Horicon, WI NATTS Network Assessment Review
Established 2009 (Relocated from Mayville, WI): Carbonyls, Chromium VI, PAHs, PMio Metals, and VOCs
o Chromium VI ended in in 2013
For the NATTS Network Assessment (2009-2018):
o 11 of 18 Method Quality Objective (MQO) Core HAPs were included in the national trends
¦ Benzene: Reported MDL to NATTS Target MDL ratio was greater than 2.0 in 2015.
¦ Benzo(a)pvrene: Analytical precision was not reported in 2014 and 2016 and Bias % Difference was
outside ±35%.
¦ Carbon tetrachloride: Reported MDL to NATTS Target MDL ratio was greater than 2.0 in 2014 and
2015.
¦ Chromium VI: Only three years of valid data.
¦ Naphthalene: Analytical precision was not reported in 2016 and Bias %Difference was outside ±35%.
¦ Tetrachloroethvlene and Trichloroethvlene: Reported MDLs to NATTS Target MDL ratios were
greater than 2.0 in 2013, 2014, and 2015.
o 127 of 156 pollutant datasets were suitable for trends analysis
o Annual Average and 3-Year Rolling Average Concentrations were generally flat over time, with the
exception of a few pollutants (acetaldehyde and nickel (PMio)).
o 100% Reporting of Datasets
Method Quality Objectives (MQO): 2009-2018
o Completeness: Met 85% completeness in 156 of 156 pollutant datasets
o Method Detection Limits: Met MDL Target Ratio of 1.00 in 131 of 175 pollutant datasets
o Bias: Met ±25% for 128 of 150 pollutant datasets
o Overall Method Precision: Met <15% CV for 45 of 74 pollutant datasets
o Analytical Method Precision: Met <15% CV for 10 of 117 pollutant datasets
Analytical Laboratories for 2018
voc
Carbonyl
PMio Metals
Chromium VI
PAHs
WSLH
WSLH
WSLH
NA
WSLH
Equipment Year Deployed
Equipment Type
VOC
Carbonyl
PMio Metals
Chromium VI
PAHs
Sampler
2009
1999
2015
2009
2017
Analytical
2006
2012
2001
2001
2004
Preconcentrator
2017
NA
NA
NA
NA
Standards Preparation
2017
NA
NA
NA
NA
Canister Cleaning
2004
NA
NA
NA
NA
Extraction
NA
NA
2016
2011
2000
-------
National Summary: NATTS data were collected at 27 locations across the United States,
with sites beginning in 2003 or later (Figure 1) for 19 core HAPs. Over 528,000 concentrations
(primary, secondary, and replicate) were generated and analyzed for this assessment. Pollutant
datasets were scored to assess whether they were suitable for trends analysis. Each
pollutant dataset was evaluated against four MQOs: Completeness; Sensitivity; Bias; and
Precision. Datasets that were suitable (A- or B-rated) for six consecutive years were used for
national trends analysis (Table 1).
National trends were determined by comparing the most recent 3-year blocked averages
(e.g., 2013-2015 vs. 2016-2018) to determine if the NATTS Trends DQO was being met:
To be able to detect a al5percent difference (trend) between the annual mean
concentrations of successive 3-year periods within acceptable levels of decision error.
Of the 19 core HAPs. 18 were assessed for the NATTS Trends DQO. Due to sampling and
analytical issues, acrolein was not considered for trends analysis (Table 2). This assessment
showed that across the network, 15 of those 18 pollutants were decreasing between the
3-year blocks, while two of those pollutants were increasing between the 3-year blocks.
One pollutant did not exhibit a trend.
Table 1. NATTS Network Assessment: Count and Percentage of Suitable
Datasets by Pollutant Group
Pollutant Group
A-rated
B-rated
Does Not Meet
#
%
#
%
#
%
VOCs
1,452
53%
737
27%
555
20%
Carbonyls
523
67%
193
25%
66
8%
PM10 Metals
1,418
61%
685
30%
213
9%
Chromium VI
159
74%
29
13%
27
13%
PAHs
410
74%
124
22%
18
3%
Total = 6,609
3,962
60%
1,768
27%
879
13%
Table 2. Three-Year Block Averages for National Trends
Pollutant
Units
# Sites
Block 1
Block 2
% Difference
Acetaldehyde
Hg/m3
19
1.51
1.39
-7.7%
Arsenic (PM10)
ng/m
21
0.71
0.68
-3.2%
Benzene
Hg/m3
19
0.65
0.59
-10.2%
Figure 1. NATTS Site and Year Established
Benzo(a)pyrene
ng/m3
21
0.113
0.087
-23.2%
Seattle, ,
Beryllium (PM10)
ng/m3
20
0.012
0.009
-26.4%
Butadiene, 1,3-
Hg/m3
19
0.071
0.063
-10.9%
Portland (#1), OR* Portland (#2), OR _ ^ / \
• > ' \ ; " I I >
Cadmium (PM10)
ng/m3
21
0.170
0.097
-43.0%
* »•* l | - Underbill.Vt
/l_a Grande (#1), OR*-' '"•••JL. • _ _ j ,,l M/ i ' \ f
} /. a V«?i-7S»" I s ') H or icon.' Wit' \ \ "-Roxbury. MA
j... ¦ La Grande (#2), OR i f c-/ . * ] Rochester, NY \ I ...-S
) / ; I | May ville.Wr >f, \~ V
/ i ! I -->.#/ \ Detroit; Ml f
- — — ; I i J \ j X. Providence, Rl
f / Bountiful'UT | X — \ ^f- .Bronx (#1), NY"
\ 1 ™ . \ Chicago, IL ¦ ; _ j \ S
_ X \ ' . 1, , Washington^D.C. "w
SanJoBB.CA j [ ^
, Grand Junction. CO V St Louis MO Grayson Lake. KY J ' Bronit (#2), NV"
\ \ _ ' 1 v. U-.--.'1" . ,-.v * Richmond. -VA
S \ _ : i . \ i i*/ '
. . . \ ' v • - — -1 _ Vs Hazard, KY*--^-""?" / j
Los Angeles, CA \J ; j_ | _ J _ r - "[¦/
- Rubidoux, CA i / £' y-""" /
• X: / >' ' 1 / T \Chesterf ield, SC
NATTS Sites phoenix.AZ / ; —J / 1 j. /
; i Karnack, TX ) South DeKalb, GA y
~ Rural \ j | J , > /
O Urban X \ t ; \ ,r(
NATTS - Year Established Houston, ri ^\
| 2003 "^T.mp,.FL
¦ 2004 \ Pinellas County, FL, 'i
1 "> ./ 'i. 1
¦ 2007 1 >
"ft
¦ 2008
| | 2009
2010
2016
?ni7 * The Hazare|. Mayville, Wl, La Grande <#1), OR, Portland (#1), OR, sites were relocated in 2008, 2009, 2016, and 2017, respectively.
"The Bronx (#1), NY site temporarily moved to the Bronx (#2), NY site from mid-2010 to mid-2012.
Carbon Tetrachloride
Hg/m3
15
0.59
0.56
-4.7%
Chloroform
Hg/m3
20
0.256
0.255
-0.4%
Chromium VI
ng/m
18
0.029
0.026
-7.7%
Formaldehyde
Hg/m3
19
2.77
2.68
-3.3%
Lead (PM10)
ng/m
21
3.08
2.81
-8.9%
Manganese (PM10)
ng/m3
20
8.06
7.93
-1.6%
Naphthalene
ng/m3
20
66.70
51.08
-23.4%
Nickel (PM10)
ng/m3
19
1.28
1.05
-18.0%
T etracliloroethylene
ng/m3
19
0.149
0.174
17.2%
T ricliloroethylene
ng/m3
19
0.020
0.022
10.7%
Vinyl Cliloride
ng/m3
17
0.0051
0.0048
-5.5%
Page 1 of 25
-------
NATTS Monitoring Site Report: Horicon, Wl
Site Information Figure 2. NATTS Site Location
Region
5
NATTS Site Type
Rural
County
Dodge
AQS Site Code
55-027-0001
NATTS Operating Agency
WI Dept. of Natural Resources
Latitude
43.466111
Longitude
-88.621111
AQS Land Use
Agricultural
AQS Location Setting
Rural
10-Mile Population
88,344
Pollutant Datasets Evaluation: Suitable for Trends (Y=ves; Y(T)=yes, and used for DQO Trends; N=No; "=not rated
Final Pollutant Name
2009
2010
2011
2012
2013
2014
2015
2016
2017
2018
Acetaldehyde
—
Y
Y
Y
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Arsenic (PM10)
-
Y
Y
Y
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Benzene
~
Na
Na
Na
Na
Na
Na'b
Y
Y
Y
Benzo(a)pyrene
~
Y
Y
Nb'c
Y
Nb'c
Y
Nb'c
Y
Y
Beryllium (PM10)
~
Y
Y
Y
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Butadiene, 1,3-
~
Nc
Nc
Y
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Cadmiuni (PM10)
-
Y
Y
Y
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Carbon tetrachloride
~
Na
Na
Na,b
Na
Na'b
Na,b
Nb'°
Y
Y
Chloroform
..
Y
Y
Y
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Chromium VI
—
Y
Y
Y
~
~
—
—
~
~
Formaldehyde
--
Y
Y
Y
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Lead (PM10)
—
Y
Y
Y
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Manganese (PM10)
—
Y
Y
Y
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Naphthalene
--
Y
Y
Y
Y
Y
Y
Nb'c
Y
Y
Nickel (PM10)
—
Y
Y
Y
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Tetrachloroethylene
~
Na
Na
Na'b
Na'b
Na'b
Na'b
Y
Y
Y
T richloroethylene
~
Y
Y
Y
Na'b
Na'b
Na'b
Y
Y
Y
Vinyl chloride
~
Y
Nc
Y
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
Y(T)
: Reported MDL to NATTS Target Ratio greater than 2.0
b: Analytical precision data (required since 2012) was not reported to EPA or AQS for this pollutant.
G: Bias % Difference was outside ± 35%.
Page 2 of 25
-------
Table 3. NATTS Network Assessment Data (2003-2018) - National Distribution Statistics By Type3
Analyte
Units
Site Type
# Data
Records
%
Detections
Arithmetic
Meanb
Percentile Value0
5th
10th
25th
50th
75th
90th
95th
Acetaldehyde
ng/m3
Urban
15,704
100%
1.77 ± 0.02
0.50
0.66
0.97
1.45
2.19
3.24
4.04
ng/m3
Rural
4,930
100%
1.20 ± 0.04
0.36
0.46
0.65
0.93
1.38
2.02
2.76
ng/m3
All Sites
20,634
100%
1.63 ± 0.02
0.44
0.58
0.86
1.31
2.00
3.02
3.86
Arsenic (PM10)
ng/m3
Urban
14,968
97%
0.89 ± 0.04
0.10
0.19
0.34
0.58
0.99
1.70
2.41
ng/m3
Rural
4,622
96%
0.49 ± 0.02
0.04
0.08
0.17
0.35
0.59
0.94
1.28
ng/m3
All Sites
19,590
97%
0.79 ± 0.03
0.06
0.14
0.29
0.52
0.89
1.54
2.19
Benzene
Hg/m3
Urban
15,984
99%
0.86 ± 0.01
0.25
0.30
0.43
0.66
1.05
1.64
2.21
Hg/m3
Rural
2,494
95%
0.43 ± 0.02
0.04
0.13
0.21
0.33
0.52
0.78
1.01
Hg/m3
All Sites
18,478
99%
0.81 ± 0.01
0.19
0.26
0.39
0.61
0.98
1.55
2.09
Benzo(a)pyrene
ng/m3
Urban
12,336
70%
0.096 ± 0.004
ND
ND
ND
0.04
0.11
0.24
0.37
ng/m3
Rural
3,179
36%
0.067 ± 0.009
ND
ND
ND
ND
0.02
0.13
0.37
ng/m3
All Sites
15,515
63%
0.090 ± 0.004
ND
ND
ND
0.03
0.10
0.23
0.37
Beryllium (PM10)
ng/m3
Urban
15,783
75%
0.051 ± 0.006
ND
ND
0.00003
0.005
0.018
0.050
0.101
ng/m3
Rural
4,687
49%
0.023 ± 0.003
ND
ND
ND
ND
0.005
0.017
0.072
ng/m3
All Sites
20,470
69%
0.045 ± 0.005
ND
ND
ND
0.003
0.012
0.049
0.100
Butadiene, 1,3-
Hg/m3
Urban
15,388
81%
0.092 ± 0.002
ND
ND
0.025
0.058
0.114
0.215
0.302
ng/m3
Rural
2,185
29%
0.012 ± 0.001
ND
ND
ND
ND
0.017
0.046
0.059
ng/m3
All Sites
17,573
75%
0.082 ± 0.002
ND
ND
ND
0.049
0.104
0.199
0.287
Cadmium (PM10)
ng/m3
Urban
16,360
92%
0.21 ± 0.02
ND
0.01
0.05
0.09
0.17
0.42
0.63
ng/m3
Rural
4,684
87%
0.10 ± 0.01
ND
ND
0.03
0.06
0.11
0.20
0.29
ng/m3
All Sites
21,044
91%
0.18 ± 0.01
ND
0.01
0.04
0.08
0.16
0.35
0.56
Carbon Tetrachloride
ng/m3
Urban
14,713
99%
0.569 ± 0.003
0.361
0.433
0.496
0.562
0.651
0.737
0.798
ng/m3
Rural
2,189
92%
0.534 ± 0.016
ND
0.180
0.402
0.537
0.633
0.727
0.798
ng/m3
All Sites
16,902
98%
0.565 ± 0.003
0.304
0.408
0.490
0.559
0.649
0.736
0.798
Chloroform
ng/m3
Urban
16,068
87%
0.265 ± 0.022
ND
ND
0.093
0.132
0.217
0.420
0.668
ng/m3
Rural
3,802
43%
0.052 ± 0.003
ND
ND
ND
ND
0.095
0.144
0.230
ng/m3
All Sites
19,870
79%
0.224 ± 0.018
ND
ND
0.064
0.113
0.196
0.364
0.586
Chromium VI
ng/m3
Urban
8,414
74%
0.036 ± 0.002
ND
ND
ND
0.020
0.042
0.081
0.120
ng/m3
Rural
2,586
41%
0.018 ± 0.004
ND
ND
ND
ND
0.017
0.031
0.051
ng/m3
All Sites
11,000
66%
0.032 ± 0.001
ND
ND
ND
0.016
0.036
0.073
0.114
Page 3 of 25
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Table 3. NATTS Network Assessment Data (2003-2018) - National Distribution Statistics By Type3
Analyte
Units
Site Type
# Data
Records
%
Detections
Arithmetic
Meanb
Percentile Value0
5th
10th
25th
50th
75th
90th
95th
Formaldehyde
ng/m3
Urban
16,118
100%
3.11 ± 0.04
0.66
0.99
1.60
2.47
3.84
5.63
7.25
ng/m3
Rural
5,002
100%
2.22 ± 0.05
0.53
0.68
1.06
1.69
2.74
4.19
5.45
ng/m3
All Sites
21,120
100%
2.90 ± 0.04
0.61
0.86
1.43
2.29
3.59
5.38
6.96
Lead (PM10)
ng/m3
Urban
16,366
100%
4.21 ± 0.13
0.72
0.98
1.55
2.64
4.56
8.35
11.90
ng/m3
Rural
4,680
99%
2.10 ± 0.16
0.37
0.50
0.84
1.41
2.37
3.91
5.36
ng/m3
All Sites
21,046
99%
3.74 ± 0.11
0.55
0.80
1.31
2.31
4.04
7.41
10.56
Manganese (PM10)
ng/m3
Urban
16,141
100%
9.80 ± 0.32
1.09
1.51
2.52
4.92
10.21
20.10
30.08
ng/m3
Rural
4,627
99%
3.96 ± 0.14
0.46
0.73
1.36
2.57
4.75
8.54
12.13
ng/m3
All Sites
20,768
100%
8.50 ± 0.25
0.85
1.23
2.15
4.18
8.89
17.98
26.70
Naphthalene
ng/m3
Urban
12,332
100%
74.63 ± 1.14
15.62
21.27
33.55
55.89
94.64
150.05
196.16
ng/m3
Rural
3,301
100%
24.47 ± 1.38
3.74
4.73
7.74
13.86
26.25
50.88
79.17
ng/m3
All Sites
15,633
100%
64.04 ± 1.00
6.58
10.92
23.37
45.59
83.31
137.54
181.75
Nickel (PM10)
ng/m3
Urban
16,125
97%
1.85 ± 0.05
0.25
0.41
0.67
1.11
2.00
3.52
5.27
ng/m3
Rural
4,623
85%
0.65 ± 0.08
ND
ND
0.10
0.28
0.64
1.15
1.89
ng/m3
All Sites
20,748
94%
1.58 ± 0.04
ND
0.15
0.47
0.92
1.73
3.14
4.74
T etrachloroethylene
Hg/m3
Urban
15,612
86%
0.25 ± 0.01
ND
ND
0.06
0.13
0.25
0.48
0.74
Hg/m3
Rural
2,272
36%
0.09 ± 0.04
ND
ND
ND
ND
0.04
0.08
0.16
Hg/m3
All Sites
17,884
79%
0.23 ± 0.01
ND
ND
0.04
0.11
0.22
0.44
0.70
T richloroethylene
Hg/m3
Urban
15,843
41%
0.040 ± 0.002
ND
ND
ND
ND
0.051
0.107
0.164
ng/m3
Rural
3,388
13%
0.021 ± 0.003
ND
ND
ND
ND
ND
0.017
0.250
ng/m3
All Sites
19,231
36%
0.037 ± 0.002
ND
ND
ND
ND
0.041
0.105
0.167
Vinyl Chloride
ng/m3
Urban
14,778
19%
0.0044 ± 0.0003
ND
ND
ND
ND
ND
0.0137
0.0257
ng/m3
Rural
2,444
8%
0.0040 ± 0.0009
ND
ND
ND
ND
ND
ND
0.0156
ng/m3
All Sites
17,222
17%
0.0043 ± 0.0003
ND
ND
ND
ND
ND
0.0126
0.0254
3 Statistics presented are from pollutant datasets which were suitable for trends.
b The arithmetic mean is the average of all samples results which include actual measured values. If no chemical was registered, then a value of zero is
used when calculating the mean.
c ND: No results of this chemical were registered by the laboratory analytical equipment.
Page 4 of 25
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Table 4. Summary Statistics for Horicon, WI
Analyte
Units
# Data
Records
%
Detection
Arithmetic Mean3
Percentile Va
b
ue
5th
10th
25th
50th
75th
90th
95th
Acetaldehyde
(ig/m3
551
100%
1.03 ± 0.04
0.47
0.56
0.71
0.94
1.21
1.55
1.89
Arsenic (PM10)
ng/m3
535
99%
0.60 ± 0.05
0.12
0.16
0.26
0.45
0.75
1.15
1.55
Benzene
(ig/m3
542
72%
0.41 ± 0.03
ND
ND
ND
0.30
0.71
1.00
1.16
Benzo(a)pyrene
ng/m3
539
16%
0.05 ± 0.01
ND
ND
ND
ND
ND
0.29
0.39
Beryllium (PM10)
ng/m3
539
3%
0.0004 ± 0.0002
ND
ND
ND
ND
ND
ND
ND
Butadiene, 1,3-
l-tg/m3
542
0%
0.000 ± 0.001
ND
ND
ND
ND
ND
ND
ND
Cadmium (PM10)
ng/m3
537
96%
0.081 ± 0.006
0.019
0.025
0.041
0.067
0.102
0.151
0.188
Carbon Tetrachloride
l-tg/m3
542
41%
0.232 ± 0.031
ND
ND
ND
ND
0.454
0.613
0.744
Chloroform
l-tg/m3
542
20%
0.020 ± 0.007
ND
ND
ND
ND
ND
0.058
0.133
Chromium VI
ng/m3
215
56%
0.012 ± 0.002
ND
ND
ND
0.010
0.020
0.030
0.037
Formaldehyde
l-tg/m3
551
100%
1.59 ± 0.07
0.58
0.68
0.97
1.42
2.03
2.71
3.08
Lead (PM10)
ng/m3
535
100%
2.26 ± 0.14
0.51
0.69
1.12
1.82
2.80
4.51
5.64
Manganese (PM10)
ng/m3
535
99%
3.70 ± 0.24
0.81
1.08
1.72
2.95
4.76
7.15
9.60
Naphthalene
ng/m3
533
99%
12.98 ± 0.96
2.44
3.39
5.34
9.07
16.84
28.43
34.61
Nickel (PM10)
ng/m3
538
86%
0.50 ± 0.05
ND
ND
0.33
0.45
0.61
0.75
0.93
T etrachloroethylene
l-tg/m3
542
10%
0.037 ± 0.021
ND
ND
ND
ND
ND
ND
0.183
T richloroethylene
l-tg/m3
542
2%
0.005 ± 0.006
ND
ND
ND
ND
ND
ND
ND
Vinyl Chloride
l-tg/m3
542
0%
0.0003 ± 0.0005
ND
ND
ND
ND
ND
ND
ND
3 :The arithmetic mean is the average of all samples results which included actual measured values. If no chemical was registered, then a value of zerc
bND: No results of this chemical were registered by the laboratory analytical equipment.
Table 5. Analytical Labs Supporting this Site
is used.
Pollutant Group
2009
2010
2011
2012
2013
2014
2015
2016
2017
2018
VOCs
WSLH
WSLH
WSLH
WSLH
WSLH
WSLH
WSLH
WSLH
WSLH
WSLH
Carbonyls
WSLH
WSLH
WSLH
WSLH
WSLH
WSLH
WSLH
WSLH
WSLH
WSLH
PM10 Metals
WSLH
WSLH
WSLH
WSLH
WSLH
WSLH
WSLH
WSLH
WSLH
WSLH
Chromium VI
ERG
ERG
ERG
ERG
ERG
-
-
-
-
-
PAHs
ERG
ERG
ERG
ERG
WSLH
WSLH
WSLH
WSLH
WSLH
WSLH
Not Applicable
WSLH: Wisonson State Laboratory of Hygiene
ERG: Eastern Research Group, Inc.
Page 5 of 25
-------
Figure 3. Horicon, \Y I Annual Average Concentrations
2.0
a
3.
§
1.2
03 0.8
i—
C
U
c
o
U
0.4
0.2
0.0
Horicon, WI
Annual Averages:
Arsenic (PM10)
2010 2011
2012 2013 2014 2015
Year
2016 2017 2018
0.60
0.48
s
w 0.36
c
o
td
is 0.24
c
o
d 0.12
0.00
Horicon, WI
Annual Averages:
Benzene
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year
0.25
0.20
B
~oh
c
o
0.15
0.10
o
U 0.05
0.00
Horicon, WI
Annual Averages:
Benzo(a)pyrene
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year
Page 6 of 25
-------
Figure 3. Horicon, \Y I Annual Average Concentrations
0.005
0.004
S
a
^ 0.003
G3
.o
¦*—»
S3
¦g 0.002
u
c
U 0.001
0.000
Horicon, WI
Annual Averages:
Beryllium (PM10)
1 I
2010 2011
2012 2013 2014 2015 2016 2017 2018
Year
0.012
0.010
¦ej) 0.008
A
| 0.006 —
C3
g 0 004
o
c
U 0.002
0.000
Horicon, WI
Annual Averages:
1,3-Butadiene
2010
2011
2012
2013
2014
Year
2015
2016
2017
2018
s
c
o
e
u
o
e
o
U
0.15
0.12
0.09
0.06
0.03
0.00
Horicon, WI
Annual Averages:
Cadmium (PM10)
i
:L4
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year
S
3
O
c
o
u
e
o
U
1.0
0.8
0.6
0.4
0.2
0.0
Horicon, WI
Annual Averages:
Carbon Tetrachloride
2010
2011
2012
2013 2014
Year
2015
2016
2017
2018
Page 7 of 25
-------
Figure 3. Horicon, \Y I Annual Average Concentrations
o.io
0.08 4-
0.06
e
o
0.04
a
u
o
a
U 0.02
0.00
Horicon, WI
Annual Averages:
Chloroform
~
i
~
<
~
4
|
~
i
i , f *
2010 2011
2012
2013
2014
Year
2015
2016
2017
2018
3.0
2.4
s
~Sb
a- 1.
a
o
a
u
o
a
o
U
1.2
0.6
0.0
Horicon, WI
Annual Averages:
Formaldehyde
f
T
i i I i 1
2010
2011
2012
2013
2014
Year
2015
2016
2017
2018
5.0
4.0
s
3 0
-S
a
o
'ia 2.0
a
-------
Figure 3. Horicon, \Y I Annual Average Concentrations
10.0
8.0
^i)
c
o
c
o
C
o
U
30.0
24.0
18.0
12.0
6.0
0.0
Horicon, WI
Annual Averages:
Naphthalene
i
I
2010
2011
2012
2013
2014
Year
2015
2016
2017
2018
Horicon, WI
Annual Averages:
Nickel (PM10)
0.120
Horicon, WI
Annual Averages:
Tetrachloroethylene
1.2
0.096
^ 1.0
"S
"Si)
4
~ 4
"e
=*- 0 072
& 0.7
C
.o
i , -
*
c
o
2 0.048
<
~
2 0.5
c
83
o
c
—^ *—
*
a
-------
Figure 3. Horicon, \Y I Annual Average Concentrations
o.io
0.08
0.06
£
~SD
=l
§
g 0.04
g
u
a
o
O
0.02
0.00
Horicon, WI
Annual Averages:
Trichloroethylene
A
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year
0.008
B 0.006
Tsti
a
•2 0.004
c
-------
2.0
Figure 4. Horicon, WI - 3-Year Rolling Average Concentrations
Horicon, WI
3-Year Rolling Averages:
Acetaldehyde
E
~Bt)
3
c
o
1.6
1.2
i
0)
u
c
o
U
0.8
0.4
0.0
'On
°t*
'A
'*3 -%
Years
*°is *>/, *>/s
Page 11 of 25
-------
Figure 4. Horicon, WI - 3-Year Rolling Average Concentrations
1.0
Horicon, WI
3-Year Rolling Averages:
Benzene
s
"Sb
C
O
c
o
U
0.8
0.6
0.4
1 *
I
t
0.2
0.0
*0,
'Oo
*0.
'A
'/J
"-V
Years
•?o.
^o.
'S
v<,,
0.25
Horicon, WI
3-Year Rolling Averages:
Benzo(a)pyrene
B
c
c
u
o
c
o
U
0.20
0.15
0.10
0.05
0.00
«£>
-
-------
Figure 4. Horicon, WI - 3-Year Rolling Average Concentrations
Horicon, WI
3-Year Rolling Averages:
Beryllium (PMI0)
0.005
0.004
£
.2 0.003
c
o
U
0.002
0.001
0.000
1
¦?0,
•to/,
°o
"0/
Vj
J0,
*0.
*0.
'S
lo.
7n
¦?o.
'4s
''8
Years
Horicon, WI
3-Year Rolling Averages:
1,3-Butadiene
3.5E-03
-T 2.8E-03
£
s
J 2.1E-03
03
•r-
C
53
u
o 1.4E-03
U
7.0E-04
0.0E+00
*0,
»0
^//
ft
<>ft
'<¦0,
7p
'A
'"'ft
'/j
Years
^ft
7r
<>ft
7x
Page 13 of 25
-------
Figure 4. Horicon, WI - 3-Year Rolling Average Concentrations
0.15
Horicon, WI
3-Year Rolling Averages:
Cadmium (PM,„)
6
~5b
G
O
§
CJ
c
o
U
0.12
0.09
0.06
i
i__£
0.03
0.00
-\o
^0,
'//
^ ^
lOj
"
-------
Figure 4. Horicon, WI - 3-Year Rolling Average Concentrations
o.io
0.08
Horicon, WI
3-Year Rolling Averages:
Chloroform
n.
c
o
0.06
C5
*
o
'2o,
¦?0.
*0,
V?.
*0,
*0,
^O,
*0,
Vs.
*0/
6\
*o,
'// ^/? ""/J -"/
°SJ % -/
-------
Figure 4. Horicon, WI - 3-Year Rolling Average Concentrations
0.030
Horicon, WI
3-Year Rolling Averages:
Hexavalent Chromium
0.024
6J)
c
G
Q
G
O
U
0.018
0.012
0.006
0.000
i
^O,
i
*°'a
1
<"<5.
'K
'/J
T
*o.
i
7*
?s
Years
5.0
Horicon, WI
3-Year Rolling Averages:
Lead (PM10)
B
G
O
O
G
O
u
4.0
3.0
2.0
* i
* \
1.0
0.0
^°Og
7?
*o.
7?.
%
-t
Years
<»/.
<
"fyr
Page 16 of 25
-------
Figure 4. Horicon, WI - 3-Year Rolling Average Concentrations
5.0
4.0
3.0
£
c
a
.o
ca
a
o 2.0
c
o
U
Horicon, WI
3-Year Rolling Averages:
Manganese (PMI0)
tin
1.0
0.0
Jo,
'0/»
AJo.
O
Jo.
Jo,
Years
'/j-
v«r
"<"0,
Jo.
'Jo.
''8
Page 17 of 25
-------
Figure 4. Horicon, WI - 3-Year Rolling Average Concentrations
1.0
0.8
to
c
G 0.6
o
o 0.4
o
U
0.2
0.0
Horicon, WI
3-Year Rolling Averages:
Nickel (PM,„)
~
1—^
^ ^
^//
Years
Horicon, WI
3-Year Rolling Averages:
Tetrachloroethylene
0.150
_ 0.120
fl
s
g 0.090
"cd
H
C
53
C 0.060
o
U
0.030
0.000
®8.
-------
Figure 4. Horicon, WI - 3-Year Rolling Average Concentrations
Horicon, WI
3-Year Rolling Averages:
Trichloroethylene
^ 004
"s
c
0
p
i-l
1 0.02
o
O
0.01
4
~
<
~
<
~
. I
I i
t
a -
~ ~
-\>3 ^ ^
/*
Horicon, WI
3-Year Rolling Averages:
Vinyl Chloride
OX)
c
o
G
OJ
G
O
O
2.0
1.6
1.2
0.8
0.4
0.0
Jo.
-?ft
'/ft
'//
^O.
*0.
VA
'/<>
-'ft
'/J
*0,
'J3.
¦2o,
20,
-?ft
'Is
'/r
-'ft
&
'/?
Jo
'1*
Years
Does not meet MQO or wasn't able to collect enough samples
Page 19 of 25
-------
Table 6. NATTS Network Assessment: MQO#l - Completeness Percentage at Horicon, WI
Pollutant Group
Year
2009
2010
2011
2012
2013
2014
2015
2016
2017
2018
Carbonyl
Acetaldehyde
a
100
103
97
102
98
98
102
100
102
Carbonyl
Formaldehyde
a
100
103
97
102
98
98
102
100
102
Chromium VI
Chromium VI
a
100
100
100
--
—
--
—
"
—
PAH
Benzo(a)pyrene
a
95
97
97
100
98
97
98
100
100
PAH
Naphthalene
a
95
97
97
100
89
97
98
100
100
PM10 Metals
Arsenic (PM10)
a
93
97
93
92
100
97
100
102
100
PM10 Metals
Beryllium (PM10)
a
93
97
93
92
100
103
100
102
100
PM10 Metals
Cadmium (PM10)
a
93
97
93
92
100
100
100
102
100
PM10 Metals
Lead (PM10)
a
93
97
93
92
100
97
100
102
100
PM10 Metals
Manganese (PM10)
a
93
97
93
92
100
97
100
102
100
PM10 Metals
Nickel (PM10)
a
93
97
93
92
100
102
100
102
100
voc
Benzene
a
97
97
97
100
100
98
100
100
98
voc
Butadiene, 1,3-
a
97
97
97
100
100
98
100
100
98
voc
Carbon tetrachloride
a
97
97
97
100
100
98
100
100
98
voc
Chloroform
a
97
97
97
100
100
98
100
100
98
voc
T etrachloroethylene
a
97
97
97
100
100
98
100
100
98
voc
T richloroethylene
a
97
97
97
100
100
98
100
100
98
voc
Vinyl chloride
a
97
97
97
100
100
98
100
100
98
A-rated: >85%
B-rated: Between 75% to 85%
Does not meet: <75%
No data available
a: Scheduled sampling began midway through the year, thus, the site did not have the opportunity
to collect enough samples to meet the 85% MQO.
Page 20 of 25
-------
Table 7. NATTS Network Assessment: MQO#2 - Reported Method Detection Limits (MDLs) at Horicon, WI
Pollutant
Group
Pollutant Name
Target
MDL
Units
2009
2010
2011
2012
2013
2014
2015
2016
2017
2018
Carbonyl
Acetaldehyde
0.45
pg/m3
2.22
0.06
0.10
0.10
0.06
0.07
0.06
0.06
0.02
0.11
Carbonyl
Formaldehyde
0.98/0.08a
pg/m3
0.395
0.065
0.058
0.058
0.80
0.59
1.88
0.70
0.16
0.75
Chromium VI
Chromium VI
0.08
ng/m"
0.05
0.01
0.05
0.04
0.05
--
--
--
--
--
PAH
Benzo(a)pyrene
0.91
ng/m"
0.07
0.02
0.02
0.31
0.31
0.31
0.31
0.24
0.26
0.32
PAH
Naphthalene
29.00
ng/m"
0.008
0.004
0.004
0.005
0.005
0.005
0.005
0.005
0.005
0.008
PM10 Metals
Arsenic (PM10)
0.23
ng/m"
0.13
0.13
0.13
0.13
0.13
0.13
0.13
0.13
0.13
0.11
PM10 Metals
Beryllium (PM10)
0.42
ng/m"
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.024
0.024
0.021
PM10 Metals
Cadmium (PM10)
0.56
ng/m"
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.02
PM10 Metals
Lead (PM10)
15.0
ng/m"
0.001
0.001
0.001
0.002
0.002
0.002
0.001
0.001
0.001
0.001
PM10 Metals
Manganese (PM10)
5.0
ng/m"
0.019
0.019
0.019
0.019
0.019
0.019
0.019
0.019
0.019
0.019
PM10 Metals
Nickel (PM10)
2.1
ng/m"
0.04
0.04
0.04
0.04
0.04
0.04
0.04
0.04
0.04
0.04
voc
Benzene
0.13
pg/m"
2.46
2.09
2.09
2.09
2.09
2.09
2.09
0.37
0.34
0.34
voc
Butadiene, 1,3-
0.10
pg/m"
2.21
1.88
1.88
1.88
1.88
1.88
1.88
0.55
0.53
0.53
voc
Carbon tetrachloride
0.17
pg/m"
3.70
3.15
3.15
3.15
3.15
3.15
3.15
0.52
0.48
0.48
voc
Chloroform
0.50
pg/m"
0.98
0.83
0.83
0.83
0.83
0.83
0.83
0.24
0.22
0.22
voc
Tetrachloroethylene
0.17
pg/m"
3.99
3.39
3.39
3.39
3.39
3.39
3.39
1.44
1.36
1.04
voc
T richloroethylene
0.5/0.2a
pg/m"
1.07
0.91
0.91
0.91
2.28
2.28
2.28
0.40
0.40
0.40
voc
Vinyl chloride
0.11
pg/m"
2.32
1.98
1.98
1.98
1.98
1.98
1.98
0.40
0.37
0.37
A-rated: MDL to Target MDL ratio < 1
B-rated" MDL to Target MDL ratio between 1 and 2
Does Not Meet MDL to Target MDL ratio>2
No data available
a: For the 2012 sampling year, the Target MDL for this pollutant was reduced.
Page 21 of 25
-------
Table 8. NATTS Network Assessment: MQO#3 - Bias Percent Difference at Horicon, WI
Pollutant Group
Pollutant Name
2009
2010
2011
2012
2013
2014
2015
2016
2017
2018
Carbonyls
Acetaldehyde
-9.1
2.0
-4.6
a
-2.4
-11.9
a
-0.9
10.6
-4.2
Carbonyls
Formaldehyde
-5.4
2.0
-5.8
a
-2.7
-8.9
a
-10.4
-2.4
3.7
Chromium VI
Chromium VI
5.6b
10.5b
a
19.5
-6.5
--
--
--
--
--
PAH
Benzo(a)pyrene
-1.7
1
©
*00
o
d
45.6
-4.7
-36.0
-28.3
-40.7
-24.5
-11.9
PAH
Naphthalene
-7.7
-26.4C
d
8.0
7.1
-16.8
-33.6
-40.0
-40.1
-22.2
PM10 Metals
Arsenic (PM10)
-4.0
-15.5
-2.7
10.8
-4.2
1.3
a
0.8
-2.2
-2.5
PM10 Metals
Beryllium (PM10)
10.5
-6.0
3.7
14.7
4.1
e
a
5.6
2.5
-7.6
PM10 Metals
Cadmium (PM10)
9.1
-17.0
-4.6
12.0
-2.2
e
a
4.2
0.2
-5.4
PM10 Metals
Lead (PM10)
-14.1
-18.9
-0.3
16.8
1.6
3.9
a
4.5
2.3
-4.2
PM10 Metals
Manganese (PM10)
-28.3
-17.3
8.1
16.5
-5.4
e
a
3.4
2.0
-5.3
PM10 Metals
Nickel (PM10)
-13.1
-13.7
-5.1
5.2
-2.3
f
a
32.0
18.9
6.6
voc
Benzene
-12.2
18.7
43.4
a
11.9
8.9
-3.5
25.2
-7.8
1.8
voc
Butadiene, 1,3-
-12.8
50.0
36.8
a
10.4
2.7
-2.2
10.8
-17.7
-37.5
voc
Carbon tetrachloride
10.9
36.7
25.4
a
16.1
-20.6
g
120.9
13.7
-6.3
voc
Chloroform
-19.3
8.2
9.1
a
1.5
-7.8
-16.4
-0.5
0.1
4.7
voc
T etrachloroethylene
-18.2
7.5
20.8
a
-14.1
-26.7
-13.0
14.8
-7.0
-3.5
voc
T richloroethylene
-9.5
29.4
20.0
a
7.3
-8.3
-11.6
14.8
00
00
1
-3.1
voc
Vinyl chloride
-1.3
31.8
37.7
a
1.3
14.5
3.4
4.2
-10.6
2.4
A-rated:±25%
B-rated: Between 25% to 35% or between -25% to -35%
Does not meet:>35% or <35%
No data available
-
a: No Proficiency Test samples were sent for this pollutant and year.
b: Proficiency Test results are from the National Contract Lab for EPA's School Air Toxics Monitoring Program. The %Difference was -5.55% in 2009 and 10.53% in 2010.
c: Bias data presented is an average of the ERG and WSLH PT results.
d: Pollutant was sampled at this site and year, but no bias data were reported.
e: The Proficiency Test sample for this pollutant was 0; the site reported a concentration as "< MDL", rather than 0. EPA accepted this result.
f: Although a Proficiency Test sample was sent to the lab supporting this site and year, the results were nullified by EPA due to QA issues.
8: Bias data result was <0.085; this entry was deemed acceptable by EPA.
Page 22 of 25
-------
Table 9. NATTS Network Assessment: MQO#4 - Overall Method Precision %CV at Horicon, WI
Pollutant Group
Pollutant Name
Overall Method precision % CV
2009
2010
2011
2012
2013
2014
2015
2016
2017
2018
Carbonyls
Acetaldehyde
--
8.7
10.0
6.3
—
3.1
31.2
--
—
--
Carbonyls
Formaldehyde
--
9.7
10.5
7.9
—
8.4
15.0
--
—
--
Chromium VI
Chromium VI
~
21.1
9.1
16.5
a
—
—
--
—
--
PAH
Benzo(a)pyrene
~
—
5.8
a
a
a
a
--
a
a
PAH
Naphthalene
~
—
9.8
4.9
16.9
31.6
9.2
--
7.3
7.3
PM10 Metals
Arsenic (PM10)
—
3.0
24.1
5.6
11.6
3.5
2.7
9.8
18.5
18.9
PM10 Metals
Beryllium (PM10)
—
11.5
16.7
a
a
a
a
a
a
a
PM10 Metals
Cadmium (PM10)
—
4.7
30.2
61.5
16.1
40.6
8.8
18.9
33.4
45.0
PM10 Metals
Lead (PM10)
—
4.4
21.6
21.4
5.3
8.5
11.1
37.3
17.1
2.4
PM10 Metals
Manganese (PM10)
—
9.5
15.6
1.6
1.0
11.2
13.4
13.0
7.6
3.7
PM10 Metals
Nickel (PM10)
—
28.5
18.3
3.4
25.0
17.1
31.2
26.9
45.4
13.6
voc
Benzene
--
2.8
0.3
1.9
0.2
2.3
--
--
--
--
voc
Butadiene, 1,3-
—
a
a
a
a
a
—
--
—
--
voc
Carbon tetrachloride
—
a
a
a
5.5
a
—
--
—
--
voc
Chloroform
—
a
a
a
a
a
—
--
—
--
voc
T etrachloroethylene
—
a
a
a
a
a
—
--
—
--
voc
T richloroethylene
—
a
a
a
a
a
—
--
—
--
voc
Vinyl chloride
--
a
a
a
a
a
--
--
--
--
A-rated:< 15% CV
B-rated: Between 15%CV to25% CV
Does Not Meet: >25% CV or did not report Precision (required in the NATTS Workplan Template since 2012)
No data available
a: Although both primary and secondary data were reported, both sets of values were less than the MDL. Thus no %CV was calculated.
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Table 10. NATTS Network Assessment: MQO#4 - Analytical Precision %CV at Horicon, WI
Pollutant Group
Pollutant Name
Analytical Method precision % CV
2009
2010
2011
2012
2013
2014
2015
2016
2017
2018
Carbonyls
Acetaldehyde
—
~
--
a
a
a
a
a
a
2.1
Carbonyls
Formaldehyde
--
~
~
a
a
a
a
a
a
0.5
Chromium VI
Chromium VI
--
5.3
4.2
6.4
a
--
--
--
--
--
PAH
Benzo(a)pyrene
--
--
~
a
a
a
a
a
b
b
PAH
Naphthalene
—
—
—
a
a
a
a
a
0.8
1.3
PM10 Metals
Arsenic (PM10)
--
~
--
a
a
a
a
a
a
a
PM10 Metals
Beryllium (PM10)
~
~
~
a
a
a
a
a
a
a
PM10 Metals
Cadmium (PM10)
--
~
~
a
a
a
a
a
a
a
PM10 Metals
Lead (PM10)
~
--
~
a
a
a
a
a
a
a
PM10 Metals
Manganese (PM10)
~
~
--
a
a
a
a
a
a
a
PM10 Metals
Nickel (PM10)
~
~
~
a
a
a
a
a
a
a
voc
Benzene
—
~
~
a
a
a
a
a
a
4.9
voc
Butadiene, 1,3-
--
~
~
a
a
a
a
a
a
b
voc
Carbon tetrachloride
~
--
~
a
a
a
a
a
a
4.6
voc
Chloroform
~
~
--
a
a
a
a
a
a
b
voc
T etrachloroethylene
—
—
—
a
a
a
a
a
a
0
voc
T richloroethylene
—
—
—
a
a
a
a
a
a
b
voc
Vinyl chloride
--
~
~
a
a
a
a
a
a
b
A-rated:< 15% CV
B-rated: Between 15%CV to25% CV
Does Not Meet: >25% CV or did not report Precision (required in the NATTS Workplan Template since 2012)
No data available
a: Per the NATTS Workplan template, analytical replicates were required to be reported to AQS for this sampling year
b: The primary and/or replicate value were less than the MDL, so no calculation could be made.
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Appendix A. Equipment Inventory
Pollutant Type Year(s) Manufacturer/Model, Extraction Type, and Year
Sampling Equipment
Carbonyls
2009-2018
Custom-built (Year Deployed: <1999)
Chormium VI
2009-2013
ERG Chromium VI sampler (Year Deployed: 2009)
PAHs
2009-2015
Thermo Andersen GPS-1 PUF Sampler (Year Deployed: 2009)
2016
Thermo Andersen Hi-Vol; Thermo PS-1 Hi-Vol (Year Deployed: 2009)
2017-2018
Tisch TE-1000 PUF+ Year Deployed: 2017)
PM10 Metals
2009-2011
Anderson housing and impactor, TISCH volumetric control (Year Deployed: 2008)
2012-2015
Anderson Hi-Vol Model 321A sampler (2 units) (Year Deployed: 2008)
2016-2018
Tisch Hi-Vol (Year Deployed: 2015)
VOCs
2009-2018
Custom-built (Year Deployed: 2009)
Analytical Equipment
Carbonyls
2009
Waters Alliance 2695 HPLC /model 2996 PDA (Year Deployed: 2005)
2010-2012
Waters Acquity UPLC/PDA detection (Year Deployed: 2006)
2013-2018
Waters Acquity UPLC/PDA detection (Year Deployed: 2012)
Chormium VI
2009-2013
Dionex 300 ion chromatography system (Year Deployed: 2001)
PAHs
2009
HP/Agilent 5890/5971 GC/MS (Year Deployed: 2008)
2010-2015
HP/Agilent 6890/5973 GC/MS (Year Deployed: 2004)
2016-2018
HP/Agilent 6890N/5973 GC/MS (Year Deployed: 2004)
PM10 Metals
2009-2018
Thermo/VG Elemental PQ ExCell ICP-MS (Year Deployed: 2001)
VOCs
2009-2018
HP/Agilent 6890N/5975 GC/MS (Year Deployed: 2006)
Preconcentrator Equipment
VOCs
2009-2016
Entech 7100A (Year Deployed: 2006)
2017-2018
Entech 7200 (Year Deployed: 2017)
Standards Preparation Equipment
VOCs
2009-2016
Entech 4600 (dynamic dilution) (Year Deployed: 2004)
2017-2018
Entech DDS PG7-50.00-PSIA (dynamic dilution) (Year Deployed: 2017)
Canister Cleaning Equipment
VOCs 2009-2018 Entech 3100A (Hot) (Year Deployed: 2004)
PM10 Extraction Equipment
PM10 Metals
2009
Branson (Sonicator) (Year Deployed: 1980)
2010-2015
Environmental Express (Hotblock) (Year Deployed: 1980)
2016-2018
Environmental Express (Hotblock) (Year Deployed: 2016)
Chromium VI Extraction Equipment
Chormium VI
2009-2010
Branson 8510 (Sonicator) (Year Deployed: 2001)
2011-2011
Branson 8510 Sonicator/ Branson Shaker (Year Deployed: 2001/2011)
2012-2013
Branson Shaker (Year Deployed: 2011)
PAHs Extraction Equipment
PAHs
2009
Dionex -300 (ASE) (Year Deployed: 2004)
2010-2018
Lab Line (Soxhlet) (Year Deployed: <2000)
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