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NANO-D-12-06483
Workplace air measurements and likelihood of exposure to manufactured nano-objects,
Derk H. Brouwer, Birgit van Duuren-Stuurman, Markus Berges, Delphine Bard, Elzbieta Jankowska, Carsten Moehlmann, Johannes Pelzer, Dave Mark
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Supplemental Material NANOSH datasetFor the analyses reported here, results of measurements of agents such as ‘welding fume’ and ‘combustion products’ are excluded. A total of 459 measurement results are available for 146 different exposure situations, including 55 results from 26 background situations
I Number of measurement results (including NAS (14 measurement results) and PAS (61 measurement results) for each exposure situation representing an activity and each agent-group for solids and liquids. The agent-groups are defined as:
- High Aspect Ratio Nanoparticles (HARNs). This group contains the following particles: carbon nanotubes (multi-walled carbon nanotubes, single-walled carbon nanotubes), carbon fibers, silicon nanofibers
- Metal oxides. This group contains titanium(di)oxide and zincoxide nanoparticles.- Plates. This group contains commercial available nanoplates, namely polymer additive,
flame retardant and a synthetic clay.- Miscellaneous. This group contains all other particles in the database namely: benzoic
acid NPs, carbon black, cadmium selenide quantum dots, ceriumoxide, fumed silica, ferric oxide, aluminium oxide, catalyst, gadalinium, iron hdroxyl hydrated apatite, metal hydroxide, nanoparticles (not specified), silica nanospheres, toner.
Solids
Agent
Situation (excl background)
HARNS Metal oxides Plates miscellaneous
Prod – comm. 35 44 4 32
Prod – non-comm. 26 4 x 7
DSU – comm. x 37 x 59
DSU – non-comm. 61 x 51* 44
*Of these 51 measurement results, 15 results are related to activities involving burning.
Liquids
Agent
Situation
HARNS Metal oxides Plates miscellaneous
Prod – comm. x x x x
Prod – non-comm. x 4 x 2
DSU – comm. x 6 x x
DSU – non-comm. 4 x x 6
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Background measurement results for each exposure situation
Situation Background measurements (n)
Prod – comm. 12
Prod – non-comm. 3
DSU – comm. 5
DSU – non-comm. 35
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Figure. Distribution of NOAA(groups) produced or used in the different workplaces: High Aspect Ratio
Nanoparticles (HARNs) Metal oxides (MeO), Plates and miscellaneous NOAAs Panel (a): Distribution
of exposure scenarios for the different NOAA (groups). Panel (b): Distribution over the various
subcategories of workplaces. Prod-com = production – commercial scale, prod-non com = production –
non commercial scale, DSU-com = down-stream-use – commercial scale, DSU-non com = down-stream-
use – non commercial scale.
II Concentrations for each exposure situationSummary tables are made presenting concentration levels for each idevice for each agent-group for each exposure situation. Separate tables are made for the activities involving burning of foam, as during burning processes resulted in very high aerosol concentrations.
Activity Non-activity FrequencyRange median Range median
Instrument-group
< 100 nm
> 100 nm
Total* < 100 nm
> 100 nm
total
Down-stream-use of ENP – non-commercial scaleSMPS 233-953 105-
177 412-1053 204-741 88-132 339-829 2
Aerotrak 2.5 X X 1.7 X X 1Production of ENP – commercial scaleSMPS 1567 965 2343 1359 901 2311 1
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CPCX X 955561458-
11965 X X 89721424-12205 3
P-trak / portacount X X 7075-8405 X X 6815-8370 2
Grimm 5400 X X 6872-
667050 X X 29920-29920 4
APS X 0.6-7.4 X X 0.4-1.7 X 5ELPI 600-
71442992-3363
4449-305308
6952-9296
2933-3363 X 6
LQ-1X X 61.2-67.6 X X 60.2-68.4 2
Production of ENP – non-commercial scaleSMPS 156794
45-18976
667-2133
234310985-19627
13597765-
12087754-2066
23119730-14336 4
CPCX X 145817473-
25895 X X 1424-1424X 3
P-trak / portacount X X 10100-
26200 X X 16900-16900 4
ELPI 17142-23470
3633-11153
4449-305308X X X X 3
LQ-1X X 39.6-77.0 X X 40.0-40.0 4
Aerotrak 20.0-45.0 X X 19.0-
45.0 X X 3
Down-stream-use of ENP – non-commercial scaleSMPS 560-
84776114-2330 720-86462 790-
34470113-2246 903-36720 16
CPCX X 2250-45368 X X X 5
P-trak / portacount X X 5650-35400 X X 4205-4205 4
APSX 369-
7096 X X 376-8359 X 3
ELPI 9613-61700
3708-7845 X X X X 3
LQ-1X X 36.0-162.0 X X 28.0-148.0 13
Aerotrak 1.5-197.0 X X 1.3-
24.0 X X 4
HARNs (liquid) Metal Oxides (liquid)
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Activity Non-activity FrequencyRange median Range median
Instrument-group
< 100 nm
> 100 nm
Total* < 100 nm
> 100 nm
total
Production of ENP – commercial scaleSMPS 5114-
32783708-4755 6448-37177 3979-
20526355-3288
4348-23016 11
CPCX X 6702-43922 X X 6579-
29535 12
APS 13.84-8989.9
12.5- 67.0 12
Down-stream-use of ENP –commercial scaleSMPS 6272-
734982236-7478 8510-77697 6211-
226882223-2980
8540-25685 9
CPC
X X8540-
2568521570-37757
X X 15351-19202 4
P-trak / portacount X X 10599-18270 X X 11842-
18933 5
APSX 14.2-
58.1 X X 12.63-39.3 X 3
HARNs (solids)Metal Oxides (liquid)
Activity Non-activity FrequencyRange median Range median
Instrument-group
< 100 nm
> 100 nm
Total* < 100 nm
> 100 nm
total
Production of ENP – commercial scaleCPC X X 4683 X X 4669 1P-trak / portacount X X 2490 X X 2570 1
LQ-1 X X 33.8 X X 23.6 1Down-stream-use of ENP – non-commercial scaleSMPS 3238-
29436771-7231 5460-30250 2609-
10996738-7659
4490-18650 16
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P-trak / portacount 3402 2422 5980-22413 3093 2565 5665-
15366 15
AerotrakX 14.0-
20.0 X X 9-15 X 4
Metal Oxides (solid)Plates (solids)
Activity Non-activity FrequencyRange median Range median
Instrument-group
< 100 nm
> 100 nm
Total* < 100 nm
> 100 nm
total
Production of ENP – commercial scaleCPC
X X 4605-17770 X X 4372-18050 5
P-trak / portacount X X 2575-12000 X X 2400-
11600 5
ELPI 4401-6646
1207-3066 X 4062-
72631088-2812 X 5
LQ-1X X 21.44-69.2 X X 19.2-65.6 5
Production of ENP – non-commercial scaleSMPS 22154 1764 23529 2049 1634 3627 1P-trak / portacount X X 5244 X X 289 1
LQ-1 X X 93.0 X X 34.0 1Down-stream-use of ENP –commercial scaleDown-stream-use of ENP – non-commercial scaleSMPS 3332-
14370382-
17039 3714-31410 3272-16648
403-18958
3707-35796 14
P-trak / portacount X X 14505-
24827 X X 15528-27825 7
Aerotrak 9.0-48.0
21.0-33.0 X 9.0-31.0 21.0-
37.0 X 14
Miscellaneous (liquid)Miscellaneous (solid)
Activity Non-activity FrequencyRange median Range median
Instrument-group
< 100 nm
> 100 nm
Total* < 100 nm
> 100 nm
total
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Production of ENP – non-commercial scaleSMPS 3915 1578 5418 4072 1427 5499 1Aerotrak 27.0 X X 31.0 X X 1Down-stream-use of ENP – non-commercial scaleSMPS 3155-
4113320-1080 3499-4640 3153-
4377403-1080
3707-4858 3
Aerotrak 8.0-26.0 X X 9.0-25.0 X X 3
Background measurements
Activity Non-activity FrequencyRange median Range median
Instrument- group
< 100 nm
> 100 nm
Total < 100 nm
> 100 nm
Total
Production of ENP – commercial scaleCPC X X X X X 33540 1P-trak / Portacount X X 2690-22900 X X 2730-
8450 7
ELPIX X X 14762-
1381811432-5723 X 2
LQ-1 X X X X X 32.8 1Production of ENP – non-commercial scaleP-trak / Portacount X X 10100-
12000 X X X 3
Down-stream-use of ENP – commercial scaleSMPS X X X 6014 2194 8190 1P-trak / portacount X X X X X 9918 1
Down-stream-use of ENP – non-commercial scaleSMPS
X X X 4083-7406
679-8550
5045-16190 11
P-trak / portacount X X 11600-
26900 2717 3639 5238-15940 15
Aerotrak X X X X 6.0-27.0 X 9
Burning of foam
Activity Non-activity FrequencyRange median Range median
Instrument- group
< 100 nm
> 100 nm
Total < 100 nm
> 100 nm
Total
Down-stream-use of ENP – non-commercial scale
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SMPS 21281-380494
3272-26214
24553-401097
2440-23227
679-3081
3207-26350 6
P-trak / portacount X X 21921-
116558 X X 5238-47830 4
Aerotrak X 36-207 X X 6-44 X 4Overview ranges per activity, substance and device
Activity N Mean (um2/cm3)
std min (um2/cm3)
max (um2/cm3)
Dumping powder (small amounts)
3 8.8 6.8 1.5 15
Handling contaminated objects 1 30 - 30 30
Mixing powder in liquid 1 27 - 27 27
Pipetting liquid containing nanoparticles
2 9.5 2.1 8 11
Preparation of carbon fibres 1 24 - 24 24
Production NP using spinning drum
1 40 - 40 40
Scooping powder (small amounts)
4 70.8 95.0 17 213
Various tasks 5 33.8 12.0 22 50
burning 1 64 - 64 64
filtering and dividing liquid in 1 2.5 - 2.5 2.5
Instrument N Mean (um2/cm3)
std min (um2/cm3)
max (um2/cm3)
NSAM (TSI AEROTRAK) 16
32.1 49.7 1.5 213
Substance N Mean (um2/cm3)
std min (um2/cm3)
max (um2/cm3)
Other 4 43 17.2 28 64
HARN 8 45.4 69.4 1.5 213
Metal Oxide 8 17.8 8.7 8 30
LQ1 onlySubstance N Mean std min max
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(um2/cm3) (um2/cm3) (um2/cm3)Other 1
557.2 42.2 17.2 171.0
HARN 19
89.5 38.1 36.0 160.0
Metal Oxide 6 57.4 21.6 36.2 93.0
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Device N Mean (#/cm3)
std min (#/cm3)
max (#/cm3)
SMPS 88 23384 46747 234 361985
Ptrak/Portacount 1 3543 - -
ELPI 26 55167 12972 2361 55167
Substance N Mean (#/cm3)
std min (#/cm3)
max (#/cm3)
Other 51 27658 59335
2361 361985
HARN 31 17443 18012
234 87348
Metal Oxide 33 12290 14387
3067 66098
III Size modeDuring a limited number of measurements performed using the ELPI en SMPS information regarding the size mode could be collected. It was not possible to include size mode information for the background measurements. For the measurements performed during the activities omly limited information about mode is available.
Activity Non-activityRange size mode (nm) Range size mode (nm)
Situation< 100 nm
> 100 nm Total < 100 nm
> 100 nm Total
Production of ENP – commercial scale
14.1-68.5 X 14.1-
74.017.5-88.2 X 17.5-88.2
Production of ENP – non-commercial scale X X X X X X
Down-stream-use – commercial scale
15.1-27.9 X 15.1-
27.916.8-18.2 X 16.8-18.1
Down-stream-use – non-commercial scale 88.2 X 88.2-
151.2 X X X
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IV Concentration during activity plotted against concentration during non-activity (background)For every combination of situation and agent-group the particle concentration and surface area concentration is plotted against background concentration, and different graphs are made for particle sizes < 100 nm, > 100 nm and total number concentration. The graphs present the difference of the concentration during the activity with respect to the non-activity (activity/non-activity * 100 %). The results related to the burning of foam are excluded.
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HARNs
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Overview of A/B ratios (for the arithmetic means) expressed in categories used for the decision logic. The
particle concentrations in the range 20 nm-1000 nm (‘total’ concentration) as measured by CPC and the
concentration of the subfraction of particles < 100 nm (SMPS and ELPI data) are distinguished.
Ratio (A/B)
Exposure scenario <1.05 (%) 1.05 – 2 (%) > 2 (%)
Total particle concentration
Production – commercial scale 12 8 2
Production – non commercial 2 4 2
Down-stream-use – commercial scale 19 5 1
Down-stream-use – non commercial 15 23 10
All n=193 n=90 (47%) n=76 (39%) n=27 (14%)
Particle concentration particles < 100 nm
Production – commercial scale 6 6 2
Production – non commercial 3 5 1
Down-stream-use – commercial scale 11 6 0
Down-stream-use – non commercial 18 29 14
All n=118 n=45(38%) n=54 (46%) n=19 (16%)
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IV SUMMARY Tables and Figures
Range in concentrationsTable summarizing the range in median particle number concentration measured for particles < 100 nm, > 100 nm and total concentration and the range for instruments measuring the active surface concentration.
Measured unit Minimum 25
percentile50 percentile
75 percentile
Maximum Frequency
Particle conc.
< 100 nm
204 4547 8476 14785 380494 184
Particle conc.
> 100 nm
0.4 750 1643 2945 26214 220
Particle conc.
Total conc
289 7492 12850 19617 667050 310
Active surface area < 100 nm
1 12 23 30 197 38
Active surface area > 100 nm
6 15 25 33 207 30
Active surface area total
19 45 69 103 162 48
The two graphs below present boxplots representing all (includes foam burning results) number and surface area concentration levels for the particles < 100, > 100 nm and the total concentration.
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Duration measurementsTable summarizing duration of measurements in minutes.
Duration Minimum (min)
25 percentile (min)
50 percentile
(min)
75 percentile (min)
Maximum (min)
Frequency (n)
Activity 0.5 5 11 35 337 349
Non-activity
0.7 10 21 38 335 273
The graph below presents boxplots representing the durations of the measurements in minutes.
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V Results TEM analysis
Production - commercial scale Activities (n=19)Particle type Frequency of observation
Distinct/ primary nano
sized particles
none
10
few
9
many
X
Agglomerates number non
2
few
8
many
9
Agglomerates open/loosely bound
5
compacted bound
5
Aggregates non
3
few
9
many
7
Configuration fiber
X
plates
X
spherical particles
9
Non-activities (n=2)Particle type Frequency of observation
Distinct/ primary nano
sized particles
none
1
few
1
many
X
Agglomerates number non
X
few
X
many
X
Agglomerates open/loosely bound
X
compacted bound
1
Aggregates non
X
few
1
many
1
Configuration fiber plates spherical particles
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X X 1
Activities + non-activities (n=13)Particle type Frequency of observation
Distinct/ primary nano
sized particles
none
13
few
1
many
X
Agglomerates number non
X
few
X
many
X
Agglomerates open/loosely bound
1
compacted bound
2
Aggregates non
2
few
4
many
1
Configuration fiber
X
plates
X
spherical particles
X
Production - non-commercial scale Activities (n=2)Particle type Code
Distinct/ primary nano
sized particles
none
X
few
1
many
X
Agglomerates number non
X
few
X
many
1
Agglomerates open/loosely bound
1
compacted bound
1
Aggregates non
1
few
X
many
X
Configuration fiber
X
plates
X
spherical particles
1
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Activities + non-activities (n=5)Particle type Frequency of observation
Distinct/ primary nano
sized particles
none
2
few
3
many
X
Agglomerates number non
X
few
X
many
X
Agglomerates open/loosely bound
1
compacted bound
2
Aggregates non
2
few
2
many
1
Configuration fiber
1
plates
X
spherical particles
1
Down-stream-use – commercial scale Activities (n=13)Particle type Code
Distinct/ primary nano
sized particles
none
5
few
5
many
3
Agglomerates number non
1
few
6
many
6
Agglomerates open/loosely bound
X
compacted bound
1
Aggregates non
1
few
8
many
4
Configuration fiber
3
plates
X
spherical particles
3
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Activities + non-activities (n=6)Particle type Frequency of observation
Distinct/ primary nano
sized particles
none
X
few
4
many
2
Agglomerates number non
X
few
X
many
X
Agglomerates open/loosely bound
X
compacted bound
X
Aggregates non
X
few
3
many
2
Configuration fiber plates spherical particles
Down-stream-use – non-commercial scale Activities (n=11)Particle type Code
Distinct/ primary nano
sized particles
none
5
few
6
many
X
Agglomerates number non
1
few
4
many
5
Agglomerates open/loosely bound
6
compacted bound
6
Aggregates non
2
few
4
many
X
Configuration fiber
X
plates
2
spherical particles
2
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Activities + non-activities (n=3)Particle type Frequency of observation
Distinct/ primary nano
sized particles
none
1
few
2
many
X
Agglomerates number non
X
few
X
many
X
Agglomerates open/loosely bound
X
compacted bound
X
Aggregates non
X
few
1
many
2
Configuration fiber
1
plates
X
spherical particles
1
Summary of the results of the TEM analysis ; a positive identification (likely)was based on detection of
small discrete particles or loose agglomerates and verification of the presence of the elements of the
NOAA by EDX.
Likelihood
Exposure scenario Not likely (n) Possibly/not
excluded (n)
Likely (n)
Scenario measured during activity and non activity period
Production – commercial scale 1 0 10
Production – non commercial 1 1 3
Down-stream-use – commercial scale 0 0 4
Down-stream-use – non commercial 0 1 2
All n=23 2 2 19
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ScenarioScenarios measured during activity period
Production – commercial scale 4 2 12
Production – non commercial 0 1 0
Down-stream-use – commercial scale 2 0 9
Down-stream-use – non commercial 2 2 6
All n=40 8 5 27
ScenarioScenarios measured during non-activity period
Production – commercial scale 1 0 0
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VI RESULTS PER ACTIVITY/TASKResults surface concentration LQ1 (variable of interest ‘atotAM’)
Task Mean Std Min Max NAll tasks 77.8 44.6 17.3 211.0 40
Dumping powder 53.0 18.5 22.0 88.4 11
Sawing of objecs 127.6 22.8 92 160 7
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Box-plots of surface area concentration for all tasks (both alveolar (a) and tracheobronchial (tb) fractions) and for a specific subtask (scooping), only a-fraction
Results number concentration SMPS (variable of interest ‘as100am’)
Task Mean Std Min Max NAll tasks 26826 51838 234 380494 88
Bagging of powder 8834 2628 5501 12478 6
Burning of foam 172418 114422 71502 380494 6
Sawing of objects 31014 8501 20354 47457 7
Scooping powder (small amounts
21397 41994 234 96475 5
Various tasks 10473 5503 3131 19087 7
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Blending/mixing of powder
12354 7541 1504 29436 18
Results number concentration SMPS (variable of interest ‘ag100am’)
Task Mean Std Min Max NAll tasks 4253 5475 120 26214 88
Bagging of powder 1393 525 712 2202 6
Burning of foam 16410 7141 7536 26214 6
Sawing of objects 2041 341 1416 2294 7
Scooping powder (small amounts)
825 688 120 1703 5
Various tasks 1166 371 694 1660 7
Blending/mixing of powder
3650 3245 523 12993 18
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Table 4 Overview of the tasks / activity groups that were studied. and distribution of A/B ratios for the measurement results of the CPC only (n=193).
Activity group Number of measured situations (N)
Number of measurements (N)
Ratio (A/B) [n]<1.05 1.05 – 2 > 2
Bagging of powder 16 66 18 6 1
Scooping of powder 6 15 4 3 1
Dumping powder 13 61 24 7 2
Dumping powder (small amounts/closed system)
8 30 9 30
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Grinding powder 4 15 3 3 0
Blending/mixing of powder
19 41 4 21 8
Mixing powder into liquid
4 13 3 4 0
Sawing of objects 7 18 6 8 0
Handling contaminated objects/bags
5 18 3 0 0
Testing of flame retardant foams
6 15 0 0 10
Miscellaneous activities 25 91 12 14 5
Activities (not specified) 7 21 4 7 0
No activity (background)
26 55 n.a. n.a. n.a.
Total146 459 N=90
(46%)
N=76
40%)
N=27
(14%)
VII CONTROL MEASURESThe table below give an overview of the control measures used for each exposure situation. For 16 measured situations no information was reported.
Exposure situations
Type of Exposure Control Frequency (n)
Prod – comm. none 3
Complete enclosure 1
Complete enclosure, natural ventilation 2
Partial enclosure, LEV exterior, mechanical ventilation 3
Partial enclosure, LEV + enclosure, mechanical ventilation 3
Partial enclosure, LEV + enclosure, partial segreagation 1
Partial enclosure, LEV integrated + handtool, natural ventilation
3
Partial enclosure, LEV integrated + handtool, mechanical ventilation
1
Partial enclosure, LEV mobile 1
Partial enclosure, natural ventilation 1
LEV exterior, walk-in-booth, complete separation 2
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LEV + enclosure 1
Prod – non-comm. Complete enclosure 2
Partial enclosure, mechanical ventilation 1
LEV exterior, natural ventilation 2
LEV + enclosure 1
Mechanical ventilation 1
DSU – comm. Partial enclosure 3
Partial enclosure, LEV + enclosure, mechanical ventilation 2
LEV + enclosure 8
Mechanical ventilation 4
Mechanical ventilation, LEV+ enclosure 1
DSU – non-comm. Mechanical ventilation, LEV+ enclosure 10
Partial enclosure, natural ventilation 2
LEV exterior 7
LEV + enclosure 28
LEV + enclosure, natural ventilation, mechanical ventilation
3
Natural ventilation 1
Mechanical ventilation 7
Effects of VENTILATIONMean surface concentration LQ-1 (variable of interest ‘atotAM’) and mean number concentration SMPS (variable of interest ‘as100am’ and ‘ag100AM’) for each ventilation type.Ventilation type LQ-1 (all
particles) (AM (n))SMPS (particles < 100 nm) (AM (n))
SMPS (particles > 100 nm) (AM (n))
None/information missing
73 (32) 37909 (40) 4012 (40)
Natural 112 (5) 21788 (13) 3452 (13)
Mechanical 76 (3) 16032 (35) 4825 (35)
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Effect of ventilationTotal dataset (particle concentration)Ventilation N Mean
(#/cm3)std min
(#/cm3)max (#/cm3)
No ventilation 67 23975 50730 1101 361985
Natural 13 15445 14831 1112 48669
Mechanical 35 15707 26052 234 114181
Total dataset (surface area concentration)Ventilation N Mean
(um2/cm3)std min
(um2/cm3)max (um2/cm3)
No ventilation 11 41.1 59.9 2.5 213
Natural - - - - -
Mechanical 9 25.8 12.8 1.5 50
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LQ1Ventilation N Mean
(um2/cm3)std min
(um2/cm3)max (um2/cm3)
No ventilation 32 68.0 39.8 17.2 160.0
Natural 5 103.4 39.5 3667.0 171.0
Mechanical 3 70.7 39.7 36.0 114.0
Effects of ventilationHARNs and metaloxide (particle concentration)Ventilation N Mean
(#/cm3)std min
(#/cm3)max (#/cm3)
No ventilation 31 19560 19581 1101 87348
Natural 11 12716 12015 1112 36564
Mechanical 22 9094 10622 234 50991
LQ1 results (HARNs + Metalox)Ventilation N Mean
(um2/cm3)std min
(um2/cm3)max (um2/cm3)
No ventilation 20 84.8 39.8 36.2 93.0
Natural 3 83.7 14.5 67.0 62.0
Mechanical 2 49.0 18.4 36.0 160.0
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VIII Correlation Surface Area Concentration and particle number concentration
Table Correlations between simultaneoulsy measured particle concentration and ‘active’ surface
area concentration .
Correlation parameters N Pearson correlation (p)
Spearman correlation (p)
Active surface area concentration and particle
number concentration
153 0.83 (<0.0001) 0.83 (<0.0001)
A-fraction NSAM and SMPS particle < 100 nm 40 0.96 (<0.0001) 0.70 (<0.0001)
TB-fraction NSAM and SMPS particle > 100
nm
39 0.67 (<0.0001) 0.86 (<0.0001)
LQ-1 and CPC 74 0.85 (<0.0001) 0.78 (<0.0001)
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Plot of measured particle number concentrations and active surface area concentration (active and lung-deposited)
Legend: particle concentration < 100nm and A- fraction lung deposited surface area concentration
particle concentration > 100nm and TB- fraction lung deposited surface area concentration
(light grey solid) particle concentration 20- 100 nm and active surface area concentration
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