLUME FLOW AUDIT
The reference flow (ReF) device used for this audit consists of a mod-
ified orifice, a wind deflector, a manometer, and five resistance plates.
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A single ReF device is supplied to each participating agency with instruc-
tions to check samplers at as many sampling sites as feasible. Before use
in the audit, each ReF device is calibrated with a positive displacement
meter traceable to the National Bureau of Standards (NBS). During the
audit, the device is mounted on top of the sampler and replaces the filter
faceplate. The wind deflector is then positioned to prevent fluctuations
in the measurements due to wind blowing across the orifice.
SULFUR DIOXIDE CONTINUOUS MONITORS
The auditing device for the S02 continuous ambient air monitors is a
dilution system that provides a mechanism to control the quantity of S02
and diluent air that are mixed and then passed into the monitor. The flow
rate of each gas is controlled by maintaining a predetermined pressure drop
across a porous plug flow restrictor, and the 502 concentration is changed
by using different combinations of these flow restrictors.
The audit device, which is housed in a compact, lightweight, impact-
resistant case, is constructed so that only the controls needed to operate
the system are exposed. By opening and closing different toggle valves, it
is possible to generate up to seven preset pollutant concentrations. Five
are used for the audit. Two compressed gas cylinders are supplied with
each unit, one as the S02 source and the other as the dilution air source.
Each audit device is calibrated at the five settings used in the audit with
the flow calibration referenced to laminar flow elements traceable to NBS
flow standards.
ACID RAIN
Five aqueous solutions in polyethylene bottles containing the anions
and cations found in rain water are shipped to each of the participating
organizations. All samples are diluted 1:50 by the participant. Three of
the five samples are analyzed for pH, conductivity, acidity and the major
cations and anions normally measured in precipitation samples and the other
two samples are analyzed for heavy metals. The latter two samples are acid
stabilized to prevent loss of metals from the solution during shipment.
The chemical composition of these samples is certified by using an NBS
standard reference material (SRM). The participants analyze the samples
using the analytical procedures they normally employ when analyzing pre-
cipitation samples. The results are reported on the basis of the sample
concentration after the 1:50 dilution.
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SECTION 2
RESULTS AND DISCUSSION
The NPAP results do not warrant a sophisticated statistical analysis for
a variety of reasons. For example, the summary statistics cannot be used to
adjust the SLAMS data base, and an individual audit result cannot be used by
itself to invalidate data from a SLAMS or PSD monitor. Also, at this time,
it is not possible to compare the precision and accuracy data reported for a
SLAMS monitor to that obtained in the NPAP except at the local level. How-
ever, the NPAP data does provide a means to detect any general trends in the
performance of organizations measuring criteria air pollutants. It also
provides each participant an opportunity to compare his result to the results
reported from all organizations that participated in the audit. The summary
statistics and the figures in this report are adequate for these two latter
purposes.
With the exception of the sulfur dioxide and the flow audit results, the
results for the 198? NPAP audits are summarized in tabular form using: the
mean (same value as the median), the mean of the difference from the assigned
value (% Ace.) and the standard deviation of the differences (% CV). The mean
is the average of all the values reported for that concentration level. The
data is presented with and without the outliers removed. Outliers were
eliminated as follows. First the results from laboratories/sites whose
values for all samples exceeded ± 20 percent of the assigned value were
removed from the data base. The excluded values represented approximately 5%
of the total number of results, which is approximately the same as for 1983
through 1986 (l, 2. 3. k). Then, individual sample results were rejected as
outliers based on Chauvenet's Criterion (5). After outliers were eliminated,
the results from all participants were normally distributed.
At each audit level, the percent accuracy (% Ace.) and the precision, as
measured by the percent coefficient of variation (% CV), were calculated
using Equations 1 and 2, respectively. The percent accuracy measures how
well the average of all participants agrees with assigned values. The per-
cent coefficient of variation measures the variability among participants.
% Ace. = audit mean - EPA assigned value x -LQO (l)
EPA assigned value
% CV = audit standard deviation x ]_QQ (2)
audit mean
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Overall accuracy and precision values for each audit were also calcu-
lated and plotted (Figures 1 through 23) to show the historical record of
performance for each type of audit. All of the figures present the results
of the performance audits after elimination of the outliers. Also, for each
audit in which the % CV remained approximately constant over the range of
audit levels, the average % Ace. can be considered a measure of the percent
shift from an ideal slope of 1.00 for a regression line (with an intercept of
zero) between the audit level mean and the EPA assigned value.
Overall, the performance of the organizations participating in the
criteria air pollutant audits (lead, carbon monoxide, sulfur dioxide, hi-vol/
SSI flow) has changed little since 1983. The types and numbers of monitors/
analytical methods employed by the participants has also changed little.
For example, the following observations on the 198? NPAP audit also apply at
least to the 1985-1986 audits and, in many cases, to the 1983-198U audits.
Carbon Monoxide Audit (Tables 2, 3 and k and Figure l). Approximately
85 percent of the monitors audited in 1987 used NDIR as their measurement
principle and the other 15 percent used as filter correlation. As in ear-
lier audits, both monitor types gave similar % Ace. and % CV results. Per-
cent ACC. and % CV have not changed since 1980 (Figure l), and the percent
frequency distribution (Table k) has been constant since 1983. For example,
in the 0187 carbon monoxide audit, 98.7 percent of the results for the Level
2 sample were within 10 percent of the assigned value. This compares close-
ly to values of 99'1 percent, 98.1 percent, 96.7 percent, and 96.9 per-
cent reported for this sample in the 1986, 1985, 198U, and 1983 audits,
respectively.
Sulfate Audit (Tables 5, 6 and 7 and Figure 2). The overall results
have been essentially constant for % Ace. and % CV since 1983 (Figure 2). In
1986, the number of organizations participating dropped approximately 15
percent from the 1983-1985 audits, and then was constant from 1986 to 1987.
Since 1983, the results for this audit have been very similar. For example,
the manual methods have always had a larger % Ace. and % CV than the auto-
mated methods. Similarly, the automated methylthymol blue method has consis-
tently yielded results that are less precise than the ion chromatographic
method (Table 6). The only major change has been in the percent of organiza-
tions that used the ion chromatograph method. Between 1983 and 1985, ^0% of
the participants who used the automated methods analyzed the samples by ion
chromatography. In 1986 this increased to 50 percent and in 1987 it increased
to 70 percent of the automated analyses. The percent frequency distribution
(Table 7) has also remained constant since 1983.
Nitrate Audit (Tables 8, 9 and 10 and Figure 3). The nitrate results
are very similar to the sulfate results concerning the percent frequency
distribution (constant from 1983 to 1987) and the shift from the automated
cadmium reduction method to the ion chromatographic method (UO percent in
1983-1985, 60 percent in 1986, and 70 percent in 1987). Since 198U, both %
Ace. and % CV have been reasonably constant (Figure 3), and the ion chromato-
graphic method has consistently yielded a smaller % Ace. than the other
automated analytical method (Table 9).
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Lead Audit (Tables 11 and 12 and Figure U). Since 1979, the % CV and
the % Ace. have remained essentially unchanged (Table 11 and Figure h) . The
percent frequency distribution (Table 12), the number of participants (90 to
100), and the percentage of the participants using atomic absorption (98 per-
cent) has also remained constant.
Sulfur Dioxide Audit (Table 13). The number of monitors audited in 1987
(262) represents a slight increase from 1985 and 1986 when 2^5 monitors were
audited. The fluorescence method continued to increase its share of the
monitors checked; that is, in 1987 at least 95 percent of the 262 monitors
audited used fluorescence as their measurement principle (the operating prin-
ciple of 8 of the 262 monitors was not identified by the participant). This
compares to 92 percent in 1986 and 90 percent in 1985. Because each sulfur
dioxide audit device has unique dilution factors, it is possible only to
provide the concentration range in ppb for each level, the mean difference
in ppb for all results for a specific level (same as the median in absolute
value), and the standard deviation in ppb about the mean difference. The
results from the 1987 audit (Table 13) compare very closely to those from
to 1986.
High Volume/PM-10 Size Selective Inlet (SSl) Flow Audit (Table ih) .
Approximately 1333 samplers were audited; aproximately 8 percent of the re-
sults were discarded because they were outliers. As in the 198^-1986 audits,
samplers equipped with pressure transducers and rotameters were the most
frequently audited samplers, comprising approximately 60 percent of the 1333
samplers audited for flow. Each NPAP audit device has unique calibration
factors, so it is possible to provide only the approximate flow in m3/min
for each resistance plate. The audit data is reported only as percent dif-
ference and not in m3/min. The data base is too large (HOOO data points)
to tabulate the results by hand and until new software is available (1989),
we can report the results only in terms of the percentage difference from the
audit device's assigned flow value. These results (Table lU) are essentially
unchanged from those obtained between 198U and 1986.
Acid Rain Audits (Tables 15 through 22 and Figures 5 through 23). Par-
ticipation in this audit increased each year from 1983 to 1986, but then
stabilized. One interesting feature is the high percentage of participants
who represent state and local agencies; that is, between 55 percent and 75
percent of the participants in the eight NPAP audits conducted since 198U
have come from this group. Although there are 19 parameters that can be
analyzed, most participants analyze only for pH (100 percent), conductivity
(85-90 percent), and the major anions (60-70 percent). Less than 50 percent
analyze for the major cations and less than 35 percent analyze for the six
heavy metals and for acidity.
The audit results for 1987 are presented in Tables 15 through 22, and
the performance of the particpants from a historical perspective are pre-
sented in Figures 5 through 23.
The short history of this audit, the small number of participants for
most of the 19 parameters and the tendency for many of the participants to
report their results to only one significant figure make it difficult to draw
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conclusions about the sample results. The lov concentrations in the sample
mean that a small absolute difference (mg/L) can appear to be a large rela-
tive difference (% CV, % Ace.). Also, sometimes removing just one or two
sample results yields a noticeable improvement in the % CV and % Ace. It
is therefore recommended that the reader not scrutinize the tables, but rather
inspect the historical performance of the audit participants as shown in
Figures 5 through 23.
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REFERENCES
1. Parr, B.F., R.L. Lampe, G. Pratt, O.L. Dovler and W.J. Mitchell. Na-
tional Performance Audit Program. Ambient Air Audits of Analytical
Proficiency, 1986. U.S. Environmental Protection Agency Report EPA
600/U-87-038. Research Triangle Park, North Carolina 27711. December
1987.
2. Parr, B.F., R.L. Lampe, G. Pratt, O.L. Dowler and W.J. Mitchell. Na-
tional Performance Audit Program. Ambient Air A\idits of Analytical
Proficiency, 1985. U.S. Environmental Protection Agency Report EPA
600A-87-002. Research Triangle Park, North Carolina 27711. January
1987.
3. Parr, B.F., R.L. Lampe, G. Pratt, O.L. Dowler and W.J. Mitchell. Na-
tional Performance Audit Program. Ambient Air Audits of Analytical
Proficiency, 198U. U.S. Environmental Protection Agency Report EPA
600A-86-013. Research Triangle Park, North Carolina 27711. Febru-
ary 1986.
U. Lampe, R.L., B.F. Parr, G. Pratt, O.L. Dowler and W.J. Mitchell. Na-
tional Performance Audit Program. Ambient Air Audits of Analytical
Proficiency, 1983. U.S. Environmental Protection Agency Report EPA
600A-8U-077. Research Triangle Park, North Carolina 27711. October
198U.
5. Chauvenet, W. A Manual of Spherical and Practical Astronomy. J.B.
Lipincott and Company, Philadelphia, Pennsylvania, 1863.pp. 558-566.
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TABLE 2. AUDIT RESULTS FOR CARBON MONOXIDE
Audit
0187
0787
0187
0787
Level
1
2
3
1
2
3
1
2
3
1
2
3
n
301
305
305
289
277
283
297
300
298
283
273
283
Assigned
value (ppm)
A. ALL
8.10
15.10
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21.20
ki.6o
B. OUTLIERS
8.10
15.10
3k. kO
5.90
21.20
ill. 60
Mean
(ppm)
DATA
8.2k
15. 11*
3U.15
5.88
21. lU
1*1.80
REMOVED
8.2U
15.15
3U.19
5.88
21.13
Ul.80
% Ace.
1.73
0.26
0.73
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-0.28
0.48
1.72
0.33
-0.6l
-0.3U
-0.33
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% CY
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3.17
2.81
5.95
2.93
2.32
3.52
2.77
2.28
5.95
2.70
2.32
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t
00
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11
-------
TABLE U. PERCENT OF CARBON MONOXIDE MEASUREMENTS WITHIN
INDICATED PERCENTAGE OF ASSIGNED VALUES
Audit
0187
0787
0187
0787
Level
1
2
3
1
2
3
1
2
3
1
2
3
Assigned
value (ppm)
A. ALL
8.10
15.10
5.90
21.20
1*1.60
B. OUTLIERS
8.10
15.10
5.90
21.20
Ul.60
10$
DATA
95.7
98.14
98.14
85.9
9^.8
9^.8
REMOVED
96.1
98.7
98.7
86.5
95.5
98.3
20%
98.14
100.0
100.0
9U.8
96.2
99.0
98.U
100.0
100.0
97.9
96.5
99.3
30%
98.7
100.0
100.0
98.6
96.6
99.3
98.7
100.0
100.0
98.6
96.5
96.5
50%
98.7
100.0
100.0
99.7
96.6
99.3
98.7
100.0
100.0
98.3
99.3
99.3
12
-------
TABLE 5. AUDIT RESULTS FOR SULFATE ON FILTER STRIPS
Audit
0287
0887
0287
Level
1
2
3
1*
5
6
1
2
3
1*
5
6
1
2
3
1*
5
6
n
50
1*9
50
50
50
50
1*3
1*2
1*3
1*3
1*2
1*3
UT
1*5
1*6
1*6
1*7
1*7
Assigned
value (yg/m3) (
A. ALL DATA
1.78
2.88
20.37
26.1*2
8.16
6.30
2.95
2.13
5.89
21*. 56
7.08
21.68
B. OUTLIERS REMOVED
1.78
2.88
20.33
26.1+2
8.16
6.30
Mean
1.91
2.73
20.01*
25.80
8.38
6.31*
2.97
2.21
5.81*
2l*.10
7.23
21.57
1.77
2.80
20.30
26.37
7.96
6.16
% Ace.
7.30
-5.21
-1.61*
-2.35
2.70
0.63
0.68
3.76
-0.85
-1.87
2.12
-0.51
-0.56
-2.78
0.3l*
-0.19
-6.1*5
2.22
% CV
56.02
20.15
16.27
ll*.53
33.53
36.12
16.81*
25.31*
12.81*
5.22
9.95
7.23
27.69
8.57
7.1*1*
1*.78
9.30
8.1*1*
0887
None removed
13
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111
-------
TABLE 7. PERCENT OF SULFATE MEASUREMENTS WITHIN
INDICATED PERCENTAGE OF ASSIGNED VALUE
Audit
028T
0887
0287
Level
1
2
3
1+
5
6
1
2
3
U
5
6
l
2
3
k
5
6
Assigned
value (yg/m3)
A. ALL
1.78
2.88
20.37
26.1*2
8.16
6.30
2.95
2.13
5.89
2U.56
7.08
21.68
B. OUTLIERS
1.78
2.88
20.37
26. h2
8.16
6.30
10%
DATA
58.0
68.0
76.0
88.0
76.0
76.0
65.1
65.1
76.7
83.1+
69.8
93.0
REMOVED
60 .1*
70.8
79.2
91.7
79.2
79.2
20%
78.0
88.0
90.0
9^.0
90.0
90.0
86.0
76.7
93.0
100.0
90.7
97.7
81.3
91.7
93.8
97.9
93.8
93.8
30%
80.0
90.0
9^.0
9^.0
92.0
9^.0
93.0
QQ.k
97.7
100.0
97.7
97.7
88.9
93.8
97.9
97.9
95.8
97.9
50%
88.0
92.0
96.0
96.0
96.0
96.0
97.7
93.0
97.7
100.0
97.7
100.0
91.7
93.8
100.0
100.0
97.9
100.0
0887 None removed
15
-------
TABLE 8. AUDIT RESULTS FOR NITRATE ON FILTER STRIPS
Audit
0287
0887
0287
Ooo7
Level
1
2
3
U
5
6
l
2
3
U
5
6
1
2
3
U
5
6
1
2
3
U
5
6
n
U5
U5
U5
U5
U5
U5
36
35
36
36
35
36
Ul
Uo
Uo
Uo
39
Ul
33
31
32
33
31
33
Assigned
value (pg/m3) (
A. ALL DATA
0.59
1.20
3.59
8.22
12.02
13.12
1.25
0.96
U.16
8.77
12. US
13.61
B. OUTLIERS REMOVED
0.59
1.20
3.59
8.22
12.02
13.12
1.25
0.96
U.16
8.77
12. U3
13.61
Mean
0.65
1.19
3.6l
8.08
11.96
13.10
1.28
0.98
U.ll
8.61
12.12
13.10
0.63
1.21
3.6U
8.25
12.12
13. lU
1.29
0.98
U.20
8.87
12. U7
13.53
% Ace.
10.17
-0.83
0.56
-1.70
-0.50
-0.15
2.UO
2.08
-1.20
-1.82
-2.U9
-3.75
6.78
0.83
1.39
0.36
0.8U
0.15
3.20
2.08
0.96
1.1U
0.32
-0.59
% CV
US. 08
31.09
21.33
22. UO
22.91
23.66
21.89
22. U5
16.06
13.70
1U.77
13.89
25. UO
11.57
6.32
5.33
U.13
8.U5
12. UO
13.27
U.76
U.62
3.U5
U.73
16
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17
-------
TABLE 10. PERCENT OF NITRATE MEASUREMENTS WITHIN
INDICATED PERCENTAGE OF ASSIGNED VALUE
Audit
0287
0887
0287
0887
Level
1
2
3
U
5
6
l
2
3
U
5
6
1
2
3
k
5
6
1
2
3
k
5
6
Assigned
value (yg/np)
A. ALL
0.59
1.20
3.59
8.22
12.02
13.12
1.25
0.96
U.16
8.77
12. U3
13.61
B. OUTLIERS
0.59
1.20
3.59
8.22
12.02
13.12
1.25
0.96
U.16
8.77
12.1+3
13.61
10*
DATA
U2.2
66.7
77.8
82.2
82.2
77.8
50.9
63.9
83.3
88.9
86.1
86.1
REMOVED
U5.2
71. U
83.3
88.1
88.1
83.3
52.9
67.6
93.8
9U.1
91.2
91.2
20$
6H.U
77.8
88.9
88.9
88.9
8U.it
75.0
69. U
88.9
97.2
86.1
91.7
69.1
83.3
95-2
95.2
95.2
90.5
79. U
73.5
9U.1
100.0
91.2
97.1
30%
75.6
86.7
91.1
93.3
93.3
91.1
91.7
80.6
9U.U
97.2
9U.U
97.2
91.7
80.6
9U.U
97.2
9U.U
9T.2
9U.1
85.3
97.1
100.0
97.1
100.0
50%
82.2
93.3
95.6
93.3
95.6
93.3
9U.U
9H.U
97.2
97.2
9U.U
97.2
9U.U
91.7
97.2
97.2
9U.U
97.2
97.1
9U.1
LOO.O
LOO.O
97.1
100.0
18
-------
TABLE 11. AUDIT RESULTS FOR LEAD ON FILTER STRIPS
Audit
0187
0787
Level
1
2
3
k
5
6
1
2
3
k
5
6
n
9^
9^
9^
9U
9^
93
88
88
89
89
89
89
Assigned
value (ug/m3)
A. ALL DATA
1.68
0.55
1.17
3.60
8.72
6.91
0.51*
1.12
1.98
3.59
6.50
7.00
B. OUTLIERS REMOVED
Mean
(yg/n:3)
1.75
0.60
1.12
3.5^
8.51
6.69
0.52
1.17
2.02
3.58
6.70
7.01
% Ace.
^.17
9.09
-U.27
-1.67
-2. ill
-3.18
-3.70
k.h6
2.02
-0.28
3.08
O.lU
% cv
5.71
15.00
5.36
6.78
5.U1
10.76
19.23
11.97
11.39
10.89
6.27
8.H2
0187
0787
None removed
None removed
19
-------
TABLE 12. PERCENT OF LEAD MEASUREMENTS WITHIN
INDICATED PERCENTAGE OF ASSIGNED VALUE
Audit
Level
Assigned
value (yg/nP)
10%
20%
30%
5or»
A. ALL DATA
0187
0787
1
2
3
It
5
6
1
2
3
It
5
6
1.68
0.55
1.17
3.60
8.72
6.91
0.5H
1.12
1.98
3.59
6.50
7.00
B. OUTLIERS
88.3
67.0
90.it
87.2
88.3
88.3
75.2
87.6
88.8
9H.U
91.0
92.1
REMOVED
98.lt
89.lt
98. 1;
98.lt
100.0
97.9
93.3
9H.H
9H.lt
96.6
97.7
96.6
98. U
93.6
100.0
98.lt
100.0
97.9
9H.lt
9H.H
97.7
97.7
98.9
96.6
100.0
97.9
100.0
100.0
100.0
97.9
95.5
96.6
98.9
98.9
100.0
100.0
0187
0787
None removed
None removed
20
-------
TABLE 13. AUDIT RESULTS FOR SULFUR DIOXIDE CONTINUOUS MONITORS8-
Flow
setting
1
2
3
k
5
6
Number of
monitors
audited
Ul
2U2
2k9
2k9
2k9
1U8
Range of
cone.
(ppb)
TTO-560
510-360
270-190
210-lUO
70-UO
0
Mean
difference
(ppb)
-32
-8
_2
_2
0
1
Std. dev.
of the mean
(ppm)
k9
28
17
1U
5.0
2.1
aData is for only those monitors that use fluorescence as their measurement
principle.
TABLE Ik. PERCENT OF HIGH VOLUME FLOW MEASUREMENTS WITHIN
INDICATED PERCENTAGE OF ASSIGNED VALUE (ALL DATA)
Plate
number
5
7
10
13
18
Number of
measurements
521
719
872
905
908
Approximate
flow (m3/min)
0.7
0.9
1.1
1.2
1.3
10%
72.6
83.6
86.7
88.8
89.8
20%
89.9
93.7
96.2
96.7
96.9
30%
9k. 6
97. k
98.2
98.3
98.2
50%
98.5
99.2
99.6
99.5
99.7
21
-------
TABLE 15. ACID RAIN RESULTS FOR pH, CONDUCTIVITY AND ACIDITY (ALL DATA)
Audit
OU87
1087
PH
Conductivity
(yS/cm)
Acidity
(yequiv/L)
PH
Conductivity
(uS/cm)
Acidity
( yequiv/L)
Level
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
n
39
38
39
35
31*
35
11*
13
11*
1*8
1*8
1*8
1*1
1*1
1*1
16
16
16
Assigned
value
1*.27
3.69
3.92
2>*.5
98.5
65.1
5^.5
211*. 3
121*. 3
U.51
3.91
3.57
16.5
62.8
128.7
33. 1*
129. U
285.3
Mean
1*.23
3.62
3.86
26.3
100.7
70.0
77. U
21*9.5
11*8.7
1*.1*7
3.86
3.55
15.6
60.2
125.3
52.1*
131.1
282.1
% Ace.
-0.89
-1.92
-1.1*5
7.1*7
2.25
7.65
1*2.03
16.1*3
19.69
-0.80
-1.23
-0.98
-5.20
-1*.03
-2.61
56.9
1.39
-1.12
% CV
6.8
6.8
6.5
61*. 2
55.9
52.7
83.1
53.7
67.U
6.2
6.9
3.6
12.3
9.U
8.0
97.1
33.1
31*. o
22
-------
TABLE 16. ACID RAIN RESULTS FOR pH, CONDUCTIVITY
AND ACIDITY (OUTLIERS REMOVED)
Audit
0487
1087
pH
Conductivity
US/cm)
Acidity
( pequiv/L)
PH
Conductivity
(uS/cm)
Acidity
( yequiv/L)
Level
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
n
38
37
38
34
33
34
13
12
13
1+7
47
47
ho
4o
39
15
15
15
Assigned
value
4.27
3.69
3.92
24.5
98.5
65.1
54.5
214.3
124.3
4.51
3.91
3.57
16.5
62.8
128.7
33.4
129. 4
285.3
Mean
^.27
3.66
3.91
23. U
91.5
63.8
63. U
219.8
125.1
4.51
3.90
3.55
15.7
60.6
126.7
4o.7
139.0
299.8
% Ace.
0.00
-0.87
-0.46
-8.11
-7.05
-1.88
16.37
2.58
0.70
0.00
-0.28
-0.59
-4.29
-3.52
-1.51
21.92
7.48
5.10
% CV
3.4
1.9
2.0
1.2
20.0
6.5
6l.5
38.3
39.6
3.4
2.3
2.4
10.3
8.4
6.3
51.2
22.3
22.4
23
-------
TABLE IT. ACID RAIN AUDIT RESULTS FOR ANIONS (ALL DATA)
Audit Level
Ql*87 SOi^ (reported
as S)
NO^ (reported
as N)
Cl
F
1087 SOij. (reported
as S)
NOo (reported
as N)
Cl
F
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
Assigned
n value (mg/L)
26
27
28
28
27
28
25
21*
25
15
Hi
17
32
31*
31*
33
33
3>*
32
33
32
ll*
17
18
0.90
1*.13
2.13
0.11
0.12
0.86
0.29
0.36
1.12
0.03
0.09
0.19
0.52
2.6H
3.76
O.lU
0.11
l.Ul
0.39
0.6U
0.93
0.05
0.08
0.25
Mean
(mg/L)
1.25
1*.1*5
2.71*
0.20
0.21
1.11
0.1*5
0.1*8
1.26
0.08
0.16
0.30
0.62
3.08
3.73
O.lU
0.10
1.31
0.1*1
0.63
0.91
0.08
0.11
0,3l*
% Ace.
38.0
7.8
28.0
81*. 0
75.0
29.0
55.0
33.0
10.0
160.0
80.0
55.0
18.0
17.0
0.7
0.0
9.9
7.6
5.1*
-1.5
-1.9
-60.0
37.0
36.0
% CV
65.0
1*5.0
55.0
192.0
187.0
81.0
lUU.O
95.0
1*6.0
132.0
121.0
117.0
1*1*. 0
1*1*. 0
28.0
29.0
31.0
21.0
37.0
ll*.0
15.0
95.0
61*. 0
12U.O
21*
-------
TABLE 18. ACID RAIN AUDIT RESULTS FOR ANIONS (OUTLIERS REMOVED)
Audit Level
OkQl SOi; (reported 1
as S) 2
3
NO-} (reported 1
as N) 2
3
Cl 1
2
3
F 1
2
3
1087 SOii (reported 1
as S) 2
3
NOg (reported 1
as N) 2
3
Cl 1
2
3
F 1
2
3
n
2k
26
25
27
26
26
23
23
2k
13
1U
16
30
32
31
31
30
32
31
32
31
13
16
17
Assigned
value (mg/L)
0.90
U.13
2.13
0.11
0.12
0.86
0.29
0.36
1.12
0.03
0.09
0.19
0.52
2.61*
3.76
O.lU
0.11
l.Ul
0.39
0.6k
0.93
0.05
0.08
0.25
Mean
(mg/L)
1.07
U.13
2.25
0.13
O.Ik
0.87
0.27
0.39
1.15
O.oH
0.11
0.21
0.56
2.76
3.80
O.Ik
0.12
1.37
0.38
0.62
0.90
0.07
0.09
0.2U
% Ace.
19.0
0.0
5.6
18.0
19.0
0.8
-7.9
8.3
2.6
30.0
27.0
11.0
7.9
U.6
1.0
0.0
9.9
-2.9
-2.5
-3.3
-3.U
1*0.0
12.0
It. 2
% cv
51.0
29.0
22.0
55.0
51.0
5.0
29.0
37.0
18.0
H6.0
68.0
30.0
18.0
15.0
10.0
20.0
13.0
9.0
lU.O
11.0
12.0
ik.Q
21.0
22.0
25
-------
TABLE 19. ACID RAIN RESULTS FOR CATIONS (ALL DATA)
Audit Level
OUST NH-zj (reported 1
as N) 2
3
Ca 1
2
3
K 1
2
3
Mg 1
2
3
Na 1
2
3
108T HH3 (reported 1
as N) 2
3
Ca 1
2
3
K 1
2
3
Mg 1
2
3
Na 1
2
3
n
20
20
21
21
20
22
21
20
23
21
20
22
23
21
23
29
29
29
27
28
22
28
28
29
27
27
27
29
29
28
Asri^ned
value (mg/L)
0.08
0.6l
0.3U
0.05
0.05
0.16
0.07
0.08
0.5U
0.03
0.01
0.06
0.18
0.2k
1.32
0.11
0.6l
0.78
0.06
0.13
0.01
0.07
0.08
0.10
0.01
0.01
0.05
0.2U
0.25
O.U9
Mean
(mg/L)
0.08
0.6U
0.38
0.12
0.15
0.20
0.12
0.11
0.5*+
O.OU
0.02
0.08
0.26
0.31
1.39
0.12
0.6l
0.76
0.08
0.13
0.08
0.11
0.12
0.11
0.02
0.02
0.05
0.26
0.28
0,51
% Ace.
0.0
6.1
10.0
120.0
200.0
25.0
70.0
38.0
0.0
33.0
100.0
33.0
H2.0
30.0
5.3
9.9
0.0
-2.5
-33.0
0.0
700.0
57.0
50.0
10.0
100.0
100.0
0.0
8.2
13.0
U-5
% CV
33.0
2U.O
25.0
1U8.0
254.0
92.0
99.0
52.0
19.0
105.0
182.0
68.0
71.0
71.0
22.0
23.0
lU.O
21.0
138.0
31.0
312.0
119.0
119.0
38.0
26.0
89.0
25.0
56.0
50.0
28.0
26
-------
TABLE 20. ACID RAIN AUDIT RESULTS FOR CATIONS (OUTLIERS REMOVED)
Audit Level
0487 NH3 (reported 1
as N) 2
3
Ca 1
2
3
K I
2
3
Mg 1
2
3
Na 1
2
3
1087 NH3 (reported 1
as N) 2
3
Ca 1
2
3
K 1
2
3
Mg 1
2
3
Na 1
2
3
n
18
19
19
20
19
21
20
19
20
20
19
21
21
20
22
27
28
27
26
26
21
27
27
28
27
25
26
28
28
27
Assigned
value (mg/L)
0.08
0.6l
0.34
0.05
0.05
0.16
0.07
0.08
0.54
0.03
0.01
0.06
0.18
0.24
1.32
0.11
0.6l
0.78
0.06
0.13
0T01
0.07
0.08
0.10
0.01
0.01
0.05
0.2k
0.25
0.1+9
Mean
(mg/L)
0.09
0.67
0.38
0.08
0.07
0.17
0.10
0.10
0.55
0.03
0.01
0.07
0.21
0.27
1.35
0.12
0.63
0.79
0.06
0.13
0.03
0.09
0.09
0.11
0.02
0.01
0.05
0.23
0.26
0.48
% Ace.
12.0
11.0
5.8
60.0
40.0
5.0
42.0
25.0
2.6
0.0
0.0
16.0
16.0
12.0
2.3
9.9
3.1
1.7
0.0
0.0
200.0
30.0
12.0
10.0
100.0
0.0
0.0
4.2
4.0
-2.0
% CV
10.0
12.0
11.0
90.0
48.0
6l.O
62.0
35.0
8.0
28.0
35.0
19.0
34.0
33.0
19.0
14.0
10.0
13.0
39.0
20.0
148.0
28.0
20.0
24.0
26.0
21.0
16.0
17.0
27.0
10.0
27
-------
TABLE 21. ACID RAIN AUDIT RESULTS FOR TRACE METALS (ALL DATA)
Audit
0148T Mn
Fe
Cd
Cu
Ni
Pb
Zn
108T Mn
Fe
Cd
Cu
Ni
Pb
Zn
Level
U
5
1*
5
1*
5
k
5
U
5
U
5
U
5
U
5
h
5
U
5
U
5
U
5
4
5
It
5
Assigned
n value (mg/L)
12
13
11
12
12
12
11
12
10
11
13
13
11
11
19
19
19
19
19
19
18
18
18
18
18
18
17
17
0.05
0.10
0.05
0.11
0.03
0.07
0.05
0.15
0.07
0.08
0.12
0.27
0.09
0.62
0.12
0.03
0.07
0.02
O.lU
0.02
0.20
0.05
0.12
0.05
O.U3
0.13
0.78
0.15
Mean
(mg/L)
0.05
0.10
0.06
0.11
0.03
0.07
0.05
0.15
0.08
0.09
O.lU
0.28
0.09
0.59
0.11
0.03
0.08
0.03
O.lU
0.03
0.21
0.05
0.12
0.05
O.U2
0.13
0.78
0.15
% Ace.
0.0
0.0
20.0
0.0
0.0
0.0
0.0
0.0
15.0
12.0
16.0
3.7
0.0
-H.6
-8.1
0.0
15.0
50.0
0.0
50.0
5.0
0.0
0.0
0.0
-2.3
0.0
0.0
0.0
% CV
20.0
2U.O
27.0
15.0
lU.O
9.0
21.0
8.0
12.0
20.0
1|2.0
17.0
1U.O
10.0
23.0
21.0
23.0
76.0
9.0
8.0
7.0
2U.O
16.0
28.0
7.0
11.0
23.0
9.0
28
-------
TABLE 22. ACID RAIN AUDIT RESULTS FOR TRACE METALS (OUTLIERS REMOVED)
Audit
Olt87 Mn
Fe
Cd
Cu
Ni
Pb
Zn
1087 Mn
Fe
Cd
Cu
Ni
Pb
Zn
Level
1*
5
it
5
1*
5
U
5
It
5
It
5
It
5
U
5
It
5
It
5
It
5
It
5
It
5
It
5
n
11
11
10
11
12
12
11
11
10
10
12
12
11
10
18
17
18
18
18
19
17
17
17
17
18
13
16
16
Assigned
value (mg/L)
0.05
0.10
0.05
0.11
0.03
0.07
0.05
0.15
0.07
0.08
0.12
0.27
0.09
0.62
0.12
0.03
0.07
0.02
O.Ik
0.02
0.20
0.05
0.12
0.05
0.1*3
0.13
0.78
0.15
Mean
(mg/L)
0.05
0.10
0.07
0.11
0.03
0.07
0.05
0.15
0.08
0.08
0.12
0.27
0.09
0.58
0.12
0.03
0.08
0.02
O.Ik
0.03
0.21
0.06
0.12
0.05
O.U2
0.13
0.83
0.16
% Ace.
0.0
0.0
1*0.0
0.0
0.0
0.0
0.0
0.0
15.0
0.0
0.0
0.0
0.0
-6.9
0.0
0.0
15.0
0.0
0.0
50.0
5.0
20. U
0.0
o.o
-2.3
0.0
9.2
6.7
% CV
llt.O
8.0
16.0
10.0
llt.O
9.0
21.0
6.0
12.0
13.0
12.0
8.0
llt.O
6.0
5.0
9.0
12.0
38.0
5.0
8.0
5.0
10.0
6.0
13.0
7.0
9.0
3.0
lt.0
-------
<1>
o
DC
O
m
3
Qr
UJ
0)
o
O
UJ
s
cc
UJ
AUDIT DATE, month/year
ACCURACY
IO/76 O3/77 O9/77 O3/7S 09/78 03/79 09/79 03/BO 09/BO O3/B1 OS/81 O3/82 C9/8Z OS/83 1O/83 O4/84 OS/85 04/88 01/07 07/87
AUDIT DATE, month/year
PRECISION
Figure 1. Carbon Monoxide Audits
30
-------
c
0)
s
09
a
O
O
LU
5
cc
LU
13 --
12
1 1
10 -|
9 -i
°l
6 Hi
O 5
i i
4-j \
3
2
It*
2 -|
-H
-4 -1
i
-6 I -,
A
~T ~T
1O//6 O2/77 O8/77 02/7S O8/7B 02/79 08/79 02/8O OB/8O 02/81 08/81 O2/82 OB/82 02/83 O8/83 O2/84 OB/84 02/86 D8/85 02/Bfl OB/86 02/87 O8/B7
AUDIT DATE, month/year
ACCURACY
50 f
c 40
0)
o
0)
a
O 30 -
LU >
tr
LU
20
10 -
0 -+n r-n
^
V
8 O2/77 08/77O2/7« 08/78 O2/7908/79 O2/8O 08/8002/8 108/81 02/8208/8202/8308/8303/84 08/84 02/8608/86 O2/8608/8602/67 O6/87
AUDIT DATE, month/year
PRECISION
Figure 2. Sulfate Audits
31
-------
X
o
<
5
o
Ul
Or
Ul
-2
i i i i T i i i i i i i ₯ i i i i i r
10/76 02/77 OS/77 02/78 O8/7B 02/79 08/79 02/80 OS/80 02/81 1,4/81 02/82 08/82 02/83 OB/89 02/84 OS/84 02/86 OB/86 02/86 O8/86 O2/87 O8/87
AUDIT DATE, month year
ACCURACY
50
-------
-3,5
01/78 06/78 01/79 07/78 01/80 O7/80 01/81 07/81 01/8Z O7/a2 01/83 07/83 01/84 07/84 01/86 07/85 O1/86 07/86 01/87 07/B7
AUDIT DATE, month/year
ACCURACY
50
45
40 --! /
35
+J
c
4>
JJ3 30 H /
a I'
O
UJ
<
tr
ui
257*:
20
15
10
5
0
O6/77 01/77 O6/78 01/78 07/70 01/SO 07/80 01/81 07/81 O1/82 07/82 01/83 07/83 O1/04 O7/84 01/86 O7/86 Qt/Bfl O7/B« 01/87 O7/B7
AUDIT DATE, month/year
PRECISION
Figure 4. Lead Audits
33
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