vvEPA
United States
Environmental Protection
Agency
Environmental Monitoring EPA/600/4-87-038
Systems Laboratory December 1987
Research Triangle Park NC 27711
Research and Development
National Performance
Audit Program
Ambient Air Audits of
Analytical
Proficiency1986
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EPA/600/4-87/038
December 1987
NATIONAL PERFORMANCE AUDIT PROGRAM
AMBIENT AIR AUDITS OF ANALYTICAL PROFICIENCY
-1986-
Blaine F. Parr, Robert L. Lampe, Gregory Pratt,
Oscar L. Dowler and William 0. Mitchell
Quality Assurance Division
Environmental Monitoring Systems Laboratory
Research Triangle Park, North Carolina 27711
ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevacd, 12th Finn*
Chicago, IL 60604-3590
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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.
ii
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ABSTRACT
This report presents the results of the U.S. Environmental Protection
Agency's 1986 National Ambient Air Performance Audit Program by pollutant
and_by analytical method. Semiannual audits were conducted for Pb, NO-j" and
SO/1 on filter strips and acid rain. Annual audits were conducted for CO
ana high-volume sampler flow rate. Continuous S02 monitors were audited
throughout the year, with no monitor being audited more than once. The
results for each 1986 audit are presented in tabular form for each concen-
tration level. The overall performance for all participants for each audit
conducted since the beginning of the program is also shown graphically.
For the most part the results of the 1986 audits are essentially unchanged
from previous audits.
111
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CONTENTS
Abstract .,......*..,.. ,,,,..,... iii
Tables ....................... yi
Figures .,...,,,....., ........... vii
Acknowledgments .................... . viii
1. Introduction ....................... 1
2. Summary and Conclusions ...,.,..,..,..,.. 3
3. Audit Materials ..................... 4
4. Audit Results ........ ....... . 7
References .... ................. 11
Tables .... .........*............ 12
Figures ,.,...,,....,..,..,.,,,.. 35
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TABLES
Number
1 Agency Participation ,...,,.,.,.. 12
2 Audit Results for Carbon Monoxide ............ 13
3 Audit Results for Carbon Monoxide by the NDIR
and GFC Methods ..................... 14
4 Percent of Carbon Monoxide Measurements Within
Indicated Percentage of Assigned Value .......... 15
5 Audit Results for Sulfate on Filter Strips ........ 16
6 Audit Results for Sulfate by the Manual Methods ..... 17
7 Audit Results for Sulfate by the Automated Methods .... 18
8 Percent of Sulfate Measurements Within Indicated
Percentage of Assigned Value ....... ... 19
9 Audit Results for Nitrate on Filter Strips ........ 20
10 Audit Results for Nitrate by the Automated Methods .... 21
11 Percent of Nitrate Measurements Within Indicated
Percentage of Assigned Value ....... 22
12 Audit Results for Lead on Filter Strips ......... 23
13 Percent of Lead Measurements Within Indicated
Percentage of Assigned Value .,,..,..,...... 24
14 Audit Results for Sulfur Dioxide Continuous Monitors
(All Data) ....... ....... 25
15 Audit Results for Sulfur Dioxide Continuous Monitors
by Various Instrumental Methods ............. 25
16 Percent of High Volume Flow Measurements Within
Indicated Percentage of Assigned Value (All Data) .... 26
17 Acid Rain Results for pH, Conductivity and Acidity
(All Data) ..... .............. 27
18 Acid Rain Audit Results for pH, Conductivity and
Acidity (Outliers Removed) ................ 28
19 Acid Rain Audit Results for Anions (All Data) 29
20 Acid Rain Audit Results for Anions (Outliers Removed). . . 30
21 Acid Rain Audit Results for Cations (All Data) 31
22 Acid Rain Audit Results for Cations (Outliers Removed) . . 32
23 Acid Rain Audit Results for Trace Metals (All Data). ... 33
24 Acid Rain Audit Results for Trace Metals
(Outliers Removed) .................... 34
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FIGURES
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
Carbon Monoxide Audits .
Sulfate Audits . , , . ,
Nitrate Audits .......
Lead Audits » . . , .
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
Acid Rain Audit Results
for pH . . . ... . .
for Conductivity . . .
for Acidity .....
for 504 (Reported as S)
for N03 (Reported as NY
for Cl , , . , , , , .
for F
for NH4 (Reported as N)
for Ca .........
for K . *
for Mg ........
for Na . . .
for Mn .. k .....
for Fe . . . . ... .
for Cd ........
for Cu .
for Ni ........
for Pb . *
for Zn ..,**-...
35
36
37
38
39
39
49
40
41
41
42
4.2
43
43
44
44
45
45
46
46
47
47
48
VII
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ACKNOWLEDGMENTS
Recognition is due to the technical staff of Northrop Services, Inc.,
Research Triangle Park, North Carolina, who produced and analyzed all of
the high quality chemical samples utilized in the audits. Also, we thank
the staff of Global Geochemistry, Inc. for their responsive analytical
services as the referee laboratory. Appreciation is due, too, to our QAD/
EMSL colleagues, who contributed to the diverse activities associated with
the audits, in particular Linda Porter and Avis Mines.
vm
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SECTION 1
INTRODUCTION
The audits of proficiency in analyzing ambient air are managed by the
Environmental Monitoring Systems Laboratory (EMSL), of the U.S. Environmen-
tal Protection Agency (EPA). These audits are a part of a continuing
program entitled the National Performance Audit Program. This program
allows EPA to monitor the performance of laboratories (agencies) making air
pollution measurements to assist EPA in assessing the quality of air moni-
toring data. It also allows participating agencies to assess their per-
formance with respect to other agencies making similar measurements. The
audits are conducted by the Quality Assurance Division (QAD) of EMSL.
Inquiries and applications to participate should be directed to: U.S.
Environmental Protection Agency, Quality Assurance Division, Environmental
Monitoring Systems Laboratory, MD-77B, Research Triangle Park, North Caro-
lina 27711.
Most agencies participating in the audits are solicited by the EPA
Regional Quality Control Coordinator in each of EPA's 10 regions. Agencies
performing ambient air monitoring of criteria pollutants are required by
Federal regulation to participate. Once a laboratory enrolls in a particu-
lar audit, it is assigned a permanent identifying code number and automati-
cally notified of subsequent audits. Federal, state, local, industrial and
foreign air pollution monitoring agencies participate in the surveys.
Sample materials furnished for the audits simulate the several types
of collected air pollution samples as closely as possible. The materials
for the manual methods evaluate only the analytical portion of the total
air measurement process; i.e., they do not determine errors in sample
collection, transportation, handling, storage, and data processing. For
the high volume method for total suspended particulate (TSP), the audit
evaluates only the flow measurement portion of the method.
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/EMSL Standards Laboratory, and the manu-
facturer of the audit material.
In 1986, audits were conducted twice for lead, sulfate, nitrate and
acid rain and once for carbon monoxide and the high-volume flow rate.
Audits were conducted throughout the year on sulfur dioxide continuous
monitors.
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Each laboratory participating in an audit received an evaluation of
its performance shortly after the audit was completed. When practical,
laboratories submitting abnormally high or low results were offered an
opportunity to analyze another set of samples. However, the retest results
are not included in this summary report. In any case, laboratories having
excessively deviant values can investigate their operations to identify and
correct the cause of the large errors.
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SECTION 2
SUMMARY AND CONCLUSIONS
Approximately 425 laboratories participated in this audit program in
1986. The category and number of participants in each audit are presented
in Table 1. Compared to the 1985 audits, participation decreased in the
following audits (percentage decline in parentheses): CO (26%), high vol-
ume flow rate (6%), Pb (17%), S04~ (20%), N03" (7%), and S02 continuous
monitor (4%). A 24% increase occurred in the acid rain audits -- the only
audit to show an increase. The performance of the participants as measured
by the percent accuracy and precision (% coefficient of variation) continued
to improve compared to the earlier audits (1,2,3).
Approximately 680 laboratories are registered in the National Ambient
Air Performance Audit Program. This report presents the results of approxi-
mately 425 laboratories that participated in the 1986 audits. The category
and number of participants in each audit are presented in Table 1. Com-
pared to the 1985 audits participation decreased in the following audits
(percentage de_cline in parentheses): CO (26%), high volume flow rate (6%),
Pb (17%), S04~ (20%), N03~ (7%), and SO? continuous monitor (4%). A 24%
increase occurred in the acid rain audits the only audit to show an
increase.
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SECTION 3
AUDIT MATERIALS
The audit sample concentrations spanned the wide range of pollutant
concentrations measured in ambient air monitoring. This is achieved di-
rectly with the CO samples, which are prepared in cylinders. Dilution is
necessary for the acid rain samples to obtain desired concentrations.
Lead, NOg", and S0^~ filter strip samples required extraction with water
and then dilution to a specified volume before analysis. The S02 contin-
uous monitor audit samples required dilution of the S02 with zero air.
Although many air monitoring sites rarely encounter pollutant concen-
trations at the higher audit sample levels, these concentrations were in-
cluded to assure that monitoring methods were verified at the higher levels.
The following paragraphs describe each sample type used in the 1986
audits.
CARBON MONOXIDE
These audit materials consist of a mixture of CO, C02 and CH4 and zero
air in a disposable pressurized gas cylinder that simulates an ambient air
sample. The concentrations of the three CO samples used in the 1986 audits
were 6, 21 and 43 ppm. Directions specify that the gas sample be intro-
duced into a continuous analyzer in the "sample" mode, which permits the
analyzer to draw the sample in the same fashion and at the same flow rate
as during ambient air monitoring.
SULFATE, NITRATE, AND LEAD ON FILTER STRIPS
The filter strip samples used in sulfate, nitrate and lead audits are
each 1.9 cm wide by 20 cm long. They were cut from 20- by 24-centimeter
glass fiber filters, spiked with an aqueous solution of the appropriate
solution and then oven dried. After analysis, pollutant concentrations
were computed by assuming that the samples were collected on the prescribed
high-volume filter with a sample air volume of 2,000 m3. Six sample strips
comprised a set.
Sulfate and nitrate audit samples were prepared from sodium sulfate and
potassium nitrate. Calculated nitrate concentrations ranged from 0.62 to
13.3 yg/m3 and sulfate from 1.6 to 28.0 yg/m3. Lead samples, which are
prepared from lead nitrate ranged in concentration from 0.39 to 8.4 yg/m3
of lead.
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HIGH-VOLUME FLOW RATE (ReF DEVICE)
The reference flow (ReF) device used for audits of high-volume flow
rates consisted of a modified orifice, a wind deflector, a manometer, and
a series of resistance plates. A single ReF device was supplied to each
participating agency with instructions to check samplers at as many sam-
pling sites as feasible.
Before use in the audit each ReF device is calibrated with a positive
displacement meter traceable to NBS. During the audit, the device was
mounted on top of the sampler, replacing the filter faceplate. A wind
deflector was used 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 was a
porous plug dilution system that provided a mechanism whereby controlled
quantities of S02 and diluent air were continuously combined in a mixing
chamber and passed into the monitor. The flow rate of each gas was con-
trolled by maintaining a predetermined pressure drop across the porous plug
flow restrictor. Variable S02 concentrations were obtained by using dif-
ferent combinations of the flow restrictors.
The audit device, which was housed in a compact, lightweight, impact-
resistant case, was constructed so that only those controls required for
system operation were exposed. By opening and closing different toggle
valves, it was possible to generate up to seven preset pollutant concentra-
tions. Five were used for the audit. Two compressed gas cylinders were
supplied with each unit, one as the S02 source and the other as the dilu-
tion air source.
Each audit device was calibrated for flow at all the settings used in
the audit. Flow calibrations were referenced to laminar flow elements
traceable to National Bureau of Standards flow standards. Sulfur dioxide
concentrations ranging from 0.0 to 0.8 ppm were used in the 1986 audits.
ACID RAIN
Five aqueous solutions in polyethylene bottles containing the anions
and cations found in rain water were shipped to each of the participating
laboratories. All samples were to be diluted 1:50 by the participant.
Three samples were then analyzed for pH, conductivity, acidity and the
major cations and anions normally measured in precipitation samples and the
other two samples were analyzed for heavy metals. The latter two samples
were acid stabilized in the concentrate form to prevent loss of metals from
the solution.
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The chemical composition of these samples was certified by using a Na-
tional Bureau of Standards SRM. The participants analyzed the samples using
the analytical procedures they normally employ when analyzing their precip-
itation samples. The results were reported on the basis of the sample
concentration after the 1:50 dilution.
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SECTION 4
AUDIT RESULTS
The results of the 1986 audit are presented in Tables 2 through 24.
The term "audit mean" in these tables denotes the average of all values re-
ported by the participants for that sample after elimination of outliers.
Elimination of outliers was accomplished in a two step procedure. First,
results from laboratories/sites whose values for all samples exceeded ± 20
percent of the assigned value were removed from the data base. The ex-
cluded values represented approximately 5% of the total number of labora-
tories/sites reporting results which is approximately the same as for 1983
through 1985 (1, 2, 3). Then, individual sample results were rejected as
outliers based on Chauvenet's Criterion (4). After outliers were elimi-
nated, the results from all participants were normally distributed about
the mean which was expected from the earlier audits (1, 2, 3).
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
percent coefficient of variation measures the variability among partici-
pants.
% Ace. = audit mean - EPA assigned value x IQQ
EPA assigned value
% CV = audit standard deviation x IQQ (2)
audit mean
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 per-
cent shift from an ideal slope of 1.00 for a regression line (with an inter-
cept of zero) between the audit level means and the EPA assigned value.
CARBON MONOXIDE
In 1986, only 246 monitors were audited -- this 24% decrease from 1985
resulted because a second audit was cancelled due to budget cuts. Eighty-
four percent of the monitors audited were NDIR compared to 86% in 1985 (1)
and 95% in 1984 (2). The remaining monitors were gas filter correlation CO
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monitors. The 246 monitors represent only 53% of the CO monitors in the
SLAMS network in 1986.
As shown in Figure 1, both precision and accuracy have stayed at ap-
proximately the same level for the last six years. Also, the number of
measurements falling within 20% of the assigned value (Table 4) closely
parallels the 1983 through 1985 results (1, 2, 3). Also, as shown in Figure
1, the accuracy has oscillated back and forth across the zero-axis for the
last seven years.
SULFATE ON FILTER STRIPS
Approximately 47 laboratories participated in each audit. The audit
mean, percent accuracy and precision are given in Table 5. Over the years
accuracy has varied quite a bit, but now it seems to have stabilized (Figure
2). Precision has also stabilized after improving continually for several
years.
As in 1985, there also is no apparent relationship between concentra-
tion and either precision or accuracy for the manual and for the automated
methods (Tables 6 and 7).
Except for the lowest sample concentration, between 70 and 100% of the
laboratories reported results within + 20% of the assigned values (Table 8)
about the same as in 1983-1985 (1, 2, 3).
NITRATE ON FILTER STRIPS
Approximately 42 laboratories participated in each 1986 audit. Parti-
cipation was down approximately 7% from 1984. As in the sulfate audits,
the number of participants has been fairly constant since 1979. Both
accuracy and precision seem to have reached a plateau because no improve-
ment is evident over the last couple of years (Figure 3).
The results from the 1986 nitrate audits show only a slight decrease
in both precision and accuracy with respect to the 1985 audits (Figure 3).
The percentage of values (90%) that fell within ±20% of the assigned
values {Table 11) is similar to that for the 1983-1985 audits.
;.-;..- \ ' f- .'.'.'"'
LEAD ON FILTER STRIPS
Eighty laboratories participated in the 0186 audit and 93 in the 0786
audit which represent 25% and 12% decreases, respectively, from the 1985
audits. This decrease was primarily due to a 10% decrease in participation
by state agency laboratories.
The audit mean, percent accuracy and percent CV (precision) are shown
in Table 12. Accuracy has continued to show the negative bias present
since the audits were initiated in 1977 (Figure 4). Precision has remained
at the same level since 1982 (Figure 4) as has the number of measurements
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within ± 20% of the assigned value (98%) (Table 13). This year all parti-
cipants used atomic absorption spectrometry for sample analysis.
SULFUR DIOXIDE (CONTINUOUS MONITORS)
The number of monitors audited totaled 246 (Table 14) -- a 4% decrease
from 1985. This decrease resulted mainly from a decrease in participation
by state agencies. This contrasts with 1985 when a 16% increase occurred
(from 1984) due to a 10% increase in state agency participitation. Overall,
approximately 48% of the monitors in the SLAMS network were audited in
1986.
The accuracy for each of the methods is shown in Table 15. The methods
most commonly used were: fluorescence (236), flame photometric (6) and
coulometric (2). In relation to 1985, these numbers represent a 2% de-
crease, 14% decrease and 50% decrease, respectively. The decrease in the
number of flame photometric and coulometric analyzers continues the shift
in user preference for the fluorescence monitor observed earlier (1, 2,
3). The accuracy of the fluorescent monitors improved compared to 1985 and
1984, but the accuracy of the other two types decreased slightly when com-
pared to this same period.
HIGH VOLUME
The number of monitors audited in 1986 was 1251 -- a 6% decrease from
1985 (1). The pressure transducer continued to be the most widely used
method of measurement (38%), the rotameter was next (19%), followed by the
flow controller (13%). Other methods which accounted for the remaining 30
percent of the results, included: orifice manometer, manometer, flow gauge,
and pressure transducer/non-continuous. Table 16 shows the percentage of
the flow measurements within -t 10, 20, 30 and 50% of the assigned value for
each resistance plate used in the ReF (audit) device. These results are
similar to the 1985, 1984 and 1983 results (1, 2, 3).
ACID RAIN
Forty-four laboratories participated in the 0486 audit and thirty-
six participated in the 1086 audit. Overall this represents a 20% in-
crease in participation compared to 1985 and it primarily resulted from an
increase in state agency participants.
Because of the short history of this audit, only general observations
can be made concerning time trends. Also, because of the low concentrations
present in some of the samplers, the relative precision sometimes appears
poor, when in absolute terms (e.g., mg/1) the precision is reasonably good.
Results for pH, Conductivity and Acidity
The results are presented in Table 17 (all data), Table 18 (outliers
removed) and in Figures 5 (pH), 6 (conductivity) and 7 (acidity). As in
the earlier audits (1, 2, 3), there is only a weak correlation apparent
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between sample concentration and precision and accuracy. In contrast, the
ambient air audits reported earlier reflect precision and accuracy that
generally decreased as concentration increased. For all three parameters,
precision and accuracy have varied erratically over the life of the audit
program.
Major Anions Results (SQ/u NOs, C1 , F)
The results for these four parameters are presented in Table 19 (all
data), Table 20 (outliers removed) and in Figures 8 ($04), 9 (NOs), 10 (Cl)
and 11 (F). As in the past, precision continued to exceed 10% in all audits
and also remained erratic. As shown by comparing the precision in Tables
19 and 20, however, removal of only a few results yields a large improvement
in precision. Thus, the precision results are not as poor as they appear
on the surface. Accuracy has also been erratic, but overall quite good.
Major Cations (NH4, Ca, K. Mg, Na)
The results for these five major ions are presented in Table 21 (all
data), Table 22 (outliers removed) and in Figures 12 (NH4), 13 (Ca), 14 (K),
15 (Mg) and 16 (Na). As in the case for the major anions, the precision
has been erratic for all five anions over the history of the audit. But,
also as in the case for the major anions, removing just one or two values
yields a dramatic improvement in precision.
Trace Metals Results (Mn. Fe. Cd, Cu. Ni , Pb, Zn)
The results for these seven metals are presented in Table 23 (all
data), Table 24 (outliers removed) and in Figures 17 (Mn), 18 (Fe), 19 (Cd),
20 (Cu), 21 (Ni), 22 (Pb), and 23 (Zn). As in the case of both the anions
and cations, the precision has varied in an erratic manner for most of these
metals (Zn and Cd continue to be the exception). It should be borne in
mind, however, that because the concentrations of these metals are low, a
small absolute difference appears as a large relative difference. Also,
most participants report only one significant figure for the metals
analyses.
10
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REFERENCES
1. 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, 1985. U.S. Environmental Protection Agency Report EPA
600/4-87-002. Research Triangle Park, North Carolina 27711. January
1987.
1. 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, 1984. U.S. Environmental Protection Agency Report EPA
600/4-86-013. Research Triangle Park, North Carolina 27711. Febru-
ary 1986.
2. 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
600/4-84-077. Research Triangle Park, North Carolina 27711. October
1984.
4. Chauvenet, W. A Manual of Spherical and Practical Astronomy. J.B.
Lipincott and Company, Philadelphia, Pennsylvania, 1863. pp". 558-566.
11
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TABLE 1. AGENCY PARTICIPATION
Distribution (%)
Survey
CO « April 1986
$04 February 1986
S04 August 1986
N03 February 1986
N03 August 1986
Pb -- January 1986
Pb July 1986
S02 (continuous)
High-Volume Flow-Rate
May 1986
Acid Rain April 1986
Acid Rain October 1986
States
56.7
58.1
51.0
56.4
48.9
49.9
47.7
51.6
41.0
55.6
54.1
Local
37.4
14.0
19.6
12.8
20.0
25.0
28.0
38.2
44.2
11.1
13.5
Industry
4
18
19
17
22
20
19
8
13
24
21
.2
.6
.6
.9
.2
.0
.4
.9
.7
.4
.6
Federal
1
2
3
2
2
1
1
1
0
8
10
.7
.3
.9
.6
.2
.3
.1
.2
.5
.9
.8
Foreign
0
7
5
10
6
3
3
0
0
0
0
.0
.0
.9
.3
.7
.8
.8
.0
.6
.0
.0
No. of
Laboratories9
43
51
39
45
80
93
45
37
(3)
(0)
(2)
(4)
(5)
(1)
No. of
Monitors3
238 (3)
246 (4)
1251 (100)
aValue in parentheses is the number of laboratories/monitors that reported all values off by more than ± 20%
from the assigned value.
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TABLE 2. AUDIT RESULTS FOR CARBON MONOXIDE
Audit
Level
n
Assigned
value (ppm)
Mean
(ppm)
% Ace.
% CV
A. ALL DATA
0486
1
2
3
238
236
234
5.81
20.70
42.80
5.74
20.72
42.64
-1.20
0.01
-0.37
6.45
3.09
4.46
B. OUTLIERS REMOVED
0486
1
2
3
231
231
230
5.81
20.70
42.80
5.76
20.75
42.76
-0.86
0.24
-0.09
5.56
2.60
2.48
13
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TABLE 3. AUDIT RESULTS FOR CARBON MONOXIDE BY THE NDIR AND GFC METHODS
Audit Level
Assigned
value
(ppm)
NDIR
Mean
n (ppm)
Method GFC
Mean
% Ace. % CV n (ppm)
Method
% Ace. % CV
0486
0486
1
2
3
1
2
3
A. ALL DATA
5.81
20.70
42.80
206
204
203
5.73
20.74
42.61
-1.38
0.19
-0.44
6.81
3.13
4.74
32
32
31
5.79
20.57
42.81
-0.34
0.62
0.02
3.45
2.58
1.47
B. OUTLIERS REMOVED
5.81
20.70
42.80
201
200
199
5.75
20.77
42.75
-1.03
0.34
0.17
6.26
2.70
2.60
31
31
30
5.76
20.64
42.86
-0.86
-0.29
1.40
2.43
1.65
1.31
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TABLE 4. PERCENT OF CARBON MONOXIDE MEASUREMENTS WITHIN
INDICATED PERCENTAGE OF ASSIGNED VALUES
Assigned
Audit _ Level _ value (ppm) _ 10% _ 20% _ 30% _ 50%
A. ALL DATA
0486 1 5.81
2 20.70
3 42.80
89.1
97.9
97.9
98.3
100.0
99.6
100.0
100.0
99.6
100.0
100.0
99.6
B. OUTLIERS REMOVED
0486 1
2
3
5.81
20.70
42.80
90.2
99.1
99.1
98.3
100.0
99.6
100.0
100.0
99.6
100.0
100.0
99.6
15
-------
TABLE 5. AUDIT RESULTS FOR SULFATE ON FILTER STRIPS
Audit
0286
0886
0286
Level
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
n
42
41
43
43
43
43
50
50
51
51
51
50
37
37
38
39
39
38
Assigned
value (yg/m3) (
A. ALL DATA
1.62
3.14
9.94
15.43
18.00
17.87
3.27
1.87
6.01
7.92
24.39
21.45
B. OUTLIERS REMOVED
1.62
3.14
9.94
15.43
18.00
17.87
Mean
ug/m3)
1.62
3.39
9.51
15.20
18.53
18.36
3.25
1.97
5.88
7.87
23.46
20.54
1.66
3.00
9.69
15.39
18.34
17.86
% Ace.
0.00
7.96
-4.33
-1.49
2.94
2.67
0.61
5.35
2.16
-0.63
-3.81
-4.24
2.47
-4.45
-2.52
-0.26
1.89
-0.06
% CV
30.25
83.76
20.40
31.91
23.42
27.29
20.92
32.99
9.52
7.12
8.91
15.68
19.28
8.67
9.60
7.09
6.05
6.72
0886 None removed
16
-------
TABLE 6. AUDIT RESULTS FOR SULFATE BY THE MANUAL METHODS
Audit
U286
0886
Level
1
2
3
4
5
6
1
2
3
4
5
6
Assigned
value
(iag/m3)
1.62
3.14
9.94
15.43
18.00
17.87
3.67
1.87
6.01
7.92
24.39
21.45
Bad?
n
3
2
3
3
3
3
7
7
7
7
7
6
Mean
Ug/m3)
1.99
3.61
10.53
15.07
17.37
18.87
3.98
2.70
6.00
8.08
23.23
20.73
B.
% Ace.
A. ALL DATA
22.89
14.97
5.94
-2.33
-3.50
5.88
8.45
44.39
-0.17
2.02
-4.76
-3.36
% CV
71.86
23.82
21.94
4.51
7.31
11.45
29.14
34.44
10.83
7.18
5.25
8.15
n
2
2
2
2
2
2
2
2
2
2
2
2
Sulfa-Ver
Mean
(yg/m3)
1.90
2.75
8.08
13.95
18.56
17.93
2.88
1.43
6.16
7.53
24.32
21.09
% Ace.
17.28
-12.42
-18.71
-9.59
3.11
0.34
-11.93
-23.53
1.83
-4.92
-0.29
-1.67
% CV
54.74
0.36
4.95
1.57
8.83
4.19
13.19
68.53
10.95
12.48
7.40
0.57
OUTLIERS REMOVED
0286
0886
None removed
None removed
-------
TABLE 7. AUDIT RESULTS FOR SULFATE BY THE AUTOMATED METHODS
co
Audit
0286
0886
0286
Level
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
Assigned
value
(pg/m3)
1.62
3.14
9.94
15.43
18.00
24.09
3.27
1.87
6.01
7.92
24.39
21.45
1.62
3.14
9.94
15.43
18.00
17.87
n
18
18
19
19
19
19
18
18
19
19
19
19
14
14
15
15
14
15
Methyl
Mean
1.62
2.89
9.51
14.03
18.41
23.74
2.98
1.78
5.66
7.86
22.95
20.13
B.
1.69
3.07
9.95
14.97
18.64
17.76
Thymol Blue
% Ace.
A. ALL DATA
0.00
-7.96
-4.33
-9.07
2.28
-1.45
-8.87
-4.81
-5.82
-0.76
-5.90
-6.15
Ion Chromatograph
% CV
27.70
11.00
26.29
48.00
34.00
39.50
19.80
32.58
11.31
6.87
13.03
23.75
n
18
18
18
18
18
18
22
22
22
22
22
22
Mean
(yg/m3)
1.61
2.97
9.54
15.20
18.07
23.29
3.27
1.94
6.01
7.84
23.87
20.77
% Ace.
-0.62
-5.41
-5.03
-1.49
0.39
-3.32
0.00
3.60
0.00
-0.76
-2.13
-3.17
% CV
11.60
7.74
8.67
4.93
9.12
14.00
11.93
22.68
7.15
7.27
5.36
9.29
OUTLIERS REMOVED
4.32
-2.22
0.10
-2.98
3.56
-0.61
13.50
8.28
5.33
8.57
3.06
3.97
17
18
17
18
17
16
1.63
2.97
9.54
15.20
18.43
18.48
0.62
-0.54
-4.02
-1.49
2.39
3.41
9.94
7.74
6.07
4.93
3.98
4.02
0886 None removed
-------
TABLE 8. PERCENT OF SULFATE MEASUREMENTS WITHIN
INDICATED PERCENTAGE OF ASSIGNED VALUE
Audit
0286
0886
0286
Level
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
b
6
Assigned
value (yg/m^)
A. ALL
1.62
3.14
9.94
15.43
18.00
17.87
3.27
1.87
6.01
7.92
24.37
21.45
B. OUTLIERS
1.62
3.14
9.94
15.43
18.00
17.87
10%
DATA
42.9
63.4
69.7
86.0
81.4
79.1
60.0
48.0
70.6
76.5
86.3
86.0
REMOVED
46.1
68.4
75.0
92.5
87.5
85.0
20%
69.8
85.4
81.4
88.4
90.7
86.0
84.0
68.0
96.1
100.0
96.1
96.0
76.9
92.1
87.5
95.0
95.0
92.5
30%
83.3
92.7
88.4
88.4
93.0
90.7
90.0
80.0
100.0
100.0
96.1
96.0
87.2
97.4
95.0
95.0
97.5
95.0
50%
90.5
95.1
97.7
93.0
95.3
95.3
92.0
86.0
100.0
100.0
100.0
98.0
92.3
100.0
100.0
97.5
100.0
100.0
0886 None removed
19
-------
TABLE 9. AUDIT RESULTS FOR NITRATE ON FILTER STRIPS
Audit
0286
0886
0286
0886
Level
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
n
38
38
39
39
39
39
43
43
45
45
45
44
34
35
36
36
36
36
38
38
39
39
39
38
Assigned
value (vig/m3) (
A. ALL DATA
0.85
1.93
5.35
8.89
11.17
11.96
1.24
0.62
4.74
8.46
13.29
12.05
B. OUTLIERS REMOVED
0.85
1.93
5.35
8.89
11.17
11.96
1.24
0.62
4.74
8.46
13.29
12.05
Mean,
pg/m3)
1.01
2.02
5.38
9.03
12.10
12.00
1.30
0.70
4.64
8.17
12.86
10.90
0.85
1.97
5.28
8.91
11.01
11.90
1.30
0.67
4.81
8.33
13.26
10.90
% Ace.
18.82
4.66
0.56
1.55
8.30
0.33
4.84
12.90
-2.11
-3.43
-3.24
-9.54
0.00
2.07
1.33
0.22
-1.43
-0.50
4.84
8.06
1.48
-1.54
-0.23
-9.54
% CV
66.30
26.71
22.52
20.41
55.52
16.51
31.54
44.29
19.40
18.73
23.72
27.61
22.32
15.21
6.44
6.72
7.31
6.72
15.38
26.87
6.44
5.40
8.37
6.33
20
-------
TABLE 10. AUDIT RESULTS FOR NITRATE BY THE AUTOMATED METHODS
ro
Audit
0286
0886
0286
0886
Level
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
Assigned
value
(ug/m3)
0.85
1.93
5.35
8.89
11.17
11.96
1.24
0.62
4.74
8.46
13.29
12.05
0.85
1.93
5.35
8.89
11.79
11.96
1.24
0.62
4.74
8.46
13.29
12.05
Ion Chromatograph
n
18
18
18
18
18
18
20
20
21
20
21
21
15
15
16
17
16
16
19
17
19
20
19
20
Mean
(ug/m3)
0.86
1.83
5.07
8.50
10.55
11.41
1.28
0.71
4.76
8.37
13.01
10.65
B.
0.86
1.91
5.32
8.85
10.85
11.91
1.27
0.63
4.75
8.27
12.97
10.68
% Ace.
A. ALL DATA
1.18
-5.18
-5.23
-4.39
-5.55
-4.59
3.23
14.52
0.42
-2.24
-2.11
-11.62
% CV
15.12
20.22
17.36
18.71
16.59
16.21
10.16
35.21
9.03
7.77
6.15
4.79
n
13
13
14
14
14
14
12
12
13
13
13
13
Cadmi urn
Mean
(yg/m3)
0.99
2.05
5.70
9.56
11.63
12.28
1.32
0.68
4.14
7.24
12.22
10.30
Reduction
% Ace.
16.47
6.22
6.54
7.00
3.96
2.68
6.45
9.68
-12.66
-14.42
-8.05
-14.52
% CV
42.42
20.49
27.37
23.74
22.53
16.53
55.30
67.65
34.54
32.60
42.47
46.10
OUTLIERS REMOVED
1.18
-1.04
-0.56
-0.45
-7.97
-0.42
2.42
1.61
0.21
-2.24
-2.41
-11.37
8.14
5.76
4.89
5.88
4.33
4.70
9.45
17.46
4.84
5.97
3.93
4.78
12
11
12
13
13
12
8
8
10
10
9
9
0.88
1.92
5.31
8.98
10.94
11.89
1.36
0.66
4.78
8.36
13.32
11.05
3.53
-0.52
-0.75
1.01
-7.21
-0.59
-9.68
6.45
0.84
-1.18
0.23
-8.30
12.50
4.71
3.58
6.46
4.20
3.78
16.18
12.52
5.85
4.56
6.01
5.43
-------
TABLE 11. PERCENT OF NITRATE MEASUREMENTS WITHIN
INDICATED PERCENTAGE OF ASSIGNED VALUE
Audit
0286
0886
0286
0886
Level
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
Assigned
value (yg/
0.85
1.93
5.35
8.89
11.17
11.96
1.24
0.62
4.74
8.46
13.29
12.05
B.
0.85
1.93
5.35
8.89
11.17
11.96
1.24
0.62
4.74
8.46
13.29
12.05
m3) 10%
A. ALL DATA
68.4
71.9
84.6
74.4
71.8
76.9
48.8
44.2
73.3
80.0
73.3
36.3
OUTLIERS REMOVED
72.2
75.0
89.2
78.4
75.7
81.1
53.8
48.7
80.5
87.8
80.5
40.0
20%
71.7
78.9
92.3
92.3
89.7
92.3
76.7
65.1
86.7
86.7
84.4
88.6
75.0
83.3
97.3
97.3
94.6
97.3
82.1
69.2
92.7
95.1
90.2
95.0
30%
76.3
86.8
94.8
94.8
92.3
92.3
86.0
72.1
95.6
93.3
88.9
88.6
80.6
91.7
100.0
100.0
97.3
97.3
89.7
76.9
100.0
97.6
95.1
95.0
50%
84.2
89.5
94.8
94.8
92.3
94.8
88.4
76.7
95.6
95.6
93.3
90.9
88.9
94.4
100.0
100.0
97.3
100.0
92.3
82.1
100.0
100.0
97.6
95.0
22
-------
TABLE 12. AUDIT RESULTS FOR LEAD ON FILTER STRIPS
Audit Level
0186 1
2
3
4
5
6
0786 1
2
3
4
5
6
0186 1
2
3
4
5
6
0786 1
2
3
4
5
6
n
80
80
80
80
80
80
93
92
92
93
93
93
72
72
73
75
73
74
91
90
90
89
88
90
Assigned
value (ug/m3) (
A. ALL DATA
0.72
1.44
2.52
3.78
7.10
7.50
0.39
1.80
2.36
4.24
5.25
8.36
B. OUTLIERS REMOVED
0.72
1.44
2.52
3.78
7.10
7.50
0.39
1.80
2.36
4.24
5.25
8.36
Mean
yg/m3)
0.69
1.38
2.43
3.62
6.93
7.20
0.38
1.73
2.32
4.03
4.95
8.09
0.70
1.39
2.46
3.69
7.12
7.37
0.39
1.75
2.33
4.10
4.99
8.22
% Ace.
-4.17
-4.17
-3.57
-4.23
-2.39
-4.00
-2.58
-3.89
-1.69
-4.95
-5.71
-3.23
-2.78
-3.41
-2.38
-2.38
0.42
-1.73
0.00
-2.78
-1.27
-3.30
-4.95
-1.67
% CV
10.14
8.69
7.00
8.01
11.98
11.25
13.16
6.94
9.91
9.43
9.49
10.63
5.71
5.71
4.04
4.61
3.51
3.12
7.69
5.14
5.15
5.37
4.81
5.84
23
-------
TABLE 13. PERCENT OF LEAD MEASUREMENTS WITHIN
INDICATED PERCENTAGE OF ASSIGNED VALUE
Audit
0186
0786
0186
0786
Level
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
Assigned
value (ug/m^)
A, ALL
0.72
1.44
2.52
3.78
7.10
7.50
0.39
1.80
2.36
4.24
5.25
8.36
B. OUTLIERS
0.72
1.44
2.52
3.78
7.10
7.50
0.39
1.80
2.36
4.24
5.25
8.36
10%
DATA
81.3
84.6
88.5
85.9
89.7
92.3
68.8
85.9
90.2
86.0
84.9
90.3
REMOVED
86.7
90.4
94.5
91.7
95.9
98.6
69.7
86.8
91.2
87.0
85.9
91.3
20%
93.8
93.6
97.4
95.0
94.9
95.0
94.6
94.7
94.7
94.6
93.5
93.5
95.9
98.6
100.0
98.6
97.3
98.6
95.7
98.9
98.9
95.7
94.6
94.6
30%
98.7
98.7
98.7
97.4
96.2
97.4
97.8
94.7
94.7
96.8
94.6
96.8
100.0
100.0
100.0
98.6
97.3
98.6
98.9
98.9
98.9
97.8
95.7
97.8
50%
100.0
100.0
100.0
100.0
98.7
98.7
98.9
100.0
98.9
100.0
100.0
98.9
100.0
100.0
100.0
100.0
98.6
98.6
98.9
100.0
100.0
100.0
100.0
98.9
24
-------
TABLE 14. AUDIT RESULTS FOR SULFUR DIOXIDE CONTINUOUS MONITORS (ALL DATA)
Flow
setting
1
2
3
4
5
6
Number of
reported
values*
35
237
246
246
244
208
Range of
values (ppm)
0.468 to 0.842
0.210 to 0.561
0.112 to 0.303
0.077 to 0.230
0.024 to 0.082
-0.006 to 0.007
Average of bias
0.3
1.9
2.4
2.6
2.6
Standard
deviation
(ppm)
0.062
0.027
0.016
0.012
0.004
0.002
*In the 1986 audit data were returned for 246 monitors
TABLE 15. AUDIT RESULTS FOR SULFUR DIOXIDE CONTINUOUS
MONITORS BY VARIOUS INSTRUMENTAL METHODS
Flame photometric
Flow
setting
1
2
3
4
5
6
average difference
n
0
6
6
6
6
5
ppm
0.012
0.013
0.010
0.002
0.000
%
2.6
5.3
5.6
3.2
___
Fluorescence
average difference
n
33
223
236
232
231
195
ppm
-0.010
0.008
0.006
0.005
0.001
0.000
%
1.4
2.0
2.4
2.7
2.6
___
Coulometric
average difference
n
0
2
2
2
2
2
ppm
-0.010
-0.004
0.003
0.0
0.000
%
-2.2
-1.8
1.7
0.7
« « _
25
-------
TABLE 16. PERCENT OF HIGH VOLUME FLOW MEASUREMENTS WITHIN
INDICATED PERCENTAGE OF ASSIGNED VALUE (ALL DATA)
Plate Number of Approximate
number measurements flow (m3/min) 10% 20% 30% 50%
5 608 0.7 80.9 90.3 95.4 97.5
7 748 0.9 78.9 94.4 97.6 98.0
10 917 1.1 87.4 96.7 98.0 98.4
13 933 1.2 91.0 97.6 98.3 98.7
18 927 1.3 91.0 97.6 98.2 98.3
26
-------
TABLE 17. ACID RAIN RESULTS FOR pH, CONDUCTIVITY AND ACIDITY (ALL DATA)
Audit
0486 pH
Conductivity
US/cm)
Acidity
(yequiv/L)
1086 pH
Conductivity
(yS/cm)
Acidity
(yequiv/L)
Level
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
n
43
44
44
39
40
40
23
23
23
36
36
36
34
34
34
18
18
19
Assigned
value
4.53
3.43
3.93
15.90
265.80
65.27
35.90
398.80
128.30
4.31
3.80
3.47
24.10
77.10
162.40
54.40
161.20
363.90
Mean
4.40
3.45
3.90
17.26
247.53
66.24
63.15
415.02
150.44
4.29
3.81
3.47
29.74
75.34
157.53
71.69
184.44
365.10
% Ace.
-2.86
0.47
-0.76
8.85
-6.87
1.49
75.91
4.07
17.25
-0.44
0.13
0.00
23.38
-2.28
-3.00
31.78
14.42
0.33
% CV
6.51
6.04
7.54
29.98
28.77
57.82
95.07
41.95
64.64
4.52
2.84
1.84
124.27
20.66
19.94
50.15
35.89
43.28
27
-------
TABLE 18. ACID RAIN RESULTS FOR pH, CONDUCTIVITY
AND ACIDITY (OUTLIERS REMOVED)
Audit
0486 pH
Conductivity
US/cm)
Acidity
(pequiv/L)
1086 pH
Conductivity
(nS/cm)
Acidity
(yequiv/L)
Level
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
n
41
43
42
38
37
39
22
23
22
35
35
35
33
33
33
17
17
17
Assigned
value
4.53
3.43
3.93
15.90
265.80
65.27
35.90
398.80
128.30
4.31
3.80
3.47
24.10
77.10
162.40
54.40
161.20
363.90
Mean
4.43
3.42
3.89
15.89
250.51
61.07
52.59
415.02
134.55
4.31
3.82
3.48
23.45
73.08
152.74
67.06
194.35
406.81
% Ace.
-2.28
-0.26
-1.01
-0.61
-5.75
-6.43
45.92
4.07
4.87
0.00
0.50
0.23
-2.69
-5.22
-5.95
23.27
20.57
11.79
% CV
4.99
3.68
4.81
56.30
11.12
4.81
59.86
41.95
45.95
3.34
1.89
1.55
20.70
11.48
9.62
46.28
27.12
25.20
28
-------
TABLE 19. ACID RAIN AUDIT RESULTS FOR ANIONS (ALL DATA)
Audit
0486 $04 (reported
as S)
NOs (reported
as N)
Cl
F
1086 S04 (reported
as S)
NOs (reported
as N)
Cl
F
Level
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
n
33
36
36
33
34
33
31
34
33
17
22
22
28
28
39
27
27
28
27
27
27
17
17
17
Assigned
value (mg/L)
0.53
7.16
2.08
O.lb
2.75
0.85
0.40
20.53
1.10
0.05
0.26
0.19
0.83
3.23
4.62
0.14
0.15
1.78
0.37
0.78
1.20
0.06
0.11
0.31
Mean
(mg/L)
0.89
7.47
2.28
0.21
2.51
0.79
0.90
24.09
1.55
0.13
0.34
0.34
1.08
3.55
4.49
0.15
0.23
1.88
0.37
0.81
1.15
0.10
0.14
0.35
% Ace.
69.70
4.30
9.62
40.00
-8.76
-7.08
125.00
17.34
40.62
160.00
30.77
78.95
30.96
9.91
-2.84
7.14
54.11
5.69
0.00
3.20
-4.69
66.67
29.09
12.90
% CV
121.81
48.51
50.22
120.00
24.55
28.41
168.33
90.28
115.34
190.30
130.67
143.11
51.89
40.07
33.98
58.28
163.11
68.10
31.35
17.47
13.38
125.74
84.51
26.51
29
-------
TABLE 20. ACID RAIN AUDIT RESULTS FOR ANIONS (OUTLIERS REMOVED)
Audit L
0486 504 (reported
as S)
V* ~r ^f /
N03 (reported
as N)
Cl
F
1086 S04 (reported
as S)
** ** w /
NOs (reported
as N)
Cl
Vs 1
F
1
.evel
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
n
32
34
34
31
31
30
29
33
31
16
21
20
26
27
26
26
26
27
25
25
26
16
16
16
Assigned
value (mg/L)
0.53
7.16
2.08
0.15
2.75
0.85
0.40
20.52
1.10
0.05
0.26
0.19
0.83
3.23
4.62
0.14
0.15
1.78
0.37
0.78
1.20
0.06
0.11
0.31
Mean
(mg/L)
0.73
6.68
2.04
0.14
2.69
0.84
0.53
20.46
1.12
0.07
0.25
0.19
0.98
3.33
4.62
0.14
0.16
1.64
0.36
0.77
1.13
0.07
0.11
0.33
% Ace.
37.73
-6.71
-1.88
-6.67
-2.22
-1.15
32.00
-0.30
1.80
40.00
-3.85
0.00
18.02
3.13
0.00
0.00
7.53
-7.38
-2.70
-1.28
-5.89
16.67
0.00
6.45
% CV
81.09
22.70
28.76
32.89
7.14
13.37
84.28
25.33
31.66
79.73
26.28
42.71
42.73
24.35
11.15
35.77
71.33
21.09
15.47
7.78
11.37
20.00
25.44
11.93
30
-------
TABLE 21. ACID RAIN RESULTS FOR CATIONS (ALL DATA)
Audit Level
0486 NH3 (reported 1
as N) 2
3
Ca 1
2
3
K 1
2
3
Mg 1
2
3
Na 1
2
3
1086 NH3 (reported 1
as N) 2
3
Ca 1
2
3
K 1
2
3
Mg 1
2
3
Na 1
2
3
n
27
28
28
23
28
28
25
29
29
22
28
27
27
29
29
22
21
21
23
23
21
24
21
22
23
22
23
22
23
23
Assigned
value (mg/L)
0.10
3.61
0.34
0.06
6.25
0.15
0.08
2.97
0.53
0.01
0.52
0.05
0.24
2.92
1.34
0.10
0.79
1.00
0.07
0.17
0.01
0.11
0.11
0.12
0.04
0.02
0.08
0.24
0.31
0.62
Mean
(mg/L)
0.13
3.51
0.39
0.07
6.37
0.15
0.14
2.96
0.55
0.02
0.51
0.07
0.32
2.89
1.24
0.10
0.78
1.02
0.07
0.17
0.04
0.13
0.11
0.13
0.04
0.02
0.08
0.25
0.31
0.62
% Ace.
30.10
-2.71
15.00
18.03
1.97
0.00
74.39
-0.40
3.55
100.00
-2.29
40.05
33.35
-0.89
-7.45
0.00
-0.88
2.02
0.00
0.00
300.11
27.36
0.00
8.33
0.00
0.00
0.00
4.94
0.00
0.00
% cv
46.97
12.44
35.81
77.78
9.56
51.30
117.48
8.53
24.91
165.00
20.39
134.72
78.80
15.73
24.40
22.22
8.71
9.98
40.28
21.71
191.89
92.59
25.23
19.69
41.03
72.00
32.89
9.41
9.32
6.49
31
-------
TABLE 22. ACID RAIN AUDIT RESULTS FOR CATIONS (OUTLIERS REMOVED)
Audit Level
0486 NH3 (reported 1
as N) 2
3
Ca 1
2
3
K 1
2
3
Mg 1
2
3
Na 1
2
3
1086 NHs (reported 1
as N) 2
3
Ca 1
2
3
K 1
2
3
Mg 1
2
3
Na 1
2
3
n
25
27
26
22
27
27
23
29
27
21
27
26
25
28
27
20
20
20
21
23
20
23
20
22
23
21
21
21
22
22
Assigned
value (mg/L)
0.10
3.61
0.34
0.06
6.25
0.15
0.08
2.97
0.54
0.01
0.52
0.05
0.24
2.92
1.34
0.10
0.79
1.00
0.07
0.17
0.01
0.11
0.11
0.12
0.04
0.02
0.08
0.24
0.31
0.62
Mean
(mg/L)
0.12
3.56
0.36
0.06
6.30
0.14
0.10
2.96
0.55
0.01
0.53
0.05
0.25
2.96
1.31
0.10
0.79
1.01
0.07
0.17
0.02
0.11
0.12
0.13
0.04
0.02
0.08
0.25
0.31
0.61
% Ace.
20.00
-1.38
5.88
0.00
0.08
-7.10
25.00
-0.40
3.36
0.00
1.92
0.00
4.12
1.47
2.01
0.00
0.00
1.00
0.00
0.00
100.00
0.00
8.41
8.33
0.00
0.00
0.00
3.70
0.00
-1.30
% CV
22.41
10.08
18.49
53.23
7.95
43.06
56.57
8.53
8.14
78.57
10.65
35.19
33.99
9.01
10.27
15.15
7.61
8.62
22.54
21.71
145.83
18.18
16.38
15.38
41.03
56.52
15.79
7.54
6.84
3.94
32
-------
TABLE 23. ACID RAIN AUDIT RESULTS FOR TRACE METALS (ALL DATA)
Audit
0486 Mn
Fe
Cd
Cu
Ni
Pb
Zn
1086 Mn
Fe
Cd
Cu
Ni
Pb
Zn
Level
4
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
Assigned
n value (mg/L)
19
19
17
18
19
19
18
19
19
19
20
20
18
18
15
14
14
12
14
13
15
14
12
12
15
18
15
14
0.04
0.10
0.04
0.14
0.03
0.14
0.03
0.29
0.49
0.06
1.36
0.26
0.10
0.83
0.05
0.03
0.07
0.02
0.06
0.02
0.44
0.05
0.02
0.05
0.43
0.13
0.47
0.16
Mean
(mg/L)
0.04
0.09
0.05
0.14
0.03
0.15
0.03
0.28
0.44
0.06
1.34
0.25
0.11
0.82
0.05
0.03
0.07
0.03
0.06
0.03
0.42
0.05
0.03
0.05
0.42
0.13
0.46
0.15
% Ace.
0.00
-10.00
25.00
0.00
0.00
7.14
0.00
-3.40
-10.00
0.00
-1.39
-3.85
10.00
-1.21
0.00
0.00
0.00
50.00
0.00
12.50
-4.55
0.00
50.00
0.00
-2.34
0.00
-2.95
-6.17
% cv
11.90
8.42
41.30
15.33
17.24
8.90
12.90
22.18
32.21
39.29
10.80
15.69
16.22
7.20
29.17
34.29
30.56
30.77
11.29
22.22
25.00
4.00
45.16
31.91
26.32
27.78
25.44
26.97
33
-------
TABLE 24. ACID RAIN AUDIT RESULTS FOR TRACE METALS (OUTLIERS REMOVED)
Audit
0486 Mn
Fe
Cd
Cu
Ni
Pb
Zn
1086 Mn
Fe
Cd
Cu
Ni
Pb
Zn
Level
4
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
n
18
19
16
17
18
18
16
18
17
17
19
19
17
17
14
13
13
11
13
13
14
13
11
11
14
13
14
13
Assigned
value (mg/L)
0.04
0.10
0.04
0.14
0.03
0.14
0.03
0.29
0.49
0.06
1.36
0.26
0.10
0.83
0.05
0.03
0.07
0.02
0.06
0.02
0.44
0.05
0.02
0.05
0.43
0.13
0.47
0.16
Mean
(mg/L)
0.04
0.09
0.04
0.13
0.03
0.15
0.03
0.30
0.49
0.06
1.32
0.25
0.11
0.83
0.05
0.04
0.08
0.02
0.06
0.03
0.45
0.06
0.03
0.05
0.45
0.13
0.49
0.16
% Ace.
0.00
-10.00
0.00
-7.14
0.00
7.14
0.00
3.44
0.00
0.00
-2.94
-3.85
10.00
0.00
0.00
33.33
14.80
0.00
0.00
50.00
2.21
20.00
50.00
0.00
4.21
0.00
3.16
0.00
% CV
11.90
8.42
41.30
12.78
14.29
6.80
6.45
5.03
7.33
20.97
7.35
13.20
13.89
5.68
15.69
24.32
14.10
24.00
8.20
22.22
5.61
28.81
22.22
13.73
7.62
10.37
4.91
7.41
34
-------
AVERAGE ACCURACY, percent
AVERAGE ACCURACY, percent
CO
en
CQ
C
-^
CD
O
05
I
cr
o
D
O
D
O
X
d.
CD
C
Q.
-o >
3D ^i
s -m
5/2 3
O o
CD
Q
O
o
o
c
33
CD
Q
-------
c
(D
O
i_
-------
c
-"
O
<
Qi
Z>
O
O
<
Ld
O
<
C£
L±J
c
CD
O
-------
0.5
c
CD
O
CD
Q.
O
o:
O
O
LJ
O
a:
-3.5
i I i i i i i i TTi i r
08/77 01/78 06/78 01/79 07/79 01/80 07/80 01/81 07/81 01/82 07/82 01/83 07/83 01/84 07/8+ 01/85 07/85 01/86 07/86
C
CD
O
!_
CD
a.
O
UJ
O
<
CK
UJ
AUDIT DATE, month/year
ACCURACY
0
i i i i i r
08/77 01/77 06/78 01/79 07/79 01/80 07/80 01/81 07/81 01/82 07/82 01/83 07/83 01/84 07/84 01/85 07/85 01/86 07/86
AUDIT DATE, month/year
PRECISION
Figure 4. Lead Audits.
38
-------
o
z>
o
o
<
LJ
O
04/83
11/83 04/84 10/84 04/85 10/85 04/86 10/86
ACCURACY
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
PRECISION
Figures. Acid Rain Audit Results for pH.
to
IO
UJ
o
-8
04/83
11/83 04/84 10/84 04/85 10/85 04/86 10/86
ACCURACY
UJ
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
PRECISION
Figure 6. Acid Rain Audit Results for Conductivity.
-------
o
<
a;
o
o
LU
O
-20
50 -
40 -
30 -
20 -
10 -
0
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86 04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
ACCURACY PRECISION
Figure 7 Acid Ram Audit Results for Acidity
o
<
rr
o
o
1 1 --
10 -
9 -
8 -
7 -
6 -
5 -
4 -
3 -
2 -
1 -
0 --
-3
04/83
11/83 04/84 10/84 04/85 10/85 04/86 10/86
ACCURACY
o
<
20 -
15 -
10
5 -
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
PRECISION
Figure 8. Acid Rain Audit Results for S04 (Reported as S).
-------
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
ACCURACY
45
40 -
35 -
25 -
20 -
15 -
10 -
5 -
0
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
PRECISION
Figure 9 Acid Rain Audit Results for N03 (Reported as N).
11
X
CJ
CE
ID
CJ
11/83 04/84 10/84 04/85 10/85 04/86 10/86
ACCURACY
o
<
cr
50
45
40 -
35 -
30 -
25 -
20
15 -
10
5 -
0 n 1 iii..
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
PRECISION
Figure 10. Acid Rain Audit Results for Cl.
-------
AVERAGE ACCURACY, percent
AVERAGE ACCURACY, percent
AVERAGE CV, percent
AVERAGE CV, percent
oo
C-J
o
00
o
\-
co
o
\ -
CO
o
\
CO
-------
100
o
or
o
UJ
o
s
UJ
110
-10
04/83 11/83 04/84 10/84 04/85 10/85 4/86 10/86
ACCURACY
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
PRECISION
Figure 13. Acid Rain Audit Results for Ca.
CjO
CJ
%
UJ
§
-1
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86 04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
ACCURACY PRECISION
Figure 14. Acid Rain Audit Results for K.
-------
o
o
o
O
<
a:
04/83
10 -
11/83 04/84 10/84 04/85 10/85 04/86 10/86 04/83 11/83 04/84 10/84 04/85 10/85 04/86HV86
ACCURACY PRECISION
Figure 15. Acid Rain Audit Results for Mg.
u
o
04/83
10 -
11/83 04/84 10/84 04/85 10/85 04/86 10/86 04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
ACCURACY PRECISION
Figure 1 6. Acid Rain Audit Results for Na.
-------
o
<
o:
o
CJ
11/83 04/84 10/84 04/85 10/85 04/86 10/86
ACCURACY
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
PRECISION
Figure 17. Acid Rain Audit Results for Mn.
cn
o
o
11/83 04/84 10/84 04/85 10/85 04/86 10/86
ACCURACY
s
<
55
50 -
45 -
40-
35-
30-
25-
20-
15-
10-
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
PRECISION
Figure 18. Acid Rain Audit Results for Fe.
-------
O1
LJ
O
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
ACCURACY
Figure 19. Acid Rain Audit Results for Cd.
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
PRECISION
5
4
3
2
1
0
-1
-2
-3
-4 -
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
ACCURACY
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
PRECISION
Figure 20. Acid Rain Audit Results for Cu.
-------
o
<
cc
Ld
20 -T
18 -
16 -
14 -
12 -
10-
8 -
6 -
4 -
2 -
0 -
-2 -
-4 -
-6 -
-8 -
-10 -
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
ACCURACY
Figure 21 . Acid Ram Audit Results for Ni.
0
04/83 11/83 04/84 10/84 04/85 10/85 04/86 1O/
PRECISION
o
<
rr
o
o
o
<
or
-12
04/83
10 -
11/83 04/84 10/84 04/85 10/85 4/86 10/86 04/83 11/83 04/84 10/84 04/85 10/85
ACCURACY PRECISION
Figure 22. Acid Rain Audit Results for Pb.
4/86 10/86
-------
1
^
5
VO
00
co
CO
rr
13
u
o
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
ACCURACY
04/83 11/83 04/84 10/84 04/85 10/85 04/86 10/86
PRECISION
Figure 23. Acid Ram Audit Results for Zn
j^
oo
I
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